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Materials Horizons: From Nature to Nanomaterials

Ashok Kumar Nadda Editor

Biochar
and its
Composites
Fundamentals and Applications
Materials Horizons: From Nature
to Nanomaterials

Series Editor
Vijay Kumar Thakur, School of Aerospace, Transport and Manufacturing,
Cranfield University, Cranfield, UK
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Ashok Kumar Nadda
Editor

Biochar and its Composites


Fundamentals and Applications
Editor
Ashok Kumar Nadda
Department of Biotechnology
and Bioinformatics
Jaypee University of Information
Technology
Waknaghat, India

ISSN 2524-5384 ISSN 2524-5392 (electronic)


Materials Horizons: From Nature to Nanomaterials
ISBN 978-981-99-5238-0 ISBN 978-981-99-5239-7 (eBook)
https://doi.org/10.1007/978-981-99-5239-7

© The Editor(s) (if applicable) and The Author(s), under exclusive license to Springer Nature
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Preface

In the past decade, several researchers are focusing on the production of biochar from
a variety of raw materials and its applications in various fields. This carbon-based
product has gained much interest due to its unique properties and its direct correlation
with carbon sequestration and mitigation of greenhouse gases in atmosphere. The
biomass from various sources of animals, plants, agriculture, and forestry can be
converted by simple techniques of pyrolysis under oxygen-deficient conditions into
biochar. The biochar particles can be amalgamated with various other materials such
as magnetic particles and nanofibers and that can improve its properties. Usually, the
synthesized biochar is a highly porous material that has high water and gas absorption
properties. Thus, it can be utilized for the removal of various water pollutants, metal
ions, soil pollutants, and dyes and to improve the texture of soil. Also, the porous
nature makes it a suitable carrier for loading the fertilizers and their release in the
soil. Biochar also works as a habitat for the growth and colonization of various
soil-inhabiting microorganisms that are useful for the health of the soil. The current
methods of biochar synthesis and its composites need upcycling of various types
of biowaste and tuning their surface properties and durability. Therefore, it is quite
important to upgrade the biochar manufacturing technologies following the demand
for various applications in energy and environment.
The contribution from various researchers, and renowned collaborators in the
field of biochar and its composites, has made this book a suitable volume for its
readers. The information provided in this book is worth of interest in the areas of
water treatment and biotransformations along with the mitigation of climate change.
The compiled chapters will provide as a suitable reference manuscript for the soil
scientists, enviornmentalists, who are keen to get the most recent advancements in
the area of energy and climate change. The book will serve as a unique reference
for environmental science professionals pursuing their work in biomass treatment,
bio-based products as well as environmental management.
The first chapter describes the general introduction of biochar, and recent updates.
The next three chapters highlight the role of biochar in catalysis, as adsorbant, and
in carbon sequestration. Chaps. 5 and 6 detail the role of biochar in wastewater
treatment and mitigation of climate change. Further to explore the application of

v
vi Preface

biochar composites in various fields, Chaps. 7–9 emphasize on the role of biochar
composites in agriculture improvement and environment. The last chapters highlight
the applications of biochar in energy and environment.

Waknaghat, India Ashok Kumar Nadda


Contents

1 Introduction of Biochar: Sources, Composition, and Recent


Updates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
J. Maniraj, M. Ramesh, S. Ganesh Kumar, and A. Felix Sahayaraj
2 Biochar in Catalysis and Biotransformation . . . . . . . . . . . . . . . . . . . . . 19
K. Sobha, J. L. Jayanthi, G. Kavitha, and A. Ratnakumari
3 Biochar: A Potent Adsorbent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
Khaled Zoroufchi Benis, Jafar Soltan, and Kerry N. McPhedran
4 Biochar in Carbon Sequestration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
Mohammad Shirzad, Mohsen Karimi, Alírio E. Rodrigues,
and José A. C. Silva
5 Biochar for Management of Wastewater . . . . . . . . . . . . . . . . . . . . . . . . . 107
Ritu Painuli, Chetan Kumar, and Dinesh Kumar
6 Biochar for Climate Change Mitigation . . . . . . . . . . . . . . . . . . . . . . . . . 123
Ehsan Shahhoseini, Moslem Arefifard, and Mohsen Karimi
7 Clay-Biochar Composites for the Agriculture Industry . . . . . . . . . . . 145
Nurhani Aryana, Witta Kartika Restu, and Bayu Arief Pratama
8 New Trends in Biochar–Mineral Composites . . . . . . . . . . . . . . . . . . . . . 169
Javier Sartuqui, Noelia L. D’Elía, and Paula V. Messina
9 Magnetic Composites of Biochar and Its Applications . . . . . . . . . . . . 185
Abhinay Thakur and Ashish Kumar
10 Biochar Composites for Environmental and Energy
Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211
Khaled Zoroufchi Benis, Kerry N. McPhedran, and Jafar Soltan

vii
About the Editor

Dr. Ashok Kumar Nadda is working as an Assistant Professor in the Depart-


ment of Biotechnology and Bioinformatics, Jaypee University of Information Tech-
nology, Waknaghat, Solan, Himachal Pradesh, India. He holds extensive research and
teaching experience of more than 10 years in the field of microbial biotechnology,
with research expertise focusing on various issues pertaining to nano-biocatalysis,
microbial enzymes, biomass, bioenergy and climate change. Dr. Nadda is teaching
enzymology and enzyme technology, microbiology, environmental biotechnology,
bioresources and industrial products to the bachelor, master and Ph.D. students. He
holds international work experiences in South Korea, India, Malaysia and People’s
Republic of China. He worked as a post-doctoral fellow in the State Key Labo-
ratory of Agricultural Microbiology, Huazhong Agricultural University, Wuhan,
China. He also worked as a brain pool researcher/ Assistant Professor at Konkuk
University, Seoul, South Korea. Dr. Nadda has a keen interest in microbial enzymes,
biocatalysis, CO2 conversion, biomass degradation, biofuel synthesis, and bioreme-
diation. Dr. Nadda has published more than 200 scientific contributions in the form
of research, review, books, book chapters and others at several platforms in various
journals of international repute. The research output includes 140 research articles,
50 book chapters and 22 books. He has presented his research findings in more than
40 national/international conferences. He has attended more than 50 conferences/
workshops/colloquia/ seminars etc. in India and abroad. His research works have
gained broad interest through his highly-cited research publications, book chapters,
conference presentations, and invited lectures.

ix
Chapter 1
Introduction of Biochar: Sources,
Composition, and Recent Updates

J. Maniraj, M. Ramesh, S. Ganesh Kumar, and A. Felix Sahayaraj

1 Introduction

In several studies biochar have been manufactured using plants and degradable mate-
rials from biowaste. Biochar is often used to improve the soil quality and suitable
for agriculture. Biochar is manufactured using hydrothermal carbonization, pyrol-
ysis, gasification, and flash carbonization, etc. [1]. Biochar comprises 70% carbon,
and the remainder consists of nitrogen, oxygen, and hydrogen. Numerous researches
carried out on biochar manufacturing and the chemical processes that increase the soil
fertility [2–5]. The micropores in biochar have the remarkable property of terra preta
soil (soil manufactured using biochar), which accompanies living organisms and
leads to a higher yield in agricultural fields. This increases the production of crops,
and the terra preta biochar soil adsorption behavior leads to holding the water content
needed for agriculture. Land requires 10 L of water for agricultural purposes [6–8].
The biochar-developed soil required only 6 L of water in the same area. Further-
more, 40% of the water requirement is reduced, whereas soil fertility is increased.
Biochar reduces soil acidity and pollution of the water table. The carbon pores in the
biochar act as the filters that filter it, leading to the natural absorption of impurities
in the water. Biochar is manufactured using paddy straw (natural fibers and crop
waste), bio-compost, and charcoal too [9–11]. Degradation of the fibers, composts,
and charcoal produced the biochar. Biochar is often used to store more carbon, which
increases agriculture efficiency.

J. Maniraj · M. Ramesh (B) · A. F. Sahayaraj


Department of Mechanical Engineering, KIT-Kalaignarkarunanidhi Institute of Technology,
Coimbatore, Tamil Nadu, India
e-mail: mramesh97@gmail.com
S. G. Kumar
Department of Mechanical Engineering, Sri Eshwar College of Engineering, Coimbatore,
Tamil Nadu, India

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2023 1
A. K. Nadda (ed.), Biochar and its Composites, Materials Horizons:
From Nature to Nanomaterials, https://doi.org/10.1007/978-981-99-5239-7_1
2 J. Maniraj et al.

Fig. 1 Overview of biochar and its applications

Crop wastes decompose slowly by partially burnt carbon, such as paddy straw and
natural fibers. Heating of biomass with low oxygen content leads to the formation of
biochar, which is said to be a pyrolysis process. Biochar is available for several years
in the soil, which makes the soil more fertile. The partial burning in an environment
of low oxygen content prevents the complete combustion of wood or biowaste. In
the biochar manufacturing process, agricultural wastes, crops, and natural fibers are
partially burned, and charcoal is manufactured, which stores the carbon content for
agriculture. In addition to agriculture, biochar is also used in treating the wastewater
and soil conditioning, and its application in various sectors is enlisted as follows
[12–15]. An overview of biochar and its applications were shown in Fig. 1.

2 Sources of Biochar

Different sources, such as manure, leaves, animal wastes, wood chips, industrial
wastes, and animal wastes, manufacture biochar through two pyrolysis processes.
The fast and slow pyrolysis processes yield a varied range of biochar productions.
The process and various sources of biochar are shown in Fig. 2 [16].
1 Introduction of Biochar: Sources, Composition, and Recent Updates 3

Fig. 2 Sources and process


of biochar [16]

3 Composition of Biochar

The biochar is black, highly porous, lightweight, with approximately 70% carbon,
and remains composed of nitrogen, oxygen, and hydrogen [17]. The chemical prop-
erties of biochar include aromatic carbon rings with various functional groups such
as nitrogen, carbon, hydrogen, and sulfur [18]. Crystals of the graphite structure were
observed at low temperatures. Morphological comparison of aged and fresh biochar
was shown in Fig. 3.
Other elements, including oxygen, hydrogen, and nitrogen, made up the remaining
percentage. There are several methods that can be used to determine the composition
of biochar, including proximate analysis, CHN analysis, and feedstock approaches.
Proximate analysis, a thermo-gravimetric technique, has historically been regarded
as the most fundamental method for establishing char quality [19]. Chars utilized as
a fuel in boilers at chosen temperatures. For this application, char moisture and ash

Fig. 3 Comparison of fresh and aged biochar [18]


4 J. Maniraj et al.

constituents were those whose energy contents were unaffected. Excellent charcoal
has a high proportion of fixed carbon, some volatiles to facilitate fire and little ash.
CHN analysis is the second most popular technique and is essential for further
characterization to measure the carbon, hydrogen, and nitrogen contents in biochar
[20]. Using this technique, carbon dioxide (CO2 ), hydrogen (H2 ), and nitric oxide
(NO) are produced when a biomass burned at extremely high temperatures with
additional oxygen. The results of this analysis were presented as a percentage of
the dry weight of the sample [21]. Additionally, sulfur and oxygen contents can be
separately trapped and measured as part of the elemental analysis. From the analysis
volume of carbon, nitrogen, oxygen, chlorine, and ash can be calculated. The method
of measuring oxygen by difference is challenging because mineral oxides in the ash
ontinue to decompose.
The feedstock with pyrolysis process have a notable impact on the biochar compo-
sition [22]. For instance, biochar produced by slow pyrolysis contain over 90%
carbon and small amount of other elements. In contrast, biochar produced by pyrol-
ysis method which could contain only 35% carbon, a small amount of oxygen, and
more than 60% ash because of the high percentage of silica of the feedstock and
yield low carbon during the process [23, 24]. The majority of inorganic components
do not volatilize at ordinary pyrolysis temperatures, and the constituents of the ash
content of biochar are largely reliant on the minerals present in the feedstock. There
are various methods for determining which components are present in biochar and
in what proportions.

4 Biochar Production

Biomass is being converted to biochar because of growing interest in its use in


various applications. Thermochemical conversion is the most common technique
used to prepare biochar [25]. The classification of thermochemical conversion tech-
niques is shown in Fig. 1. To obtain maximum biochar yield, choosing an appropriate
fabrication technique and operating factors (temperature and heating time) is crucial.
These factors significantly influence the properties of the fabricated biochar. In addi-
tion, during biochar fabrication, the weight loss from biomass changes with respect
to time and environmental conditions. While heating at 100 °C, water vapor in the
biochar evaporated, and further heating tend to the degradation of cellulose, hemi-
cellulose, and lignin contents in the biochar [26]. The combustion of carbonaceous
waste is the final cause of weight loss. Various biochar production techniques were
shown in Fig. 4.
1 Introduction of Biochar: Sources, Composition, and Recent Updates 5

Fig. 4 Biochar production techniques

4.1 Pyrolysis

Pyrolysis is a frequently adopted technique to convert waste biomass into valuable


biochar [27, 28]. In this process, organic compounds are thermally degraded without
oxygen. This process involves various reaction mechanisms, such as depolymer-
ization, fragmentation, and cross-linking, which are carried out on lignocellulosic
components. The output is obtained in multiple states, such as biochar (solid) and
bio-oil (liquid), whereas CO, CO2 , H2 , and syngas are the gaseous outputs. The
biochar fabrication requires a variety of reactor designs, including agitated sand-
rotating kilns, wagon reactors, bubbling fluidized beds, and paddle kilns. The type
of biomass and process variables like temperature and time affect, how biochar
develops. Generally, as the temperature increases during production, the biochar is
reduced, and gaseous product output is increased. Pyrolysis is further divided into
two processes, fast and slow, based on various factors. Fast pyrolysis is thought to
be a direct thermochemical method with a high heating rate that has great poten-
tial for converting solid biomass into biochar and bio-oil [29]. Meanwhile, the slow
pyrolysis heating rate was low, with a longer residence time.
Biomass consists of the following components: cellulose, hemicellulose, and
lignin. In slow pyrolysis, cellulose decomposition at a low heating rate and long resi-
dence time produce biochar at a higher volume. Levoglucosan is produced by fast
pyrolysis, which takes place at a higher temperature for a shorter time. Furthermore,
Levoglucosan undergoes dehydration for producing the bio-oil and syngas. Addition-
ally, this process yields solid product biochar. Hemicellulose degradation is similar to
cellulose degradation. Depolymerization of the hemicellulose results in the formation
of oligosaccharides. Various chemical reactions occur during pyrolysis to produce
biochar, bio-oil, and syngas. The lignin decomposition mechanism is different from
those of cellulose and hemicellulose. Free radicals are created when the lignin bonds
break [30]. By absorbing protons from different species, these produces free radicals
form degraded compounds. These free radicals are transferred to different molecules
and initiate new chain reactions.
6 J. Maniraj et al.

4.2 Hydrothermal Carbonization

Hydrothermal carbonization is another technique used to produce biochar at low


processing temperatures (180–250 °C) [31]. This is a cost-effective way to produce
biochar compared to pyrolysis. In this process, biomass was mixed with water and
kept in a closed reactor. To increase stability, the temperature was gradually increased.
The following items were created at various temperatures. Hydrothermal carboniza-
tion, which produces biochar below 260 °C, and hydrothermal liquefaction, which
yields bio-oil between 260 and 420 °C, are terms used to describe the production of
syngas at temperatures above 420 °C. The biochar (hydrochar) fabrication process
involves condensation, polymerization, and intramolecular dehydration [32]. The
conversion of lignin to hydrochar is a difficult process. Dealkylation and hydrolysis
are the first steps in the degradation of lignin, which produces phenolic compounds.
The final product, char, is formed by polymerization and cross-linking of the interme-
diates. The dissolved parts of lignin in the liquid phase are converted into hydrochar,
which is similar to pyrolysis.

4.3 Gasification

It is a thermo-chemical process that produces syngas and hydrocarbons from carbona-


ceous material. The gasification was performed at higher temperatures in the presence
of oxygen [33]. The reaction temperature most significantly influence the syngas
production. CO and H2 production increase with increasing temperature, but the
production of CH4 , CO, and hydrocarbons decreased. Syngas is the major end-
product of this process, and char is to be a by-product with a minimum yield. The
biomass moisture content was fully evaporated during this process, and no energy
was recovered. When biomass has a huge moisture content, drying is done separately
during the gasification process. The primary sources for the gasification process are
the oxidation and combustion of the gasification agents. CO2 , CO, and water are
produced in the gasifier as a result of the interaction between these agents and the
combustible species.

4.4 Torrefaction and Quick Carbonization

Torrefaction is a recently developed method for biochar preparation at a slow heating


rate [34]. This process uses inert ambient air without oxygen at 300 °C. The oxygen,
moisture, and CO2 available in the biomass are eliminated during various break-
down processes. Biomass parameters were modified during torrefaction. Torrefaction
involves the following processes:
1 Introduction of Biochar: Sources, Composition, and Recent Updates 7

(a) Steam torrefaction: In this process, steam was used to treat biomass at a
temperature (260 °C) for 10 min.
(b) Wet torrefaction: This process occurs due to biomass being in contact with water
in a temperature range of 180–260 °C for 5–240 min.
(c) Oxidative torrefaction: This method involves treating biomass with oxidizing
agents, such as gases used in combustion, to produce heat. This heat is employed
to create the necessary temperature.
Torrefaction is a form of incomplete pyrolysis that occurs under the following
conditions: 200–330 °C, less than 40 min of residence time, less than 60 °C/min
heating rate, and an absence of O2 . Heating, drying, torrefaction, and cooling are
some processes that make up the dry torrefaction process [35]. There are two types
of drying processes: pre-drying and post-drying. The biomass was heated through
this process until the necessary temperature was maintained and the biomass moisture
content evaporated. This process continued at 100 °C until all the biomass’s moisture
evaporated. The water content get fully evaporated when the temperature was raised
to 200 °C. A higher temperature causes bulk content to be lost. During this procedure,
a stable temperature of 200 °C was attained.
Room temperature is attained by allowing the temperature to cool after product
production before it comes into contact with air. High pressure is used to ignite the
flash fire on a tightly packed layer of biomass, which causes it to transform into solid-
and gas-phase products. The entire procedure was completed in less than 30 min at
a temperature of 300–600 °C. With increasing pressure, the process slows down to
where approximately 40% of the biomass is transformed into solid products. Flash
carbonization is a technique that has rarely been utilized in the literature.

5 Properties of Biochar

5.1 Physical Properties

5.1.1 Particle Size

The particle size of the feedstock before pyrolysis was comparable to that of particle
size of chars produced at low temperature [36]. The char steadily loses the volatile
compounds throughout the pyrolysis process and becomes increasingly porous while
maintaining its general size and shape. The incomplete feedstock combustion and
creation of dust from rubbing the now-friable char particles during pyrolysis resulted
in fine particles that were produced, such as those found at the bottom of charcoal
kilns. The quick escape of volatiles is thought to produce fine at higher heating rates
as particles fracture under the internal pressure created. Chars from these processes
often have a very small particle size (1–100 µm) owing to the preprocess grinding
of feedstock, which is typically performed to facilitate the heat transfer for quick
gasification and pyrolysis [37]. The risk of problems arising from dust increases as
8 J. Maniraj et al.

the particle size decreases. The easiest way to quantifying the particle size is through
a sieve down to approximately 50 µm. Techniques for counting laser particles may
be useful for smaller particles.
The low density of chars makes it challenging to apply settling techniques such
as those used to categorize soil texture (char floats instead of sinking in water).
Both bulk density, which accounts for structural and pore space volume, and particle
density, also known as skeletal or true density, which solely accounts for the volume
occupied by solid molecules, can be used to determine the density of the char. The
bulk density can be calculated by incorporating a known quantity of sample mass into
a known volume container. Because of the enormous impact of compaction on pore
volumes, measurement standards usually incorporate specific guidelines for sample
packing or settling. Biochar has a low bulk density of 0.2–0.5 g/cc, although this may
change depending on the feedstock and manufacturing procedure. For instance, the
contribution of the mineral material will result in much greater densities of chars from
high-ash feedstocks or methods that produce low char carbon levels. A pycnometer
was used to measure the particle density, higher than the bulk density for a particularly
solid material because the pore volume was no longer be considered. The compaction
did not affect the particle density. As carbon condenses into dense, aromatic ring
structures at high pyrolysis temperatures, the biochar particle density typically ranges
between 1.6 and 1.8 g/cc. The particle densities of some high-temperature chars may
even be close to that of solid graphite (2.25 g/cc) [38]. Particle density increases with
ash content, much like bulk density, and for high-ash chars can exceed 2.0 g/cc.

5.1.2 Pore Size

Based on pore size, biochar has one of three types of porosity. Material scientists
categorize pores into micropores, mesopores, and macropores based on their internal
dimensions, which are 2, 2–50, and >200 nm, respectively [39, 40]. Each range of
pore sizes influences the characteristics of the sample. The majority of the surface
area of activated carbon (AC) is contributed by micropores (2 nm), which are essential
for adsorption applications. Biochar macropores impact soil hydrology and micro-
biological habitats when used in soil applications. The easier it is for water, roots,
and fungal hyphae to pass through the particle with greater the number of pores.
Pores offer protection to micro-organisms from larger predatory organisms. Due
to plant structure maintenance, biochar frequently has specific pore size distribu-
tions and arrangements. Numerous approaches have been used to measure the pore
distribution in solid materials [41]. Micropore analysis with CO2 and N2 are exam-
ples of this technique used for chars. Mercury porosimetry is another technique that
determines the size of a pore depending on the force needed to pore. Macro and meso-
pore measurements are frequently performed using mercury porosimetry. Mercury
porosimetry has the drawback of simultaneously measuring both the internal and
external pores [42]. When given as a single sample attribute, porosity is the ratio
between the total pore volume to the total sample volume.
1 Introduction of Biochar: Sources, Composition, and Recent Updates 9

Fig. 5 Key parameters affecting the efficiency of a typical biochar

5.1.3 Surface Area

The amount of interaction of biochar and the soil environment is highly influenced
by the surface area of the biochar; the higher the surface area, the more chemical
interactions per gram of biochar are possible [43]. The method for calculating the
surface area, which is useful for soil applications, has been a topic of debate. The
measurement of the gas sorption isotherm was the most systematic analysis. Surface
area measurements can vary depending on the isotherm temperature and gas used
for analysis. The surface area of the AC is typically measured using the Brunauer–
Emmett–Teller (BET) N2 gas physisorption method at 77 °K over the normal
pressure range. The BET surface areas for lower-temperature biochar are about
1 m2 /g, which is slightly greater than that of lingo-cellulosic biomass since the
majority of pores are macropores. Long residence duration, higher temperatures,
and activation techniques, such as steam heating, all lead to high BET surface areas,
which encourage the growth of micropores in the carbon. Depending on the feedstock
and pyrolysis technique, some biochar can have surface areas of 100 or even 1000 m2 /
g, potentially making them appropriate for AC applications. However, the maximum
achievable surface area was reached because the surface area was lost as the micro-
pore structure finally transformed into macropores. The parameters considered in the
manufacturing of biochar and the key parameters that determine the performance of
biochar are shown in Fig. 5.

5.2 Chemical Properties

5.2.1 Heating Value

The high heating value (HHV) of the char, which increases with the energy it
contains, influences whether it is used as charcoal or biochar [44]. Bomb calorimetry,
which assumes that all combustion products are allowed to cool to 26 °C, is used to
10 J. Maniraj et al.

calculate the amount of energy that can be produced from the char by burning. A
different approach to figuring out the energy content using the lower heating value
examines the energy of burning. Generally, the HHV increases as the carbon and
H2 contents increase and decreases respectively and the moisture, oxygen and ash
contents increase. The HHV of chars also differs because feedstock and technique
considerably impact the char composition. Char co-products from the processes have
substantially lower HHVs than low-ash slow pyrolysis chars, which can have HHVs
of around 35 MJ/kg.

5.2.2 Carbon Fraction

The majority of the chemical characteristics of biochar are relevant to “carbon frac-
tion” ideas called aromaticity and functionality [45]. Aromaticity is the measure of
how much carbon in char participates in aromatic bonding. Because lignin (aromatic
rings) and sugar polymers have only aliphatic carbons, lignocellulosic feedstocks
have limited aromaticity. During the pyrolysis process, oxygen and hydrogen were
destroyed, allowing the excess carbons to form new bonds. The structures get increas-
ingly “orderly” as the temperature rises, generating ever larger sheets of interlinked
aromatic rings. At the greatest temperatures, the organization of these sheets changes
from chaotic to aligned, stacked sheets that resemble graphite. The value of aromatic
condensation in biochar is assumed to be connected to environmental noncompli-
ance because carbons in dense, aromatic structures are more resistant and few micro-
organisms have enzymes that can break down such bonds. Aromatic molecules are
more stable because they have many bonds where electrons are shared. By “spreading
out” electrons across the molecule, these molecules are able to reside in lower energy
states than non-aromatic compounds. Electrons can be efficiently shared by graphite
and some other highly condensed chars, and they can even conduct electricity. The
majority of techniques for determining the degree of aromatic condensation in char
are comparable to those for determining surface functionality. The two other ways
being researched are electrical conductance/resistivity and particle density.
Numerous chemical inter-relations between biochar and the environment are influ-
enced by the surface chemistry of the biochar [46]. In lignocellulosic feedstocks, -OH
groups, COOH, and short alkyl groups, like methyl groups, are the most common
surface functional groups. This form of surface chemistry typically results in feed-
stocks that are polar, hydrophilic, or mildly reactive. The chars created by pyrolysis
have very different surface chemistry. After the majority of functional groups have
volatilized off, aromatic carbon surfaces are still present. The surfaces were nonpolar,
decreased, and hydrophobic (carbon was in the CO oxidation state). As these surfaces
are exposed to air over time, carbon oxidation causes the surface to become polar
once more.
There is a production of new functional groups with oxygen, such as hydroxyl,
carbonyl, and carboxylic acids [47]. These functional groups are essential for the
interactions between biochar and soil. First, depending on the pH, these functional
groups can take or donate protons (H+) due to their varying charges. At higher pH
1 Introduction of Biochar: Sources, Composition, and Recent Updates 11

values, some hydroxyls (-OH) and carboxylic acids (−COOH) acquire a negative
charge. Under low pH, these similar groups can take up protons. When using high-ash
alkaline chars, the feedstock’s ash percentage can counteract the effects of the carbon
fraction on the pH. Secondly, positively charged cations can be drawn to negatively
charged surface functional groups, significantly raising soil CEC. The hydrophobic
and hydrophilic portions of the biochar surface allow for the adsorption of polar and
nonpolar organic molecules from the environment. For instance, when char absorbs
organic molecules or contaminants from the environment, this adsorptive potential
might be useful. A pesticide may, on the down side, adhere to these surfaces and
lose some of its potency. To find out more about the potential chemical interactions
of biochar, various aspects of its surface functioning might be investigated. It is
important to keep in mind that in all of these processes, especially at initially, the
surfaces of the biochar alter with contact to the environment [48]. Fresh char that has
just been removed from the pyrolizer has surface properties that are very different
from biochar that has been buried for many years or left out in the open for a number
of weeks.

5.2.3 pH

When choosing the right char for a particular application, it is crucial to understand
how biochar impacts pH because soil pH has a significant impact on a variety of
physical, chemical, and biological characteristics [49]. Another method for figuring
out the acidity of char is titration. By titrating the char with progressively stronger
bases, this method determined the kinds of acidic functional groups that were present.
Acids of different potencies can be used to make comparable measurements of char
alkalinity. For high-ash content of chars, which might act as liming agents in soils,
the general ability of biochar to neutralize acids is especially important.
The pH of the biochar varies from 4.6 to 9.3. Biochar is often used to reduce the
soil’s acidity, directly increasing soil pH, making it suitable for agricultural use [50].
Biochar is produced at 300–400 °C. The properties and behavior of fresh and aged
biochar vary with the carbon content. The SEM images show the surface smoothness
of aged biochar and fresh biochar. A reduction in oxygen content and an increase in
carbon content were observed in aged biochar. The physical properties of a typical
biochar include its surface area, particle size, grinding ability, bulk density, and
particle density [51].

6 Applications of Biochar

Biochar is used in various sectors such as the food industry, wastewater treatment,
building sector, energy production, soil conditioner support for catalyst development,
cosmic industries, and metallurgy etc. [52]. It is used as a natural filter in wastewater
treatment. The micropores in the biochar led to water filtration, leading to purification.
12 J. Maniraj et al.

Biochar is often used for the removal of pesticides, volatile compounds, contami-
nants, chlorine, etc. The removal of volatile organic compounds is done using the
biochar by carbon adsorption technique. Numerous studies have been conducted on
biochar filtration of organic compounds. Active biochar filters are the most effec-
tive filters for volatile compounds, odors, etc., and have proven that the presence
of hydroxyl and carboxyl ions acts as cation exchangers. The classical structure of
graphite connects neighboring atoms with carbon atoms, increasing the absorption
property of biochar [53–55].
Due to its low thermal conductivity, biochar is often used in the building sector.
Biochar restricts heat transfer through the walls. Hence, it is used as an insulator for
fences. The biochar was mixed with cement mortar and lime at a 1:1 ratio for wall
insulation. This leads to an excellent breathing property of the walls that maintains a
relative humidity of 45–70% in summer and winter. This, in turn, prevents the user
from respiratory disorders, allergies, etc.
Biochar was used as a soil conditioner. It enhances soil quality and increases
the water-absorbing capacity owing to its porous nature. Thus, this reduces the cost
and frequency of irrigation. The water consumption of agricultural fields is reduced,
resulting in a reduction in water evaporation. In addition, biochar has a liming effect,
which leads to increased alkalinity to maintain the pH value of the acidic soil. In
metallurgy industries, biochar significantly improves leach and pulp carbon. Mining
companies use biochar to reduce carbon content. AC is used in floating circuits, and
powdered carbon is used as a modifier. Molybdenum, zinc, and copper are examples
of the application of biochar in the mining industry. In 2010, the Japan Consulting
Institute suggested that biochar be produced in the place of coke and coal. Palm
shell biochar has been proven to be the best alternative fuel for furnaces [56–58].
The biochar process completely replaces environmental pollution caused by heavy
metals such as mercury, arsenic, and selenium. The ash residue is free from hazardous
waste and reduces pollution.
The application of biochar in the food industry in the form of AC is used in
sugarcane refining, purification of liquid sugar, manufacturing of beverages, fruit
juices, star-based food products, biochemical food products, natural glycerin, food
oils, lactose, and flavoring [59]. Biochar is used in energy production, the most
cost-effective way of producing electrical energy, and it acts as a substitute for coal.
Syngas is produced as a coproduct, whereas biochar is used as an alternative fuel to
diesel and petrol in internal combustion engines. Syngas and bio-oil are substitutes
for gasoline and biodiesel oils. The energy density of syngas oil is higher than that
of biochar; hence, it acts as a promising energy storage material used for burning
to produce electricity and is used in gasoline engines [60]. Biochar oils have a high
vapor content, leading to the corrosion of steel surfaces.
1 Introduction of Biochar: Sources, Composition, and Recent Updates 13

7 Potentials of Biochar in India

In India, most work is concentrated in the agricultural industry. Improvement in


soil fertility leads to farm production efficiency. The global demand for biochar
has been analyzed and is based on the production of biochar in India [61]. It has
increased considerably in past decades. 80% of India’s biochar is used to improve
soil fertility in agricultural lands. An average of 376.11 megatons of carbon dioxide
equivalent carbon in the soil could help India reduce emissions from 41 to 61% of
farming fields. Since biochar has the potential in food, mining, agricultural, water
treatments, and soil conditioning, the biochar potential is more and is needed for
multiple industries to manufacture the commercial products. Agriculture is India’s
backbone. Hence, the biochar will definitely help the manufacturers for mass produc-
tion of goods to increase the country’s economy. Biochar is applied to sandy desert
soil for low water consumption to cultivate crops [62]. Researchers have demon-
strated a 16% increase in the efficiency of crop production in sandy desert soils.
Nitrogen is a crucial component of plant growth and reproduction.
The presence of nitrogen in biochar helps plant reproduction and growth. Among
the manufacturing processes for biochar, pyrolysis is an efficient process often used
to manufacture biochar. During pyrolysis, the biomass is heated and partially burnt
without oxygen. During pyrolysis, biomass generates power and syngas. Biomass is
stored and dried initially in dedicated biomass storage equipment. The dried biomass
was transferred to the pyrolysis reactor through a conveyor or bucket feeder. The
biomass was allowed to flow into the pyrolysis reactor, where hot and dried air
flowed into the biomass chamber before entering the reactor. Hot airflow reduces
the moisture content, which allows it to burn efficiently during pyrolysis. Biomass,
such as husks, natural fibers, wood pieces, and animal waste, is fed to the pyrolysis
reactor. The moisture content accumulated depended on the biomass process mate-
rial. The upper part of the reactor was maintained at a high temperature to reduce
the moisture content of the biomass. After the biomass process material dehumidi-
fies, the degasification process is carried out in the process chamber at 300–400 °C to
remove volatile components such as carbon monoxide, carbon dioxide, and nitrogen.
After degasification in the reactor, the biomass was treated at a high temperature for
carbonization. In this phase, the disappearance of the fiber structure and its transfor-
mation into carbon leads to biomass production, which improves the grindability and
porosity of the biomass material. After the carbonization process, the process mate-
rial (biomass) weight was reduced, allowing suitable transportation from one place
to another [63]. After the carbonization reaction, the biomass material had a calorific
value of 29–31 MJ/kg of biochar. The biochar produced was allowed to cool in the
cooling chamber using cross-flow heat exchangers at ambient temperature after the
carbonization reaction.
14 J. Maniraj et al.

8 Conclusion

Biochar is a gift of nature that supports agriculture, metallurgical fields, food, mining,
etc. Due to the broad scope of biochar, its suitability is higher, and its manufacturing
potential is high in India due to the agricultural backbone of the nation. From the
research, the following statements are concluded.
• The porosity of the biochar was high, which reduced the irrigation frequency. The
suitability of biochar for desert sandy soils was high.
• High carbon content increases the plant growth and acts as a filter for organic
impurities and volatile compounds.
• Porosity in nature leads to water treatment plants’ application and increases plants’
adsorption effect.

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Chapter 2
Biochar in Catalysis
and Biotransformation

K. Sobha , J. L. Jayanthi , G. Kavitha , and A. Ratnakumari

1 Introduction

Biochar, a high-carbon solid, is produced by the thermal decomposition of feedstocks


like crop waste, livestock manure, and cellulose-rich materials under low oxygen
conditions [1]. Rapid industrialization, urbanization, and population growth result in
the generation of massive amounts of organic waste, which include agro-, industrial-
, sea-, forestry-, domestic-, or municipal-solid waste (MSW), and animal manure.
Along with these, the global energy requirement is also increasing. The prepara-
tion and utilization of biochar to improve soil fertility is followed since ancient
times by agriculturists across the globe. Biochar is most commonly made by smol-
dering agricultural waste in pits or trenches [2]. Organic wastes, the major fraction
of solid biomass, can be turned into biochar. The physico-chemical characteristics
like the high surface area to volume, porosity/voidity, organic reactive groups, ion
exchange ability, and stable strength make it suitable for various ecological appli-
cations. Process parameters, viz. temperature, biomass nature, persistence/residence
time, temperature rise per unit time (heating rate), and pressure decide the yield of
biochar [3]. The major components of all biochar are carbon and minerals, but the
ultimate composition and characteristics are determined by the biomass type, reaction
conditions, and reactor types used for the carbonization. The activated carbon from
coal approximately contains 80–95% carbon, while biochar contains 45–60 wt%
carbon and carbon black have the highest, about 98% [4]. The physical and chemical
characteristics of biochar produced vary with temperatures employed for processing.
The lightweight black deposit, called ‘Biochar’ (BC), contains inorganic elements
like K, Na, Ca, Mg, and Fe in small quantities [5]. The amount and composition of
inorganics will vary greatly depending on the chemical build-up of raw biomass [6].

K. Sobha (B) · J. L. Jayanthi · G. Kavitha · A. Ratnakumari


Department of Chemical Engineering, RVR and JC College of Engineering (A), Guntur,
Andhra Pradesh 522019, India

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2023 19
A. K. Nadda (ed.), Biochar and its Composites, Materials Horizons:
From Nature to Nanomaterials, https://doi.org/10.1007/978-981-99-5239-7_2
20 K. Sobha et al.

Functionalization of biochar, using its surface functional groups, facilitates the


manufacture of biochar-supported metal-catalysts [7]. Kitano et al. [8] investigated
cellulose hydrolysis by a 2D carbon allotrope, viz. graphene sheets containing SO3 H,
−COOH, and phenolic −OH groups, functioning like solid-catalytic agents. The
sulfonated carbon is reported to be better at hydrolyzing cello-hexose than sulfonic
acid (SO3 H)-bearing resins. The carbon material contains fatty acid (−COOH) and
phenolic-hydroxyl (-OH) groups as sites for the adsorption of ligands. Research
reports suggest that biochar-based solid-acid catalysts with a combination of these
functional groups show good efficiency for hydrolyzing cellulose and 1,4-glucan.
Biochar adsorbs toxic heavy metals and contaminants, and its sorption efficiency is
directly related to its physicochemical attributes, augmented by treatment with acid/
alkali/oxidizing chemical substances [9–11]. The advantages of biochar include its
eco-friendliness, ease of preparation, reusability, cost-effectiveness, and ability to
convert waste into repurposed products [12, 13].
An essential property of biochar is its porosity, along with the availability of
numerous surface functional groups. Due to this feature, it can immobilize diverse
chemical pollutants present in the soil and thereby decrease their bioavailability and
toxicity. Biochar and the electroactive bacteria present in the habitat can exchange
electrons [14, 15] and thus mediate oxidation–reduction reactions [16]. In addition,
biochar serves as a nutrient substrate for electroactive bacteria [14] and plants.
Biochar has immense potential to sequester soil pollutants in agricultural fields.
Several varieties of crop refuge like the straw of cereals, viz. paddy and wheat [17,
18], wood scrap [19], sugar-beet tailings [20], and maize cob [21], are utilized for
producing BC. Plant refuges (e.g. rice husk, wood bark, sugar beet tailings, skele-
tons of fruit-free bunches, pinewood, and woodchips) and animal-derived organic
wastes (e.g. human, cattle, and poultry manure) are the common feedstocks for
biochar production. The raw materials and the production methods influence the
heavy metals, viz. Cu, Zn, Ni, Pb, Cr, Mn, and several organic pollutants, viz. per-
fluoro-octane-sulfonic acid (PFOS), polycyclic-aromatic hydrocarbons (PAH), per-
fluoro-octanoic acid (PFOA), phenols/dioxins/furans (PCDD/F), and organic acids
[22]. Furthermore, BC produced from animal discards has a specific pore character-
istic (generally, on the lower side) due to the ash and other inorganic compositions
of the feedstock, as compared to BC generated from plants at the same process
(pyrolysis) conditions and retention time [23, 24].
Biochar applications include soil fertility enhancement, increased seed germina-
tion rate, improved growth rate of plants, enhanced pathogen deprivation of soil,
adsorption of toxicants, reduction of greenhouse gas emissions [25, 26], wastew-
ater treatment [27], energy production [28], and catalysis [29, 30]. Besides, biochar
serves as an energy fuel and carbon sink. Magnetic biochars (MBCs), with their high
adsorption capacity and total recovery due to magnetic properties, have fascinated
researchers across the globe toward their development from diverse biomass feed-
stocks. Magnetic biochar/c-Fe2 O3 is prepared by keeping the biomass submerged
in a solution of FeCl3 for 2 h followed by keeping it at 80 °C for 2 h in ambient
2 Biochar in Catalysis and Biotransformation 21

environmental conditions and then, pyrolyzed in a furnace at 600 °C for 1 h in N2 -


enriched ambience. When compared to conventional BC, the adsorption capacity of
MBC increases 3–4fold [31–34].
In terse, the first and foremost benefit is the simplicity of the BC production
and economic feasibility because of the possibly uninterrupted supply of biomass
feedstocks and evolved techniques. Second, the physical and chemical properties
can be designed as per the requirement of the application [35]. Third, biochar can
also aid catalysis because of its inherent structure, availability of inorganic species,
surface charges, etc. [36].

2 Characterization of Biochar

The methods employed in characterization give valuable information about the struc-
ture/topology of the material, constituent functional groups, and elemental compo-
sition, and thereby help in the determination of functional characteristics. Structural
and molecular characterization is done by thermogravimetric analysis (TGA), trans-
mission electron microscopy (TEM), X-ray diffraction (XRD), Nuclear Magnetic
Resonance (NMR), and Raman spectroscopy methods. Of these, scanning elec-
tron microscopy is used to identify biochar morphology; functional/reactive groups
through Fourier transform infrared, nuclear magnetic resonance, and Raman spec-
troscopy; and surface elements are identified through scanning electron microscopy
and energy dispersive X-ray analyses. Physical properties like pH, electrical conduc-
tivity, and chemical properties (surface area/expanse, particle size distribution, bulk
density, and pore dimensions) are determined by Brunauer–Emmett–Teller (BET)
analysis.

3 Properties of Biochar

Biochar’s ‘void fraction’ and ‘expanse’ are two factors that influence its metal sorp-
tion capacity. Depending on the pyrolysis temperature, pore sizes of biochar range
from micro (<2 nm) to macro (>50 nm) through nano (<0.9 nm). Biochar comprises
moisture, ash components, fixed and labile carbons, and volatile compounds. BC with
diverse ‘C’ compounds is very stable up to 100 or 1000 years, and hence supports
perennial ‘C’ seclusion [37].

3.1 Hydrogen Ion Strength (pH) of Biochar (BC)

pH of BC is neutral to alkaline, because of the metal oxides generated from cations


(e.g. potassium, calcium, silicon, and magnesium) during pyrolysis. If the feedstock
22 K. Sobha et al.

of biochar is rich in mineral concentration, it will have a higher ash content, and
consequently higher pH [38]. The inclusion of biochar with a higher pH into the soil
leads to the reduced solubility of metal cations and finally their precipitation [39].

3.2 Biochar Cation Exchange Capacity (CEC)

The positive ion exchange is determined by surface area with functional groups
and structure; CE materials like resins provide negative surface charges which are
able to attract cations like Na+ , Ca2+ , NH4+ , K+ , and Mg2+ and thereby increase
the concentration of nutrients in the soil and its fertility [40]. CEC gives the total
exchangeable positive ions, which are the potential binding groups of a material [41].
Biochar, produced at temperatures >500 °C, has a low CEC due to aromatization and
loss of binding groups [39], while biochar formed at a lower temperature has a high
CEC and can hold cations like ammonium [42].

3.3 Stability of Biochar (BC)

The stability of biochar depends on its source material characteristics and the pyrol-
ysis temperatures; enhanced pyrolysis produces sturdier biochar [43]. Such stable
biochar is ideal for long-term soil amendments like nutrient retention [44], carbon
sequestration, and pesticide-remediation of contaminated soils.

4 Biochar in Catalysis

Salient features of biochar that contribute to its catalytic activity include its unique
chemistry and measurable, maneuverable surface functional groups that could be
employed for functionalization. This offers effective support for diverse chemical
processes, including the upgradation of biomass, its hydrolysis, dehydration, pyrol-
ysis, gasification, and bio-oil generation. With increasing efforts to explore renewable
energy sources in sufficient quantities, the production of biofuels like biodiesel with
the use of carbon-based catalysts has emerged. It was reported by Konwar et al. [45]
that biodiesel production can be enhanced with the use of biochar as a catalyst.
However, biomass-derived biochar has inherent limitations with respect to its
catalytic and/or catalytic support activity, in terms of low surface area, porosity, and
a lesser number of functional moieties. Therefore, activation and functionalization
processes are pre-requisites for tapping the highest catalytic potential of the biochar
produced from different types of feedstock material. As aforementioned, the activa-
tion process results in an increased number of active sites and high loading and mass
transfer capacities that are crucial to catalysis and increase the yield of the desired
2 Biochar in Catalysis and Biotransformation 23

products. The steps involved in the activation or functionalization needed to override


the innate limitations in terms of low surface area, porosity, and a lesser number of
functional moieties, are outlined in the flowchart (Fig. 1).

Fig. 1 An overview of biochar activation/functionalization and major applications


24 K. Sobha et al.

The regulated stream of water vapor, CO2 , or both at a temperature of 700 °C


causes the separation of ‘C’ from C–H2 O and/or C–CO2 by erosion, and with the
result, the surface carbons get stripped off, the biochar matrix gets opened up, and the
specific surface area gets significantly enhanced. In general, the extent of activation
is influenced by the biomass type and its microstructure, the activating gas, and
the reaction conditions. However, the general outcome of the reported experimental
studies suggests a dramatic enhancement in the porosity and surface area of the
biochar material.
In general, the porosity and the surface area increase with the increase in temper-
ature up to 1000 °C, but a further rise in temperature decreases the surface area due
to the collapse of the pore walls, leading to the formation of a graphite-like structure
in the biochar matrix. Dehkhoda et al. [46] reported more than twofold higher elec-
trosorption capacitance at 675 °C as compared to 1000 °C. In general, the biochar
produced at temperatures below 400 °C demonstrates a low pH, a small surface area,
and low electrical conductivity [47], and from researchers’ reports, it can be inferred
that the properties of biochar are closely related to the charring temperature range
of 100–600 °C and, in turn, related to the functional groups [47, 48]. It is important
to note the following with respect to the functional groups and the transition in the
charring temperatures:
1. 1D-NMR spectra demonstrate a two-phase characteristic; the transition temper-
ature for charring occurs at 300 °C.
2. Aliphatic O-alkylated carbons (HCOH) were predominant at 73 ppm, and these
were replaced by fused-ring aromatic structures (128 ppm).
3. For biochars produced at temperatures below 300 °C, the NMR bands over-
lapped in the region of 50–100 ppm, while for temperatures above 300 °C, the
overlapping region was between 100 and 150 ppm [49, 50].
4. Further, for wood char, treatment at 300 °C produced lignin and cellulose-
enriched residues, with carbohydrates being totally lost at 350 °C, and at 450 °C,
the aromatic structures completely replaced those of lignocellulose.
From the synchronous and asynchronous maps of 2D C13 NMR correlation spectra,
it can be inferred that the biochar production from plant-derived polymers is by
dealkylation, dihydroxylation/dehydrogenation, and aromatization, as the intensity
of aliphatic O-alkylated (73 ppm) and fused-ring aromatic structure (128 ppm)
changed with the increasing charring temperature. The order identified from asyn-
chronous maps is from 73–105 ppm (cleavage of aliphatic O-alkylated groups and
aromatic O–C–O carbons) to 128 ppm (generation of fused-ring aromatic structures).
Further, research studies suggest the determination of the properties of biochar, viz.
pH and electrical conductivity (EC), as negatively correlated to O-alkylated groups
and positively correlated to fused aromatic ring structures.
Two major steps are involved in converting the produced biochar into an effi-
cient catalyst: one is the physical and/or chemical modification, followed by surface
functionalization through acidification, amination, oxidation, and metal impregna-
tion; the second is better activation of the biochar by providing higher temperatures,
which in turn results in better yields (Table 1). The raw biomass, or biochar, is treated
2 Biochar in Catalysis and Biotransformation 25

Table 1 Yields of biochar from different bio-resources with the values of surface area and void/
pore characteristics
Feedstock Expanse/surface Void/pore characteristics Yield References
area Volume Size
(m2 /g) (cm3 /g (nm)
Maize residue 5.5 0.0142 17.3 90% @300 °C Lee et al. [29]
Palm shell 570.85 0.260 3.6 80% @550 °C Yek et al. [53], Chen
et al. [54]
Pine cone 375 0.0289 2.9 43% @380 °C Lee et al. [29]
Rice husk 24 0.0189 4.8 58% @350 °C
Japanese wood 371 0.0177 2.9 56.4% @380 °C
Mixed wood 1.3 0.0019 10.6 53.9% @380 °C

Table 2 Feedstocks for biochar and derived catalysts with their generation methods
Feedstock/raw Generation (production) method Solid References
material Biochar (BC) Biochar-derived catalyst
catalyst
Banana Carbonization Moisture-loaded Alkali Jitjamnong [55]
(Combustion) (wet impregnation)
Corn stover Hydrolysis Sulfonation Acid Sihan et al. [56]
Switch grass Hydrolysis Sulfonation Acid Sihan et al. [56]
Woody biomass Fast pyrolysis Chemical Alkali Cao et al. [4]
activation
Kitchen waste Slow pyrolysis Physical activation Alkali Lishan Niu et al.
[57]
Pamelo peel, Palm Carbonization Moisture loaded Alkali Zhao et al. [58]
kernel with shell (Combustion) (wet impregnation)
Calcination

with metal salts of FeCl3 , FeCl2 , and MgCl2 to form metal oxide–biochar composites
by raising the pH. Magnesium is considered a suitable cation for metal impregna-
tion due to its role in the chlorophyll formation of plants. Avocado seed biochar
was impregnated with iron or magnesium oxide by post-pyrolysis and used for the
removal of phosphate [51]. By impregnation method and pyrolysis [52], using sugar-
cane as feedstock and Fe/Mn, metals are impregnated, and the adsorption of ozone
was 122 and 116.2 mg/g by Fe- and Mn-impregnated catalytic biochar, respectively.

5 Classification of Biochar-Derived Solid Catalysts

The biochar-based catalysts are solid and classified into two types: acid and alkali
catalysts.
26 K. Sobha et al.

5.1 Acid Catalysts

When carbon-rich biochar is acid-treated, particularly with an acid reagent containing


sulfur, a solid-acid biochar catalyst is formed. Sulfonation is the main process for
making biochar into a solid-acid catalyst, which has many applications such as the
production of biofuels, energy conversion, as electrodes, heavy metal removal from
industrial effluents, helping to prevent contamination of soil and water, etc. Ager-
atina sp. and Quercus sp. biochars are converted to solid-acid biochars by sulfonating
with concentrated sulfuric acid, chlorosulfonic acid, and p-toluenesulfonic acid. The
biochar was treated with a solid-to-acid ratio of 1:20 for concentrated sulfuric acid and
chlorosulfonic acid and 53.52 g of p-toluene sulfonic acid, which contain equivalent
mole numbers of sulfonic acid, using hydrothermal, simple heating, ambient temper-
ature, and CHCl3 -assisted treatments. Chlorosulfonic acid, concentrated sulfuric
acid, and p-toluenesulfonic acid show acidification efficiency in increasing order
under hydrothermal treatment [59]. The reagents commonly utilized for the sulfona-
tion of biomass and/or biomass-derived biochar include concentrated sulfuric acid,
oleum, gaseous sulfur trioxide, chlorosulfonic acid, sulfamic acid, sulfosalicylic acid,
and p-toluene sulfonic acid [60–62]. Direct sulfonation of incompletely carbonized
organic matter produced amorphous carbon with SO3 H, COOH, and OH groups that
demonstrated exceptional, insoluble bronsted acid activity for various acid-catalyzed
reactions (e.g. cellobiose hydrolysis). These acid catalysts showed higher reactivity
and efficacy for crystalline cellulose, glucose, and cellobiose hydrolyses than with
niobic acid, H-mordenite, and resins like Amberlyst-15 and Nafion NR50 [8, 63,
64]. Sihan et al. [56] used solid biochar-derived acid catalysts for the hydrolysis of
biomass. A sulfonating rice husk char with concentrated H2 SO4 was prepared as
a catalyst for the esterification of oleic acid and methanol conversion [65]. Cheng
et al. [36] prepared a solid-acid catalyst with the biochar of a partially carbonized
peanut shell by sulfonation, while Joyleene et al. [66] made a heterogeneous biochar-
derived catalyst via KOH activation and fuming H2 SO4 sulfonation. They found that
the transesterification yield of canola oil was 44.2% at 150 °C and 1.52 MPa with
this catalyst (Table 2).

5.2 Alkali Catalysts

An alkali-based BC catalyst is prepared by impregnating alkali chemicals into biochar


at high temperatures [67]. The biochar surface chemistry and porosity properties can
be altered by impregnating with alkali metals. Anthonysamy et al. [68] modified the
biochar with four different alkali chemicals, viz. Potassium hydroxide, Potassium
bicarbonate, Sodium Hydroxide, and Sodium bicarbonate, by varying their mass
ratio from 1:1 to 3:1 parts, respectively (alkali chemical/biochar) for adsorption of
nitric oxide (NO). The KOH-impregnated biochar demonstrated 62.0 and 63.0 mg/g
adsorption capacity for an impregnation ratio of 1:1 and 3:1 respectively, and it shows
2 Biochar in Catalysis and Biotransformation 27

maximum NO uptake (87.0 mg/g) for 2:1 impregnation ratio at an optimum temper-
ature of 600 °C. A porous carbon melaleuca bark alkali biochar, synthesized with
KOH at a temperature of 1023 °K, had a high expanse of 3170 m2 g−1 , a large void
volume of 0.86 cm3 g −1 , and numerous surface oxygen groups, and presumably these
factors contributed to its high H2 storage capacity (4.08 wt% at 77 °K and 1 MPa)
[69]. Anthonysamy et al. [70] studied the BC catalyst (derived from biomass)-driven
oxidation of NO to NO2 , at ambient temperature. Lignocellulosic waste derived
from rubber seed shell (RSS) was converted to biochar for NO capture. The NO
adsorption capacity of pristine biochar was low, about 17.61 mg/g at 30 °C. Hence,
Cerium (Ce) was impregnated into the biochar surface; this 3 wt% Ce-loaded biochar
demonstrated the NO adsorption of 75.59 mg/g at the same adsorption conditions.

6 Biochar—A Favorable Catalyst

Biochar can be a good heterogeneous catalyst and/or catalyst support by virtue of


its intrinsic properties [55]. It has a good thermally, mechanically, and chemically
stable, hierarchical structure that originates from biomass. As a supporter of cata-
lysts for carbon-rich nanoparticles, biochar provides more active sites to undergo
catalytic degradation reactions [71]. Metal-supported biochar catalysts promote the
performance of bio-refineries and electrochemical industries [4]. The incorporation
or fixing of copper (Cu), cadmium (Cd), and lead (Pb) into biochar pores results in
less metal escape into the aqueous phase [4, 72, 73]. The following are some of the
distinctive characteristics of biochar:
(i) Heterogeneity: The reaction mixture can be segregated from other reactants.
(ii) Bifunctionality: Both esterification and transesterification could be effected;
(iii) Recyclability: Easy desorption of the adsorbate confers recyclability.
(iv) Porosity: Different pore types, viz. cavities, channels, or interstices, present in
biochar could be altered or introduced during pyrolysis to serve as microbial
carriers.
(v) Non-graphiţable: do not form crystals when heated to high temperatures [74].
There are many applications of biochar as a catalyst [73] in many different fields
(Fig. 1), like transesterification [56], biodiesel and syngas production [66], elec-
trochemical industries [75], agriculture, environment (degrading organic contami-
nants) [57], energy [67], tar removal, wastewater treatment [76, 77], and production
of chemicals [78]. Due to the presence of inorganic elements including Fe and K,
biochar is catalytically active in cracking tar [79]. Biochar-based catalysts are, in a
nutshell, economical, environmentally friendly, easy to synthesize, and recyclable
when compared with other solid-based catalysts.
28 K. Sobha et al.

6.1 Biodiesel Production with Biochar-Derived Catalysts

Xiong et al. [30] studied the catalytic use or support of biochar for different high-
impact applications, including the production of methyl esters, commonly called
biodiesel. Biodiesel produced from plant sources like cotton stalks, waste wood chips,
pine chips, palm kernels, vegetable oils, etc. is a potential alternative to petrochemical
diesel. From the literature, sulfonated biochar could be identified as an efficient
catalyst for biomass hydrolysis and subsequent biodiesel production. However, for
viable practical application of biochar catalysts for biodiesel generation [80, 81],
the strength of biochar catalysts must be ensured and remove the need for Ca or S
removal by post-treatment methods.
Biochar is used as a catalyst in the production of biodiesel from the esterifica-
tion of free unsaturated fats or the transesterification of vegetable oils with alcohol
(Fig. 1). Biodiesel production using heterogeneous (solid) catalysts offers a number of
advantages, such as lower corrosion risk, easy separation, and being eco-friendly and
reusable. For biodiesel production, CaO or biochar or K2 CO3 or KOH-functionalized
biochar can be used as catalysts. A conventional solid catalyst is CaO for the trans-
esterification of oils from their respective feedstocks. The advantages of CaO-based
catalysts are that they are highly basic in nature, so they require mild conditions and
are easy to prepare from natural resources with little or no cost. Calcium carbonate
from palm kernel shell biochar (PKSB) is an excellent source material for producing
a CaO-based catalyst by gasification [82]. The time required for the catalyst for the
transesterification of sunflower oil to their corresponding fatty acid methyl esters
(FAMEs) and glycerol is 4 h. The optimum reaction conditions calculated from the
kinetic model are a 3% catalyst amount based on the oil mass, a 65 °C tempera-
ture, and a methanol-to-oil molar ratio of 9:1. The PKSB catalyst can be reused
for three consecutive runs without any modification. Weldeslase et al. [83] prepared
Zn–Cao nanocatalyst from the calcinated limestone and 5% Zn by wet impregna-
tion process for large-scale production of biodiesel. The size of Zn-doped lime-based
CaO nanoclays is 12.51 nm. The process of biodiesel production from waste cooking
oil and CaO nanocatalyst was optimized using the box-Behnken design of response
surface methodology, and the optimized parameters are a methanol-to-oil molar ratio
of 14:1, or 5% weight, catalyst loading rate at 57.5 °C temperature, and 120 min time
obtained 96.5% highest biodiesel conversion. By box-Behnken design of response
surface methodology, the production of biodiesel from allamanda seed oil (ASO) was
optimized by Abdullahi et al. [84] using a KOH-modified metakaolin catalyst. With
the optimized conditions of reaction temperature (52.5 °C), time (180 min), catalyst
concentration (0.5% wt), and methanol/ASO molar ratio (5:1), a maximum yield of
90.14% biodiesel was obtained, which met the fuel standard specifications of ASTM
D-6751 and EN 14,214. Alsaiari et al. [85] reported that with CaO nanoparticles
synthesized at 950 °C from eggshells and used as a catalyst with date seed oil as
the feedstock, 85% biodiesel yield was obtained. The other optimum conditions are
4 wt.% catalyst loading, a 1:12 oil–ethanol ratio, and a 75 °C temperature, and the
2 Biochar in Catalysis and Biotransformation 29

characteristics of the formed ethyl esters were consistent with the ASTM D-6571
and EN 14,214 specifications.

6.2 Energy Storage

In electrical and electronic devices like lithium-ion batteries and super capacitors,
energy storage is required, which mainly depends on the type of electrode mate-
rial (Fig. 1). Carbon nanotubes, activated carbon, and graphene are generally used
electrodes that have a high surface area and porosity, providing active sites for the
oxidation process. The use of carbon materials as electrodes is limited due to their
high cost; the alternative is biochar, which possesses all the required characteristics
of an electrode at a lower cost. In microbial fuel cells and super capacitors, biochar
acts as an electrode [86]. Super capacitors have a high power density, good stability,
and a swift capacity to charge and discharge. The biochar prepared from the Syzygium
cumini (Jamun) seeds by acid pretreatment and CO2 activation [87] is used in the
preparation of symmetric super capacitor devices. For the de-ashing of biochar, acid
pretreatment was performed, and the CO2 activation of raw biochar at 900 °C for
1 h showed a higher surface area than that of acid-treated biochar. Both biochars are
fabricated in a super capacitor device to test the capacitance. Acid-treated biochar
exhibited a specific capacitance of 33.5 F/g, while activated biochar had a superca-
pacitance of 42.3 F/g at a 0.1 A/g current density comparable to commercial activated
carbon. The fabricated coin cell super capacitor had an energy density and power of
19.8 Wh/kg and 2096.5 W/kg, respectively.
Recent advancements in biochar-based catalyst applications have enabled the
identification of their potential as novel electrode materials for super capacitors.
Their high electrical conductivity and porosity confer on them the capacity to func-
tion as electrodes [88]. The functionalized surfaces with bound nitrogen groups are
preferably used as electrical terminals (anode/cathode) for super capacitors. Super
capacitors, made of carbon materials, are used as energy storage devices. Since BC is
a carbon-rich solid material with a high surface-to-volume ratio and voidity, it serves
as a good energy storage device, which in turn can help some developed countries
back up their excess energy generation.

6.3 Remediation

There has been a positive correlation between metal uptake and BC-based catalysts.
Adsorption capacity depends on the active sites available on the catalyst’s surface. So,
the selection of biochar should be made based on the type of heavy metal to be treated
or the source of water pollution. By changing the temperatures for biochar production
and the type of feedstock, activated biochar suitable for the desired heavy metal
removal can be developed. Since biochar is economically feasible, environmentally
30 K. Sobha et al.

friendly, and can be manufactured with ease, it has a remarkable potential in the
heavy metal seclusion from wastewater [54]. Biochar contains high levels of oxygen,
functional groups, and minerals, all contributing to the efficient removal of Cr (III)
and Cd (II) [89]. Using fish scales as a precursor [90], self-doped biochar composites
with MgO-loaded N and P were produced through an impregnation method that
demonstrated good adsorption of Cu, Pb, and Cd in soils.

6.3.1 Remediation of Organic and Inorganic Pollutants

Organic Pollutants

The biochar acts as a catalyst for the removal of organic and inorganic pollutants
(Fig. 1). The addition of biochar to the soil adsorbs agricultural organic pollutants
such as insecticides, pesticides, fungicides, herbicides, viz. atrazine, simazine, and
carbofuran, and others; antibiotics and drugs such as acetaminophen, tetracyclin,
sulfamethazine, tylosine, and ibuprofen; and industrial chemicals such as polycyclic
aromatic hydrocarbons (PAH). The size and functional groups present on the surface
of the biochar influence its capacity to remediate pollutants. The smaller the particle
size, the higher the surface area and capacity of remediation. The interaction between
biochar and pesticides is due to the presence of phenolic and carboxylic functional
groups on the biochar surface. The type of biomass, temperature, pH, and ratio of
pollutant to biochar are the major factors that influence the biochar–pollutant interac-
tion. The main mechanisms involved in remediation are physi-sorption (electrostatic
attraction and repulsion, pore diffusion, hydrophobicity, and H-bonding), chemisorp-
tion (electrophilic interaction) (Fig. 2), and other mechanisms such as chemical trans-
formation, partitioning, and biodegradation [91]. The biochar from agricultural waste
and zero-valent iron composite was used for the removal of tetracycline [92], and
the removal efficiency was 275 mg/g.

Inorganic Pollutants

Biochar produced at low temperatures possesses many functional groups that are
helpful in the adsorption process. Its porous structure and high organic carbon
content help in the removal of inorganic pollutants, mainly heavy metals like copper,
zinc, cadmium, lead, nickel, and mercury, by ion-exchange mechanisms. Copper,
chromium, and lead metals have a strong affinity for OH and COOH groups, and
their removal depends on the type of biomass, pH, biochar dosage, and porosity.
An increase in pH decreases the zeta potential and cation exchange capacity. At pH
6–7, the removal of heavy metals was by an ion-exchange mechanism, and at higher
pH 7–9, the removal was by complexation and electrostatic attraction. Chromium
removal was found to be maximal at pH 2, whereas lead removal was high at pH 2
and 5.
2 Biochar in Catalysis and Biotransformation 31

Fig. 2 Biochar particle and its diverse non-covalent interactions with the ligands (adapted from
Ahmad et al. [93] with a few modifications)

6.4 Soil Amelioration

The addition of biochar to the soil enhances the porosity, surface area, oxygen uptake,
water holding, and adsorption capacity of the soil (Fig. 1). Increased porosity of the
soil maintains the moisture and aeration that are useful in colonizing the bacteria
and fungi and increases the absorption of nutrients from the soil [94]. The surface
of the biochar, consisting of carboxylic, phenolic, amino, and hydroxyl groups, can
interact with the hydrogen ions in the soil and increase the soil pH, whereas carbonate,
bicarbonate, and silicate neutralize the soil pH by interacting with hydrogen ions in
the soil. The addition of biochar to the soil increases soil fertility, cation exchange
capacity, and microbial activity, and reduces greenhouse gas emissions. The presence
of Ca, K, N, and P in biochar adds nutrients to the soil. Nanoparticles prepared from
biochar of pinewood and rice straw at 20 mg/L showed the mobilization of positively
polar (trimethoprim and ciprofloxacin) and nonpolar contaminants (naphthalene and
pyrene) while inhibiting the transport of sulfamethoxazole and bisphenol A, which
32 K. Sobha et al.

are negatively charged and neutral hydrophilic compounds [95]. The addition of
wood, sunflower, and rice husk biochar to soil increased the adsorption capacity of
Cu, Zn, and Pb by more than 77%, which is due to the presence of hydroxyl, phenolic,
and ester functional groups on its surface [96]. Zn adsorption increased to 11–21%,
while Cu and Pb adsorption increased by 9–19%.

7 Biochar and Biotransformation

As has been stated earlier, the carbon-enriched solid product obtained by the thermal
treatment of bio-organic material in a low-O2 atmosphere is called ‘biochar’ [97].
There are a myriad variety of organic materials available as discards in nature that are
good enough to be used as raw materials for biochar synthesis. Although large-scale
synthesis of biochar by established preparatory methodologies appears to be simple
and straightforward, there are a number of challenges in preparing suitable biochar
precursors intended for specific purposes. Findings from recent research indicate
‘biochar’ as a suitable medium for the growth of plants and microorganisms [98].
Segregation of inorganic and organic compounds from the source by sorption and
cation exchange capability to support microbial growth [99], soil pH conditioning,
and providing hormone analogues for plant growth are some of the notable functions
of biochar. Since biochar is generated from plant or animal waste and/or microbes, it
contains several important nutrients of biological significance. Some of the important
literature related to the role of biochar is presented in Table 3.
Biotransformation, a biological process in which organic compounds are modi-
fied into reversible products, is a natural and essential phenomenon in nature. The
biochemical reactions are catalyzed by biocatalysts called ‘enzymes’ synthesized
by microbial, plant, and animal cells. Microbes, which include bacteria, archaea,
and fungi, are ubiquitous in nature and have tremendous catabolic capacities for
minimizing environmental chemical impurities by converting them to less reactive
compounds and completing mineralization [102, 103]. Microbial transformation is
the prime degeneration process in environmental transformations when compared to
photolysis or abiotic redox reactions [104]. Increasing chemical contaminants in the
ecosystems adversely affect the biota and the environment.

Table 3 A few constituents of biochar and their role in paddy cultivation


S. No. Substance in biochar Biological significance References
1 2-Acetyl-5-methyl furan Hormone analog for rice Yang et al. [100]
seedling growth
2 14 candidate drugs Cold tolerance of rice Yuan et al. [15]
seedlings
3 Mineral, nitrogen, and Microbial growth Lehmann [101], Yang [98]
sulfur content
2 Biochar in Catalysis and Biotransformation 33

For optimized microbial transformation, the system designer needs to consider the
cause–effect relationship between contaminant removal and the microbes’ catabolic
pathways, including the level of enzymes and the conditions required for biotrans-
formation. A number of factors influence the rate at which a given contaminant is
removed and the type of yielding product. Some of them are the existing concen-
tration of the contaminant, the microbial community’s capability and composition,
e− —donors or acceptors, and the availability of substrates [105, 106]. Different
bio-physico-chemical factors, viz. redox potentials, ambient temperatures, atmo-
spheric moisture, nutriment availability, hazard exposures, and microbial continu-
ance time, influence the biotransformation. For each contaminant type, the range of
biotransformation is determined by its chemical structure and ability to interact with
enzymes.

8 Bicohar in Bioremediation

Biotransformation is a ‘remediation’ method for both contaminated soil and water.


Biochar in the soil increase the rate of bioremediation process as it provide natural
habitat for the growth of microbes. If the treatment of the contaminated site is effected
at its location, then it is termed ‘in situ’ biotransformation. In opposition to this
type, ex situ biotransformation requires excavation of contaminated soil or pumping
of groundwater to a separate treatment location before it can be treated. ‘On-site’
or in situ biotransformation has the advantages of being less expensive, achieving
complete contaminant removal, having lower equipment and operating costs, posing
a lower risk to workers, creating less dust, and treating a large area of soil at a time.
The disadvantages are that they are slow to process, can be difficult to manage, and
work best in permeable soil. The advantages of ex situ biotransformation are that it is
fast, easier to monitor, and can be used to treat a broad spectrum of contaminants and
soil types. However, the disadvantages are that they require excavation and treatment
of contaminated soil before and after biotransformation.

9 Role of Biochar in Biotransformation—A Few Studies

9.1 Degradation of Roxarsone by Shewanella oneidensis


MR-1

Roxarsone (3-nitro-4-hydroxyphenylarsine) is a feed additive that controls intestinal


parasites and improves meat pigmentation [107, 108]. Although the current use of
roxarsone in the poultry industry is banned in several countries, its earlier extensive
use created the problem of bio-accumulation along the food chains in the food web
[7, 109]. In an animal body, roxarsone is decomposed and excreted in its unmodified
34 K. Sobha et al.

form along with animal waste [110]. Due to its aqueous dissolution, roxarsone easily
finds its way into the surface of groundwater and soil [108, 109]. Roxarsone under-
goes oxidation–reduction and methylation–demethylation [111–114] via a variety of
physical, chemical, and biological reactions, yielding an array of arsenic compounds.
Natural organic matter (NOM)-mediated microbial redox reactions, in the cyclic
flow of carbon and redox-active compounds, are important. Biochar was prepared
using dried wheat straw powder by heating in a stainless steel reactor for 2 h at
three different temperatures (300, 500, and 600 °C) in a muffle furnace under anoxic
conditions. Roxarsone degradation by MR-1 was evaluated with and without BC
for 68 h. Roxarsone was almost completely degraded, and the decreasing order of
degradation rates was 600 BC biotic to only MR-1 through 500 BC biotic and 300 BC
biotic. Decomposition rates were elevated by 9.79%, 6.84%, and 3.23% respectively,
with the addition of 600 BCC, 500 BCC, and 300 BCC. The addition of biochar causes
an apparent increase in the biomass of microorganisms. The combination of biochar
with MR-1 when used for oxidation–reduction [115], the biochar produced at 400–
600 °C showed the optimal capability for electron ‘to and fro’ transfer and vice versa
for biochar produced at low temperatures. MR-1 growth adapted itself to the high
temperature because biochar provides nutrients and habitat for microorganisms.

9.2 Glucose to L-Histidine Through Escherichia Coli


Metabolism

Since the composition of biochar is complex, it is difficult to establish the significance


of each of its constituents and map the same to a particular biological function. Hence,
Yang et al. [116] performed molecular docking studies with the compounds in biochar
as ligands against the receptor proteins of the L-histidine synthetic pathway. The
carbon compounds present in biochar were extracted by both polar and nonpolar
solvents and analyzed by Yang et al. [116] using GC–MS, employing 1 μl ml−1 IPA
(diluted at 1 μg ml−1 in methylene chloride) as an aromatic hydrocarbon-certified
standard for reference. Out of the nine functional groups identified to contribute to
different biological functions, >C = O, −COOH, and –OH were the predominant
ones in the biochar extraction solution. Based on GC–MS results, the molecular
structures of carbon compounds were constructed by GaussView and subjected to
docking against the 1H3D receptor molecule downloaded from the RCSB protein
database. From the docking results, the inducer molecules for the biosynthesis of
L-histidine were identified. This study inferred the ‘switching on’ of his G gene
expression by different biochar treatments, and consequent promotion of L-histidine
biosynthesis in E. coli. Among the four biochar concentrations in percent tested (viz.
1, 3, 5, and 7), a low biochar treatment of 3% was found beneficial for the biosynthesis
of L-histidine because of the highest amounts of different bioactive ingredients at that
concentration. The sum of the three major compounds, viz. eugenol, salicyl alcohol,
2 Biochar in Catalysis and Biotransformation 35

and cyclopentane, 1, 2, and 3-trimethyl, was reported to function like a hormone


analogue in stimulating his G gene expression.

9.3 Denitrification and Mitigation of N2 O Production

Denitrification is an important activity that facilitates the survival of essential and


beneficial microbes in the soil that aid plant growth through their metabolites and
soil enrichment. Microbes that grow in oxygen-deficient soils are endowed with
the ability to convert toxic soluble nitrates (NO3 − ) to nitrites (NO2 − ), N2 O (GHG
causing environmental pollution and global warming), and finally N2 in order to
obtain the oxygen required for their metabolism [117, 118]. Nitrous oxide (N2 O),
a potential greenhouse gas, is produced and consumed in the soil by a network
of processes, including abiotic redox and biotic nitrification/denitrification and/or
nitrifier denitrification [119–121] reactions. Incomplete denitrification is one of the
leading causes of N2 O emissions in agricultural soils. In this context, it has been
found that the addition of biochar to the soil will amend and enrich the soil biota,
and augment crop production without the release of potential greenhouse gases like
N2 O.
Biochar, as an established electron shuttle and conductive material, is believed to
mediate extracellular electron transfer and influence microbial metabolism. However,
many soil bacteria that effect denitrification (such as the electricigenic, humic, Fe–
Mn, and others) do not exhibit extracellular respiration. Recently, an interesting
study on the mitigation of N2 O emission from bacterial denitrification through the
distribution of reducing power among the enzymes of the denitrification cascade via
modulation of carbon metabolism was reported [122]. The denitrification response of
the model soil bacterium (Paracoccus denitrificans) to biochar addition was analyzed
by ‘proteomic’ and ‘metabolomic’ data, and reported a positive correlation between
the efficiency of biochar and its pyrolytic production temperatures of 300–500 °C,
and dosages between 0.1 and 1% [122]. Further, the study revealed that the sources of
biochar tested, namely corn (CS) and wheat straw, did not contribute to the biochar’s
efficiency. According to the study, the ‘stimulant nature’ of CS biochar built at 500 °C
was purely due to the gross particles, and not the dissolvable compounds released in
the process. It was proposed that the bulk CS-500 particles adsorb to the cell’s extra-
cellular metabolites and direct the reactions of the cell’s carbon metabolic pathway. A
major part of the reducing power generated through oxidative metabolism and growth
assimilation is utilized for nitrogen reduction, and this could be corroborated with the
upregulation of the proteinaceous-enzyme expression and activity of nitrite-, NO-,
and N2 O-reductase. This was evident from the maximum electron-sharing among the
denitrifying enzymes and reduction of N2 O accumulation by 98%. Consequently, the
growth kinetics of P. denitrificans increased, implicating biochar in denitrification
and N2 O mitigation reactions.
Bacteria depend on the energy supplied by the reduction reactions of nitrogen
oxide species for their growth and assimilation. But when the biochar adsorbs to
36 K. Sobha et al.

the extracellular metabolites of the bacterial cell, like in P. denitrificans, the cell
depends on the reactions of oxidative metabolism for the supply of needed energy,
and in the process accumulate PHA (polyhydroxyalkanoate) as a carbon/energy and/
or reducing power storage molecule [122– 124]. As stated earlier, in biochar-enriched
soils containing denitrifying bacteria with genome-based PHA storage ability, the
high N2 O-reduction potential of denitrifying bacteria would be explained through
the adsorptive potential of biochar for extracellular metabolites. As this may not be
the only mechanism, further investigations to unravel the mechanism in denitrifiers
without the capability of PHA storage are imperative.

9.4 Biotransformation of Phosphorous

Enhanced biological phosphorus removal (EBPR) bio-solid, turned into BC, is a


potential phosphorus (P) fertilizer. Pseudomonas putida, a soil microorganism, regu-
lates the ‘P’ turnover in soil. Biochar was produced at two different temperatures, viz.
400 and 700 °C; of the two, biochar produced at 700 °C (E700) released molecules
that were readily absorbed by the microbe P. putida and are not the same with the
biochar produced at 400 °C (E400); this could presumably be induced by the low
pH [125] and the role of microbial organic acids in complexation [126]. E400 has a
detrimental affect on intracellular poly-P formation in P. putida due to free-radical-
induced oxidative stress. This in turn affects the bacterial survival and their interaction
with the surroundings. Besides ‘P’, a number of heavy metals [127, 128] and harmful
organic constituents of biochar [129, 130] passively enter the soil and cause contam-
ination. This was evident from the study by Khan et al. [127] which demonstrated
a rise in soil levels of Cu, Zn, and Cd when treated with bio-solid-derived biochar.
Additionally, the free radicals (FR) [131–134] adhered to some biochar can induce
cytotoxicity and inhibit seed germination and plant growth.

9.5 Remediation of Chromium Toxicity by Biochar, Poultry


Manure, and Sewage Sludge (Biosolids) in Rice Crop

Agronomic plants suffer from chromium concentrations of 0.5–5 mg ml−1 in nutrient


solutions and 5–100 mg kg−1 in soil. Biochar as well as poultry manure and bio-
solids/sewage sludge augment the activity of microbes. The mechanism involved in
the remediation of chromium by the microbes is that the microbes act as electron
donors and reduce the toxic Cr6 + to non-toxic Cr3 + and further lower the oxygen level
of the soil, creating reducing conditions. High chromium concentrations in soil are
toxic to rice [135]. Chromium is shown to have a direct effect on rice grain and rice
straw yield as well. The lowest rice grain yield value of 23.37 g pot−1 was found in
the treatment at Cr50, with the yield lowered by 13% in comparison with the control
2 Biochar in Catalysis and Biotransformation 37

(26.7 g pot−1 ). The greatest direct effect on rice straw yield was observed at Cr50
(28.20 g pot−1 ). Out of the three materials tested, viz. biochar, poultry manure, and
sewage sludge, a significantly higher rice grain yield of 31.73 g pot−1 was achieved
upon treatment at Cr0+ biochar, while the minimum yield recorded was at Cr50
(23.80 g pot−1 ) without amendment.

9.6 Adsorption of Manganese and Its Biotransformation


by Streptomyces Violarus Strain SBP1 Cell-Immobilized
Biochar

Manganese levels in potable water were set at 0.05 mg L−1 (ppm) by the Water
Act for safe drinking. Above the normal level, manganese tends to damage the
central nervous system and cause Parkinson’s-like symptoms. Natural biochar, i.e.
carbonized wood waste, is obtained from the wood vinegar industry through the
pyrolytic process. Both raw biochar and H2 O2 -modified biochar were subjected to
immobilization with a manganese-oxidizing potent bacterial strain, Streptomyces
violarus strain SBP1. Modified biochar showed a significantly higher adsorption
capacity of 1.15 mg g−1 in opposition to the adsorption capacity of unmodified
biochar which was 0.77 mg g−1 , and a removal efficiency of 78%—all attributed
to the presence of a higher proportion of functional groups with oxygen. Pseudo-
second-order and Langmuir models are the best fit for Mn adsorption studied with
native and modified biochars. A synergistic combination of biochar and biological
oxidation by SBP1, in which biochar adsorbs the dissolved manganese (Mn2+ ) while
the microbial cells oxidize the dissolved manganese to particulate Mn3+ and/or Mn4+ ,
contributes to the removal of manganese. The results of X-ray Fluorescence Spec-
troscopy (XRF) and X-ray Absorption Near Edge Structure (XANES) confirmed
the dispersal of microbial cells and their adhesion to deeper layers [136] resulting
in manganese adsorption and bio-oxidation. These findings suggest the potential
application of cell-immobilized biochar as a bio-filtration medium.

9.7 Microbial Biotransformation of Arsenic in Paddy Soil


After Straw-Biochar and Straw-Amendments

Arsenic (As) biogeochemical cycling in the soil-rice system is remarkably altered by


the application of straw biochar, and straw to paddy soil. High-throughput sequencing
of microbial 16S rRNA gene showed that both straw biochar and straw enrich
iron-reducing bacteria, while methanogens were enriched by the straw amend-
ment [137]. It is proposed that arsenate [As(V)] reduction is mediated by arsA-
gene containing iron-reducing bacteria (e.g. Geobacter and Shewanella) in biochar
and arsC-containing Gamma-proteobacteria in straw amendments. Methylated As
38 K. Sobha et al.

concentration is regulated by methanogens and sulfate-reducing bacteria (SRB) in


the soil-rice system, by virtue of the arsM gene. Arsenic (As) biotransformation
microbes (ABMs) are demonstrated to have stronger interactions in the rhizosphere
zone as compared to bulk soil by the network analysis. Arsenite [As(III)] methylators
carrying arsM gene [138] showed a stronger co-occurrence pattern with arsC-gene
containing As(V) reducers than with arsA-containing As(V) reducers.

9.8 De-chlorination of Pentachlorophenol in a Microbial


Consortium

Biochar, generated from raw materials like rice husk, bamboo, caragana, and garbage
by pyrolysis at 500 °C for 4 h under an N2 flow of 1.5 L min−1 , was studied for its effect
on the reductive de-chlorination of pentachlorophenol (PCP). Pentachlorophenol (a
halogenated aromatic compound), popularly used as a wood preservative, insecti-
cide, and anti-mold agent, is toxic to the liver and kidneys. Microbial anaerobic
de-chlorination occurs in soils and sediments. In recent years, biochar has been
investigated as a solid-phase electron shuttle to support redox transformations by
microbes. Capacities for the transfer of electrons were found to be within the range
of 61.63–155.83 mol g−1 , and stable electron transfer was found to be mediated only
by caragana-derived biochar. Electrochemical analyses using a potentiostat revealed
the electrical conductivity of caragana biochar to be of the highest value of 2.22 ×
106 S cm−1 . Hence, its electron transfer was enabled at its maximum, resulting in
the greatest promotion of reductive de-chlorination activity, while those of the other
biochar were around 1500 S cm−1 only. However, the cyclic voltammetry suggested
no obvious redox peaks for the biochar, and FTIR analysis revealed that all biochar
possessed similar structural and functional classes of reactive chemical groups [72],
and, therefore, the enhancement of PCP de-chlorination was not attributed to the
redox reaction.

9.9 Chemical and Microbial Transformation


of Pentachlorophenol in Paddy Soil

Rapeseed straw was processed to generate biochar for the transformation of


pentachlorophenol in paddy soil. The biochar promoted de-chlorination of PCP by
reduction and acted as an electron mediator between the soil organic compounds
and the bacteria, which in turn enhanced the growth and metabolism of bacteria.
Biochar improved the sorption and transformation of PCP and the generation of Fe
(II) in soils amended with rapeseed-straw biochar that was HCl-extractable. From
the findings of Tong et al. [139], it could be inferred that the PCP de-chlorination
rates obtained were higher with higher dosages of biochar.
2 Biochar in Catalysis and Biotransformation 39

10 Conclusion

The versatile biochar characteristics, like its porous structure, labile calcium, high pH,
and electrochemical properties, greatly influence the microbial communities present
in the soil. India plays a pivotal role in the agricultural domain. Agricultural residues
of different crops can be converted to produce biochar of different physicochemical
properties, which can be used in various fields as catalysts or catalytic support. The
production of renewable chemicals and advanced transportation fuels from waste-
derived sugars through a low-temperature process results in a good hybrid solid
catalyst with tunable acid/base character. However, the stability of biochar is impor-
tant, which can be improved by pyrolysis under certain temperatures for different
feedstocks. Biochar as a catalyst has emerging applications in various fields, which
include biofuel production, syngas production, heavy metal removal, wastewater
treatment in different sectors (agriculture, industrial, and domestic wastewaters),
composting, electrochemical and microbial fuel cells for energy storage, environ-
mental applications, etc. Biochar can be tailored to meet specific needs by modifying
its surface morphology and functional groups. Therefore, conventional chemical
catalysts can be replaced by biochar-based catalysts. Furthermore, biochar could be
employed in several significant biotransformation reactions and effect the synthesis
of desirable compounds, convert toxic metabolites, or alleviate their production.

11 Future Perspectives

Although the advantages of green catalysts like biochar appear to outweigh the disad-
vantages, the development of these catalysts is still in its infancy. So, there is a need to
explore novel techniques that can facilitate the industrial-scale production, activation,
and functionalization of biochar for its improved catalytic performance. Researchers
are concentrating on the modifications that may be made to biochar-based and nano-
materials for their application in domains like catalysis for the production of specific,
selective, qualitative, and quantitative products for efficient industrial operations and
environmental safety. Future research should focus on the temperature and reaction
time of the production processes so that it could become a ‘single-pot’ synthesis with
easy activation and functionalization methods to achieve high-quality and reusable
catalysts. These catalysts would then make biotransformations simpler and more
effective, leading to the generation of value-added products for human use.

Acknowledgements The authors express their sincere gratitude to the principal and management
of RVR and JC College of Engineering (A) for their encouragement and moral support.
40 K. Sobha et al.

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Chapter 3
Biochar: A Potent Adsorbent

Khaled Zoroufchi Benis , Jafar Soltan, and Kerry N. McPhedran

1 Introduction

Adsorption is a process in which components (atoms, ions, or molecules) of a gaseous


or liquid phase are accumulated on the surface of the adsorbent. Adsorbates refer
to the accumulated components, while the adsorbent refers to the solid phase that
accumulates the adsorbates. Adsorption is often characterized as a physisorption or
chemisorption process, depending on the nature and intensity of bonding among the
adsorbents and the adsorbates. In physical adsorption (physisorption), the adsorbent
and adsorbate interactions are mainly controlled by weak electrostatic interactions,
such as dipole–dipole interactions and Van der Waals forces. In comparison, chem-
ical adsorption (chemisorption) entails strong bonds between the adsorbate and the
adsorbent [1]. Of these two processes, chemisorption interactions are stronger than
physisorption interactions.
Generally, adsorption consists of three steps (Fig. 1): (1) adsorbate transfers from
the bulk medium to the outer adsorbent surface; (2) adsorbate diffuses into the adsor-
bent pores; and (3) adsorbate is adsorbed onto the adsorbent’s active sites (physisorp-
tion or chemisorption) [2]. Therefore, an effective adsorbent should have features
that reduce the time required to complete these steps. Effective commercial adsor-
bents possess both a highly porous structure and a large surface area, however, are
typically high cost. Other qualities of excellent materials for adsorption are low cost,

K. Zoroufchi Benis · J. Soltan (B)


Department of Chemical and Biological Engineering, University of Saskatchewan, Saskatoon,
Canada
e-mail: j.soltan@usask.ca
K. N. McPhedran
Department of Civil, Geological and Environmental Engineering, University of Saskatchewan,
Saskatoon, SK, Canada
K. Zoroufchi Benis · J. Soltan · K. N. McPhedran
Global Institute for Water Security, University of Saskatchewan, Saskatoon, SK, Canada

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2023 49
A. K. Nadda (ed.), Biochar and its Composites, Materials Horizons:
From Nature to Nanomaterials, https://doi.org/10.1007/978-981-99-5239-7_3
50 K. Zoroufchi Benis et al.

Fig. 1 Schematic of the mass transfer phenomena in adsorption process

sufficient structural and mechanical properties to withstand attrition and mechanical


forces due to fluid flow in a fixed-bed adsorption process, high adsorption capacities
and high adsorption rates, and regeneration capabilities [3].
Adsorption techniques are widely used in numerous fields, such as pollution
control, chromatography, purification or separation of gas and liquid mixtures,
organic solvent drying, gas masks, gas deodorization, etc. [4, 5]. Synthetic, natural,
and semi-synthetic adsorbents are the three major categories of adsorbents. Synthetic
adsorbents are manufactured materials with a high adsorption capacity that are
often more expensive than other adsorbents. Natural adsorbents are natural mate-
rials like agricultural residues and minerals that usually suffer from low adsorption
capacity. Semi-synthetic adsorbents are comprised of natural materials that have been
chemically or physically modified to produce a highly porous surface [6].
Considering the high cost of synthetic adsorbents and the low adsorption
capacity of natural adsorbents, semi-synthetic adsorbents are cheaper than synthetic
adsorbents while having sufficient adsorbent capacities.
Different types of natural biomaterials, such as wood residues, wastewater sludges,
and agriculture residues, are widely available, inexpensive, and sustainable for use
in adsorption processes [7]. However, low adsorption capacities, coloration prob-
lems, and possible release of soluble organic compounds into the treated water are
their inherent disadvantages that may hinder their use as adsorbents [1]. However,
the production of semi-synthetic adsorbents from biomaterials can overcome these
drawbacks and allow them to be widely employed in adsorption processes. The three
types of treatment processes for producing biomaterial-based semi-synthetic adsor-
bents documented in the literature are chemical treatments using acids and alkaline
solutions, composites, and biochars. Chemical treatment improves the adsorption
capacity, surface area, and porosity of biomaterials by removing soluble organic
3 Biochar: A Potent Adsorbent 51

compounds, oxidizing the surface to create oxygen-containing functional groups,


altering or adding functional groups, and eliminating coloration problems [8–10].
The surface of biomaterials, either untreated or chemically treated, is modified by the
deposition of activating agents (e.g., metal oxides) to create composites [1]. Biochar
is a carbon-rich solid that is produced through the thermochemical degradation of
biomaterials in an oxygen-depleted condition. Biochar has most of the desirable
characteristics of an effective adsorbent including a high specific surface area (SSA)
and porous structure and a large number of diverse functional groups [11]. With a
porous structure comparable to activated carbon, biochar is a popular and very effi-
cient adsorbent worldwide for treating various contaminants in air and water [12,
13]. Biochar is cheaper to produce and requires less energy than activated carbon
which is usually produced at high temperatures. The environmental and economic
benefits of biochar make it an attractive material for use in environmental remedi-
ation [14]. Pristine biochar can be used directly in adsorption processes, however,
it can also be employed as a precursor to produce biochar composites or activated
biochar. Physical and chemical activation using steam, acids, and base improve the
porosity, SSA, and functionality of biochar. Biochar composites, on the other hand,
are created by utilizing activated or pristine biochar as support for embedding new
materials and functional groups such as metals, and organic compounds to adsorb the
target contaminants [10, 15]. In this chapter, emphasis has been placed on the appli-
cation of pristine and activated biochar in the adsorption process and mechanisms
involved in contaminants removal.
Adsorption performance is influenced by biochar characteristics, contaminant
concentration and characteristics, operating conditions, adsorbent dosage, tempera-
ture, contact time, solution pH, and the presence of interfering species. The current
chapter first overviews the effects of biochar characteristics on adsorption perfor-
mance (Sect. 2), and then provides a framework for understanding the capability of
biochar to be used to remove inorganic and organic chemicals from water (Sect. 3)
and air (Sect. 4). Finally, future research directions for using biochar as an adsorbent
are discussed (Sect. 5).

2 Effects of Properties of Biochar on Adsorption


Performance

The mechanisms underlying adsorption may be better understood by examining the


connections between the characteristics of biochar and its adsorption capabilities.
This section outlines the major parameters, including surface functional groups,
SSA, pore volume and pore size distribution, and pH of biochar that significantly
impact its absorption capacity. Figure 2 illustrates the porous structure of biochar
containing various functional groups.
52 K. Zoroufchi Benis et al.

Fig. 2 Schematic of a porous biochar and its surface functional groups

2.1 Surface Functional Groups

Adsorption of contaminants by biochar occurs through various mechanisms such as


ionic exchange, surface complexation, surface precipitation, electrostatic attraction,
hydrogen bonding, and π-π electron donor–acceptor interactions. These mecha-
nisms are driven by a wide variety of functional groups on the biochar surface,
such as minerals and hydroxyl, carbonyl, carboxyl, and amino groups [16, 17]. The
distribution and types of surface functional groups of biochar depend on the feed-
stock (biomass) composition and the applied pyrolysis and activation process condi-
tions. Several technologies can be utilized to investigate these functional groups [18],
such as Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, X-ray
diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and X-ray absorption
fine structure spectroscopy (XAFS).
In general, hydroxyl functional groups serve as electron donors, whereas carboxyl
functional groups are electron withdrawing. Oxygen-containing functional groups
may increase the cation exchange capability and polarity of biochar, hence boosting
the removal of hydrophilic volatile organic compounds [19]. Additionally, more
oxygen-containing functional groups improve the adsorption capacity of biochar
toward organic compounds, partly due to π-π interactions between electron donor-
receptors (i.e., C–C bonds of biochar with the aromatic rings of an organic
compound). Moreover, oxygen-containing functional groups can enhance the adsorp-
tion of contaminants through complexation between adsorbate and biochar and
hydrogen bonding [20, 21]. In addition, the inclusion of sulfur or phosphorus atoms
3 Biochar: A Potent Adsorbent 53

in the surface functional groups can raise the positive charge density of nearby carbon
sites and enhance the hydrogen bonding interactions. On the other hand, nitrogen
atoms can act as either electron donors or acceptors depending on their location at
different sites [22]. The minerals on the biochar surface enhance the co-precipitation
and complexation of heavy metal ions. Biochar has a higher cation exchange capacity
due to the abundance of negatively charged surface functional groups [15, 23]. Addi-
tionally, biochar’s electrostatic attraction towards positively charged heavy metal
ions is enhanced by its negatively charged functional groups.

2.2 Specific Surface Area (SSA)

Specific surface area (SSA) and porosity are significant factors in the assessment
of the adsorption capacity of biochars. The majority of research indicates a linear
relationship between SSA and adsorption capacity [17, 24, 25], however, some litera-
ture has also indicated no correlations between adsorption capacity and the biochar’s
SSA [26]. Typically, improving the SSA of biochar using chemical or physical acti-
vation is viewed as a viable technique for enhancing its adsorption capacity [27, 28]
Specifically, physical activation produces a microporous structure and larger SSA.
For example, raising the pyrolysis temperature can expedite the formation of porosity
[29] by conversion of unstable components (e.g., cellulose, lignin, and hemicellu-
lose) and opening up the pore channels, forming more porous structures, and creating
new active sites [30]. However, it has been observed [10, 31], that increasing pyrol-
ysis temperatures reduces the oxygenated functional groups that result in decreasing
the surface charge negativity, which may reduce the adsorption of positively charged
ions.
Chemical activation has been utilized extensively to improve the SSA of biochar.
For example, the SSA can be greatly increased by impregnating biomaterial with
chemical activators before pyrolysis. Some of the common activators are H2 SO4 ,
H3 PO4 , NaOH, and KOH [32], however, the SSA of biochar may change depending
on the type of activator used. In addition, the biomaterial/activator ratio and impreg-
nation time have been shown to substantially affect the SSA of the activated biochar
[33]. Thus, the amount of activator and the activation process should be optimized
to obtain the desired SSA.

2.3 Pore Size Distribution and Pore Volume

Pore size is the average pore diameter of an adsorbent. The International Union of
Pure and Applied Chemistry (IUPAC) classifies pore sizes as macropores (>50 nm),
mesopores (2–50 nm), and micropores (<2 nm) [34]. Figure 1 demonstrates how the
size of the pores affects the adsorption of adsorbates of assorted sizes. A larger pore
size enables quicker adsorption of adsorbates resulting in a shorter contact time.
54 K. Zoroufchi Benis et al.

The pore volume is the volume occupied by the pores of an adsorbent which has
the same correlation with adsorption as the SSA. Like the SSA of biochar, the pore
size distribution and pore volume are affected by the feedstock type and pyrolysis
conditions [35, 36]. For instance, raising the pyrolysis temperature causes pores to
enlarge, making it easier for adsorbates to fill the pores.
Overall, the pore size distribution significantly affects biochar’s adsorption ability.
Only when the biochar has an appropriate pore width can the contaminant diffuse
successfully into the biochar channels and be adsorbed. A biochar with large pore
width and small SSA will have a low adsorption capacity [37]. However, too narrow
pores will prevent adsorbates from diffusing and increase the shielding effect for
molecules with higher sizes.

2.4 The pH Value of Biochar

The biochar pH is its degree of acidity or basicity and is an important factor that can
influence adsorption efficiency. Biochar pH is affected by a number of variables, such
as the temperature of pyrolysis, feedstock type, and the activation or modification
method. The higher pyrolysis temperature leads to a greater amount of ash and the
degradation of acidic functional groups leading to a higher pH of the biochar produced
[38]. On the other hand, biochar created at lower temperatures has lower pH due to
a higher amount of acidic functional groups such as carboxylic and phenolic. In
addition, chemical activation of biochar can change its pH depending on the type
and concentration of applied acidic or alkaline solution [17]. Therefore, a large pH
range, from 4 to 12, has been reported in the literature [39]. It is important to note that
the pH of the adsorption solution also changes the surface chemistry of the biochar
(e.g., point of zero charges (pHPZC )) that alters the accessibility of adsorbates to the
binding sites [38]. Thus, the effect of both biochar pH and solution pH should be
considered in adsorption studies.

3 Biochar for Water Treatment

Water contamination is one of the most serious global challenges nowadays, owing
to the century-long development of human activities such as industry, agriculture,
and urbanization. In developing countries, investment in clean drinking water infras-
tructure is inadequate and there is a widespread problem with water-borne infectious
diseases because of a lack of clean water and proper sanitation [40]. While a lack of
sufficient water treatment before usage is a big issue in developing countries, the high
cost of wastewater recycling is a major issue in developed countries. Low-cost water
treatment is desired in industry and is an effective measure for safeguarding public
health and reducing outbreaks of water-borne diseases. Adsorption is regarded as an
3 Biochar: A Potent Adsorbent 55

economical and simple method for treating water, and biochar has been shown to be
a cost-effective and efficient alternative for commercial adsorbents.
Heavy metals, microbes/pathogens, dyes, pharmaceuticals, and other organic
compounds are the most prevalent environmental contaminants. Biochar’s adsorption
behaviour for various contaminants is variable and depends on the characteristics of
contaminants in addition to the water chemistry. In addition, typically biochar has
abundant functional groups, however, there are several forms of biochar (depending
on the feedstock and preparation condition) with unique functional groups that impact
the adsorption capacities of different contaminants. Therefore, a wide variety of
mechanisms can occur in the adsorption of contaminants from aqueous solutions. In
the following sections, the capability of biochars for adsorption of organic, inorganic,
and microbial contaminants is discussed including proposed adsorption mechanisms.

3.1 Adsorption of Organic Contaminants

Organic contaminants include a broad range of compounds that pose threats to the
environment and human health including dyes, personal care products, pharmaceu-
ticals, and pesticides. The adsorption of organic contaminants onto biochar can be
governed by pore-filling, hydrophobic interactions, electrostatic interactions, π-π-
electron donor-acceptor interactions, and hydrogen bonding [27, 28, 41, 42]. These
mechanisms are shown schematically in Fig. 3 and overviewed in the following
sub-sections.

Fig. 3 Major mechanisms in adsorbing organic contaminants onto biochar


56 K. Zoroufchi Benis et al.

3.1.1 Pore Filling

Pore filling is a process where adsorbate molecules occupy the pores in the struc-
tures of biochar. Typically, biochar’s pore network consists of micro-, meso-, and
macro-pores that are discussed previously. However, it is suggested that micro- and
mesopores comprise the majority of the biochar’s surface area and play a major
role in the adsorption of organic chemicals by biochar [43]. Therefore, the adsorp-
tion of organic chemicals onto biochar via pore-filling processes is dependent on
its total mesopore and micropore volumes. The pore-filling adsorption mechanism
predominates in biochars with low volatile content or occurs in relatively low adsor-
bate concentrations [44]. For example, pore-filling was reported as the governing
mechanism in the adsorption of catechol by oak-biochar [44], and nitrobenzene
by bamboo-biochar [45]. In most circumstances, the adsorption kinetics for pore-
filling processes are rapid with a high initial removal rate and frequently followed by
non-linear, Langmuir-like adsorption isotherms [46]. However, pore-blocking often
occurs with the pore-filling process.

3.1.2 Hydrophobic Interactions

Hydrophobic interaction takes place between the hydrophobic binding sites of


biochar and nonpolar groups of organic compounds [47]. The hydrophobic interac-
tion mechanism in the adsorption of organic chemicals includes both partitioning and
hydrophobic adsorption. This mechanism’s action depends on the type of biochar
and organic adsorbate. For instance, fresh biochar with low surface oxidation has
been shown to adsorb hydrophobic and neutral organic chemicals [46]. Moreover,
the biochar’s hydrophobicity increases as the pyrolysis temperature rise. In addition,
activation with NaOH may potentially improve the hydrophobicity of biochar [48].
The octanol–water partition coefficient (K ow ) is a determining factor in the
hydrophobicity of organic compounds, and organic adsorbates with high K ow values
have a higher affinity towards biochar [49]. In the adsorption of organic contaminants
such as carbamazepine [50], trichloroethylene [51], and perfluorooctane sulfonate
[52] hydrophobic interaction mechanism has played a key role.

3.1.3 π-π Interactions

The π-π interactions are non-covalent interactions in π systems such as benzene,


ethylene, and acetylene. For example, these interactions can occur between the C–C
bonds of biochar and the aromatic rings of an organic compound [21]. Biochar with
a greater number of oxygen-containing functional groups shows higher adsorption
capacity for organic contaminants, partly due to π-π electron donor-receptor interac-
tions. The carboxylic acid, ketonic, and nitro groups on the biochar surface improve
its adsorption capacity for aromatic molecules. These functional groups interact with
aromatic compounds through—electron donor acceptor interactions, in which they
3 Biochar: A Potent Adsorbent 57

serve as electron acceptors. Moreover, hydroxyl and amine groups on the biochar
surface can serve as π-electron donor sites [41]. Overall, π-π interactions can play
an important role in the adsorption of organic compounds.
Low pyrolysis temperatures produce biochar containing π-systems with func-
tional groups that are deficient in electrons which serve as acceptors and interact
with the electron donor functional groups of organic molecules. In contrast, biochar
pyrolyzed at higher pyrolysis temperatures comprises both electron donors and
acceptor groups and can act with both functions [53]. The π-π interactions have
been demonstrated to be the prevalent adsorption mechanisms in the adsorption of
different organic compounds, such as antibiotics and pesticides [54]. It is important
to note that adsorbate and solution properties can also impact the π-π interactions.
For example, [55] observed that electron-rich (π-donor) aromatic compounds, such
as naphthalene, and phenanthrene, had better adsorption under acidic conditions.

3.1.4 Electrostatic Interactions

Electrostatic interactions occur between an ionic adsorbate and an adsorbent with a


charged surface. Therefore, it is a principal mechanism in the adsorption of ionic and
ionizable organic chemicals using biochar. Generally, cationic organic compounds
are adsorbed on biochar with negatively charged surfaces, while anionic compounds
show a greater affinity for positively charged biochar. At high pyrolysis tempera-
tures, more oxygen-containing functional groups are removed from the surface of
the biochar, which decreases surface charge negativity and makes the biochar more
favorable for negatively charged compounds [10]. However, the pH of the adsorp-
tion medium alters electrostatic interactions between the biochar and contaminant
by changing the surface charge of the biochar. At solution pH levels below the pHPZC
of the biochar, the biochar surface charge of biochar is positive and is favorable for
anionic adsorption. On the other hand, at pH values higher than the pHPZC the surface
charge of biochar is negative and favorable for cationic adsorption [19]. Therefore,
both pH of the solution and pHPZC impact the adsorption capacity of biochar.
The ionic strength of the adsorption solution is another factor impacting electro-
static interaction. Increasing the ionic strength of the solutions can increase adsorp-
tion when the electrostatic interaction between the adsorbate and biochar is repulsive
and will decrease in the case of attractive electrostatic interaction. For example, by
increasing the solution’s NaCl concentration from 0.01 M to 0.1 M, the amount
of adsorbed cationic methylene blue decreased from 4.5 to 3 mg/g [56]. This was
attributed to the competition between the cationic methylene blue and Na+ for the
negatively charged functional groups on the surface of biochar.

3.1.5 Hydrogen Bonding

Hydrogen bonding can be an intermolecular attraction between hydrogen in one


molecule and an electronegative atom of another molecule. Hydrogen bonding is
58 K. Zoroufchi Benis et al.

a plausible mechanism for the removal of polar organic contaminants by biochar


adsorbents [46]. Biochar is abundant in polar groups enabling the adsorption of
organic compounds containing electronegative elements via hydrogen bonding. In
particular, different groups of organic contaminants, such as amino and hydroxyl
groups, can facilitate hydrogen bonding with several functional groups on the surface
of biochar, such as alkoxy and hydroxyl. For example, [50] observed that hydrogen
bonding between carbamazepine and –OH on minerals on the biochar surface has
been reported as a fast adsorption mechanism.

3.1.6 Summary

Biochar can be a promising adsorbent for removing organic contaminants from


different water matrices. However, the adsorption strength of biochar is markedly
impacted by the feedstock, pyrolysis conditions, and applied chemical activation.
Additionally, the properties of the target contaminant (e.g., charge, size) and the
adsorption solution (e.g., pH, ionic strength) are also factors in biochar’s adsorption
mechanism and performance. Reviews of recent studies on using biochar for the
adsorption of various contaminants [21, 22, 38, 57–59], including antibiotics, dyes,
and emerging pollutants, provide more insights into the effectiveness of biochar for
the adsorption of a wide range of organic pollutants.

3.2 Adsorption of Inorganic Contaminants

Inorganic pollutants can be anthropogenic or naturally occurring including heavy


metals and nutrients that are present in various water matrices. Heavy metals, such
as As, Cu, Cd, Pb, and Zn, and toxic ions, such as NO3 − , NH4 + , F− , and PO4 3− are the
most prevalent inorganic pollutants detected in water [60]. As mentioned previously,
the adsorption behavior of biochar depends on the characteristics of the contami-
nants and biochar. Physical adsorption, electrostatic attraction, ion exchange, surface
complexation, and precipitation are the main adsorption mechanisms [61]. These
mechanisms are shown schematically in Fig. 4 and are explained in the following
sections.

3.2.1 Physical Adsorption

Physical adsorption (or surface adsorption) is a weak interaction between adsorbate


and adsorbent surface caused by the Van der Waals forces and does not include
chemical bonds. Physical adsorption is a reversible process because it is mostly
induced by weak intermolecular dipole–dipole forces between the adsorbate and
the adsorbent [62]. Electronegative atoms, such as nitrogen, oxygen, fluorine, and
chlorine in neutral compounds, are able to attract an electron cloud from their less
3 Biochar: A Potent Adsorbent 59

Fig. 4 Major mechanisms in the adsorption of inorganic contaminants onto biochar

electronegative neighboring atom(s) via covalent bonds. This phenomenon generates


partial negative and positive poles within the molecule giving it a dipolar character.
These charges are formed when one molecule’s negative end aligns with another’s
positive end [63]. The adsorption solution’s composition and biochar characteristics
[64], such as composition, roughness, surface area, geometry, and type of adsorbate,
can influence the Van der Waals forces.

3.2.2 Electrostatic Interactions

Electrostatic interactions are the forces between charged molecules/compounds that


are either attractive or repulsive. Electrostatic interactions have been reported as the
major mechanism in the biochar adsorption of different ions such asPb2+ [65], Cr6+
[66], and Cd2+ [28, 67, 68]. In general, the intensity of electrostatic interactions
depends on the solution pH, pHpzc of biochar, the oxidation state of the adsorbate,
and the ionic radius. The surface of biochar is protonated and becomes positively
charged in a solution with a pH less than pHpzc of biochar, which makes it a favorable
adsorbent for the adsorption of anions. In contrast, a solution with a pH greater than
pHpzc is beneficial for the adsorption of cations because the biochar surface becomes
deprotonated and negatively charged.
Additionally, solution pH regulates the adsorbate’s ionization degree. Therefore,
the electrostatic interactions can be repulsive or attractive depending on the solu-
tion pH and pHpzc of biochar [69]. Typically, pristine biochar has an acidic point
of zero charge (pHpzc < 5)due to negatively charged groups on its surface. Adsorp-
tion of positively charged ions is facilitated by the negatively charged surface due
to electrostatic attraction [10]. Increasing the pyrolysis temperature promotes the
removal of oxygenated functional groups that results in lower surface negativity,
higher pHpzc , and potentially more favorable adsorption of negatively charged ions
60 K. Zoroufchi Benis et al.

[31]. For example, [70] observed that the affinity of perilla leaf biochar for arsenic
oxyanions increased by increasing the pyrolysis temperature.

3.2.3 Surface Complexation

Surface complexation is the creation of stable complexes between functional groups


on the adsorbent surface and compounds or ions in solution. A molecule that contains
a core of one or more atoms surrounded by ligands is called a complex. The complexes
may be mononuclear, containing one metal ion and a number of ligands, or polynu-
clear, containing more than one metal atom centre. The surface complexation is
generally categorized as inner- and outer-sphere complexations [23]. Inner-sphere
complexation is driven by complex formation, while outer-sphere complexation
is determined by the ionic strength of the aqueous solution. Thus, inner-sphere
complexes are stronger and more stable than outer-sphere complexes.
Surface complexation is an important mechanism for metals with partially filled
d-orbitals that have a strong affinity for ligands [62]. Oxygen-containing functional
groups of biochar, such as carboxyl and phenolic can, can play a key role in binding
with heavy metals such as Cd, Cu, Pb, and Ni [71]. Furthermore, it has been found
that the oxidation of a biochar surface over time can increase oxygen-containing
functional groups leading to improved metal complexation [72]. For example, the
surface complexation of Cd2+ with ionized oxygen-containing functional groups on
the surface of Canna indica-derived biochar has been described as the main adsorp-
tion mechanism [73]. Similarly, the major role of oxygen-containing functional
groups in adsorbing of Sb [74] and Cu2+ [75] using biochar has been reported.

3.2.4 Ion Exchange

Ion exchange involves the exchange of ions between an adsorbent and contaminated
water. The performance of ion exchange in holding contaminants on the biochar
surface depends on the contaminant size and the surface functional groups of the
biochar. The ionic exchange of metals involves the substitution of positively charged
ions on a biochar surface with a metal contaminant. According to Goldschmidt’s
geochemical classification, alkaline and alkali earth metals such as K, Na, Mg, and
Ca are more susceptible to being exchanged with other species within the same
group due to their similar characteristics. In addition, some transition metals have
demonstrated a great affinity for these exchange sites [62]. The cation exchange
capacity (CEC) of biochar is governed by adsorption functional groups present in the
biomaterial and the pyrolysis conditions. For example, [76] observed that a biochar
pyrolyzed at a low temperature had a larger CEC and, thus, a greater NH4 + adsorption
capacity due to replacing NH4 + by other positively charged ions with lower affinities
for the biochar surface.
3 Biochar: A Potent Adsorbent 61

3.2.5 Precipitation

Precipitation is the formation of insoluble compounds during the adsorption process


both in solution and directly on the surface of the adsorbent. Precipitation can be
due to the formation of a macro-component or by reaching the solubility limit of
the chemical. The precipitation of inorganic pollutants by biochar can occur via
two mechanisms: (1) changing the pH of the medium, which precipitates contami-
nant ions, and (2) interaction of the contaminant with surface components such as
CO3 2− and PO4 3− [77]. For example, the removal of Zn, Cu, and Cd using a dairy
manure-derived biochar was because of the formation of metal-phosphate and metal-
carbonate precipitates [78, 79]. Similarly, the high phosphate removal performance
of a peanut shell-derived biochar was attributed to the precipitation of phosphate
due to the high amount of Mg and Ca on the surface of biochar [80]. On the other
hand, biochar with alkaline pH values can lead to the “lime effect” and precipitate
inorganic pollutants. For instance, [62] reported that the formation of a metal(OH)2
(e.g., Pb2+ + 2OH− → Pb(OH)2 ) was the primary mechanism in adsorbing Cd, Pb,
Zn, and Cu using municipal sludge-derived biochar.

3.2.6 Summary

Different possible mechanisms for the interaction between biochar and inorganic
contaminants were discussed in this section. The presence of diverse and abundant
functional groups on the surface of biochar enables it to adsorb a wide range of
heavy metals. The factors controlling the adsorption process, such as the properties of
biochar and contaminants, were overviewed. For further information, the most recent
research on using biochar for the removal of inorganic chemicals is summarized in
review papers [62, 55, 81, 82].

3.3 Microbial Contaminants Removal

Current disinfection methods can successfully eliminate microorganisms including


treatment with ozone and chlorine compounds. However, the creation of harmful
disinfection by-products from the interaction of disinfectants with natural organic
matter in wastewater has become of considerable recent interest leading to the consid-
eration of alternate disinfection methods [46]. Thus far, most previous studies have
only focused on using biochar to remove Escherichia coli from water [83–85].
Overall, the type and characteristics of microorganisms and their concentrations,
as well as the biochar dosage and its properties, are the main parameters that alter
the functionality of biochar-based disinfection processes [60].
It was observed that increasing the hydrophilic nature of biochar can increase the
removal of less hydrophobic bacteria. Surface attachment via hydrophobic and elec-
trostatic deposition has been suggested as the controlling mechanism in the removal
62 K. Zoroufchi Benis et al.

of E. coli from water [83, 85]. For example, studying the E. coli removal perfor-
mance of four activated biochars (activated with H2 SO4 , KOH, H3 PO4 , and amino)
showed higher adsorption capacity of H2 SO4 -activated biochar that was attributed
to its higher hydrophobicity, porosity, and surface area [83]. Gram-negative bacteria
such as E. coli have a negative surface charge because of 2-keto-3-deoxyoctonate
carboxylate and phosphoryl groups that create negative electrostatic cell surfaces
[86]. On the other hand, the negative surface charge of Gram-positive bacteria is due
to teichuronic acid residues, teichoic acids, and unsubstituted carboxylate groups
[87]. The net negative surface charge of bacteria can lead to electrostatic deposition
on the biochar surface having a net positive surface charge.
In fact, the solution chemistry and the species of microorganisms, and biochar
properties are the determinant factors in the biochar disinfection performance. There-
fore, more study is required to further understand the effects of these parameters and
prepare efficient biochar for microbial contaminants removal.

4 Biochar for Air Treatment

Industrial processes, along with the extensive combustion and exploitation of fossil
fuels, have produced a wide variety of air contaminants such as carbon dioxide,
VOCs, acidic gases, and toxic metals. According to a World Health Organization
(WHO) assessment more than 80% of metropolitan residents are exposed to poor air
quality [88]. Common methods for the treatment of contaminated air are membrane
separation, absorption, catalytic methods, biological treatment, and adsorption [89].
Considering the unique characteristics of biochar (explained in Sect. 2), it can be a
less expensive alternative for air treatment in comparison with commercial adsor-
bents such as activated carbon. In contrast to extensive research on using biochar
for water treatment, its application for the treatment of gases has received rela-
tively less attention with only a few studies published [90]. As explained in Sect. 3,
biochar has shown a high affinity to both inorganic and organic chemicals. The
reported organic gaseous contaminants in the literature are acidic gases and metals,
notably mercury [91–93], whereas organic contaminants include VOCs, aromatics,
and odorous substances [28, 67, 68, 94, 95]. The mechanisms of adsorption of these
contaminants from air using biochar are the same mechanisms that are discussed in
Sects. 3.1 and 3.2. Therefore, the following discussion is a more general overview
of some of the most recent studies on removing inorganic and organic contaminants
from the air using biochar.

4.1 Adsorption of Organic Contaminants

The VOCs are the major organic air contaminants that have been treated using
biochar. Their severe toxicity, even in trace amounts, compels their removal from
3 Biochar: A Potent Adsorbent 63

the air. For example, benzene in the air is harmful even at trace concentrations [96].
A recent study showed that a KOH-activated biochar derived from mixed feedstock,
including wood chips, food waste, and chicken manure, was a strong benzene adsor-
bent in both low and high-pressure ranges [97]. Methyl tert-butyl ether (MTBE) is
one of the commonly used gasoline oxygenate, and typically 25–33% of the added
MTBE is released from vehicle exhausts in an unburned state. MTBE is a harmful
VOC and can enter the body through skin contact and inhalation. In a compara-
tive study, bagasse-derived biochar had a higher MTBE adsorption capacity than
bone-derived biochar [98]. The lower adsorption capacity of bone-derived biochar
was due to its high ash content and unsuitable functional groups, such as ethers and
phosphates, which lack affinity for MTBE. However, the low ash content of bagasse-
derived biochar and its MTBE-suitable functional groups, such as ester and carbonyl,
resulted in higher adsorption capacity.
In another study, the acetone, cyclohexane, and toluene adsorption onto15
biochars produced from five feedstocks at three temperatures of pyrolysis of 300, 450,
and 600 °C was investigated [28, 67, 68]. It was found that physisorption and parti-
tioning were the dominant VOCs adsorption mechanisms. The biochars pyrolyzed
at lower temperatures had higher adsorption capacities due to their higher noncar-
bonized organic matter (NOM) content. Although raising the temperature of pyrolysis
increased the surface area of biochar, it resulted in lower NOM content and lower
VOCs adsorption capacity [28, 67, 68]. Similarly, physisorption and partitioning
were reported as the primary mechanisms in the adsorption of benzene, chloroform,
toluene, carbon tetrachloride, methyl chloride, and xylene onto biochars derived
from sugarcane, neem, and bamboo feedstocks [12]. In this study, feedstock mate-
rial, contact time, pyrolysis temperature, and surface area of biochars significantly
affected the VOC’s adsorption capacities. Studying the adsorption of 15 different
odorous organic compounds emitted from the swine manure onto nine different
biochars showed insignificant roles of biochar’s volatile matter, carbon content, pH,
and surface area in the adsorption of odorous compounds [99]. However, the possible
adsorption mechanisms were not discussed.
Overall, despite the limited number of studies on the application of biochar
removing organic contaminants from the gaseous phase, it is evident that the type of
feedstocks and the pyrolysis conditions are the major parameters affecting organic
contaminant adsorption onto biochar. In addition, the major adsorption mechanisms
of organic contaminants from the gaseous phase are the same as the aqueous phase
(Sect. 3.1).

4.2 Adsorption of Inorganic Contaminants

Air pollution can lead to both short- and long-term human health problems and these
problems vary by pollutant and exposure level and time. There are several inorganic
gas contaminants, such as carbon dioxide, hydrogen sulfide, nitrogen dioxide, and
metals, which need to be treated in both outdoor and indoor air.
64 K. Zoroufchi Benis et al.

Carbon dioxide (CO2 ), the main gas resulting from anthropogenic activities,
contributes significantly to the worldwide greenhouse gas effect. Based on this signif-
icance, research has focused on preparing biochar-based adsorbents to capture CO2 .
Overall, pristine biochar is not an efficient CO2 adsorbent but modified or activated
biochar has been shown to enhance CO2 adsorption [100]. For example, it has been
reported that nitrogen-containing functional groups on the surface of biochar enhance
CO2 capture [101]. Therefore, several studies have applied different chemical treat-
ments to introduce nitrogen functional groups on the surface of biochar [101]. In the
majority of these studies, ammonia was employed as the nitrogen source, and the
influence of various pre-pyrolysis and post-pyrolysis activation methods was inves-
tigated. For example, post-pyrolysis activation of a chicken manure-derived biochar
with HNO3 and ammonia gas significantly increased CO2 absorption capacity due
to added nitrogen-containing functional groups [102]. In another study, a high-
temperature CO2 –ammonia mixture was used to activate biochar with a high CO2
adsorption capacity [103]. The other common activation methods are the chemical
treatment of feedstock or pristine biochar with KOH, NaOH, or metal salts and
physical treatment using steam and CO2 [100].
Hydrogen sulfide (H2 S) is a dangerous air pollutant because of its toxicity and
corrosiveness. In a comparative study, three biochars derived from bamboo, camphor,
and rice hull, respectively, showed higher H2 S adsorption capacity than commercial
activated carbon [104]. Studying the effect of temperature of pyrolysis (100–500 °C)
on H2 S adsorption capacity showed that biochar prepared at 400 °C has a higher
adsorption capacity that was attributed to its higher surface area [105].
Sulfur dioxide (SO2 ) is a challenging pollutant. It is a colorless gas that is
mainly released from burning fossil fuels. Comparing the SO2 adsorptioncapacities
of KOH, CO2 , and superheated steam-activated biochars showed no linear relation-
ship between porosity and surface area of activated biochar and their SO2 adsorption
capacity [106]. For example, a KOH-activated biochar was found to be the most
porous biochar produced (1,700 m2 /g), but had less SO2 adsorption capacity as
compared to two other biochars. This was because of the unsuitability of surface
functional groups.
Mercury (Hg) is an airborne metal that has received considerable attention in the
biochar literature [107–110]. It is a toxic and volatile metal that is mainly emitted
into the atmosphere from coal-fired boilers [108]. Investigating the effect of pyrolysis
temperature and type of feedstock such as almond shells, cottonseed hulls, lignin,
and chicken manure, showed the higher mercury adsorption capacities of manure-
derived biochar [107]. The reaction of Hg0 with C–Cl groups on the surface of
NH4 Cl-activated biochar and the formation of HgCl2 was reported as the primary
mechanism. The co-existence of a high concentration of SO2 in the air decreased the
Hg0 adsorption because of competition of SO2 and Hg0 for the same adsorption sites
on the biochar surface [93].
In summary, understanding the effects of pyrolysis conditions and applied acti-
vation processes will assist in designing efficient biochar for the adsorption of inor-
ganic chemicals from air. The pyrolysis and activation conditions can be optimized to
3 Biochar: A Potent Adsorbent 65

enhance the porosity and SSA and introduce proper functional groups to the surface
of biochar.

5 Future Directions

Biochar can be a promising adsorbent as demonstrated by the preceding discussion


on the use of biochar for treating contaminated water and air. This is due to its
ability to effectively adsorb various contaminants while also having both economic
and environmental viability. Despite the increasing trend in using biochar in adsorp-
tion processes, particularly in water treatment, these processes have not been fully
developed and optimized. A significant body of research has been done to deter-
mine the performance of biochar for adsorption. However, the vast majority of these
studies have been primarily based on laboratory scale studies and with biochars
designed for a particular contaminant prepared in simple matrices. Further research
is needed for the scale-up design to pilot and industrial scales while using actual
waters, wastewater, and polluted airstreams.
Additionally, adsorption experiments were conducted in the short-term without
investigating the structural stability and removal performance of biochar in long-
term adsorption tests. As a result, it is necessary to conduct long-term adsorption
experiments to monitor the biochar stability and the fate of the adsorbed contami-
nants. Besides the stability, the regeneration capacity of biochar is a crucial factor
in its application in real-world conditions that should be investigated. Moreover,
co-existing contaminants’ effects on the adsorption of target contaminants must be
assessed. Using biochar in large-scale water or air treatment systems will allow us to
examine the obstacles that may be encountered in actual deployment. Particularly, the
decontamination performance of biochar in large-scale treatment systems needs to
be evaluated in the co-contaminated media with inorganic, organic as well as micro-
biological contaminants. For example, in air treatment studies an important factor
that is typically overlooked is the effect of humidity. This is important as humidity
changes the properties and surface functional and active groups of the adsorbent, and
also it competes with the adsorbate for the surface.
The majority of biochar research on water treatment has concentrated on removing
inorganic and organic contaminants. However, there is a dearth of information
regarding biochar applications for removing microbiological contaminants. More
research is necessary to understand the interaction between living microorgan-
isms and the biochar surface to determine if biochar can be an effective treatment
application for these contaminants.
It is also important to use advanced characterization techniques to investigate inter-
actions between the adsorbed contaminants and created biochars to better understand
the adsorption mechanism. Secondary pollution is another potential issue that was
rarely investigated in previous research. Biochar derived from different feedstocks,
such as industrial or agricultural wastes, may release secondary contaminants into the
66 K. Zoroufchi Benis et al.

air or water. Therefore, monitoring the adsorption process, particularly in long-term


adsorption, for the release of secondary contaminants is important.
Although pristine biochar is considered to be an economical and eco-friendly
adsorbent, activated or modified biochar may not be cost-effective, and their appli-
cation may impact the environment. Therefore, cost analysis and studying the envi-
ronmental impacts of the activated/modified biochar are needed in future studies.
Systematic methods such as Life-cycle assessment and Life Cycle Cost Analysis can
be used to determine the environmental and economic sustainability of the produced
biochar from the cradle to the grave.

6 Conclusion

Biochar can be effectively utilized as an eco-friendly material for the treatment of


air and water contaminated with a variety of inorganic and organic contaminants.
The main factors impacting the adsorption efficiency of biochar are feedstock type,
pyrolysis condition, activation or modification method, the matrix of contaminated
air or water, and characteristics of target contaminants. Furthermore, the complex
structure of biochar makes adsorption a complicated process with the possibility
of different adsorption mechanisms such as electrostatic interactions, π-π interac-
tions, hydrophobic interaction, surface complexation, and others. Overall, substan-
tial research has been conducted to examine the performance of biochar; however,
more research is needed with a focus on biochar application in air treatment and
water disinfection. In addition, further information is required about the cost and
eco-friendliness of activated or modified biochar applications for both water and air
treatment processes.

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Chapter 4
Biochar in Carbon Sequestration

Mohammad Shirzad, Mohsen Karimi, Alírio E. Rodrigues,


and José A. C. Silva

1 Introduction

Increasing rate of greenhouse gas (GHG) emissions, such as carbon dioxide (CO2 ),
methane (CH4 ), sulfur dioxide (SO2 ), nitrogen oxide (N2 O), and fluorinated gases
(HCFs, CFCs), has led to propel the earth temperature towards higher levels and
consequently, the global climate change that adversely affects the human normal life
[1, 2]. Among GHGs, CO2 is the principal gas contributing to global temperature
enhancement with the emission share of about 76% [3, 4]. Between 1960 and 2020,
the global average atmospheric CO2 as the most crucial one among other GHGs
has been enhanced around 31%, which directly contributes to global warming [5, 6,
7]. About 80% of released CO2 in the earth’s atmosphere has been emitted through
the fossil fuel consumption including natural gas, crude oil, coal, petroleum, oil
shale, and tar sands [8], which quantitatively is estimated about 32 Gt emission per
year [3, 9]. On the other hand, scientists believe a disappointing rising level in CO2
emission (triple growth of current reported values) till 2050 [10]. Scientific literature
indicates that greenhouse gas emissions through human activities lead to about 3–5
C. Average global temperature enhancement before the twenty-first century finishes
and consequently 95 cm rising in sea level as well as extreme climate events [11, 12].
In line with that, the International Energy Agency (IEA) opted Carbon Capture and
Storage (CCS) strategy (including diverse technologies), as BLUE Map Scenario,

M. Shirzad · M. Karimi (B) · A. E. Rodrigues


Laboratory of Separation and Reaction Engineering (LSRE), Associate Laboratory LSRE/LCM,
Faculty of Engineering, University of Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal
e-mail: mohsen.karimi@fe.up.pt
Faculty of Engineering, ALiCE—Associate Laboratory in Chemical Engineering, University of
Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal
M. Shirzad · M. Karimi · J. A. C. Silva
Centro de Investigação de Montanha (CIMO), Instituto Politécnico de Bragança, Campus de
Santa Apolónia, 5300-253 Bragança, Portugal

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2023 73
A. K. Nadda (ed.), Biochar and its Composites, Materials Horizons:
From Nature to Nanomaterials, https://doi.org/10.1007/978-981-99-5239-7_4
74 M. Shirzad et al.

to reduce and sequestrate global CO2 emitted [13], leading to a reduction around
19% in average global CO2 by 2050 [14]. The main global share of CO2 emissions
is attributed to China with almost a third of total emission, and in the following
United States, European Union (EU), India, and Russia with 15.0%, 9.9%, 6.4%,
and 4.5%, respectively [9]. In this way, CO2 emission from coal-fired power plants,
which generate about 27% of the global energy requirement [9, 13, 15], is among
the main focus of CCS studies to develop advanced technologies for carbon capture
processes [16, 17].
There are some most-studied technologies for general gas separation processes
including adsorption, absorption, cryogenic separation and membranes, which are
different in capital and operational cost, CO2 selectivity and recovery, reliability, eco-
friendship, and process maturity [11, 18]. In the refineries and petrochemical indus-
tries, amine-based chemical absorption is frequently employed [10, 2]. High energy
consumption through regeneration step, high probability of equipment corrosion,
the solvent cost, and also the negative impact to the environment by GHG emissions
are various drawbacks that make chemical absorption noxious [19, 20]. Currently,
high CO2 selectivity and recovery, high reliability, and significant eco-friendship
of adsorption technology led that process becomes promising among diverse CO2
capture and sequestration technologies [21]. In this way, different sorbents including
activated carbons (ACs) [22], metal–organic frameworks (MOFs) [5, 23], zeolites
[24], metal oxides materials [25], lithium zirconate [26], silica [27], etc. [28] have
emerged potential for CO2 mitigation through the adsorption process. Various char-
acteristics such as sustainability, loading capacity, stability, bulk density, regenera-
tion conditions, and hydrophobic/hydrophilic characteristic shall be investigated to
discriminate a high-performance adsorbent for industrial-scale applications [29].
There are many positive characteristics that point out carbon-based adsorbents as
an attractive one for gas capture and storage [16, 29]. Massive sustainable sources
for carbon-based adsorbents such as animal and agricultural wastes [27, 30], coals
[31], fly ash [32], carbon-containing resins [6], and raw biomass [33, 34] led to
synthesize excellent low-cost sorbents (Fig. 1). Likewise, hydrophobicity of carbon-
based adsorbents is one of the most crucial priorities compared to those of zeolites
and MOFs to solve the problem of sorbent degradation in the presence of moisture
through the gas purification processes [35, 36, 37]. Also, lower heat of adsorption
[29], simplicity in adsorbent synthesis as well as eco-environmental aspects are taken
into account of another positive characteristic of carbon-originated adsorbents [19,
38, 25].

2 Biochar

Biochar with the source of agricultural wastes, municipal solid wastes, natural
biomass, etc. is a porous substance that is synthesized in an insufficient oxygen
condition through incomplete combustion (regularly by pyrolysis process) [39]. The
pyrolysis output is a wide range of gases and liquids as well as a residue called
4 Biochar in Carbon Sequestration 75

Fig. 1 Different precursors


of carbon-based adsorbents

biochar. Biochar is actually a variety of substances rather than a simple individual


homogeneous product.
Formerly, biochar was considered as a fertilizer to the soil and today, is known as
an adsorbent with high performance for CO2 separation purposes. Among all carbon-
based sorbents, biochar is significantly the cheaper one [40]. Annually, regarding the
information reported by UNEP (United Nations Environment Program), almost 140
billion tons of biomass is produced globally [41], (Ani et al. 2010). The majority of
generated biomass is constituted of agricultural wastes, animal wastes [42], wooden
wastes (wooden shells, etc.), and residual wastes (wood processing residues, etc.)
[41, 43]. Table 1 indicates some types of agricultural and wooden products, wooden
residues, and animal waste capacity. Vast renewable resource for biochar production
is one of the priorities of biochar-based adsorbents toward other carbon-based adsor-
bents. As indicated in Table 1, every region in the world may possess high potential of
biochar production from specific waste/wastes. Figure 2 reveals the waste-to-biochar
process schematically.
76 M. Shirzad et al.

Table 1 Some agricultural and wooden products, animal wastes, and wooden residues’ capacity
in the world by region
Product Year Region Capacity References
(1000 ton/year)
Argan fruit shells 2015 Morocco 80 [44]
Peanut shells 2010 Globally 6000 [45]
Bagasse 2020 Brazil 758,000 [46]
Pine cones 2012 Andalusia 55.2 [47]
Palm kernel cake 2018 Malaysia 2500 [48]
Palm 2012 Indonesia 25,400 [49]
Sunflower seed 2018 Italy 282.4 [50]
Coffee grounds – Globally 7000 [51]
Olive 2020 Spain 6559.9 [52]
Sugarcane – Brazil 758,000 [46]
Corncob 2015 China 20,000 [53]
Bagasse 2020 India 306,000 [54]
Pine sawdust 2019 Mexico 280 [55]
Sugarcane – India 306,000 [54]
Almond 2020 United States 2002.7 [56]
Animal manure 2017 Vietnam 26,361 [57]
Oat 2020 Russian Federation 4761.4 [58]
Coconut 2019 Indonesia 17,130 [59]
Coconut 2015 Malaysia 631.2 [60]
Rice 2020 China 148,500 [61]
Oil tea 2018 China 56,250 [62]

Basically, raw biochar needs to pass through a modification process to be able to


adsorb CO2 . Regularly, biochar surface properties and sorption capacity are engi-
neered and modified through the physical and/or chemical processes, grafting, and
impregnation by elements [63]. Table 2 summarizes the process of biochar activation
methods and their impact on raw biochar for CO2 adsorption enhancement [64–69].

2.1 Biochar Production

As mentioned earlier, biomass combustion through insufficient oxygen atmosphere,


called as thermochemical conversion (e.g. pyrolysis, gasification, hydrothermal
carbonization, and torrefaction [70]), plays the most crucial role in the biochar
production. Consequently, thermochemical conversion temperature, heating rate,
4 Biochar in Carbon Sequestration 77

Fig. 2 Waste-to-biochar process

Table 2 Different biochar modifications and their impact on biochar


Activation method Impact on raw biochar
Alkali modification Enhancement in oxygen content and surface area by using NaOH and
KOH
Amino modification Alkalinity enhancement and consequently, increase of affinity to adsorb
CO2
CO2 flow Enhancement in micropores
Steam flow Enhancement in devolatilization and crystalline structure formation
Metal impregnation Alkalinity enhancement and increase in basic sites

type of feedstock [42], and process duration are four major parameters affecting
produced biochar yield and structural composition.
Each conversion method requires specific energy, media, and procedure. For
instance, there is no need for drying process before the hydrothermal carboniza-
tion. In the following, Table 3 [71–75] reveals some characteristics of different
biomass-to-biochar methods.
The pyrolysis process as the most-applied one for biochar production is catego-
rized into two major processes: slow and fast [76]. Typically, higher yield of biochar
production is observed in slow pyrolysis rather than fast pyrolysis. The fast and slow
pyrolysis characteristics are summarized in Fig. 3. Basically, slow and fast pyrolysis
78 M. Shirzad et al.

Table 3 Characteristics of different biomass-to-biochar conversion methods


Conversion method Advantage Disadvantage
Pyrolysis • Maturity and frequently usage • Mid-residence time
• Better biochar characteristics
• Low ash content
Gasification • Low residence time • High temperature
• Low biochar yield
Hydrothermal carbonization • No need to pre-drying • High residence time
• Low cost
Torrefaction • Low temperature • Need for pre-drying
• High biochar yield

Fig. 3 Slow and fast pyrolysis characteristics

is used for biochar and bio-oil production, respectively [76, 77]. In line with that, the
biomass conversion process is opted according to the final desired product.
It is worth indicating that a mass loss is observed through the biomass-to-biochar
conversion process. In low temperature, the biomass mass loss is attributed to the
water vaporization, and higher temperature contributes to mass loss resulted in
burning of carbonaceous residue through thermochemical conversion.
4 Biochar in Carbon Sequestration 79

2.2 Biochar Modification

Today, biochar is known as a polar and hydrophobic derived substance with high
porosity and surface area, which can participate in sorption processes [78]. Hence,
one of the most significant current discussions in CO2 sequestration is the modifi-
cation of conventional biochar [79]. According to precursor nature, type of additive,
desired condition for adsorption, etc., modification process may be implemented
prior and/or after pyrolysis step [80]. However, pre-treatment steps (washing and
then drying the samples at about 100 °C) before the carbonaceous precursor modifi-
cation process are necessitated to eliminate impurities and any contaminations [29].
After pre-treatment steps, the raw samples need to pass a milling and sieving process
to prepare an in-range size of pre-treated raw material [81]. The final step of biochar
modification, called as activation, is divided into physical (thermal) and/or chem-
ical processes [29]. In some studies, impregnation by elements is also mentioned
as a biochar modification method, but the majority of studies have identified those
physical and chemical activations as the regular modification procedures [67].
There is no specific procedure for physical activation and it varies based upon
the nature of carbon precursor; but all activation procedures are implemented at high
temperature (400–900 °C) by means of a gaseous media like N2 , CO2 etc. or steam
[82]. CO2 and steam are most popular in biochar physical activation process. Through
the physical activation, CO2 flow enhances the micropores and steam increases
devolatilization and crystalline structure formation [67, 69]. Basically, any process
that leads to an improvement in biochar surface characteristics is favorable for CO2
sequestration process [78]. The major parameters that have an impact on biochar
porosity are gaseous media flow rate, temperature, and modification duration [69].
Through the physical activation process, a massive amount of carbon in biochar is
lost and a high-porous carbon is yielded [83].
In chemical activation, washing step is conducted before the activation process,
due to the elimination of the impurities left from the pyrolysis step. The washed
sample is then soaked in a chemical agent. Duration of soaking in chemical agent is
pertained to the carbon precursor nature and type of chemical agent. After immersing
the biochar in a specific chemical agent, biochar is dehydrated by chemical agent and
tar formation is prohibited; consequently, an enhancement of carbonization occurs
[84]. It is worth indicating that chemical activation enhances the biochar surface
area by controlling the microporosity [85]. On the contrary, the chemical agent fully
distribution in biochar is crucial to achieve a high-porous biochar, which emphasizes
on the importance of appropriate mixing [86]. In recent days, various chemical agents
have been considered as biochar activating agent comprising H3 PO4 , HNO3 , HCl,
H2 O2 , ZnCl2 , KOH, NaOH, H2 SO4 , K2 CO3 , MgCl2 , MgO, AlCl3 etc. [87, 41, 84, 88].
The consideration should be given that the modified biochar porosity after chemical
activation [89, 90] is related to the mixing rate, duration and temperature of process,
type of chemical agent, and the nature of carbon precursor.
In some studies, to achieve a higher porosity and greater surface area, a physical
activation step is implemented after the chemical activation process. Indeed, physical
80 M. Shirzad et al.

Fig. 4 Biochar modification


processes

activation in higher temperature leads to fully carbonization of organic matter that


prepares new pores to develop a more efficient biochar with higher surface area [91].
A final washing step also eliminates the substances left after carbonization process
and can modify the biochar CO2 sequestration potential.
Figure 4 illustrates the biochar modification process schematically [65, 67, 92, 93].
Also, Fig. 5 shows the first-to-end steps of a modified biochar production process.
Table 4 indicates some carbon precursor and modification procedures for instance. As
observed, physical activation by CO2 flow possesses more than half of total studies,
which was devoted to biochar activation process.

3 Biochar for CO2 Sequestration

Newly, CO2 adsorption on the modified biochar has been the subject of concern in
numerous investigations and various efforts devoted to modify that process. These
cheap and available biochar require serious efforts to develop their sequestration
characteristics, as every neoteric technology. In the following, we assorted almost
all investigations carried out on biochar as CO2 adsorbents, which is an assorted
epitome that emphasizes the potential of these renewable sources for more attention
and scientific efforts. Today, numerous carbon precursors have been introduced for
4 Biochar in Carbon Sequestration 81

Fig. 5 Biomass-to-biochar production scheme

CO2 sequestration purposes comprising whitewood, maple wood, soybean straw,


maritime wood, cotton stalk, pine shell, sawdust, coconut shell, walnut shell, cotton
wood, olive stone, cherry stone, sunflower seed, municipal solid waste, almond shell,
rice husk, peanut shell, horse manure, grass cutting, green coffee, rambutan peel,
corn cobs, argan fruit shells, algae, sugarcane bagasse, paulownia sawdust, tobacco
waste, agaricus, populus wood, eucalyptus wood, lignin waste, kenaf, poplar anthers,
Mesua ferrea L. seed, and etc. [22]. In this chapter, we categorized almost all biochar
investigated for CO2 sequestration purposes in five sections (according to Fig. 6)
comprising (1) wooden biochar, (2) seeds/kernel-originated biochar, (3) shell/husk-
originated biochar, (4) leaves/green plants-originated biochar, and (5) other biochar.
In the following, each section will be discussed comprehensively.

3.1 Wooden Biochar

From the literature, a major share of biochar investigation in CO2 sequestration


purposes has been devoted to wooden biochar. High carbon content and negligible
sulfur/ash are specific characteristics of biochar, which make them known as an
economic precursor for AC production in CO2 adsorption processes. In 2014, EU-27
countries produced around 60 million tons of wood waste, which shows the potential
of biochar production from this precursor [113]. Annually, tons of woods are wasted
82 M. Shirzad et al.

Table 4 Carbon precursor and the modification method


Carbon precursor Type of modification Modification media References
Cotton Physical CO2 [69]
Chemical NH3
Physical/chemical CO2 /NH3
Sawdust Chemical MEA (Monoethanolamine) [94]
Coconut shell Physical CO2 [95]
Coconut shell Chemical KOH [96]
Coconut shell Physical Steam [97]
Coconut shell Physical CO2 [98]
Betung bamboo Chemical H3 PO4 and K2 CO3 [99]
Soybean Physical CO2 [68]
Chemical NH3
Physical/chemical CO2 /NH3
Grass Physical CO2 [100]
Whitewood Physical Steam [101]
CO2
Chemical KOH
Maple wood Physical CO2 [98]
Municipal solid wastes Physical/chemical N2 /H2 SO4 [79]
(MSW)
Olive stone Physical CO2 [102]
Olive stone Physical CO2 [103]
Olive stone Physical CO2 [104]
Olive stone Physical CO2 [105]
Olive stone Physical CO2 [103]
Olive stone Physical CO2 [106]
Cherry stone Physical CO2 [105]
Rambutan peel Non – [107]
Almond shell Physical CO2 [106]
Almond shell Physical CO2 [102]
Kenaf Impregnation Alcoholic amin solution [108]
Horse manure Physical CO2 [100]
Pine sawdust Physical CO2 [109]
Wood sawdust Mechano-chemical KOH [110]
Beech wood Physical N2 [111]
Oil tea shell Chemical KOH [112]
4 Biochar in Carbon Sequestration

Fig. 6 Categorization of CO2 sequestration biochar


83
84 M. Shirzad et al.

through different industries and operations including packaging, construction and


demolition, and bulky waste [113]. Industries have the maximum share of wood
waste generation globally. Roughly, 20% of the total quantity fed into the wood
industry changes toby-product and consequently, known as residual wastes, which
is categorized into three sections comprising offcuts, sawdust, and chips [113].
After surveying the literature in this section, it is perceived that chemical activation
has attracted more attention than physical activation for wooden biochar activation.
A wide range of CO2 adsorption uptakes (in the range of 0.25–10.8 mmol.g−1 ) has
been reported for this type of adsorbent.
• Sawdust

Sawdust is one of the low-cost and available precursors for biochar production
purposes, which is potentially a by-product in different industries, and produced from
the trimming, cutting, shaving, and grinding of wood during the raw wood-to-stuff
process. This by-product is generally casted off or burnt for producing heat. Sawdust,
due to the molecular characteristics, is an excellent candidate for being changed
into biochar through an incomplete combustion [114]. Zhu et al. [115] employed
paulownia sawdust to produce biochar for utilization in CO2 sequestration purposes.
They employed a one-step carbonization and carbon activation method. Afterward,
the crucial parameters in activation process constituting KOH/biochar mass ratio,
temperature, and activation period were investigated and biochar structure as well
as, CO2 sequestration capacity were evaluated. At the activation conditions of KOH/
biochar mass ratio of 4, temperature of 700 °C, and activation period lasting for 1 h,
the CO2 uptake was estimated 8 mmol.g−1 at 0 °C and 1 bar.
• Wood

Wood is recognized as the most popular substance for producing lignocellulosic


materials, which is employed as one of the major carbon precursors. In spite of a
decreasing trend of forest area in the world, there is a significant potential of forest
products, especially wood, to be applied as the economic and eco-friend precursor for
biochar production process. In 2015, the global forest area was estimated 3.99 billion
ha in the world [116]. Russia, Brazil, Canada, and United States are the countries
with the largest area of forest in the world, respectively. Russian Federation with 815
million ha possesses the first rank of wood production potential globally [117], which
is predominant in forestry practices for sustainable purposes [118]. To this context,
Yorgun and Yildiz [119] employed the Paulownia wood and investigated the impact
of two parameters including the impregnation ratio as well as, the carbonization
temperature on the porosity of the final synthesized AC, in which 4 and 400 °C were
revealed as the optimal quantities of impregnation ratio and carbonization tempera-
ture, respectively [119]. Furthermore, Ekhlasi et al. [120] evaluated the economical
aspect and the CO2 adsorption capability of populus wood-originated biochar. First,
the populus wood biomass was carbonized and then, chemically activated by KOH.
In their study, some important parameters in biochar modification process consti-
tuting KOH/carbon (mass ratio), temperature, and heating period were studied. The
4 Biochar in Carbon Sequestration 85

optimal KOH/carbon mass ratio, activation temperature, and heating period were
observed 3:1, 850 °C, and 60 min, respectively, in which the highest CO2 uptake
resulted at 0 °C and 1 bar was about 7.2 mmol.g−1 . In the final step, they concluded
that the investment required for biochar production with populus wood precursor at
the industrial scale is around 25 $/kg. In another study, Heidari et al. [121] focused
on investigation of various chemical activating reagents (H3 PO4 , ZnCl2 , and KOH)
impact on biochar CO2 adsorption capacity. They employed Eucalyptus camaldu-
lensis is wood (ECW) and found that the biochar activated by KOH showed the
highest surface area and according to the CO2 loading experiments at 30 °C and
1 bar, maximum CO2 capacity was observed around 4.10 mmol.g−1 . Kacem et al. [98]
studied the biochar application possibility for pilot-scale applications through CO2
mitigation concept. The biochar was originated from some precursors including pine
and coconut shells as well as, maritime wood, which was activated physically through
the high temperature procedure by CO2 and water vapor. In line with that, CO2 selec-
tivity toward N2 and CH4 , and also sustainability of the synthesized biochar were
investigated. It was reported that the maple wood/maritime wood/pine shell/coconut
shell-originated biochar, modified by PICACTIF SUPERCAP, showed a higher CO2
loading capacity at 8 bar and 20 °C (11 mmol CO2 g−1 adsorbent), which the adsorp-
tion capacity is comparable with high-efficient zeolites produced through a matured
technology. Afterwards, they proved a reliable efficiency for produced biochar in
large scale through a PSA (pressure swing adsorption) unit and pressure up to 30 bar
[98].
• Lignin waste

Lignin is the product of natural evolution of organic materials on the earth, which is
estimated 100 million tons production in 2015 globally [122]. Lignin contains up to
60% of carbon, which emphasizes on the importance of that precursor for biochar
production [123]. The advantages of lignin utilization for biochar production have
attracted a massive attention these days. Lignin is efficiently derived from the wood or
the mixture of the wood with other biomass (e.g. straws, and etc.) through a chemical
process like Kraft pulping method, for instance [123]. It is worth noting that chemical
agents (e.g. Na2 CO3 , NaHSO3 , etc.) are applied in human-made lignin, which is in
controversy of the sustainability limitations [122]. Lignin waste as the precursor
was the subject of Sangchoom and Mokaya [124] and Balahmar et al. [110] studies.
They employed a chemical process by KOH and utilized KOH/carbon mass ratio of
2 to activate the samples. Sangchoom and Mokaya [124] observed CO2 loading of
7.4 mmol.g−1 at 0 °C and 1 bar. Furthermore, Balahmar et al. [110] also employed
the physical activation at 600–650 °C to maximize the biochar structural properties
of porosity and surface area. Balahmar et al. observed 4.1 mmol.g−1 CO2 adsorption
through the post-combustion process by a PSA (pressure swing adsorption) at 25 °C
and 1.2 bar.
86 M. Shirzad et al.

• Cotton stalk

Tons of cotton is produced annually, which leads to a massive remnant of cotton stalk
waste on the field. For instance, China produced 5.6 million tons of cotton in 2015
[42]. Regularly, cotton stalk is not the livestock feed; hence, farmers burn them or
grind the stalks to burry in the farmland. In line with that, sustainable cotton stalk
recycle is crucial based upon environmental and agricultural issues [125]. Xiong et al.
[93] employed cotton stalk and focused on biochar modification by new method of
physical and chemical activation. In line with that, the chemical and physical acti-
vation was implemented by ammonia and CO2 , respectively. The biochar modified
at 800 °C exhibited a significant surface area and maximum CO2 adsorption about
627 m2 .g−1 and 2.25 mmol.g−1 at 20 °C and 1 bar, respectively.

3.2 Seeds/Kernel-Originated Biochar

This sector is devoted to various biochar originated from any type of seeds and kernels
with high carbon content. These types of material are economic and useless, which
can be changed into valuable products through a sustainable process.
• Coffee grounds

Coffee grounds processing (main steps comprise milling, roasting, grinding, and
brewing) is companied with residue production in different steps. For final synthesis
of 1 kg of soluble coffee, the wasted grounds (spent coffee) are estimated around
2 kg [126]. Annually, the potential of spent coffee generation is estimated about 6
million tons through the industrial activities [126]. It is worth implicating that, in spite
of other organic materials, burying spent coffee in the landfill is on the contrary of
environmental issues; due to some ingredients which make it toxic. Hence, employing
an eco-friendly process in which spent coffee is transformed to valuable products is
attracted more attention nowadays [126]. Plaza et al. [127] activated the pyrolyzed
coffee grounds through physical/chemical activation method by carbon dioxide and
KOH, respectively. Afterwards, they compared the CO2 capacity of two synthesized
activated biochar. From the results, the sample activated chemically exhibited higher
adsorption capability (4.9 mmol.g−1 at 25 °C and 1 bar). In another study, activation
temperature as well as activating agent/biochar mass ratio was investigated by Travis
et al. [128]. They showed that the maximum biochar CO2 loading was 23.27 mmol.g−1
at 0 °C and 10 bar, which was attributed to the biochar with 2785 m2 .g−1 surface
area and activated in 400 °C.
• Cherry stone

Recently, Turkey, United States, and Iran with 600, 288, and 220 thousand tons
per year ranked first to third in cherry production in the world [129]. Different
types of cherries possess hard stones, which are able to be employed in biochar
4 Biochar in Carbon Sequestration 87

production process. According to literature review, olive and cherry stones are two
of the most repeated carbon precursor utilized in CO2 adsorption purposes [130].
Recently, biogas upgrading by CO2 separation from methane was studied by Alvarez-
Gutierrez et al. [105]. First the olive and cherry stones were pyrolyzed; afterwards,
the samples were activated at high temperature by CO2 flow. Then, the possibility
of adsorbent application in an industrial condition was investigated by means of a
PSA unit. Alvarez-Gutierrez et al. observed a steady state operating condition after
six cycles (adsorption/desorption) through the pressure range from 3 up to 18 bar,
which proved the adsorbent potential in industrial conditions applications.
• Olive stone

In 2019, Spain with 9.2 million tons of olive production ranked the first in the world
[131]. Low ash content as well as high carbon content introduced olive stone as a
significant source of biochar in CO2 sequestration purposes [132]. Plaza et al. [103]
studied the biochar with olive stone origination, by a PSA unit for CO2 capture
from the effluent flue gases. In their study, activated biochar represented CO2 loading
of 1.1 mmol.g−1 in a cyclic process. They concluded that olive stone-originated
biochar showed satisfying characteristics for cyclic adsorption applications. Plaza
et al. [103] also tried to model the CO2 adsorption by modified biochar originated
from olive stones. Through their study, the highest CO2 adsorption reported was
around 3.1 mmol.g−1 at 1.2 bar and 0 °C. Plaza et al. [104] developed their efforts
on olive stone biochar by investigation of CO2 sequestration in the humid condition
through the post-combustion operating conditions. They reported that CO2 and H2 O
were adsorbed by modified biochar in a same way and no interaction between H2 O
and CO2 was observed. They observed a faster desorption of CO2 than H2 O through
the cycle of adsorption–desorption in a TSA (temperature swing adsorption) unit.
Furthermore, Plaza et al. [106] compared the CO2 adsorption capacity of two sorbents
originated formal mond shells and olive stones in the post-combustion treatment
purposes. They employed chemical and physical activation by ammonia and CO2 ,
respectively. It is worth mentioning that biochar from olive stones exhibited a little
higher affinity (4.4 mmol.g−1 ) compared to almond shells (4.2 mmol.g−1 ) toward
CO2 at 1.1 bar and 0 °C. Furthermore, sample evaluation in different cyclic processes
such as TSA, VSA (vacuum swing adsorption), and VTSA (vacuum temperature
swing adsorption) units proved that the VTSA showed higher potential than other
cyclic processes in stability aspects.
• Sunflower seed

Sunflower seed is a well-known crop in oil production industry, which is respon-


sible for about 10% of total oil production in the world [133]. Ukraine, Russia, and
Argentina (3.5 million tons annually [134]) are known as the largest sunflower seed
producers globally [133]. The waste generated in oil production process from seeds
as well as sunflower seed hulls (constituting 50% of seed weight) can be employed
in activated carbon synthesis process. Deng et al. [135] studied the important condi-
tional parameters in activation process including activating agent/carbon mass ratio
88 M. Shirzad et al.

and activating temperature. They utilized sunflower seed and peanut shells as biochar
precursors and compared the CO2 uptake capacity. The samples were activated in
700 °C by KOH and according to the results, the biochar generated from sunflower
seed had a higher loading capacity with 7.05 mmol.g−1 CO2 at 0 °C and 1 bar. They
also evaluated the sequestration operation of biochar from sunflower seed and peanut
shells in five adsorption–desorption cycles and proved a stable adsorption capacity
for both samples.
• Mesua ferrea L. seed

Mesua ferrea is an evergreen plant growing around the eastern region of Asia in the
countries of India, Cambodia, Sri Lanka, Vietnam, etc. In some cases, this plant was
employed as a source of biodiesel production in India [136]; recently, it can also
be utilized as the activated carbon precursor. Modification of biochar from Mesua
ferrea L. seed cake was the subject of Bhatta et al. [136] study. They mentioned that
a four-hour calcination process by N2 flow at 650 °C optimized the loading capacity
significantly up to 2.6 mmol CO2 .g−1 at 25 °C and 1 bar.

3.3 Shell/Husk-Originated Biochar

In this sector, shells and husks utilized as the activated carbon precursor are investi-
gated. These types of materials have been barely utilized before and, in many cases,
discarded and led to lots of environmental concerns. Activated carbon production
from bio-based materials is a promising technology that helps to decrease the envi-
ronmental issues through a sustainable process. The bio-based materials with shell/
husk origination and employed as the carbon precursor are mentioned below.
• Rice husk

Rice is accounted as the main food in many Asian daily meals. This plant is culti-
vated in various countries constituting China, Thailand, India, Bangladesh, Vietnam,
Indonesia, Pakistan, etc. China with annual rice production of 236 million tons
supplies around 28% of the total world’s rice production [137]. Rice cultivation,
similar to any other crop production, accompanies with waste generation. Rice husk
and straw are two major wastes, which are burnt or buried in the landfill. Annually,
across the world, up to 1000 and 120 million tons of rice straw and rice husk are
generated, respectively. This huge capacity of waste generated through the rice plan-
tation requires a sustainable method for the management [137]. In this context, rice
husk ash, which is plentiful and low-cost, is accounted as a potential silica source in
porous silica synthesis process. Rice husk ash is known as the by-product of pyrol-
ysis process. The porous silica material synthesized from rice husk ash is utilized as
the support of polyethyleneimine (PEI), which is identified as a high-efficient CO2
adsorbent. In many cases, silica content of rice husk in the form of biochar as support
of a polymer (PEI) was the subject of various studies [138, 139 140, 141]. Recently,
4 Biochar in Carbon Sequestration 89

rice husk ash-originated biochar was introduced as the precursor of a Si-based mate-
rial production. In this way, the synthesized Si-based material was considered as a
support and usually been impregnated by other elements [142]. For instance, Wang
et al. [143] utilized the rice husk ash as silicon source to synthesize Li4 SiO4 -based
CO2 adsorbent through the thermal activation process at 700 °C. According to the
experimental results, the highest loading was around 6.92 mmol CO2 .g−1 at 680 °C
and 1 bar attributed to Li4 SiO4 -originated sorbent synthesized from rice husk ash. In
addition, Zeng and Bai [144] synthesized a large-pore silica-based sorbents through
a physical activation procedure through a temperature-controlled process (400 °C)
using the rice husk ash. The developed mesoporous adsorbent exhibited an adsorption
loading capacity around 3.93 mmol CO2 .g−1 at 75 °C and 1 bar.
• Palm kernel shell

Oil palm tree is planted in about 40 countries in the world, and Indonesia, Malaysia,
and Thailand stand from first to third ranks with 160, 86, and 12 million tons of
annual productions, respectively [145]. Recently, palm fruits have been utilized to
produce cooking oil. Increasing rate of palm oil production for cooking purposes has
led to more palm residue production. Palm oil mill residue mainly constitutes palm
fruit bunches, oil palm fibers, and palm kernel shells. However, the air pollution due
to the incomplete combustion is the main concern in direct usage of the palm oil mill
residue in a boiler to generate heat. Hence, biochar production from the palm oil mill
residue is a sustainable way to manage the residue problem [146]. In line with that,
Promraksa and Rakmak [146] focused on biochar modification for CO2 adsorption
purposes. They employed oil palm residue and synthesized biochar by pyrolysis
process. Three crucial parameters in pyrolysis process including N2 flow, pyrolysis
temperature, and particle size were investigated in line with the most efficient CO2
adsorbent production process. The highest CO2 capacity of biochar originated from
palm kernel shell was estimated around 0.46 mmol.g−1 with an adsorbent pyrolyzed
at 525 °C by 2 L.min−1 N2 stream and particle size of 750 µm. Nasri et al. [147]
studied the CO2 capacity of biochar from palm kernel shell pyrolyzed at 700 °C and
activated by CO2 flow through a physical procedure. They reported CO2 loading of
7.32 mmol.g−1 at 30 °C and 4 bar and introduced biochar from palm kernel shell
as a favorable sorbent enhancing the CO2 adsorption through the carbon capturing
concept.
• Peanut shell

Through the peanut production industry, a huge mass of peanut shell, as the useless
by-product, is generated annually. The global production of peanut (40.5 million
tons) leads to 7.44 million tons of peanut shells, which is potentially a serious envi-
ronmental problem [148]. Although a minor proportion of generated peanut shell
becomes the animal feed, the major proportion accounts as the waste [148, 149].
Hence, the peanut shell as an economic and abundant precursor can play an impor-
tant role in the worldwide capacity of biochar production. Accordingly, Li et al. [150]
employed peanut shells to synthesize a microporous adsorbent to sequestrate CO2 in
90 M. Shirzad et al.

post-combustion purposes. They employed a one-step chemical method to activate


the samples. The impact of chemical activation (by KOH) at different temperatures
from 680 up to 780 °C was investigated and finally reported that the sample acti-
vated at 680 °C and 1 bar exhibited the maximum loading of CO2 estimated around
7.25 mmol.g−1 at 0 °C and 1 bar.
• Argan fruit shell

Argan tree is a local plant of Morocco and Algeria. Argan fruit is mainly utilized for
oil production and its waste is basically considered as animal food [151]. Recently,
Boujibar et al. [152] gathered the argan fruit shells wasted around the southern
Morocco to evaluate the aspects of derived biochar potential for CO2 adsorption
purposes. They employed KOH and NaOH for chemical activation of the samples.
They concluded that the chemical activation had a remarkable positive impact on the
biochar porosity and surface area, in which at the optimal conditions, CO2 uptake of
around 5.65 mmol.g−1 at 25 °C and 1 bar was reported.
• Coconut shell

Coconut is a tropical crop growing mostly in Indonesia with annual production


of 16.82 million tons, India with 14.7 million tons, and Philippines with 14.49
million tons, followed by Brazil, Sri Lanka, Vietnam, etc. [59]. Coconut shell, as
the waste of coconut processing, is the main problem by environmental aspects.
Today, only a small quantity of coconut shell passes through an incineration process
to generate energy while, the major proportion is discarded in the environment in a
non-ecofriendly way [59, 153]. According to the environmental point of view, Costa
Vilella et al. [95] utilized two economic and abundant wastes of babassu and coconut
shells and compared the CO2 capacities for biogas upgrading purposes. To this end,
physical activation by CO2 flow was implemented and surface areas of two biochar
were estimated around 1452 m2 /g for babassu samples and 809 m2 /g for coconut
shell, respectively. They reported that the CO2 loading capacities are approximately
in the same range. Finally, they revealed that biochar derived from coconut shells
represented a higher stability through PSA process for CO2 mitigation purposes.
Xu et al. [154] were the first researchers who introduced biochar in a VSA unit for
CO2 adsorption. The biochar utilized in this study was originated from the coconut
shells and possessed a surface area of 921.7 m2 .g−1 . Furthermore, Xu et al. reported
the CO2 loading capacity around 3.1 mmol.g−1 at 20 °C and 1.20 bar for synthe-
sized samples and proved that H2 O presence had no significant negative impact on
CO2 loading through the VSA cycles. Furthermore, coconut shells were utilized by
Adelodun et al. [96] and activated through two different chemical activation methods:
pre-calcination by KOH at 600 °C and under N2 atmosphere for 2 h as well as, pre-
ozonation by ammonia at 800 °C. The maximum loading capacity of CO2 attributed
to biochar activated by KOH reagent was 2.525 mmol.g−1 at 20 °C and 1 bar. Also,
they investigated the adsorbent regeneration process by temperature increase up to
500 °C. The regeneration experiments showed that biochar from coconut shells has
4 Biochar in Carbon Sequestration 91

the potential to be applied through TSA cycles. Wawrzynczak et al. [97] investi-
gated the coconut shell-originated biochar in a VPSA process. In their study, the gas
inserted as feed contained 81.5% CO2 , and 18.5% of N2 , O2 , and Ar, aggregately.
The experiments showed that the maximum CO2 uptake observed through the modi-
fied biochar was 7.15 mmol.g−1 at 30 °C and10 bar. The energy consumption results
proved the VPSA potential (128 kWh/t CO2 ) for CO2 adsorption compared to phase
separation method (116 kWh/tCO2 ).
• Almond shell

The United States is the pioneer of almond production in the world [56]. Almond
shell and hull are two types of waste generated in almond production industry. These
abundant and inexpensive wastes as lignocellulosic materials can be employed as
the carbon precursor to synthesize biochar. Gonzalez et al. [102] considered almond
shells and olive stones as the carbon source and pyrolyzed them followed by a
one-step physical activation by CO2 to achieve a high-efficient CO2 adsorbent. The
maximum CO2 uptakes observed by Gonzalez et al. were 3.7 (at 0 °C and 1.20 bar)
and 4.65 (at 0 °C and 0.95 bar) mmol.g−1 for almond shell and olive stone biochar,
respectively. In the end, Gonzalez et al. reported that biochar prepared from almond
shell and olive stone have significant characteristics in CO2 adsorption purposes.
• Oil tea shell

Oil tea is similar to the regular tea, which is planted in part of China. It is consumed
as a daily drink in some regions of China or in some ceremonies for welcoming the
guests. Oil tea seeds are covered by a shell, which can be utilized to generate biochar.
Theultra-microporous biochar, synthesized from oil tea shells (OTS) was the subject
of Zhang et al. [112] study. From the experiments, they estimated a remarkable
surface area (2676 m2 .g−1 ) for biochar activated chemically by KOH, which led to a
significanCO2 loading of 6.15 mmol.g−1 at 0 °C and 1 bar. They also investigated the
CO2 selectivity towards N2 and CH4 , at 0 °C and 1 bar. The selectivity results were
43.5 and 7.4, which considered significantly high and reasonable. Finally, Zhang
et al. introduced the VSA process as an efficient technology to separate CO2 by the
modified biochar.
• Rambutan peel

Routinely, Rambutan is a local plant of Malaysia, which grows seasonally. In Thai-


land and Malaysia, rambutan’s seeds are withdrawn and the fruit is utilized in the
canning industry. The seeds taken off can be considered as a valuable by-product
in the biochar production steps. Zubbri et al. [107] considered rambutan peel to
synthesize metal-impregnated biochar for CO2 capture purposes. They pyrolyzed
the rambutan peel samples in three temperatures ranging 500 to 900 °C and reported
900 °C as the optimal temperature for rambutan peel pyrolysis, by having the CO2
loading capacity around 1.56 mmol.g−1 at 30 °C and 1 bar. They also observed an
improvement in CO2 capacity (0.19 mmol.g−1 more adsorption at the same opera-
tional conditions) by 5% magnesium nitrate impregnation. The biochar regeneration
92 M. Shirzad et al.

capability was investigated through a TSA process with 30 and 110 °C adsorp-
tion/desorption cycles. They reported a stable adsorption through 25 cycles, which
approved the biochar capability to sequestrate CO2 efficiently in cyclic processes.
• Walnut shell

In 2019, walnut production capacity was 4.96 million tons, globally [155]. China,
with more than half of the total walnut production, is recognized as the first ranking
followed by United States and Iran [66]. Walnut shell with hard lignocellulosic
structure is a potential source of biochar [156]. In the study conducted by Lahijani
et al. [66], walnut shell was pyrolyzed at three temperatures: 500, 700, and 900 °C.
The biochar pyrolyzed at 900 °C was impregnated by Mg and physically modified by
N2 flow. At the optimal condition of biochar, 2 mmol.g−1 CO2 was adsorbed at 25 °C
and 1 atm. Finally, they reported a high-efficient and rapid regeneration in adsorption/
desorption cycles, which proved the biochar advantages for CO2 adsorption purposes.

3.3.1 Leaves/Green Plants-Originated Biochar

Any organic part of materials with bio-origination possesses the potential of being
the carbon precursor. In this section, leaves and green plants, which are non-edible
or useless but appropriate for biochar synthesis, have been investigated:
• Tobacco waste

Tobacco is a green plant, cultivated in around 120 countries, which is originated


from Southwest Africa, Australia, South Pacific area, and America. Total tobacco
production in the world, in 2019, was estimated around 6.7 million tons, in which
China stood on the first rank of tobacco production globally [157]. This plant is vastly
utilized in cigarette industry. Based upon the literature review, around 1.25 million
tons of waste is generated through the tobacco processing [157]. Tobacco wastes are
arduous to discard, due to the high concentration of nicotine. In line with that, it is
necessary to develop a sustainable way to manage the tobacco wastes [157]. Li et al.
[158] employed tobacco stems in pyrolysis process followed by chemical activation
via H3 PO4 to produce activated biochar. They reported the temperature enhancement
in pyrolysis process is on the contrary of biochar yield, due to the more weight loss.
Furthermore, Sha et al. [159] pyrolyzed the tobacco waste at 700 °C and derived an
efficient biochar with a remarkable surface area around 1104 m2 .g−1 and maximum
CO2 loading of 3.6 mmol.g−1 at 0 °C and 1 bar.
• Algae

Algae are aquatic plants growing in the lakes, surface waters, wastewaters, etc. They
are a huge source of proteins, lipids, and polysaccharides. As they are useless and
vastly produced in wastewater treatment processes, a sustainable method to intro-
duce algae as a note-worthy material would be impressive. To this context, Sevilla
et al. [160] studied the algae/glucose mixture as the biochar precursor. They found
4 Biochar in Carbon Sequestration 93

amines as high-efficient modifier in the porosity of derived biochar for CO2 capture,
compared to pyridonic/pyrrolic-N, pyridinic-N, and quaternary-N.
• Kenaf

Kenaf is a tropical-originated plant with woody stem and outer fibrous bark. It is
normally 5–6 m and around 0.3 m in length and diameter, respectively [161, 162]).
Kenaf is famous as a high-productive plant with 30 tons/ha efficiency and almost
has a short harvesting period (5–6 months). Hence, this lignocellulosic plant with
significant characteristics has a potential to be utilized as the feedstock of biochar
production [161, 162]. Kamarudin et al. [108] investigated the biochar derived from
kenaf for CO2 adsorption purposes. In this context, they considered two columns
through cyclic process. Afterwards, they compared the CO2 capacity of raw biochar
with impregnated biochar. The results indicated that the raw biochar and modified
biochar with TEPA had CO2 adsorption around 0.62 and 2.09 mmol.g−1 at 0 °C
and 1 bar, respectively. But, the raw kenaf showed simple regeneration conditions,
compared to TEPA-functionalized kenaf.
• Grass cutting

Generally, grass is made of cellulose, lignin, and hemicellulose and consequently has
the potential to be considered as a carbon precursor [163]. Hao et al. [100] employed
grass cutting, bio-sludge generated in a wastewater treatment plant, beer waste, and
horse manure activated through both chemical (by H3 PO4 ) and physical (by N2 )
procedures. Afterwards, the CO2 adsorption experiments showed higher capacity of
grass cutting-originated biochar compared to other ones, which were modified in a
same way. The grass cutting biochar modified physically at 600 °C had CO2 uptake
of 4 mmol.g−1 at 0 °C and 1 bar. Hao et al. also investigated the stability of modified
biochar through nine cycles of adsorption–desorption processes and observed only
3% reduction in the adsorption capacity.

3.3.2 Other Biochar

In this section, some other biochar samples, which are not categorized in the former
sectors, have been investigated.
• Poplar anthers

CO2 capture from post-combustion flows was studied by Song et al. [164]. They
introduced poplar anthers to the pyrolysis process followed by a chemical activation
step for biochar production. The CO2 uptake by a modified-structure biochar was
studied by considering the activation temperature, the activating agent/biochar mass
ratio, and also the activation duration, which the highest reported CO2 adsorption
capacity was around 2.04 mmol.g−1 at 25 °C and 1 bar [164].
94 M. Shirzad et al.

• Mixture of starch, sawdust, and cellulose

Recently, the mixture of starch, sawdust, and cellulose modified by chemical activa-
tion was considered by Sevilla and Fuertes [165] to develop porous CO2 adsorbent.
Two different ratios of 2 and 4 were opted for KOH/biochar mass ratio while the
activation process was implemented at a temperature range of 600 up to 800 °C. The
experimental results proved that the biochar activated by KOH/biochar = 2 at 600 °C
showed the highest CO2 loading with 4.8 mmol.g−1 at 25 °C and 1 atm.
• Sugarcane bagasse

Alhassan et al. [166] investigated the effect of modification procedure on the CO2
adsorption capacity of derived ACs originated from sugarcane bagasse. To this end,
firstly, the biochar from sugarcane bagasse was mixed with ZnCl2 solution for hours
(unmodified biochar). Afterwards, two approaches were implemented: 1) unmodified
biochar was mixed with H3 PO4 and 2) unmodified biochar was mixed with NaOH.
The adsorption experiments proved that the procedure 2 resulted in larger pore size
and also, larger surface area (800.6 m2 .g−1 ) as well as, higher CO2 loading capacity
(1.1 mmol.g−1 at 25 °C and 1 bar).
• Corn cobs

Tsai et al. [167] employed the corn cobs biochar for CO2 capture purposes. They
implemented a chemical activation process by KOH/K2 CO3 and physical activation
using CO2 . They concluded that higher activation temperature is more efficient by
having better structural properties. They reported 1806 m2 .g−1 for biochar activated
in 800 °C by impregnation ratio of 15 wt% KOH. They proposed modified biochar
with excellent and economic characteristics as a promising alternative for industrial
applications.
• Agaricus

Agaricus, for the first time, was employed by Wang et al. [168] to form chemically-
modified biochar. The sample was pyrolyzed at 500 °C and then activated by KOH.
The maximum CO2 loading observed by Wang et al. [168] was around 5.5 mmol.g−1
at 0 °C and 1 bar. Finally, they introduced Agaricus as a promising precursor for
biochar production by indicating some excellent characteristics such as CO2 selec-
tivity towards N2 , high-efficient regeneration capacity, and also high stability in
adsorption–desorption cycles.
• Soybean oil cake

Tay et al. [169] investigated the soybean oil cake, lignocellulosic waste of soybean
processing industry, as the precursor of activated carbon. The raw samples were
pyrolyzed at a temperature range of 600–800 °C. Afterwards, the biochar was acti-
vated chemically by KOH and K2 CO3 . The results proved that the modified biochar
by K2 CO3 had better structural characteristics, as well as lower ash content.
4 Biochar in Carbon Sequestration 95

A summary of CO2 adsorption capacity of various biochar precursors is indicated


in Table 5.

Table 5 CO2 sequestration capacity of investigated biochar


Carbon precursor Temperature (zC) Pressure (bar) CO2 adsorption References
capacity (mmol.g−1 )
Coconut shell 20 1 1 [110]
Coconut shell 20 1.2 3.5 [154]
Coconut shell 20 1 2.53 [96]
Coconut shell 30 10 7.15 [97]
Peanut shell 0 1 7.25 [150]
Peanut shell 0 1 5.25 [135]
Argan fruit shell 20 1 5.65 [152]
Almond shell 0 1 3.7 [102]
Rambutan peel 30 – 1.75 [107]
Walnut shell 25 1 1.86 [66]
Oil tea shell 0 1 6.15 [112]
Mesua ferrea seed 20 1 2.6 [136]
Sunflower seed 0 1 7.05 [135]
Olive stone 23 1.4 7 [170]
Olive stone 0 0.95 4.65 [102]
Olive stone 0 1.2 3.1 [103]
Olive stone 30 1.3 1 [104]
Olive stone 30 1.15 4.4 [106]
Coffee ground 0 1 5.09 [128]
Coffee ground 0 1 4.9 [127]
Palm kernel 30 4 7.32 [147]
Cherry/olive stone 25 3 2.53 [105]
Cotton stalk 20 1 2.26 [69]
Cotton stalk 20 1 2.18 [93]
Wood sawdust/lignin 25 1.2 4.1 [110]
Maple wood 25 8 10.8 [98]
Lignin 0 1 7.4 [124]
Populus wood 0 1 7.2 [120]
(continued)
96 M. Shirzad et al.

Table 5 (continued)
Carbon precursor Temperature (zC) Pressure (bar) CO2 adsorption References
capacity (mmol.g−1 )
Eucalyptus 30 1 4.1 [121]
camaldulensis wood
Paulownia sawdust 0 1 8 [115]
Tobacco 0 1 3.6 [159]
Grass cutting 0 1 3.9 [100]
Kenaf 25 1 2.09 [108]
Algae 0 1 7.4 [160]
Agaricus 0 1 5.5 [168]
Sawdust/cellulose/ 20 1 4.8 [165]
starch
Sugarcane bagasse 20 1 1.10 [166]
Poplar anthers 20 1 2.04 [164]
Horse manure 0 1 3.8 [100]

4 Conclusions and Future Directions

Over decades, human activities within the industrial world have increased the green-
house gas emissions extensively, mostly owing to energy consumption originated
from fossil fuels, which this phenomenon contributed to the climate changes and
global warming. According to reports, carbon dioxide emissions have increased at
a 250 times faster rate than that estimated in ice age because of increasing anthro-
pogenic activities. The impact of global warming is not only limited to the rising
temperature; but also, changing rainfall patterns, coastal erosion, lengthening seasons
in some areas, melting ice, and variations in the range of some infectious disease are
other effects. Accordingly, carbon capture and sequestration has received remarkable
attentions lately. To this end, different technologies including membrane, absorp-
tion, cryogenic distillation and adsorption have been recognized as promising tech-
nologies. Among mentioned strategies, adsorption with solid sorbents due to the
cost environmentally friendly and energy consumption is among the most favorable
one. Accordingly, various categories of sorbents such as zeolite, ACs, MOFs, etc.
have been evaluated for carbon sequestration purposes. To this context, biomass/
biochar carbon materials as an economic, sustainable and abundant precursors for
CO2 capture are interesting candidates not only for climate change mitigations but
also in the view of solid waste management. On the grounds, this chapter was devoted
to the high potential of biochar as a new window toward novel adsorbents develop-
ment inCO2 mitigation processes. To this end, the key concepts on climate changes,
adsorption, CO2 capture, biochar potential and its different modifications/activation
techniques were discussed in detail. However, there are still some challenges in this
area that require further considerations, which can be considered as future directions:
4 Biochar in Carbon Sequestration 97

• From the literature, most of accomplished studies in this area were dedicated to
the synthesis of derived activated carbons from the biochar samples, and loading
capacities were tested using conventional lab adsorption techniques; but to have
a precise knowledge for large scale applications developing cyclic adsorption
processes are highly recommended.
• Tailoring the surface chemistry and tunabling the characteristics of derived
biochar-originated ACs by applying functionalized biohybrid samples as well
as employing the organic and/or inorganic nanostructures, is the area which
requires more efforts.
• However, various branches have progressed markedly in machine learning
science, but still, the blank of notable studies in this area is tangible.
• Routinely, developing a highly efficient technology for CO2 capture and seques-
tration needs “considerations, evaluations and employing” several key factors
for “designing, developing, construction and operations” in terms of cost, safety,
energy and environmentally prospects. Accordingly, using novel robust topologies
including life cycle assessment (LCA) as well as response surface methodology
(RSM) can be as valuable assets, which can be considered in future attempts.

Acknowledgements The financial support of this work was provided by UIDB/50020/2020, LA/
P/0045/2020 (ALiCE), and UIDP/50020/2020 (LSRE-LCM), funded by national funds through
FCT/MCTES (PIDDAC). Furthermore, European Regional Development Fund (ERDF) under
Programme PT2020 awarded to CIMO (UID/AGR/00690/2020). At the end, Mohsen Karimi also
acknowledge research grant awarded by Foundation of Science and Technology of Portugal (FCT)
under SFRH/BD/140550/2018 project.

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Chapter 5
Biochar for Management of Wastewater

Ritu Painuli, Chetan Kumar, and Dinesh Kumar

1 Introduction

The world’s population growth is driving up the need for water, food, and energy,
all of which are already limited due to conflicting demands for scarce resources
[1]. However, effective and coordinated management of these resources could help
in tackling some of the major global concerns, including food security, environ-
mental security, climate change, and water management [2, 3]. Water management
has received very little attention thus far. As the water resources in the world are
being deteriorated owing to the continual discharge of organic as well as inorganic
contaminants from the municipalities and industries into the water bodies [4]. The
continuous and uncontrolled contaminants is a reason of concern due to their unde-
sired and deleterious impacts on the environment [5, 6]. The numerous traditional
technologies that have been employed for the removal of wastewater pollutants
involves membrane filtration, reverse osmosis, electrochemical method, adsorption,
and ion-exchange, etc. [7–10]. However, all these methods suffer from the draw-
backs of process complexity, being time-consuming, expensive, and their inefficacy
in removing of pollutants at less concentration and so forth [11–13]. Therefore, a
trustworthy, efficient and feasible water treatment technologies is needed that must
meet the criteria of both environment and economic requirements in order to be

R. Painuli
Department of Chemistry, School of Applied and Life Sciences, Uttaranchal University,
Dehradun, Uttarakhand 248007, India
R. Painuli · C. Kumar
School of Pharmaceutical and Populations Health Informatics, Faculty of Pharmacy, DIT
University, Dehradun, Uttarakhand 248009, India
D. Kumar (B)
School of Chemical Sciences, Central University of Gujarat, Gandhinagar, India
e-mail: dinesh.kumar@cug.ac.in

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2023 107
A. K. Nadda (ed.), Biochar and its Composites, Materials Horizons:
From Nature to Nanomaterials, https://doi.org/10.1007/978-981-99-5239-7_5
108 R. Painuli et al.

applied in large scale and to be marketed [14]. In addition, the involvement of inex-
pensive and easily available materials in various treatment process would decrease
the global treatment and enhance the process efficiency. As a result, the paradigm
for wastewater management must change from treatment and disposal to resource
recovery, recycling, and reuse.
Water and wastewater treatment is one of the evolving subsets of biochar (BCR)
application. Biochar is a thermochemical decomposition product with rich carbon
content derived from the biomass feedstock in the presence of little or absence of
oxygen [15]. Biomass feedstock can be organic waste materials like forestry and crop
residues, sewage sludge, and organic municipal wastes [16–19], etc. The organic
wastes can be transformed into BCR by different techniques for instances, pyrolysis,
gasification, microwave heating, hydrothermal carbonization, and torrefaction [20–
22]. BCR is getting noteworthy interest owing to its two distinctive advantages: First,
the BCR production itself can reduce greenhouse gas emissions because it stores
carbon in a stable form, thus stopping the breakdown of biomass from releasing
greenhouse gases into the atmosphere [23]. Second, BCR is a powerful, inexpensive,
and eco-friendly adsorbent which is related to its relatively large surface area (SA)
and abundant surface functional groups (SFG) [24, 25]. The physicochemical char-
acteristics of biochar, such as SA, porosity, acid–base behavior, SFG, and element
composition, have been shown to be highly dependent on the pyrolysis tempera-
tures and feedstock types [26–28]. This in turn has important implications for the
biochar’s effectiveness and suitability in removing target contaminants, such as a
variety of organic contaminants (such as dyes, phenols) as well as inorganic contam-
inants, i.e., heavy metals (HMs), inorganic ions, etc. [29–31].Various mechanisms
involved for the removal of organic and inorganic pollutant for instances, hydrogen
bonding, hydrophobic as well as physical adsorption, electrostatic attraction and ions
exchange, etc. [32] (Fig. 1). Thus, with the increased application of BCR in water
and wastewater treatment, the present chapter explores the application of BCR tech-
nology for the removal of heavy metals (HMs), organic pollutants, inorganic ions,
etc., including a brief discussion of the biochar modification methods. Furthermore,
the viewpoints along with the future research directions for promoting the further
application of BCR in practical water and wastewater treatment are also discussed.

2 Modification of Biochar

Numerous strategies for modifying the characteristics of BCR have been suggested
by researchers [33]. These methodologies involve treatment like steam, clay minerals,
carbonaceous materials, biofilms, acids, bases, and organic chemicals, etc.
5 Biochar for Management of Wastewater 109

Fig. 1 Various mechanisms involving the removal of organic and inorganic pollutants by biochar
[Reprinted with permission from Enaime et al. [32]. Copyright 2020. MDPI-Publisher of Open
Access Journal]

2.1 Biochar Activation by Physical Methods

It involves methods like steam activation that uses high-temperature steam that is
driven into the pores of the biochar. After pyrolysis, a typical modification technique
called steam activation is utilized to improve the structural porosity of the BCR
and eliminate contaminants. The adsorption of Cd2+ , Cu2+ , and Zn2+ on the surface
of BCR made from poultry manure feedstocks that were prepared at 700 °C were
reported to experience increased water flow rates and longer activation durations at
pyrolysis temperature of 800 °C [34]. Another study found no significant difference
in the Cu2+ sorption for Miscanthus charcoal before and after steam activation [35].
It was discovered that surface area (SA) and aromaticity enhanced in biochar, and
abundance of surface functional groups reduced after being steam activated [35]. The
sorption capacity of the veterinary antibiotic sulfamethazine increased by 55% in the
steam-activated invasive plant derived BCR produced at 700 °C when compared to
BCR that was not activated and produced at the same temperature. Therefore, steam
activation could be a method for improving the biochar’s porosity and SA as well
as its aromaticity to achieve improved inorganic pollutants sorption in the water
treatment [36].

2.2 Biochars Chemical Activation Using Acidic and Alkaline


Solutions

The BCR activation by acidic solutions creates -COOH groups on the surface of
BCR and also develops micropores, thereby increasing the SA [37, 38]. Oxygenated
surface functional groups (SFG) are more prevalent on BCR surfaces, which raises the
possibility of BCR to bind positively charged contaminants via adsorption. The pH
110 R. Painuli et al.

dependent Cu2+ adsorption capability of cactus fiber BCR activated by HNO3 showed
chemical adsorption on oxygen-containing SFG on the surface of the BCR. Prior to
pyrolysis, pine tree sawdust was acid-treated with dilute H3 PO4 to enhance the SA,
volume of micropores as well as incorporate P-O-P into the C structure [39]. Due
to phosphate precipitation and surface adsorption, the phosphoric-treated biochar’s,
Pb2+ sorption capacity amplified by 20% when compared to an untreated sample
[39]. Similar to pinewood biochar, 30% H2 O2 treatment resulted in a nearly two-fold
increase in cation exchange capacity due to oxygen-containing SFG on the BCR
surface that were more prevalent in the activated BCR [40]. Compared to unmodified
carbon rich solid hydrochar, hydrochar treated with a 10% H2 O2 solution showed
increased Pb2+ adsorption ability [41]. This is because modified hydrochar contains
more −COOH groups, which underwent complexation with Pb2+ . Adding acid or
oxidizing chemicals causes mineral components (CO3 2− , SiO4 4− , and PO4 − ) in the
BCR arrangement to dissolve and be removed from the BCR medium. These elements
in BCR are especially crucial for the elimination of metal cations from water [42], the
capability of which could be decreased via acid treatment. Alkali activation of BCR
(most frequently potassium hydroxide and sodium hydroxide) enhances sorption
by increasing porosity, SA, and oxygenated SFG. When a cation like Pb2+ adsorbs
chemically, oxygenated surface functional groups offer proton-donating exchange
sites [43]. The ipomoea plant charcoal was activated with KOH, and then pyrolysis
showed an increment in Cd2+ sorption from aqueous system [44]. After activation with
2 M KOH, an increment in As5+ adsorption capacity was observed in BCR made from
municipal solid waste [45]. Thus, it can be concluded that BCR activation by alkali
significantly improved the altercation of the SFG and surface area.

3 Biochar as an Adsorbent of Organic and Inorganic


Pollutants

3.1 Organic Pollutants

BCR obtained from diverse biomass has been extensively applied for the removal
of various organic compounds from water that involve aromatic dyes, organic
compounds, polycyclic aromatic hydrocarbons, antibiotics (Table 1) [46–49], etc.
Due to higher SA and microporosity, BCR produced at higher temperature is expected
to be more significant for the removal of organic compounds (nonpolar nature)
[50]. Whereas BCR synthesized at temperature below 500 °C possess extra H-
and O- containing surface functional groups and are anticipated to possess higher
tendency for organic compound with polar nature [51]. For instance, BCR derived
from rice husk and soya bean at 600–700 °C enables the removal of carbofuran
and trichloromethylene from polluted water [51]. Red-gum wood chips and BCR
made from broiler litter were found to be effective at removing pyrimethanil and
diesopropylatrazine (fungicide/pesticide) when the temperature was above 700 °C,
5 Biochar for Management of Wastewater 111

Table 1 List of biochar produced from various feedstock for organic pollutants adsorption
Feedstock Preparation conditions Organic pollutants References
Durian rind Pyrolysis 800 °C Congo red [62]
pine fruit shell Slow pyrolysis 550 °C Phenol [58]
Chicken manure Pyrolysis 500 °C phenol, 2,4-Dinitro phenol [57]
Coconut shell Pyrolysis 500 °C Methylene blue [63]
Corn-stover Torrefaction 250 °C Methylene blue [64]
Switch grass Pyrolysis 450 °C Reactive red 195 A [65]
Barley straw Torrefaction 250 °C Methylene blue [66]
Pecan nutshell Pyrolysis 800 °C Reactive red 195 A [67]
Crabshell Pyrolysis 800 °C Chlortetracycline [68]
hydrochloride
Bamboo sawdust Pyrolysis 600 °C Sulfamethazine [69]
Shoreine Pyrolysis 400 °C Methylene blue [70]
Peanut shell Pyrolysis 800 °C Trichloroethylene [71]
Rice husk Pyrolysis 650 °C Iodine, methylene blue [72]
Reed Pyrolysis 600 °C Florfenicol [73]
Cornstalk Pyrolysis 400 °C Crystal violet [62]
Bagasse Pyrolysis 600 °C Sulfapyridine, Sulfamethoxazole [74]

whereas the same BCR at less than 500 °C temperature was inefficient [52, 53].
Additionally, polar pesticide and herbicide were removed with BCR formed at or
below 300 °C as a result of the interaction between the contaminant and the surface
functional group of the BCR [54, 55]. BCR possessing more O- and H as SFG
produced at (<400 °C) displayed greater sorption of harmful dyes such as methyl-
blue and methyl-violet however, the mechanism for sorption was depending on pH
of the medium [49, 56]. Softwood/Hardwood derived BCR (300–700 °C) has pH-
dependent interaction that involves the sorption of polar antibiotic sulfamethazine
[21]. Thus, pH is the utmost significant aspect for removal of polar organic pollutants
as well as BCR interactions. BCR derived from microalgae via pyrolysis have been
efficiently employed for the removal of highly resistant and stable textile dyes like
Congo red, crystal violet, malachite green, etc. [31]. Methylene blue, orange G, and
Congo red were successfully removed using other BCR made from switchgrass at
much higher temperature than typical pyrolysis temperatures [32]. The outcomes
showed that orange G was not as well absorbed as the cationic dye methylene blue.
This was reported due to methylene blue’s low molecular weight, its advantageous
electrostatic property, and robust contact with BCR surface. Adsorption was likewise
more for BCR made at 900 °C compared to those prepared at 600 °C owing to the
greatly increased SA and the maximum pyrolysis temperature. Additionally, BCR
has been noted to be an efficient phenols adsorbent in water treatment [57, 58]. The
possibility of using BCR made from chicken manure to eliminate harmful phenol
and 2,4-dinitrophenol from aqueous solution was examined in the study by Thang
112 R. Painuli et al.

et al. [57]. The produced BCR displayed enhanced adsorption capacities, including
good stability up to five cycles and phenol adsorption capacities of 106.2 mg/g and
2,4-dinitrophenol adsorption capacities of 148.1 mg/g. The sorption of phenols on
BCR under several conditions may be interfering, via hydrogen bonding, electro-
static interaction [58]. BCR made from polymer or biomass was employed in the
work by Oh and Seo [59] to remove ionizable halogenated phenols from an aqueous
solution. According to a correlation analysis of the maximal hydrophobicity and
deprotonation of compounds, solution pH was found to be a key regulating factor.
According to Qiu et al. [60], commercial activated carbon is less effective than straw-
based BCR at removing harmful dyes like reactive brilliant blue and rhodamine B.
Both carbon materials displayed a strong ability to adsorb reactive brilliant blue and
rhodamine B at pH levels of 3.0 and 6, owing to increased interactions by the SFG
of the BCR, with a slight difference in favor of the ability of the BCR to adsorb
rhodamine. Ferreira et al., examined the adsorptive abilities of commercial activated
carbon and BCR made from paper mill sludge for removing the fish anesthetics
from water [61]. In spite of the fact that biochars had a greater adsorption ability
than commercial activated carbon, it was demonstrated that biochar based on paper
mill sludge-based adsorbents could be a more affordable alternate for removing the
fish anesthetics. Since the budget of the starting material for the adsorbents is zero,
their manufacturing technique doesn’t employ any harmful chemicals, and it permits
the energy recovery from wastes, thus, the entire procedure can be seen as being
ecologically benign.

3.2 Inorganic Pollutant Removal

HMs (Cr, Cu, Pb, Cd, Hg, Fe, Zn, and As ions) and substances like nitrate (NO3 − ),
nitrite (NO2 − ), ammonium (NH4 + ), phosphorus (P), and hydrogen sulfide (H2 S) are
among the inorganic pollutants found in wastewater that pose a serious concern to
the environment and the general public’s health [75]. Inorganic component removal
is more suited to the features of BCR formed at less pyrolysis temperature. The
sorption properties of BCR are significantly influenced by its chemical composition
and morphological structure [76].

3.2.1 Heavy Metal Ions

It is usually accredited that the properties of the BCR and the nature of the target
metals plays a noteworthy part in the adsorption ability of BCR toward HMs (Table 2)
[77–79]. Due to the wide SA, porous structure, and abundance of surface func-
tional groups, such as phenolic, hydroxyl, and carboxyl groups, it has been emerged
to be an efficient material for the sorption of HMs [80, 81]. The characteristics
of biochars made from rice straw, chicken manure, and sewage sludge, as well as
their effects on the removal effectiveness of Pb2+ and Zn2+ , were examined in study
5 Biochar for Management of Wastewater 113

Table 2 Biochar for the adsorption of various heavy metal ions in aqueous solutions
Feedstock Preparation conditions Heavy metal ions References
Sewage sludge Pyrolysis 300 °C As5+ , Cr3+ [88]
Green waste Pyrolysis 600 °C Cd2+ [89]
Rice husk Pyrolysis Cr6+ [33]
400- 500 °C
Maple wood Pyrolysis 500 °C Pb2+ [90]
Rice straw Pyrolysis 550 °C Pb2+ , Zn2+ [81]
Almond shell Pyrolysis 650 °C Ni2+ , Co2+ [91]
Coconut fiber Pyrolysis 300 °C Pb2+ [92]
Pineapple peels Pyrolysis 350 °C Cr6+ [93]
Rice husk Pyrolysis 650 °C Cu2+ [72]
Canola straw, Pyrolysis 400 °C Cr3+ [94]
Rice straw, Soybean straw,
Peanut straw
Papermill sludge Pyrolysis 720 °C As5+ [95]
Pamelo peel Pyrolysis 250 °C Ag+ [96]
Peanut shell Pyrolysis 400 °C Pb2+ , Cd2+ [97]
Pinewood Pyrolysis 600 °C As3+ [98]

conducted by Zhao et al. [81]. The rice straw BCR displayed the largest carbon and
hydrogen concentrations, the maximum pH, the most negative surface charge, and
the maximum physical stability. It also shows the highest adsorption capacity toward
Pb2+ . BCR obtained from rice straw was also confirmed for the Cd2+ removal by
Liu and Fan and coworkers. It was observed that the minerals present on the BCR
surface possessing Ca2+ and Mg2+ interchanged their ions with Cd2+ , which thereby
results in precipitate within BCR matrix [82]. BCR has been emerged as a noteworthy
alternate for the heavy metal adsorption as compared to traditional adsorbents like
activated carbon. A study by Kolodynska and coworkers demonstrated that even a
lesser SA, BCR removed heavy metal more proficiently as compared to commercial
activated carbon. The maximum adsorption was observed owing to the presence of
oxygen surface functional groups on BCR surface [83]. BCR activation has been
proven to be a significant approach for enhancing the adsorption capacity toward
HMs. As the KOH activated BCR allowed 3 times more adsorption for Cu(II) than
that of non-activated BCR [78]. Fang et al. also showed that CO2 activated hydrochar
from HTC of hickory significantly increased the adsorption capability of metal ions
like Cu2+ , Cd2+ , Pb2+ . The increased adsorption was noticed due to the improved
SA of hydrochar and the presence of surface acidic surface functional groups after
CO2 activation [84]. An investigation on the As5+ and As3+ adsorption by Fe-coated
biochars derived from empty fruit bunches and rice husk was reported. The formation
of complex of As5+ and As3+ with Fe2+ on the charcoal was the described sorption
mechanism [85]. Researchers have also worked on understanding the competition in
114 R. Painuli et al.

adsorbing the HMs on biochars along with the mobility of single versus multiple HMs
species [79]. Sesame-straw-based BCR was found to be more efficient in adsorbing
HMs in alone metal systems than in multi-metal systems [86]. It was demonstrated
that in a coexisting system in anaerobically digested sludge caused Pb2+ adsorption
more than Cd2+ adsorption, whereas in a alone system, Pb2+ ions are adsorbed on
the same adsorption sites as Cd2+ ions [87].

3.2.2 Inorganic Ions

The enhanced SA, abundance of both nonpolar and polar groups, and internal porosity
allow BCR to adsorb nutrients such as phosphorus and nitrogen in aqueous phase
[99, 100]. PO4 3− , NH4 + , and NO3 − are the utmost usual forms of reactive phosphorus
and nitrogen that results in eutrophication in wastewater. It has been showed that the
BCR has carried out the adsorption of different inorganic ions like PO4 3− , NH4 + ,
NO3 − irrespective of different charges. [101]. For instance, BCR was pyrolyzed at
600 °C and obtained from digested sugar tailing adsorbed PO4 3− ions upto 73% [102].
Additionally, BCR pyrolyzed at temperature between 200 °C and 700 °C results in
the removal of PO4 3− ions upto 83% from aqueous systems [103]. Also, BCR derived
from bamboo charcoal leads to adsorption of NO3 − ions from solution [104]. Based
on the presence of surface functional groups and higher carbon and hydrogen ratios,
pine sawdust BCR produced at 300 °C displayed maximum adsorption for NH4 +
ions. It was demonstrated that the polar interactions and chemical bonding between
surface functional groups and NH4 + ions could be the reason for the maximum
adsorption. BCR synthesized from wood waste pretreated with MgO was utilized to
recover phosphate and ammonium [105].

4 Future Prospective and Outlook

BCR is a novel material that has considerable potential to tackle numerous environ-
mental issues in the realm of wastewater treatment. BCR is used as an adsorbent with
higher adsorption capacity for a variety of pollutants, but a thorough knowledge of the
various mechanisms driving the adsorption process is still lacking [106]. Because the
efficient utilization of BCR in wastewater treatment is dependent on properties such
as SA, functional groups, feedstock availability, and the conditions of the thermal
conversion routine used for its fabrication. Therefore, more research is needed to
focus on “tuning” the BCR properties for tailored applications. Modification of BCR
is another significant topic that must be explored in order to improve biochar’s capa-
bility for removing explicit pollutants. Current BCR research in wastewater treatment
is mostly focused on the small laboratory level, which lacks a clear theoretical under-
standing. Potential environmental concerns and future study directions on identified
issues of biochar are briefly outlined in Fig. 2. There are hard fabrication conditions
in the actual operation and application process, the production method is difficult to
5 Biochar for Management of Wastewater 115

Fig. 2 Potential environmental concerns and future study directions of biochar [Reprinted with
permission from Guo et al. [108]. Copyright 2020. Peer J- Open Access Journal for Life and
Environmental Research]

realize, expensive, and challenging to promote on a big scale, restricting the large-
scale manufacture and use of biochar. As a result, additional tests are required to
enhance its practical application while also paying attention to its long-term stability
in the environment. Together with the widespread use of BCR in wastewater treat-
ment, researchers should consider its potential detrimental impact on the ecosystem.
When using biochar, one of the most crucial qualities to consider is the stability of the
material. The aromaticity and degree of aromatic condensation of BCR determined
its stability [107]. When BCR is used to decontaminate wastewater, the probable
carbon discharge from the BCR can escalate the carbon content in the solution for
treatment [108]. Furthermore, HMs may be released, particularly in BCR generated
from sludge. Another critical component is BCR regeneration and recovery after
usage. Thus, it is critical to transform the harmful contaminants associated with
BCR into a less harmful condition for proficient management.

5 Conclusion

Biochar is an environmentally benign, affordable, and easily synthesized unique


functional material. It has inimitable structural benefits like suitable surface factional
groups, enhanced surface area, extensive sources, and environmentally friendly that
makes its application more feasible in wastewater treatment. The chapter thoroughly
presented an overview of biochar modification methods as well as adsorption for
organic and inorganic pollutants, together with potential role in the area of wastewater
management. The ability of biochar for removing the contaminants from aqueous
116 R. Painuli et al.

systems is straight related to its physicochemical qualities, which are affected by the
feedstock, thermal conversion process, and preparation conditions. Generally, it is
undeniable that the use of biochar provides numerous assistances and prospective
financial and ecological benefits. Its efficacy in removing various pollutants in the
laboratory scale has also been extensively stated. Conversely, further in situ studies
must be carried out to assess the biochar efficacy using existent effluents and then
investigate true environmental effect of biochar before its large-scale application.
Additionally, the biochar stability after numerous cycles of practice, as well as its
regeneration, require additional investigation.

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Chapter 6
Biochar for Climate Change Mitigation

Ehsan Shahhoseini, Moslem Arefifard, and Mohsen Karimi

1 Introduction

1.1 Carbon Capture and Climate Change

Climate change derived from anthropogenic greenhouse gas (GHGs) emissions


resulted in serious global challenges in the recent years [1, 2]. Based on reports [3],
CO2 is the main GHGs, which is the major responsible for global warming. Also,
among the different anthropogenic activities, fossil fuels consumption related to the
combustion of fossil fuels in the petroleum and petrochemical complexes [4, 5], is the
reason for more than 32 Gt CO2 emissions per year [6], while the available rising rate
of CO2 emission a significant growth is predicted till 2050 [7]. Since preindustrial era
till now, the CO2 concentration in the atmosphere has increased by 120 ppm, while
the maximum allowable value is 350 ppm, currently is 420 ppm [2, 7]. On the other
hand, the International Panel on Climate Change (IPCC) has assessed that this value
reaches 570 ppm by 2100, which results in 2–6 °C temperature enhancement [8].
Accordingly, the CO2 emission contributes to serious climate changes including: the

E. Shahhoseini
Faculty of Law and Political Sciences, Allameh Tabataba’i University, Dehkade-Ye-Olympic,
14368-63113 Tehran, Iran
M. Arefifard
Faculty of Economics, Allameh Tabataba’I University, Shahid Beheshti Avenue, 15136-15411
Tehran, Iran
M. Karimi (B)
Department of Chemical Engineering, Faculty of Engineering, University of Porto, Rua Dr.
Roberto Frias, 4099-002 Porto, S/N, Portugal
e-mail: mohsen.karimi@fe.up.pt
E. Shahhoseini · M. Arefifard · M. Karimi
Centro de Investigação de Montanha (CIMO), Instituto Politécnico de Bragança, Campus de
Santa Apolónia, 5300-253 Bragança, Portugal

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2023 123
A. K. Nadda (ed.), Biochar and its Composites, Materials Horizons:
From Nature to Nanomaterials, https://doi.org/10.1007/978-981-99-5239-7_6
124 E. Shahhoseini et al.

Fig. 1 The global share of


CO2 emissions of main
emitters

prolongation of the Frost-free season, variations in the weather pattern, heat waves,
hurricanes, melting of glaciers in the Arctic, and between 30 and 240 cm sea level
increment by 2100 [9, 10]. In this way, based on the BLUE Map Scenario of the
International Energy Agency (IEA), the CO2 emissions can reduce 19% by 2050,
by employing the CCS strategy [11–13], using sustainable techniques to reduce the
carbon emissions [14]. Currently, the major attempts on the CCS have been devoted
on developing highly efficient technology (in terms of engineering perspective) or
the discovery of novel sorbents (in terms of material science) for GHGs capturing
[14, 15], while more attention regarding the policymaking through the governments–
industries are required for a sustainable future. It is worth mentioning, up to date,
China (28.0%), United States (15.0%), European Union (9.9%), India (6.4%), and
Russia (4.5%), are the main sources of CO2 emissions [5]. The global share of CO2
emissions of main emitters is depicted in Fig. 1.

1.2 Biochar

Generally, adsorption, absorption, membrane and cryogenic separation are the main
processes for CO2 capture and storage [16]. Currently, among the different technolo-
gies, adsorption process with solid samples is considered as one of the most appealing
methodologies, because of the wide operating range of pressures and temperatures,
eco-friendly technique, and the simplicity of desorption process [13, 17]. Accord-
ingly, in the recent years, numerous sorbents including zeolite, metal–organic frame
works (MOFs), activated carbons, engineered carbon nanomaterials and mesoporous
carbons have been investigated as a source of sorbent for environmental protec-
tion applications [2, 7, 12, 14]. However, in spite of the high performance of these
materials for gas adsorption, the high cost still has remained as a main challenge
for large-scale applications of these adsorbents [14, 18]. In this way, recently, the
biochar samples as sustainable carbon materials received a significant interest [19].
6 Biochar for Climate Change Mitigation 125

Generally, biochar is derived from the pyrolysis of organic materials, generally at a


temperature lower than 700 °C [20], which is synthesized from plentiful sources of
biomass including: municipal solid waste [21], crop residues [18], wood waste [14,
22], animal manure, food waste [23], and sewage sludge [14]. On the grounds, biochar
has been introduced as a valuable source regarding its applications for wastewater
treatment [24], energy [22, 25] or adsorbent for GHGs mitigation [21], which these
novel usages can be considered as a sustainable route for waste management [21]. It
is worth noting, the potential applications of biochar are relied on the feedstock type
and operating conditions of pyrolysis process. In addition, while activated carbon
(AC) is currently the most popular carbon-based sorbent for different environmental
applications, its synthesized cost is one of the main drawbacks of AC as an effective
adsorbent [26]. Routinely, AC is synthesized in a temperature range of (800–1000 °C)
[27], and activated at a high temperature where the average required energy is around
97 MJ/kg, while the biochar is usually produced in a temperature lower than 700 °C,
also the required energy for its activation is about 6.1 MJ/kg [28]. Accordingly, the
price of biochar synthesis is almost one sixth of commercial activated carbons [29],
and around one tenth of other commercial adsorbents [30].
As already discussed, biochar as an eco-friendly sorbent is prepared from abundant
sources of biomass and solid wastes. But, biochar to be employed as a remarkable
adsorbent for gas adsorption processes, requires some other chemical modifications,
besides the mentioned thermal activation treatment. In this way, some chemical
solutions such as H2 SO4 , NaOH, H3 PO4 , KOH, K2 CO3 , MgCl2 , MgO, HCl, ZnCl2 ,
AlCl3 , etc., [2, 12, 14, 21], as chemical agents are applied to elevate the textural char-
acters of biochar samples. More details, regarding the different activation techniques
of biomass/biochar materials can be found in [14].

1.3 Sustainable Development and Climate Change

In recent decades, population growth, industrial advances, and significant growth


of agricultural, industrial, and service activities, also the expansion of metropolitan
areas have put the environment at a serious risk of degradation [31]. Deforestation,
soil erosion and water pollution at the national level, the phenomenon of fine dust at
the regional level, acid rains, ozone depletion, global warming and climate change at
the international level are some of the serious challenges which threaten our planet
[31]. Totally, environmental issues and problems are raised at three levels including:
regional, national and international.
In the meantime, climate change seems to be a major challenge facing human
beings in the twenty-first century [14]. According to the reports, greenhouse gas
(GHGs) emissions are the main cause of climate change [12]. While some of these
gases are derived naturally, but anthropogenic activities are the main cause of GHGs
emissions to the atmosphere [14]. Economic growth, which for many countries was
the only way out and the ultimate goal of development, became a major problem, as
this growth was on the agenda regardless of the consequences [32]. As the results
126 E. Shahhoseini et al.

of one-dimensional growth appeared, countries gradually turned their attention to


other aspects of life and development [33]. To this end, numerous indicators were
employed to evaluate the development and among them, the Human Development
Index was highly regarded [34].

1.4 Applying Biomass/Biochar for Development

Today, energy is a key element in the life quality, which is utilized in all sectors of
the economy [35]. The growing need for energy has been supplied by fossil fuels
in the past years. Considering the population growth and economic progress, 1.1%
annual increment in the energy consumption has been predicted till 2030, which
mostly (~84%) is provided by fossil fuels sources [35]. However, fossil fuels cause
climate change and there is a necessity for a sustainable and clean energy [36], one
that can be applied to reduce GHGs emissions and the risk of oil reserves [37].
Today, biomass is recognized as one of the most appealing resources of renewable
energy [38] and many developed countries apply it as a renewable energy source [37].
Biomass is widely utilized in developing countries and especially in rural regions
as the energy source for domestic applications [18, 37]. These resources have the
capability to supply energy with the lowest emissions of GHGs [37]. The large
volume of biomass is wasted and that creates the problem of disposal [37]. To solve
this problem, biomass wastes are converted into biochar, through some new and green
chemical and biological processes, called pyrolysis [18, 37]. Biochar is a carbo-rich
product that is comparable with fossil fuels and has a potential to be considered as
an energy supplier, soil remediation, and a source of sorbent for carbon capture and
waste water treatment [39]. Accordingly, many countries with high development
data are struggling moving towards sustainable development. Applying biomass/
biochar as a renewable energy resource and reducing the exploitation of fossil fuels,
in addition to reducing CO2 emissions will consider the environmental aspect of
sustainable development and can impact development indexes, as shown in Fig. 2.

2 Sustainability and Development Indexes

2.1 Human Development Index (HDI)

“Human Development Index” (HDI) has been introduced since 1990, which as a
global index, evaluates the development of countries annually. According to this
factor, human is considered as the ultimate goal of development and it measures the
economic and social aspects of life [40]. However, some features, which are impor-
tant to improve the living conditions, have been ignored in this index [40]. A simple
schematic of HDI is represented in Fig. 3. Despite the wide acceptance and credibility
6 Biochar for Climate Change Mitigation 127

Fig. 2 Sustainable development by employing the potential of biochar

of the HDI, there is almost a consensus that important parts of human development
are not included in this index [41]. In this way, environment, security, human rights,
governance, poverty, and happiness are some key factors, which require to be included
in HDI [42]. Accordingly, environmental problems and human activities, which exac-
erbate them made “United Nations Development Program (UNDP)” to publish its
2020 report as “Human development and the Anthropocene” [42], in which, the
new evaluation strategy emphasizes on CO2 emissions and climate change as an
index called “Planetary Pressures-Adjusted Human Development Index” or PHDI
that ranks the countries based on their impact on the environment and the quality of
life of the people [42]. Also regarding the BLUE Map Scenario of the International
Energy Agency (IEA) [12, 13], Carbon Capture and Sequestration (CCS) strategy
and developing sustainable sources of energy have been introduced as key elements
of development [27]. On the grounds, biomass/biochar carbon materials as abundant,
low cost and sustainable materials with double-applications as a source of energy
and a source of adsorbent have received a remarkable interest, recently [22, 25].
Accordingly, employing biomass/biochar samples as a source of energy [22, 25],
contributes to the reduction of fossil fuels consumption, or as a source of adsorbent
reduces the CO2 emissions [16, 21, 43]. Hence, based on new definition of UNDP for
“development of counties”, biomass/biochar samples have a remarkable potential to
open new windows for developing/developed countries regarding the development,
peace and security, which these phenomes have been extensively discussed in this
chapter.
128 E. Shahhoseini et al.

Fig. 3 A simple schematic of HDI

2.2 HDI Calculation

There are different ways to evaluate the development. However, HDI is the most
popular index to determine the economic and social performance [42]. Generally,
countries are ranked based on people and how development enlarges their choices
[42]. This quality has three dimensions including a long and healthy life, being
knowledgeable, and have a decent standard of living [40].
Totally, for calculation of HDI, the lowest and highest values are employed to
normalize the indicators as indexes between zero and one. The maximums are the
highest values observed over time [40]. The lowest value for life expectancy at birth
(which measures the long and healthy life) is 20 years [44, 45], for education (which
measures the knowledge) is zero [40], and for gross national per capita income
(GNI)(which measures a decent standard of living) is $ 100 [34]. The weights of
different parameters of HDI is reported in Table 1. While, before 2010, HDI applied
arithmetic mean [46], which was calculated by:

Health index + Education index + Income index


HDI = (1)
3
But since 2010, geometric mean has been replaced arithmetic mean [46].

actual value-minimum value


Dimension index = (2)
maximum value-minimum value
This equation is applied for both parts of the education index and then the arith-
metic mean of the obtained numbers- with equal weight- is calculated [40]. For the
income index, dimension index is calculated by [47]:
6 Biochar for Climate Change Mitigation 129

Table 1 The weights of different parameters of HDI


Dimension Indicator Minimum Maximum Refs.
Health Life expectancy at birth 20 85 UNDP [40]
(years)
Education Expected years of schooling 0 18 UNDP [46]
(years)
Mean years of schooling 0 15 UNDP [46]
(years)
Standard of living GNI per capita (2017 PPP$) 100 75,000 UNDP [46]

ln(actual value) − ln(minimum value)


Dimension index = (3)
ln(maximum value) − ln(minimum value)

which:

HDI = I health ∗ I education ∗ I income
3
(4)

here, “I” indicates the dimension index.


Routinely, the human development index has a value in the range of 0–1, which
the higher value in this range specifies the higher rank of development of a country
and vice versa [40]. In this way, concerning the human development index, countries
are divided in four categories including: very high human development countries
(hdi ≥ 0.8), high human development countries (0.7 ≤ hdi ≤ 0.8), moderate human
development countries (0.55 ≤ hdi ≤ 0.7) and low human development countries
(hdi ≤ 0.55) [40]. For example, HDI is 0.926 for the United States and it is in the
17th place-very high human development- in the HDI table in 2020 (HDR 2020).
China which is a high human development country takes the 85th position and its
HDI is 0.761 [42].
Despite the widespread acceptance of the HDI, there is a consensus that some
main aspects of human development have not been taken into account in this index
[41]. As a result, there is a requirement for developing a comprehensive index that
considers various aspects of the quality of human life, and indicates the development
of countries regarding the environment and sustainability.

2.3 Sustainable Development

Sustainable development is a progress that considers the requirements of the present


without compromising the capability of future generations to meet their own require-
ments [40]. Generally, sustainable development is a three-dimensional concept [31],
and its different aspects have been schematically depicted in Fig. 4.
As shown in Fig. 4, the environment is one of the dimensions of the sustainable
development and as a result, the natural resources of nations, the preservation of
130 E. Shahhoseini et al.

Fig. 4 Different aspects of


sustainable development

which is vital for future generations to use these God-given resources. In this way, in
2015 seventeen goals were defined for sustainable development by United Nations
General Assembly (UN-GA) to achieve till 2030 as Sustainable Development Goals
(SDGs) [48]. Based on this strategy, one of the main goals in this blueprint is”
climate change and its impacts” [48]. On the grounds, environment protection and
climate change mitigations require paying more attention to the reduction of green-
house gases (GHGs) and their destructive effects on health, quality of life, as well
as the future of the planet [42]. In the meantime, CO2 emissions through anthro-
pogenic activities-mostly by fossil fuels combustion- have the largest share in global
warming [14, 49]. In this way, several strategies have been developed for CCS, which
adsorption technology due to the high CO2 selectivity and recovery, high reliability
and significant eco-friendship, is among the most promising ones [7, 12, 16]. Gener-
ally, different classes of sorbents are employed in adsorption processes including
activated carbons [5], zeolites [7, 10], metal organic frames works (MOFs), etc.
[21, 43], but bio-based carbon materials derived from biomass/biochar samples are
among the favorable ones [16]. Routinely, carbon sorbents derived from animal and
agricultural wastes, coals, carbon-containing resins etc. are resources that are found
in almost every country [14, 18]. According to the United Nations Environment
Program (UNEP) report, annually 140 billion tons of biomass is produced world-
wide, and this huge capacity of biomass has a promising capacity to be considered in
different aspects of environmental protection [14, 22, 25, 43]. As already discussed,
commonly, biochar as a promising carbon sample, is derived from the pyrolysis of
biomass materials under specified operating conditions [22, 25], which as a low cost
and ubiquitous material has an excellent potential to be applied to store and reduce
CO2 and assist to protect the environment on the path of the sustainable development
[14, 21].
As written in the first human development report in 1990 “People do not isolate
different aspects of their lives. Instead, they have an overall sense of well-being”
[40]. So there was a need to create a composite index including more dimensions
6 Biochar for Climate Change Mitigation 131

especially CO2 emissions that can influence the life of the people. Thus a new chapter
began in the promotion of holistic economic indexes.

2.4 HDI: Progress and Improvement

As already discussed, one of the dimensions of development which has been


neglected in the human development index is the environment [42]. Due to the
growing importance of this issue, it is necessary to reconsider the development index
and accordingly address the environmental aspects in examining the level of develop-
ment of countries [42]. Among the different available aspects, climate change, which
is largely because of anthropogenic activities and the production of greenhouse gases
(GHGs), is the vital one. Since GHGs and especially CO2 have a strong effect on the
quality of human life, it is required to be added as a new dimension to HDI [50]. In
this way, following its indicators and annual reports, the HDI was redefined and it
addressed the aspects of the environment by providing statistics and environmental
concerns [34]. To this end, the 2011 Human Development Report addressed this
issue in more detail and it notices several environmental sub-indexes [34]. In the
past, several efforts have been made to address this shortcoming of HDI to create
a more comprehensive index, among which the Human Sustainable Development
Index (HSDI) was nominated as one of the promising ones [50].

2.4.1 Human Sustainable Development Index (HSDI)

As already discussed, sustainability is one of the key criteria which is required to


be taken into account by the United Nations for the evaluation of the quality of life
as well as to encourage the governments for a responsible development [50]. That
was the reason [50] to introduce Human Sustainable Development Index (HSDI)
instead of HDI as a more efficient index, which is more comprehensive than HDI
and considers a new sub-index as: Per capita carbon dioxide [50]. In fact, HSDI
consists of 4 sub-indicators including: healthy life, knowledge, a decent standard of
living, and environment [50], which has been schematically demonstrated in Fig. 5.
The latter is the amount of CO2 per capita that indicates the environmental index
[50]. By adding the carbon emissions to HDI, a more complete index is developed. In
this way, the development of a country with a high value of HDI and a high amount
of CO2 emissions simultaneously will be at the cost of harming the health of the
people and future generations [50]. Generally, the HSDI is calculated by [50]:

Sustainability Index = carbon efficiency ∗ equality (5)

In which:
132 E. Shahhoseini et al.

Fig. 5 A simple schematic


of HSDI

GDP per capita


Carbon efficiency = (6)
CO2 per capita

and:

Equality = Gini Coefficient (7)

So:

HSDI = 4
I health ∗ I education ∗ I income ∗ I sustainability (8)

As already extensively discussed, the emission of CO2 is the major challenge


of mankind in the current century, which imposes additional pressure on the nature
and the quality of life [42]. On the grounds, based on huge capacity of biochar as
a source of energy as well as a source of sorbent for CO2 capture [14, 22, 25, 43 ],
employing biochar can be considered as a green route for environmental protection
and sustainable development. Adding a new indicator (sustainability) to HDI and
proposing HSDI not only redefines the rank of countries in terms of development
but also can encourage them to pay more attention to the potential of biochar as an
excellent candidate for assistance in the way of sustainable development. In this way,
biochar reduces the amount of CO2 per capita and produces a more clean energy and
thus enhances carbon efficiency in Eq. 6 and as a result, HSDI increases. Accordingly,
when a country applies biochar capacity, this results in lower carbon emissions, that
can obtain a higher rank based on the development index. For instance, China, world’s
largest producer of CO2 emissions to the atmosphere (28% of total emissions) [5],
has a huge capacity of biomass/biochar production, which in one case, 20 × 106 tons/
year of Corncob is produced in this country [14]. This biomass/biochar capacity can
be employed as a promising strategy to improve China’s HSDI and HDI. Also, India-
the second most populated country in the world—that emits 6.4% of the global CO2
has also excellent capacity in terms of biomass/biochar and sustainable development
[14].
6 Biochar for Climate Change Mitigation 133

Fig. 6 Polluting countries and regions in terms of carbon dioxide emissions from 1970 to 2020

Figure 6 shows the most polluting countries and regions from 1970 to 2020 in terms
of carbon dioxide emissions (World Bank). China has the highest CO2 emissions
followed by the United States. Both countries fail in the development ranking when
it comes to HSDI as it calculates the CO2 efficiency. So there will be a decline in
the development indexes for CO2 emitters. Not only these two countries but also EU
members, India and Russia will face similar results. Capturing and reducing CO2
with low cost, available and abundant products (biochar) can be a promising solution,
that each country can take its benefit in the way of sustainable development.

2.4.2 Planetary Pressures-Adjusted Human Development Index


(PHDI)

Between 1960 and 2020, CO2 in the atmosphere has increased by 31%, which
contributes to several serious global challenges [1] that around 80% of the
CO2 emission is originated from fossil fuels (equivalent to 32 Gt per year) [1]. Based
on reports, current GHG emissions from anthropogenic activities result in global
temperature increment by 3–5 °C degree till 2100 [7]. Accordingly, the pressure that
human activities impose on the planet, made the United Nations to address another
development factor as PHDI in 2020 [42], that has been illustrated in Fig. 7. This
index considers the environmental aspect of development for sustainable develop-
ment by evaluating the pressures that human activities inflict on the environment.
Totally, this pressure includes two main factors such as: carbon dioxide emissions
per capita and material footprint per capita [42].
134 E. Shahhoseini et al.

Fig. 7 A simple schematic


of planetary
pressures-adjusted human
development index (PHDI)

In an ideal state where CO2 and the biological footprint of human activities are
zero, PHDI equals to HDI. However, in reality, the two are different and the purpose
of introducing PHDI is to specify the effect of human activities on the environment
and the quality of life [42]. Accordingly, when a country’s PHDI moves toward HDI,
it represents higher human development. According to HDR 2020, the impact of
this index is not significant for “countries with low human development”, but it can
have a remarkable effect on the development rank of “high and very high human
development” countries [42].

PHDI Calculation

In order to calculate the PHDI, it is necessary to normalize CO2 emissions per capita
and material footprint per capita, then normalize the values in (0–1) range [42]:

Aj index = (maximum j −− observed value j)/(maximum j −− minimum j) (9)

where j = 1, 2 indicates the two considered planetary pressure indicators.


Minimum = 0.
Maximum for CO2 emissions per capita is 69.85 tones observed for Qatar in 1997
[42].
Maximum for material footprint per capita is 152.58, observed for Guyana in 2000
[42], which the ranking of countries is sensitive to the selection of the maximum.

A = (carbon dioxide emissions index + material footprint index)/2 (10)

The index of planetary pressures, P, is determined as the complement of A: P =


(1 – A),
6 Biochar for Climate Change Mitigation 135

PHDI = HDI. A (11)

Or,

PHDI = HDI. (1 − P) (12)

Biochar for PHDI

Since biochar is a vast resource and is almost available everywhere, each region in the
world has the potential to produce biochar from specific wastes [14, 22]. As already
mentioned, this chapter is trying to create an index that considers environment in
measuring the development of countries. The development in which the quality of
life is of great importance and along with economic growth, the environment is also
noticed. An important issue that influences the environment is the amount of CO2
that countries emit through the burning of fossil fuels in the way of development,
which contributes to global warming. Applying biomass/biochar not only captures
CO2 emissions but also, as mentioned earlier, has the potential to replace fossil fuels.
It reduces CO2 and via the pyrolysis process, it generates energy, which can be
considered as a substitute for conventional fossil fuels energy. This energy, which
is clean and renewable, is more sustainable and is not exclusive to a few countries.
Many countries consider biomass/biochar as a source of renewable energy [14].
Although most of the world’s energy needs are provided by fossil fuels, it is vital
to alternate them with a less pollutant energy. Reducing CO2 and replacing it by
renewable energy impacts PHDI and brings it closer to HDI, as shown in Fig. 8.

Fig. 8 A simple schematic


of HDI based on PHDI factor
136 E. Shahhoseini et al.

As there are different capacities of biochar regarding the huge potential of biochar/
biomass samples for CO2 capture and storage [14] the result could be different. Those
countries that make the most of their biochar capacity will achieve a better position
in development ranking. For example, China which is ranked 85th in the PHDI
table could apply its biochar capacity to reduce CO2 emissions and improve in PHDI
ranking [42]. Also, United States which is ranked 17th in the ranking, could also exert
its biochar capacity to move towards sustainable development goals. Therefore, it is
possible to bring PHDI closer to HDI [42].

2.5 Potential of Biochar to Bring PHDI Closer to HDI

Figure 9 shows the HDI trend from 1990 to 2019 for the most polluting countries
[42]. As can be observed, all have a positive slope in HDI, while the US has a
better performance than other ones. According to HDR 2020 [42], the difference
between HDI and PHDI is 22.5% for the US and this country would fall 45 places if
the calculations are done taking into account PHDI. As already discussed, biochar
capacity of each region provides a special potential to reduce CO2 emissions and
also for climate change mitigation. As mentioned earlier for HSDI, similar results
can be obtained for PHDI. Reducing CO2 emissions leads to a reduction in PHDI
and getting closer to HDI. Applying biochar on the other hand, imposes less pressure
on the planet and increases the quality of life, based on development indexes, as the
main goal of development [40]. In this way, CO2 reduction through biomass/biochar
capacity, also reduces the difference between HDI and PHDI that is a great step
toward sustainable development.

3 Climate Change: International Security Paradigm

3.1 Climate Change and Global Warming

Global warming and climate change are often used interchangeably, while, they are
various concepts. Global warming is a concept related to the long-term heating of
the Earth’s climate system over the last century, which is caused by human activities
[51]. Climate change, on the other hand, includes man-made and nature warming
and its effects on the planet [52, 53]. Climate change is considered to measure the
average temperature rise on the planet’s surface, which is the long-term change in
the average climate pattern that defines the Earth’s local, regional, and global climate
[52]. According to report [8], human activity is the reason for 95% of global warming,
in which carbon dioxide emissions as the main GHGs have increased at a rate of about
250 times faster than the estimated ice age due to increasing human activity [8, 52].
6 Biochar for Climate Change Mitigation 137

Fig. 9 HDI trend from 1990 to 2019 for the most polluting countries

Consequently, carbon dioxide emission as well as increasing temperature, changes


the natural carbon cycle of the earth [51].

3.2 Consequences of Global Warming and Climate Changes

During the last 5,000 years, global temperature has increased between 4 and 7 °C
[51]. However, in the last century, there was 0.7 °C increase in temperature, which is
almost 10 times faster than the average global warming since the Ice Age [51]. As a
consequence of climate changes sea levels have risen by 20 cm over the past century,
and this rate has almost doubled over the past two decades [54]. In this way, rising
sea levels cause coastal erosion and increased flooding in the coastal areas some of
them probably disappear. It is worth noting, 10% of the world’s population lives in
areas that are located in places with less than 10 m above sea level [51]. Changing
rainfall patterns, coastal erosion, lengthening seasons in some areas, and changing
the range of some infectious diseases are other effects of global warming [51].

4 The Evolution of the Security Paradigm

The results of climate change, in addition to the direct threats in human health, will
also be a major factor in social and political instability. Countries that have fragile
stability, and the potential for various social, identity, political and cultural conflicts
138 E. Shahhoseini et al.

as part of their political reality have a higher potential for vulnerability [55]. However,
this is not the only issue. Environmental crises probably lead to devastating results
that jeopardize the national security of countries and thus international security.
Accordingly, security in its global and collective form will be more fragile than ever
and will affect the whole world.
Security as the most vital factor of each society is very relative, which includes
a lot of weakness and intensity that is promoted and reduced in different situations
[56]. Lippmann sees security as a term meaning military power, which depended
on the ability of nations to repel and eliminate military aggression in the past [57].
During the Cold War, new issues such as economic development, population growth,
increasing demand of energy, increasing carbon emissions, and climate and environ-
mental change emerged in international relations. Accordingly, there were drastic
changes in many concepts in this area, one of which was security. Barry Buzan
[58] considered the traditional definition of security a simplistic conception and
introduced security as a more complex category. He divided the security into five
dimensions including: military, economic, political, cultural and environmental [59].
Bouzan prioritizes international security and considers it as a study between the toler-
able threat and the threat of immediate action, which means that security is neither
power nor peace, but a concept between the two [58]. This new definition is a precise
and practical one which has the potential to be studied by examining the trend of
conceptual changes in security.

4.1 Climate Change Mitigation: Global Efforts

Recently, serious efforts have been organized in the form of international initia-
tives and treaties over several decades, which can show the importance of global
warming and environmental issues in world security. The First International Climate
Program was established in 1980 as The World Climate Research Program (WCRP)
by the World Meteorological Organization (WMO) in Geneva and the International
Council of Scientific Unions (ICSU) was founded in Paris. In November 1988, the
United Nations established an Intergovernmental Panel on Climate Change (IPCC)
to prepare and publish climate change reports. In June 1992, in Rio de Janeiro, Brazil,
the international community met to address climate change, and 166 countries signed
the United Nations Framework Convention on Climate Change, known as the Earth
Summit. 197 countries have signed this convention until the last meeting of this
summit in 2021. One of the most significant events of the last years of the twentieth
century dates back to the International Emission Reduction Treaty of September 11,
1997, held in Kyoto, Japan, which aimed to reduce emissions by 5.2%. The Launch of
the European Union Emissions Trading System in January 2005 is another attempt to
tackle climate change. The Copenhagen Climate Change Conference in 2009 sought
a new deal for the Kyoto Protocol, which could be described as a global failure to
reach an agreement because the participants failed to achieve a binding agreement to
reduce GHGs emissions. However, the most important international event on climate
6 Biochar for Climate Change Mitigation 139

change and the environmental crisis, which for the first time in history was agreed
upon by all countries of the world, was the Paris Agreement in 2015. The agree-
ment stressed the need to limit global warming below 2 °C in the current century,
in which developed countries must accept financial support and technology transfer
to developing countries. The adoption of the European Green Deal in December
2019 is a serious and pragmatic move to achieve carbon neutrality by 2050 [60].
This means the EU ensures that it does not produce more GHGs than it can adsorb
[19, 20, 23, 43].
As already discussed, currently fossil fuels are the main sources of energy of
almost all countries while GHGs and especially CO2 emissions have been the major
global concerns, and more environmentally friendly strategies/solutions are required.
Accordingly, reducing carbon production and increasing carbon capture methods are
considered as international security concerns that are pursued in various fields [14]. In
this way, recently, carbon-based adsorbents attracted a significant interest regarding
their low cost, vast majority, sustainability as well as being eco-friendly [14]. To
this end, massive sustainable sources have been considered which have the potential
to be employed as carbon absorbents including biomass, biochar and slide wastes
samples [16, 43]. Biochar and biomass, as sustainable adsorbents own the source of
agricultural wastes, which are among the cheapest carbon-based sorbents [14, 16].
On the grounds, following the concern of international security, climate change and
international agreements, applying biochar already demonstrated excellent potential
as a source of adsorbent for carbon capture or energy supplier, which is an appealing
strategy to achieve the goals and aspirations of another part of the international
community [14], (Senthil and Lee 2020). Utilization of biochar as a CO2 absorbent
can pave the way for international agreements and remove political and economic
obstacles that prevent an agreement from being reached. It should be considered,
scientific and laboratory efforts have always been one of the most important tools for
achieving peace and increasing international security. International agreements such
as Paris agreement [11] and the European Green Treaty [60] as a world perspective on
tackling the risk of climate change are in dire need of expertise and scientific efforts
such as biochar, which by solving the problems in a practical way, its implementation
process is followed by international institutions and governments and put on the
agenda as a process [61]. Considering climate change and carbon sequestration using
biochar, can place this product as part of scientific and effective efforts to reduce the
risks of international security in different parts of the world. Also, it is a practical
way to reduce CO2 emissions and therefore an effective tool for the purposes of the
Paris International Agreement [11].

5 Conclusions

Global warming as a consequence of climate change originated from the human activ-
ities is considered as the main concern of mankind in recent decades. According
to reports [52], NASA Goddard Institute for Space Studies [53], over the past
140 E. Shahhoseini et al.

5,000 years, global temperature has increased between 4 and 7 °C, while, in the
last century, there was 0.7 °C increment in the temperature, which is almost 10 times
faster than the average global warming since the Ice Age. On the grounds, the growth
rate of fossil fuel consumption as a consequence of the modern era and industrial
revolution has significantly enhanced the GHGs emission, particularly CO2 , as the
main cause of global warming. Accordingly, in recent years, several efforts have
been made for CO2 capture and climate change mitigation. To this end, adsorption
technology using solid sorbents has already represented a great potential for CCS
strategy. On the grounds, biochar derived activated carbons have been considered as
a promising one not only because of hydrophobic specification of samples and plenty
resources, but also as a green route for sustainable development. On the grounds,
this chapter was dedicated to the high potential of biochar as a source of adsorbent
for climate change mitigation and its key role for sustainable development. To this
end, several key indexes of development introduced by “United Nations Develop-
ment Program” including: Human Development Index (HDI), Human Sustainable
Development Index (HSDI) and Planetary Pressures-Adjusted Human Development
Index (PHDI) considering the potential of biochar have been evaluated in details.
Also, the effect of global warming and climate change in variations of the interna-
tional security paradigm has been investigated. Furthermore, the role that biochar
and its high potential can play in this scenario has been discussed.

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Chapter 7
Clay-Biochar Composites
for the Agriculture Industry

Nurhani Aryana, Witta Kartika Restu, and Bayu Arief Pratama

1 Introduction

Biochar is a solid residue produced from a thermochemical decomposition pyrol-


ysis process of lignocellulosic biomass under an oxygen-limited environment at
different heating rates. Biochar can be processed from various types of biomass, such
as wood, crop straw, algae, industrial by-products, and municipal waste, making it
environment-friendly [1, 2]. Besides, its feedstock is abundant and low cost of produc-
tion. Its characteristics, such as wide surface area, high capacity of ion exchange, very
high stability, high porosity, large surface functional groups, excellent carbon content,
and abundance of nutritional contents, are high potential for the biochar utiliza-
tion in environmental remediation, energy storage and conversion, and catalysis [3].
Biochar is commonly used directly without any further treatment. However, current
research found that feedstock pretreatment and biochar post-treatment can improve
its performance [4]. During the last decade, research in the growth of biochar-based
functional materials, particularly biochar-based composites, has been increasing to
provide more efficient and versatile platforms for various applications. Biochar-based
composites were found to have enhancement characteristics, such as large surface
area and high porosity compared with regular biochar, involving adjustment to the
functional groups on the surfaces of biochar.
One of the biochar-based composites that were interestingly studied is clay-
biochar composites. Clay possesses valuable and important physical and chemical
properties, including its surface area, shape, particle size, and surface chemistry [5].

N. Aryana (B) · W. K. Restu


Research Center for Chemistry, National Research and Innovation Agency (BRIN),
South Tangerang, Kawasan PuspiptekSerpong, Banten 15314, Indonesia
e-mail: nurh028@brin.go.id
B. A. Pratama
Research Center for Ecology and Ethnobiology, National Research and Innovation Agency
(BRIN), Jl. Raya Bogor Km. 46, Cibinong, West Java 16911, Indonesia

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2023 145
A. K. Nadda (ed.), Biochar and its Composites, Materials Horizons:
From Nature to Nanomaterials, https://doi.org/10.1007/978-981-99-5239-7_7
146 N. Aryana et al.

Its characteristics, such as high surface area and ion exchange capacity, support its
application for removing environmental contaminants, such as heavy metals, dyes,
organic compounds [6, 7]. Montmorillonite and kaolinite are the most explored type
of clays that have potential to be utilized as adsorbents with low-cost production.
Over the last 30 years, clay minerals have been broadly applied in numerous sectors
such as industrial engineering, agriculture and petroleum discovery, refining and
recovery [8]. The clay-biochar composite was developed in 2014 by Yao et al. [8] as
an adsorbent for environmental applications. Since then, the number of publications
related to clay-biochar composites was kept increasing.
Several reviews were discussed comprehensively on producing biochar-based
materials for various applications. The utilization of biochar-based composites in the
conversion and storage of energy has been reviewed by Liu et al. [1]. In addition, the
utilization of biomass-derived materials for the storage, conversion, and production of
energy has been reviewed by Kumar et al. [9]. Related to environmental issues, Trakal
et al. summarized the effect of biochar characteristics on metal-sorption mechanisms
and the surface-modification methodologies to improve the metal-sorption efficiency
of biochar [10]. Recent updates on the improvement of biochar-based composites as
adsorbents or catalysts in eliminating dangerous organic pollutants from wastewater
have been reviewed by Huang et al. [3]. A review focusing on the functionaliza-
tion and interaction process of engineered biochar for environmental remediation
has been reviewed comprehensively by Monga et al. [11]. Current developments in
catalytic utilization of biochar-based composites have been studied by Shan et al.
[12]. The amalgamation of biochar with clay for environmental remediation has been
reviewed by Atugoda et al. In this chapter, the production methods of clay-biochar
composites, as well as the enhancement in the physical and chemical characteristic
of the composites, were summarized. Furthermore, the use of clay-biochar materials
for agriculture applications was highlighted.

2 Document Search and the Co-occurrence-Keywords


Analysis

A search for documents related to the synthesis methods and current uses of clay-
biochar composites was done in the Scopus database on January 2023. The keyword
“clay-biochar” was used to search the related publications within an article’s title,
abstract, and keywords. This search has resulted in about 24 documents, summarized
in Table 1. A bibliometric analysis was done on these documents using VOSviewer
to see any keywords that may have been related to the clay-biochar composites in
the agriculture field. The co-occurrence-index keywords analysis of these documents
has resulted in four clusters of keywords shown by four different colors of 68 items
in the map of keywords weighted by total link strength (Fig. 1). The top 10 keywords
weighted by occurrence and total link strength are shown in Tables 2 and 3. From the
7 Clay-Biochar Composites for the Agriculture Industry 147

Table 1 Summary of publications related to clay-biochar composites in the Scopus database


Publication Publication source Document Refs.
year type
2014 Chemical Engineering Journal Article [8]
2016 Environmental Science and Technology Article [13]
2017 Journal of the American Ceramic Society Article [14]
2017 Colloids and Surfaces A: Physicochemical and Article [15]
Engineering Aspects
2018 Water (Switzerland) Article [16]
2018 Journal of Polymers and the Environment Article [17]
2018 Environmental Arsenic in a changing world—the Conference [18]
International Congress and Exhibition Arsenic in the Paper
Environment, 2018
2018 Environmental Arsenic in a changing world—7th Conference [18]
International Congress and Exhibition Arsenic in the Paper
Environment, 2018
2019 Journal of Environmental Management Article [19]
2019 Journal of Hazardous Materials Article [20]
2019 Environmental Science and Pollution Research Article [21]
2019 Desalination and Water Treatment Article [22]
2020 Journal of Environmental Management Article [23]
2020 Journal of Ocean University of China Article [24]
2020 Wuji Cailiao Xuebao/Journal of Inorganic Materials Article [25]
2020 BioResources Article [26]
2021 Advances in Colloid and Interface Science Review [27]
2021 Journal of Environmental Management Article [28]
2021 Materials Chemistry and Physics Article [29]
2021 Advances in Chemical Pollution, Environmental Book Chapter [30]
Management and Protection
2022 Environmental Pollution Article [31]
2022 Separation and Purification Technology Article [32]
2022 Heliyon Article [33]
2022 Environmental chemistry, pollution and waste Article
management

analysis of the co-occurrence-index keywords, two keywords can relate to the imple-
mentation of clay-biochar composites in the agriculture field, namely soil pollution
and soil amendment. The keyword of soil pollution was in the first cluster, which
is shown by the red items on the map of keywords weighted by total link strength
(Fig. 1). The keyword of soil pollution has occurred 2 times. It has 9 links with a
total link strength of 10. Meanwhile, the keyword of soil amendment was in the third
cluster, which is shown by the blue items on the map of keywords weighted by total
148 N. Aryana et al.

link strength (Fig. 1). The keyword of soil amendment has occurred 2 times. It has
14 links with a total link strength of 16. This co-occurrence-index keywords anal-
ysis revealed that the utilization of clay-biochar materials in agriculture still needs
improvement.

Fig. 1 Co-occurrence keywords map weighted by total link strength

Table 2 Top 10 keywords


Rank Keyword Occurrences
ranked by occurrence
1 Adsorption 18
2 Biochar 15
3 Clay 15
4 Article 7
5 Composite 7
6 Water pollutant 6
7 Scanning electron microscopy 6
8 Pseudo-second-order model 6
9 Aqueous solution 5
10 Wastewater treatment 5
7 Clay-Biochar Composites for the Agriculture Industry 149

Table 3 Top 10 keywords


Rank Keyword Total link strength
ranked by total link strength
1 Adsorption 198
2 Biochar 187
3 Clay 181
4 Article 132
5 Composite 105
6 Aqueous solution 97
7 Water pollutant 94
8 Scanning electron microscopy 92
9 Antibiotics 81
10 Unclassified drug 74

3 Clay-Biochar Composites: Production Methods


and Current Applications

Generally, there were three methods that were already developed for the production of
clay-biochar composites, namely, pyrolysis method, slurry method, and calcination
method (Table 4). The physicochemical characteristics of clay-biochar composites
are highly determined by the thermal treatment to produce a final product that can
counter-balance with the water molecules by retaining the cations and structure
of clay [30]. The yield of product was also influenced by the biomass or biochar
utilization in the preparation of clay-biochar composite.
Pyrolysis is defined as the chemical decomposition of organic materials by
applying a thermal treatment in moderate to high heating rate in the absence or
near absence of oxygen [34]. One of examples of the preparation of clay-biochar
composite by pyrolysis method was done by Nigay et al. [14]. The aim was to
study the relationship between structure and property of clay-added organic addi-
tives (biomass and biochar). The clay was available in the form of lumps with a size
of around 3 mm. Hard wood was used as the source for biomass. Pyrolysis at 500 °C
of the biomass was done to produce the biochar. The clay was mixed with 5, 10, and
15 wt% of organic additives. After kneading for 5 min, the mixtures were added by
water and then formed as clay blocks of 60 mm × 30 mm × 10 mm with a bench
extruder. The clay blocks were then dried at 25, 65, and 105 °C in an electric oven for
24 h. After that, the clay blocks were fired at 30, 600, 800, or 1000 °C. Calcium alumi-
nosilicates were formed during the firing process. Regardless, the biomass or biochar
stayed at the macroscopic scale with no interaction to the matrix at temperatures up
to 1000 °C.
Rawal et al prepared clay-biochar composites by combining the slurry and pyrol-
ysis methods [13]. In this work, bamboo was chosen as a biomass source and was
cut into cubes. Kaolinite and bentonite were selected as clay minerals to observe the
influence of various clay formation. Bentonite is made up of sodium and calcium
Table 4 Summary of feedstock, preparation method, and current applications of clay-biochar composite
150

Biochar feedstock Preparation of Size of biomass/ Clay Ratio of Preparation Application Refs.
feedstock biochar clay:biochar method of
clay-biochar
composites
Bamboo, bagasse, Milled into ~2 mm Montmorillonite, 1:5 Slow pyrolysis at Methylene blue [8]
hickory chips powders ~2 mm kaolinite 600 °C for 1 h adsorption of from
aqueous media
Bamboo Chopped into Cubes with a size Bentonite, kaolinite Not available Pyrolysis at 250, – [13]
cubes of approx. 10 mm 350, 450, and
550°C
Hardwood Grinded and 20 μm Lumps of clay from 100:5 or 10 Pyrolysis at 30, Thermal energy [14]
pyrolyzed at the Toulouse, France or 15 600, 800 and storage
500 °C 1000 °C
Potato stem Washed and <20-mesh Natural attapulgite 1:5 Slurry method Norfloxacin [15]
overnight removal from
oven-dried at aqueous media
80 °C
Bagasse Washed and <0.25 mm Natural attapulgite 1:3 and 1:5 Pyrolysis at Brilliant Red X-3B [16]
overnight 700 °C adsorption in
oven-dried at aqueous media
105 °C
(continued)
N. Aryana et al.
Table 4 (continued)
Biochar feedstock Preparation of Size of biomass/ Clay Ratio of Preparation Application Refs.
feedstock biochar clay:biochar method of
clay-biochar
composites
Residual bark chips Air-dried <2 mm Clay (unexplained) 1:10 Slurry method Immobilization of [17]
overnight, heavy metals in acid
pyrolyzed at soil environment
600 °C ramped
with a rate of
10 °C/min at 2 h
with nitrogen flow
of 3 L/min
Municipal solid waste No preparation Not available Red earth 1:5 Slurry method Arsenic removal of [18]
from aqueous
solution
Municipal solid waste No preparation Not available Montmorillonite, red 1:5 Slurry method Tetracycline [19]
earth antibiotic removal
7 Clay-Biochar Composites for the Agriculture Industry

of aqueous solution
Cauliflower leaves Washed and dried <0.85 mm Natural attapulgite 1:5 Pyrolysis at Oxytetracycline [21]
at 80 °C for 24 h, 500 °C for 6 h removal from
and then crushed aqueous solution
and sieved
Sawdust, powdered No preparation Not available Clay (unexplained) 99:1, 95:5. Pyrolysis at Bioremediation of [23]
fruit of Acacia 90:10 700 °C hydrophobic
concinna organic
contaminants in soil
(continued)
151
Table 4 (continued)
152

Biochar feedstock Preparation of Size of biomass/ Clay Ratio of Preparation Application Refs.
feedstock biochar clay:biochar method of
clay-biochar
composites
Reed straw Cleaned and dried 0.15 mm Clay (unexplained) 5:1 Pyrolysis at Removal of [24]
at 105 °C for 24 h, 600 °C for 3 h ammonia nitrogen
then crushed, from aqueous
sieved, and solution
pyrolyzed at
600 °C for 3 h
Peanut shell Washed and dried 150 μm Kaolinite, bentonite 1:1 Slurry method Removal of Cr(VI) [25]
at 60 °C, milled in water
into powders,
pyrolyzed at
250 °C for 2 h
Macadamia nutshells, Washed, dried at 90–150 μm Natural attapulgite 4.3:1:1 Calcination at Removal of Cr(VI) [29]
groundnut shells 105 °C for 24 h, 365, 555, and in water
and then treated 700 °C for 30 min
with H2 O2
Corn straw, pine wood Air dried, ground 0.25–0.5 mm Kaolinite, 1:5 Pyrolysis at 500 Removal of ionic [31]
through 10–60 montmorillonite or 700 °C ramped NOR and nonionic
mesh, and with a rate of D.E.P. organic
pyrolyzed at 500 5 °C/min for 2 h contaminants
or 700 °C rampe
dwith a rate of
5 °C/min for 2 h
(continued)
N. Aryana et al.
Table 4 (continued)
Biochar feedstock Preparation of Size of biomass/ Clay Ratio of Preparation Application Refs.
feedstock biochar clay:biochar method of
clay-biochar
composites
Populus nigra (mainly Washed, air-dried 0.074 mm Bentonite Not available Slurry method Removal of Cr(VI) [32]
the discarded trunk) at room and pyrolysis at
temperature, 450 °C
ground, sieved
through a 200
mesh
Cottonwood Cut into small Not available Clay (unexplained) 1:1 Pyrolysis ramped Removal of [33]
pieces, washed, with a rate of glyphosate from
dried at 80 °C for 15 °C/min up to aqueous solution
12 h, milled, and 650 °C for 2 h
pyrolyzed ramped
with a rate of
15 °C/min up to
7 Clay-Biochar Composites for the Agriculture Industry

650 °C for 2 h
153
154 N. Aryana et al.

montmorillonite belonging to the smectite group. FeSO4 .7H2 O was selected as an


iron source to see the influence of mineral addition to the biochar properties. The
bamboo cubes were soaked in the mineral (iron-bentonite and iron-kaolinite slur-
ries). The temperature and time for the soaking process was 80 °C for 3 h. Prior to
pyrolysis, the samples were ovened at 110 °C for 24 h. The pyrolysis process was
done by placing the samples in a purpose-built high nickel chromium reaction vessel
placed in an electric kiln. The pyrolysis temperatures were 250–550 °C, gained by
ramping the temperature with a rate of 3 °C/min until the required temperature was
achieved. The final temperature was held for 30 min to form biochar.
The SEM analysis showed that at higher temperature (450 and 550 °C), clay
and iron formed a coating on the surface of the biochars, and the biochar has a
microporous structure. Meanwhile, TEM analysis indicates that biomass soaking in
an iron-clay slurry continued with applying pyrolysis to support the integration of
mineral phases nanostructure inside the biochar’s porous structure.
The pyrolysis, calcination, and slurry methods, respectively, were applied to
prepare the clay-biochar composites from natural attapulgite clay. Different from
bentonite clay, attapulgite is a kind of needle-like clay composed of hydrated magne-
sium aluminum silicate as the main mineral component [35]. The pyrolysis method
was applied in the synthesis of clay-biochar composites from natural attapulgite with
bagasse as the feedstocks [16]. In this work, water was added after the mixing of clay
and biomass. Then, the paste was dried in an oven at 105 °C and ground into powder
form before pyrolyzed under argon atmosphere in a muffle furnace. The tempera-
ture was ramped about 7 °C/min until reached the pyrolysis temperature at 700 °C
and kept for 4 h. The resulted biochar products were then washed with deionized
water after cooled down to room temperature, followed by oven-dried at 105 °C for
overnight. By applying this method, the bagasse-based biochar has better affinity
and hydrophobicity compared to the native bagasse biochar. The aluminum oxide
(Al2 O3 ) and silica oxide (SiO2 ) particles presented on the carbon surface inside the
matrix of bagasse biochar after pre-treatment with attapulgite. These particles were
able to increase the oxygen-binding group on the surface.
Attapulgite clay and potato stem were utilized in the preparation of clay-biochar
materials by the slurry method, as visualized in Fig. 2 [15]. In this method, a slurry
suspension was prepared by blending clay and biochar with a certain ratio. There
were several ways to prepare biomass as the feedstock for biochar. The biomass can
be washed and dried overnight at a certain temperature, milled to reach the desired
particle size, and pyrolyzed at a certain temperature. The municipal solid waste can
be used as feedstock without any preparation. The addition of a desire amount of
deionized water into clay produced a clay suspension. This clay suspension was then
sonicated. The biochar or biomass feedstock was then put on to the clay suspension
and stirred for a certain period. This aimed to have the biochar hydrated in the clay
suspension. The phase of solid–liquid was separated with centrifugation where the
solid phase is gathered and dried in oven.
In the preparation of clay-biochar materials from macadamia nutshells, groundnut
and natural attapulgite, the calcination method was used by mixing the attapulgite
first with sulfuric acid solution with a ratio of 1:4 then stirred continuously [29]. Next,
7 Clay-Biochar Composites for the Agriculture Industry 155

Fig. 2 Synthesisof clay-biochar composites from natural attapulgite and potato stem. Reprinted
with permission from [15]. Copyright (2019) Elsevier Ltd

the macadamia nutshells and groundnut were mixed into the solution and stirring was
continued. Different from the pyrolysis and slurry methods, a large quartz particles
were resulted from this reaction. The quartz particles were removed and the aqueous
phase was gathered and centrifuged to obtain the solid product. This solid phase was
then dried in oven at 105 °C. The resulting lumps were then crushed and sieved to
have the size of a particle of 150 μm. The resulting powders were then entered into
a furnace for calcination process. It was observed that calcination at a temperature
of 700 °C resulted in the best biochar among the tested calcination temperatures.

4 Improvement in the Physico-Chemical Characteristics


of Clay-Biochar Composites

The elemental composition of biomass or biochar and clay as feedstock in the prepa-
ration of clay-biochar materials influenced the porosity, specific surface area, and
morphology of the final product. Plant biomass mostly consists of carbon about 42–
47%, oxygen about 40–44%, and hydrogen about 6%, all percentage in dry basis
[36]. Meanwhile, the condition of feedstock and pyrolysis influenced the chemical
composition of biochar, comprising a minimum of 65% of carbon [37]. By applying
pyrolysis, the elements of biomass were degraded and volatilized into CO, CO2 ,
CH4 , and H2 , resulted in a decrease in the biochar yield. Meanwhile, the biochar,
which is composed of hydrogen and carbon elements, just converts into CH4 and
H2 at high temperatures and was conserved in the clay ceramic through the firing
process. Therefore, the addition of biomass into the clay induces higher porosity of
the composite than the addition of biochar into the clay. The BET analysis showed
that clay-biochar composites from natural attapulgite and potato stem has smaller
156 N. Aryana et al.

specific surface area than the pristine biochar, whereas the average pore width and
the total pore volume of the composites were larger than to pristine biochar [15].
The clay addition into the biochar increased mineral contents of the clay-biochar
composites. Meanwhile, the carbon content increased without the addition of clay
into the biochar. The variation of carbon percentage (wt.%) for the biochars is not
monotonic, and this is an indication of the difference in ash content and molecular
structures [13]. Without the addition of biomass or biochar, the clay ceramic has a clay
heterogeneous structure with quartz particles and pores. Compared with the biomass
addition, the biochar addition into the clay ceramic has resulted in larger defects and
a greater heterogeneity of the composite. The mineral phases from the clay coated
the biochar’s internal pore surface. The mineral areas have a nanostructured dendritic
morphology.
It was found that the biomass with high oxygen concentrations formed higher
porosity, which resulted in a reduce in specific heat capacity. Meanwhile, the addition
of 30 wt% of biochar that has low oxygen concentrations has increased the specific
heat capacity for the clay ceramic. The addition of large particles size of biomass
gave impact to decrease the flexural strength in consequence of stress concentration
effects. Otherwise, the organic additives with small particles (biochar) proceeded in
a minor degradation of the fracture toughness and flexural strength. The addition
of toughening related to the organic additives particles even affected to the thermal
reliability conservation.

5 Clay-Biochar Composite Applications for Agriculture


Industry

Based on F.A.O. prediction, world population growth will be up to 9.7 billion by


2050. To meet the world demand, food production should be increased by about
70%. Currently, agriculture is the dominant channel of food supply. Until the present
time, the utilization of clay-biochar composites for the agricultural industry includes
its application in soil remediation, particularly in the removal of the contaminant in
agricultural wastewater, and as fertilizer.

5.1 Clay-Biochar Composite Application in Soil Remediation

Various techniques have been conducted to repair soil contaminated by pollutants.


One of these techniques is using clay-biochar materials. The use of biochar is consid-
ered capable of providing advantages such as increasing soil nutrients and water-
holding capacity, increasing soil fertility while reducing greenhouse gas emissions
[8]. The combination between clay mineral and biochar is expected to provide the
best results in an effort to enhance soil quality. The utilization of biochar succeeded
7 Clay-Biochar Composites for the Agriculture Industry 157

in increasing arenosol soil nutrients [38], although it decreased the retention of nutri-
ents when used repeatedly. But on the contrary, the use of clay is able to provide a
fairly good effect, especially in sustainable land management. The study conducted
by Beusch et al. [38] shows the difference in results obtained in a certain period due
to the addition of clay minerals and biochar. The results revealed that the traditional
woody biochar reduced NO3 − —N leaching from the soil in the first eight months.
Meanwhile, clay sediment showed a decreasing in NH4 + and K+ leaching in arenosol
soils. However, the use of clay-biochar composites on arenosol soil still needs to be
studied further. In addition, the application of agricultural waste as a raw material
in the production of biochar also shows promising results with the right formula-
tion and temperature optimization during pyrolysis [39]. The use of biochar also
shows satisfactory results in efficient fertilization and increasing soil fertility [40].
Ding et al. [40] found that biochar can be used to make fertilizers more efficient and
increase soil fertility due to biochar has good stability, a large number of various
functional groups, and could be wide-scale applied. Furthermore, several previous
studies have also demonstrated the ability of clay-biochar composites to increase the
ability to store water [41]. Biochar with large particle sizes can retain groundwater
longer in rough soil conditions and has limited water retention capability. The same
results shown in Edeh’s study [42] showed that rates 30–70 t/ha were effective on
coarse-textured soils. Meanwhile, Mekuria [43] showed that biochar and a combi-
nation of clay and organic matter increase water production in plants, which can
increase agricultural productivity.
Furthermore, Mekuria et al. [43] delivered significant results on the use of organic
matter (biochar) and clay in increasing water productivity in agricultural crops. This
provides an opportunity for more intensive production capacity on rainfed land.
Biochar was known to retain organic matter and dissolved organic matter from
leaching [44]. Microbials dissolved organic matter are important in maintaining soil
properties. In addition, clay-biochar composites were known to reduce pollutants [45]
and carbon dioxide (CO2 ) emissions [46] with the correct composition of composting
agents, feedstocks, and species of worms.

5.2 Clay-Biochar Composite Application in the Removal


of the Contaminant in Agricultural Wastewater

Various researchers have been synthesizing the clay-biochar composites and utilizing
them for pollutant removals such as ammonium, nitrate, methylene blue, a tetra-
cycline antibiotic, lead and zinc from the aqueous solution. Yao et al. studied
clay particle-impregnated biochar that disseminated on the carbon surface from the
biochar form. The three types of biomass as the raw materials were processed with
clay type of montmorillonite or kaolinite [8]. The capability to eliminate methy-
lene blue from an aqueous solution was conducted for all samples. The biochars
from the new feedstocks showed very low methylene blue removal. Modifying the
158 N. Aryana et al.

bagasse surface and hickory biochars with clays improved methylene blue adsorp-
tion. However, there was a slight reduction of methylene blue removal by the bamboo
biochar. This might be unsuitable for clay-bamboo biochar composites to apply for
methylene blue removal. The modification of montmorillonite and kaoline in bagasse
enhanced the rate of methylene blue elimination. The increasing adsorption ability
was about five folds. This might be due to the distribution of clay on carbon surfaces
from the biochar form. Likewise, clay-biochar composites from montmorillonite
and bamboo powder were prepared for the intake and release of ammonium and
phosphate ions in wastewater treatment and the maintenance of soil richness [47].
The physical and chemical characteristics of montmorillonite-biochar composites
were investigated. The adsorption affinity of montmorillonite-biochar composites
for phosphate ions was much stronger than that for ammonium ions. The compos-
ites acquired specific adsorption and slow-release characteristics for ammonium and
phosphate ions.
Similar to the previous studies, Viglasova et al. also studied the elimination of lead
by the adsorption of biochar composites from bamboo and using montmorillonite as
the clay mineral [48]. The montmorillonite particles were allocated along the surface
of the biochar. The nitrated removal from aqueous media with adsorption was studied
with a batch system at laboratory temperatures. The three types of adsorption models
from Langmuir, Freundlich and DR were appropriate to the experimental data with
R2 > 0.93. Premarathna et al. investigated the composites by blending the clay type of
montmorillonite and red earth into municipal solid waste-based biochar to eliminate
tetracycline from the aqueous solution [19]. It exhibited that the particles of clay
were allocated on the surfaces of biochar. The FTIR gave further confirmation for
a successful composite structure. The differentiation in adsorption that seized in
the kinetic models was primarily because of the formation in the clay combination.
The data from the adsorption isotherm of all adsorbents were closely matched to
the Freundlich model. These results showed that the tetracycline adsorption to the
clay-biochar developed through physical and chemical adsorption (Fig. 3).
Regarding lead, Zhang et al. explored the biochar derived from watermelon rind
coated with magnesium oxide (MgO) as a potential material in environmental appli-
cations [49]. The magnesium purity of the biochar could be adjusted by tailoring the
mass ratio of magnesium toward raw material during exaggerated impregnation. The
lead elimination capacity of the composites escalated with rising magnesium content,
with the highest lead elimination of 558 mg/g for the composites with a magnesium
percentage of 10.1%. The lead elimination from the composites with a magnesium
content of 1.89–2.51% was also found to boost from 81.7 mg/g in 400 °C to 742 mg/
g in 700 °C. The magnesium pyrolysis temperature affected the composites’ lead
elimination.
Similarly, Ramola et al. studied biochar-mineral composites synthesized at
different temperatures [50]. The samples were conducted under various conditions
for efficient lead removal from aqueous media. The composites removed about 12%
more lead from water than biochar. The clay-biochar and calcite-biochar processed at
700 °C showed their suitability for the most efficient lead elimination, about 99.9%.
Functioning as catalysts, bentonite and calcite played roles in yield, pH, functional
7 Clay-Biochar Composites for the Agriculture Industry

Fig. 3 a The kinetic models of tetracycline adsorption and b the adsorption isotherm fittings for clay-biochar composites to the Freundlich model. Reprinted
with permission from [19]. Copyright (2019) Elsevier Ltd
159
160 N. Aryana et al.

groups, minerals texture, and carbonization changes that support the effective lead
elimination.
In a study by Song et al., montmorillonite-biochar composites adsorbed around
241% more zinc from water media than simple biochar in 24 h [51]. It is found that
350 °C might be the optimum temperature to get biochar that had an influential func-
tional group and provided a catalytic efficiency. The experimental adsorption data
found that the Langmuir adsorption capacities of zinc were maximum at 8.163 mg/g.
Generally, the research finding simplied that biosorption of various inorganic pollu-
tants in water, soil, or water–soil system could be obtained from different types of
biochar. However, the efficiency of biochar may further be enhanced by synthesizing
clay-biochar with mineral composites. In terms of soil as the agricultural area, the
contamination might be derived from the use of pesticides. The ability of clay-biochar
composites has ability to adsorb the contaminants and reduce their quantity in the
soil. This might be due to the high porosity of the composites that provide more
sites for adsorption. The mechanism for pesticide residue removal by clay-biochar
composites in soil contaminated with pesticides is complex due to the diversity of the
soil matrix. There were several mechanisms for the adsorption of pesticide residue
onto various kinds of clay-biochar composites. The adsorption mechanisms generally
are pore-filling, hydrogen bonding, electrostatic interaction, and hydrophobic inter-
actions. The specific process of various pesticides are also different and associated
with the properties of clay-biochar composites.
Rallet et al. studied glyphosate as a pesticide and biochar composite for its removal
[33]. The study investigated the composites of clay-biochar that were prepared from
clay mineral and local cottonwood, which were utilized for glyphosate elimination
by adsorption through batch experiments. The composites of biochar, clay, and clay-
biochar were identified using Fourier transform infrared, X-ray diffraction, scanning
electron microscope, and thermal analysis. The XRD pattern of clay-biochar compos-
ites exhibited the primary reflection at 8.77, which did not appear in both clay and
biochar. Silicon dioxide was also detected in clay–biochar composites as a natural
mineral in clay. The differences in results displayed that the production method of
composites used embedded biochar in the clay matrix. The comparison to the results
of the native materials, the composites showed particular peaks that attributed to
Si–O–Si, Si–O–Al, Al–OH–Al, C = O and C = C. These bands from the func-
tional groups were identified in clay and biochar but with low values of intensities.
Thermal analysis showed that during thermogravimetric decomposition, the weight
loss was composed of four stages for both raw materials. The pure clay and cotton-
wood displayed a loss in weight of about 31% and 71% up to 1000 °C, respectively.
From the SEM images, the surface of the clay was smooth with the formation of
concave surfaces. Biochar possesses a rough surface with a porous structure. While
for composites, clay particles were distributed on the surface of biochar. The clay
did not fully cover the surface. The EDX spectra of the composites also revealed
evidence of the clay appearance on the biochar.
The pH, adsorbent dose, contact time, and initial concentration influenced the
adsorption concentration. It demonstrated that the composites had better intake ability
compared to clay and biochar. The glyphosate intake to the composites was higher
7 Clay-Biochar Composites for the Agriculture Industry 161

Fig. 4 The effect of a contact time and b initial concentration on glyphosate adsorption by various
adsorbents. Reprinted with permission from [33]. Copyright (2022) Elsevier Ltd

than clay and biochar. This might be due to the high content of clay’s mineral and
electrical conductivity. Besides, there is a better capacity for ionic exchange from the
biochar. The adsorption process could occur due to the surface complex’s formation
from phosphonate groups and amine coordination to the surfaces of adsorbents. In
adsorption kinetics, glyphosate carried out the pseudo-second-order model in line
with the highest R2 values of 0.999 for the clay-biochar composites. At the same time,
the equilibrium adsorption was fitted to the Langmuir and Temkin model with the
highest R2 values for the clay-biochar than for clay and biochar. As can be seen from
Fig. 4, the composites had their best adsorption value of glyphosate compared to clay
and biochar. Three adsorption isotherm models were matched to the experimental
data.

5.3 Clay-Biochar Composite Application as Fertilizer

Odukkathil et al. prepared clay-biochar materials for the intake of pesticides. The
composites were processed by blending and pyrolyzing clay with part of the plant,
then continued to clay-biochar composites with improved porosity and adsorption
ability [23]. The clay-biochar composites were proven to be an effective adsorbent
for pesticides and a part of the biobed. Due to the limitations of a biobed, an effi-
cient adsorbent was needed. Biobed is one purification system with potential water
treatment systems for agriculture drainage. This system’s active part is composed
of a biomix that consists of three parts. Each part played a significant role and
crucial section in pesticide degradation. In this study, lignocellulosic, as the signifi-
cant component in biobed, was replaced with clay and biochar, then proven a practical
component for biobed. These composites were utilized in cypermethrin adsorption
and gave alternative methods for biochar utilization in agricultural soil.
162 N. Aryana et al.

Among all composites, the composites of clay and Acacia concinna, with 7.6 and
0.4 ratios had better structural stability and were applied as the biomix in a biobed.
Approximately 20% of clay-biochar composites were added with bacteria-forming
biosurfactant, then blended with sandy soil in a biobed system with a laboratory
scale. On the initial day, the chemical oxygen demand (COD) reduction was about
87% and elevated to 95% (Fig. 5a). The range of removal efficiency was about 90–
95%. The increasing contact time increased the intake of pesticides on the biobed
consisting of biomix. The high COD discharge in the biobed composed of clay-
biochar materials represented the capability of the composites inside the biobed.
Besides, the cypermethrin biodegradation with clay-biochar composites in soil was
monitored. The observation showed that composites of clay-biochar modified with
bacteria-forming biosurfactant were a valuable biomix in the biobed structure due to
its removal of 98% (Fig. 5b). Therefore, the utilization of biosurfactants that produced
bacterial consortium supported clay-biochar composites became a potential solution
for the limitations of soil bioremediation due to hydrophobic organic contaminants.
Pollution in the nutrient has a distinct effect on the climate and human well-being.
Nutrients, like phosphate and ammonium, spread all over the surroundings due to
broadenuse in agricultural areas and extraction from several resources. The nutrient-
maintaining capacity of the soil can be enhanced by the clay-biochar composites. The
investigation from Medha et al. aimed to establish bentonite-biochar composites and
use them to repair the soil nutrient due to the percolation of ammonium and phosphate
ions [52]. The bentonite-biochar composites were prepared from native rice straw
and commercial bentonite clay. The pyrolysis temperature of 400 and 600 °C was
used in the production of clay-biochar composite by using the solvothermal method.
The composites were characterized for their physicochemical properties. Besides,
the composites were also investigated for the adsorptive removal of phosphate and
ammonium ions in the batch system of adsorption and leaching processes within the
column. The composites with pyrolytic temperatures of 600 °C showed adsorption
capacity with a maximum value of 33.77 and 64.23 mg/g for the ammonium and
phosphate ions adsorption, respectively. At the same time, the pyrolytic temperatures
of 400 °C showed better sorption attraction for ammonium ions in the soil. This
is due to a low surface of negative charge and plenty of polar functional groups.
The integration of bentonite to biochar as the soil composites showed a significant
reduction in the leaching of phosphate and ammonium ions. Therefore, this improved
soil fertility due to the availability of nutrient content. Furthermore, this treatment
might reduce the chances of a nutrient contaminant in body water.
Liu et al. investigated the composites that consist of urea-loaded biochar with
bentonite and polyvinyl alcohol as the nutrients’ controlled release [53]. The
microscopy images showed urea and bentonite filling in the biochar’s inside pores.
The characterization showed the interactions among urea, bentonite and biochar,
which support controlling the water diffusion and bentonite perforation to support
nutrient detainment. The obtained results from controlled-release properties showed
that the high percentage of bentonite, biochar, and polyvinyl alcohol greatly enhanced
the release durability of composites. However, the excessive amount of them reduced
7 Clay-Biochar Composites for the Agriculture Industry

Fig. 5 The removal of a COD and b cypermethrin of the biobed. Reprinted with permission from [23]. Copyright (2020) Elsevier Ltd
163
164 N. Aryana et al.

Fig. 6 The mechanism of


controlled release from
composites in soil. Reprinted
with permission from [53].
Copyright (2019) Springer
Nature

the nutrient level and increased the cost. Therefore, the content of ingredients should
be appropriately controlled.
The controlled-release mechanism consisted of several stages (Fig. 6). The absorp-
tion of water by the granules led the bentonite to swell. At the same time, osmotic
pressure was developed, and irrigation water entered bentonite and the tunnel case
of biochar to thicken the solid fertilizer, then continued by the dissolution of nutri-
ents partially. Most of irrigation waters were absorbed by biochar, and some parts
of the nutrient solution were kept in the biochar pores. In these steps, the bentonite
acted as a controller in which the swelling and shrinkage of bentonite regulated
the diffusion and perforation of water and nutrient solution. In the last stage, the
complex of C-NH-C and CH2 -CO–NH from biochar, urea and bentonite signifi-
cantly declined with as low release. This might be due to van der Waals bonding
and π-π interactions dissipated on the change in ion exchange, pH and microor-
ganism. The degradation of the C-NH-C and CH2 -CO–NH complex can maintain
higher temperatures with higher moisture content. The cumulative release amounts
of nitrogen within 28 days was 61.3% when nurtured in water and up to 98 days
was 54.6% when nurtured in soil. This showed suitable controlled-release properties
from the composites. The composites possessed the improvement of nutrient release
characteristics and controlled the nutrient release that was kept in the biochar.

6 Conclusion

This chapter summarizes the production methods of clay-biochar composites, as


well as their utilization in agriculture field, such as in soil remediation, particu-
larly in the removal of the contaminant in agricultural wastewater, and as fertil-
izer. There are three common methods that have been developed for the production
7 Clay-Biochar Composites for the Agriculture Industry 165

of clay-biochar composites, namely pyrolysis method, slurry method, and calci-


nation method. Most of the application of clay-biochar composites in agriculture
showed that the pore structural properties play important roles. The addition of unpy-
rolyzed biomass increases the composite’s porosity, while biochar reduces specific
heat capacity. Future study may explore the use of multiple materials to get a novel
clay-biochar composite with better properties. Furthermore, study with utilizing acid
in the synthesis method of clay-biochar composite may also be potential in future
research.

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Chapter 8
New Trends in Biochar–Mineral
Composites

Javier Sartuqui, Noelia L. D’Elía, and Paula V. Messina

1 Introduction

Human activities are affecting the environment in a harmful way. The continuous
industrial growth and development in almost every aspect of human activities produce
a high amount of waste that is commonly discharged into natural environments threat-
ening in several ways human health and life quality. This everyday practice could
cause problems that include productivity decline, pest problems, malnutrition, and
heavy metal pollution. In a very frequent number of cases, the available possible
solutions for pollutant issues are too expensive. As a consequence, it is a prime
necessity to find less expensive alternatives. In this sense, the production of biochar
raises as an appropriate and economic path to start solving some of these problems
[1–3]. However, no singular remediation technique can effectively remove or immo-
bilize organic and inorganic contaminants in the environment. The scientific evidence
has demonstrated that a merge of minerals and biochar efficiently removes contam-
inants when compared with pristine ones [4]. The enhanced adsorption could be
attributed to their synergic properties. On the one hand, biochars have high pH,
cation exchange capacity, well-developed porous structure, large surface area, high
carbon content, and enriched surface functional groups [5]. On the other hand, natural
minerals are abundant in nature, inexpensive, sustainable, and could improve the
adsorption properties of biochars and provide new ones [6].
Moreover, as a pyrolysis product of different biomass waste sources, biochar
is gaining importance, thanks to, among other things, the large number of mineral
elements that its raw materials can contain. Besides, it is also frequent to find organic

Javier Sartuqui and Noelia L. D’Elía contributed equally to this work

J. Sartuqui · N. L. D’Elía · P. V. Messina (B)


Department of Chemistry, Universidad Nacional del Sur, INQUISUR-CONICET, B8000CPB,
Bahía Blanca, Argentina
e-mail: pmessina@uns.edu.ar

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2023 169
A. K. Nadda (ed.), Biochar and its Composites, Materials Horizons:
From Nature to Nanomaterials, https://doi.org/10.1007/978-981-99-5239-7_8
170 J. Sartuqui et al.

substances within raw materials such as acetone, toluene, propionaldehyde, ethy-


lene, propylene, methyl acetate, and benzene [7, 8]. This particular aspect is worth
mentioning as those compounds may give the final obtained biochar special abili-
ties and properties regarding its structural or adsorbent characteristics which can be
improved through different processes [9].
In the first section of the chapter, we will discuss the particularities and importance
of nanotechnology to obtain biochars. The synthesis control in this part of the scale
allows controlling characteristics that could change and improve biochar’s proper-
ties. For instance, surface area increment would give higher pollutant adsorption
levels. After that, the main attention will be on the participation of microorganisms
in a synergistic way to improve or modify some of the already present properties
of biochar–minerals. Indirectly, the presence of different species of bacteria and
fungi showed significant differences in performances when, for example, dealing
with adsorption and posterior remotion of metals. Finally, we described relevant
publications about novel biochar–mineral composites applied to solve environmental
issues.

2 Nanoscale Influence in Composite Synthesis


and Properties

The bibliography indicates that, in the last years, biochar has improved its applica-
tion complexity by developing, for example, electrodes and catalysts [10]. Biochar is
known for being a highly recommended material for water pollution treatment, soil
amendment, and carbon sequestration [11–13]. Having vastly explored the proper-
ties of biochar on the macro scale, some members of the scientific community are
focusing on particle size reduction. By controlling the micro/nanoscale of the devel-
oped materials, we could improve properties such as mobility, porosity, and specific
surface area [14].
In this context, Kumar et al. utilized ball milling to reduce particle size and
obtained a high-performance absorbent material [15]. Supporting this proposal,
Amusat et al. treated wastewater with nanomaterials obtained through the ball milling
method. According to them, this method could also produce surface modification
processes on the material [16]. In another study, with another technique, Ramanayaka
et al. developed materials for electrochemistry and health. They utilized microwave
pyrolysis and thermos-flash exfoliation, considering the economical aspect of the
whole process [17]. Some researchers are mentioning the “biochar effect”, refer-
ring to the wide range of applications that this kind of material already has and the
opportunity to solve different environmental issues [18].
It is inevitable to differentiate biochar from fly ash and soot. Even though they
might look comparable and have similar origins (it may also be biomass), these
particles are products of a combustion process. Moreover, fly ash is usually composed
of metallic species or minerals (Al2 O3 and SiO2 ), though the composition can vary
8 New Trends in Biochar–Mineral Composites 171

depending on the feedstock used, while biochar and soot have high amounts of carbon
[19]. Both the biochar produced at de macro- or nano-scale, is prepared through a
carbonization process of biomass in a low-oxygen environment. In consequence, the
difference in size is considered the main one. In general terms, the whole particle
scientific community refers to size <100 nm when talking about the nanoscale. In
this case, some authors consider nano-biochar, the materials up to 500 or 600 nm.
This fact is not only a matter of definition; it raises difficulties when comparing the
different materials as the size has an intimate relationship with properties such as
specific surface area [20], 21.
The most frequent methods to prepare nano-biochars are several [22]. In general,
all those protocols share some of the stages, giving the possibility to adapt the
researcher´s needs to the synthesis. We can describe three main steps as follows:
transformation into bulk biochar, size reduction, and fractionation.
• Bulk-biochar preparation: To obtain nano-biochar, the first step is to put the
organic material through a thermochemical carbonization treatment (200–700 °C)
to which the organic material has to be put through. Classical and traditional
processes such as hydrothermal treatment (bio-crude production) and fast pyrol-
ysis (oil production) can provide biochar but with a very fluctuating yield [23].
The yield is also affected by the severity of the treatment selected. The general rule
indicates that with an increment in the mentioned factor, the elemental proportion
is affected by a decrease in the yield. It is worth mentioning that as nano-biochar
may accomplish more complex tasks or applications than bulk biochar, and consid-
ering the costs of its synthesis, there might even be an economic increment for
the companies which dare to develop this field [22].
• Size reduction: Some researchers reported that nano-biochar is present in every
biochar bulk produced but in a small proportion. Consequently, the goal is to follow
the bulk formation process with a size reduction technique [21]. The grinding and
ball milling processes are among the most utilized to achieve this [15, 24, 25],
being the second recommended one for its larger material production. In this sense,
variables such as milling time, presence or absence of liquid, and diameter of balls
must be considered in the protocol development [26]. One of the obstacles in ball
milling is particle agglomeration. Naghdi et al. suggested a freeze treatment of
biochar to solve this issue. They achieved a decrease in size by storing the samples
at −80 °C before the ball milling process [27]. An alternative process to reduce
the size of the particles is to carry a wet milling utilizing a solvent or water. As an
example, Ramanayaka et al. chose ethanol to develop the ball milling and obtained
the desired less agglomerated sample [17].
• Fractionation: In general terms, filtration and sedimentation are the two main tech-
niques to separate mixtures of particles of different sizes. Sedimentation, which
may be static or dynamic, uses the natural propensity to deposition of particles and
may vary depending on the characteristics and properties of the system object of
work. On the other hand, membrane utilization to filter the dispersion of particles
is a more expensive method but allows to control the separation of the different
sizes. The methodology selection often depends on the accuracy grade needed in
172 J. Sartuqui et al.

the separation process. Sometimes, and if possible, both methods are combined
[25, 28, 29].

3 Biotechnology and Interaction of Composites with Living


Organisms

The attention on biochar has been diverging in recent decades. First, the main focus
was on its ability to stimulate microbial activity. Nowadays, with an increasing
struggle against pollution, heavy metal immobilization and removal have gained
importance. Batool et al. discussed the differences between the performances of
biochar and biochar–mineral in matters of nutrient enrichment and heavy metal pollu-
tion remedy [4]. When comparing the metal immobilization activity, even though
they showed similar mechanisms, the differences resided in the raw material and the
metal involved. In the case of living organism’s implication, high pH fluctuations,
enzymatic action (bacteria), mycelium sorption, metal sorption (fungi), and iron
exchange, chelation, and surface sorption (algae) were important factors to consider
[4].
As is already well known, bacteria may have an important role in the remediation
of the environment. They can help in the struggle against heavy metal contamination
through their natural metabolic activities. Hamid et al. reported the As(V) to As(III)
conversion, a less harmful form of arsenic [30]. The genus Geobacter is known
for being able to induce As(III) reduction and Fe(II) quantity in the soil environ-
ment while some fungi hyphae have also been reported as organisms able to favor
plant growth under circumstances of heavy metal contamination [31]. According
to Horak et al., the performance of each pair of microorganism–biochar/mineral–
biochar depends on the characteristics of the biochar surface, as they directly influ-
ence the cell’s easiness to attach and colonize [32]. Moreover, biochars enriched with
different minerals might increase soil porosity and functional groups available which
leads, in the first place, to better microbial growth and, later, to a better remediation
performance [33].
The sources of contamination as a consequence of the activities of human life
are several. In this particular section, we will focus on the participation of living
organisms in the struggle against chromium contamination. The presence of harmful
forms of this metal may be a product of wood treatment, dye industries, and leather
tanning, among others [34]. Specifically, we can find Cr(III), a form characterized
by poor solubility with low toxicity, and Cr(IV), a form that is commonly known for
being a carcinogenic agent with high toxicity. The scientific community is making
efforts to find ways to solve this problem. In this sense, one of the possibilities
implies a reduction of the Cr(IV) to Cr(III) [35, 36]. This treatment is not purely
a scientific invention, as there are different reducing agents present in natural (soil
and aquifer) environments. Richard and Bourg, 1991, have long reported the role
of Fe(II), an iron form able to promote, in determined circumstances, the reductive
Cr(IV) transformation [37, 38].
8 New Trends in Biochar–Mineral Composites 173

According to the bibliography, the activity of the microbial community in the


environment consists of iron oxide reduction, such as goethite, and iron-containing
clay minerals, such as illite or montmorillonite [39]. Briefly, through a several-
step process, a secondary mineral formed is achieved, which has a surface with
higher reactivity and, consequently, an improved Cr(IV) reduction performance.
This process leads to the precipitation of Fe–Cr compounds known for their insol-
ubility and amorphism [40, 41]. The performance of the formed co-precipitates in
chromium immobilization depends on several factors: the structure, the chemical
composition, and some factors of the surrounding media such as pH, Fe–Cr ratio,
and ionic strength [42].
The presence and utilization of biochars may be related to the already existing
remediation methods. According to the bibliography, the vegetal carbon can directly
reduce Cr(IV) adsorbed on its surface or indirectly through microbial activity activa-
tion. The ability to induce the activation of the microbial community is not the only
positive aspect when talking about adsorbing contaminants. Biochars are known for
their high degree of porosity, large surface area, and the number of functional groups
which can adhere to them [43, 44]. The previously mentioned characteristics added
to the fact that it can act as an electron shuttle promoting the reduction of iron oxides
and generating mineral-biochar compounds, make biochar an important alternative
in the fight for remediation [45, 46]. It is also worth mentioning that the differences
among biochar, mineral, and biochar–mineral regarding their behavior against pollu-
tants are a current object of study. Sun et al., Tan et al., and Li et al. have found a
synergistic effect when comparing the iron-modified biochar against the individual
components [47–49].
Liu et al. worked on the possibility to solve this particular problem by devel-
oping different materials. They obtained two composites based on iron–biochar–
mineral from two distinct biological reduction reactions. They understood the natural
Cr(IV) remotion mechanism, evaluated the Cr(IV)-composite reaction, and studied
the Fe–Cu products. They utilized wheat straw, the main waste in China’s agricul-
tural activities, as the raw material to achieve the first step of biochar. To prepare
it, they followed their previously published protocol [50] which consists of an N2
atmosphere to carry on with the pyrolysis. Before storage, they sieved and washed
the particles with an HCl/HF solution to eliminate possible impurities. Separately,
they synthesized magnetite, goethite, and ferrihydrite through a known method. The
production of iron–biochar–mineral composites occurs in natural environments. Liu
et al. attempted to mimic this natural process with Shewanella oneidensis MR-1,
an iron-reducing strain [46, 51, 52]. Besides the biochar, the ferrihydrite and the
goethite, anthraquinone-2,6-disulfonate, and sodium lactate were sources of natural
humic substances and electron donors, respectively. Finally, they obtained different
reduction products, depending on the iron mineral utilized in the synthesis [51]. They
investigated the distinct Fe(II) species reactivities, the pH influence, and the ionic
strength through reactions between Cr(IV) and each of the composites, two different
buffer systems, and several concentrations of NaCl, respectively.
In their work, Liu et al. compared the different ways to reduce Fe(II). On the
one hand, the biochar bio-reduction and the biochar ability to directly reduce the
174 J. Sartuqui et al.

iron minerals resulted, in agreement with the bibliography, in negligible amounts


of extractable Fe(II) [46, 50, 52]. On the other hand, they achieved a significant
improvement, approximately 21% in 1 day of ferrihydrite and 132% in 6 days of
goethite, in the amount of extractable Fe(III) when the biochar was added to the
systems previously developed. The bibliography proposes that biochar plays a role
in the electron transfer from bacteria to the Fe(III) minerals. Results indicated that
biochar π–π networks and their surface redox-active places are responsible for the
transference [46, 50, 52].
After the crystallographic study of the resulting minerals, an inevitable hetero-
aggregation was found in natural environments. In the first place, considering the
general close to neutral conditions, negatively charged biochar suffers an electro-
static attraction to the positively charged Fe-minerals [21]. After that, following the
formation, adsorption and complexation processes take place. Through them, the
Fe(II) released from the iron reduction precipitates onto biochars [46]. Iron minerals
and biochars showed very distinct morphologies and the presence of both Fe and Cr
on their surface. Both elements’ distribution seemed closely related, pointing to the
potential possibility of a co-precipitate [51].

3.1 Interaction of Biochar with Rhizosphere in Natural


Environments

It is easy to observe the current tendency of the research volume regarding reme-
diation with biochar. It has been growing and maturing nonstop and one important
feature, as mentioned before, is the size of the materials produced. The reports on
the nano-sized biochars emphasize the fact that there are two main advantages: the
hydrodynamic dispersity and the large surface area [53]. Even though the size of the
material is an important aspect to consider, when referring to environmental reme-
diation we cannot avoid talking about the interactions with the environment. In this
sense, the rhizosphere, the surroundings of any plant roots, may have a key role in
the performance of the remediation tool. In soils inhabited by plants, their roots and
the processes involved around them are factors worth considering. Despite it being
a thin stratum rounding the roots, it is a very dynamic and complex zone with the
potential to take large gradients of materials and soil components in and out of the
plants [53].
The first approach in the remediation of soil is the application of the material.
In this first step, the material will suffer agglomeration and aggregation (homo and
hetero), processes that affect the performance and the final result. The agglomeration
of the material is the process through which the basic units join together achieving
a larger functional unit. Besides, a step of aggregation may occur, in which the
early association acquires other different properties, i.e. the development of a crystal
(strengthening the structure), and depends on the intrinsic characteristic of the biochar
precursor [17].
8 New Trends in Biochar–Mineral Composites 175

Even though homo- and hetero-aggregation are processes frequently found in the
soil environment, the second is the more relevant one regarding the whole soil system.
The interaction between soil minerals and nano-biochars is becoming a specific
subject of the soil remediation research field. Liu et al. reported that different Fe
oxides and multivalent cations on soil clay may trigger the hetero-aggregation and
immobilization with the negatively charged biochars through electrostatic interaction
[21]. This role was also conferred to Al by Mai et al. [54].
Among the infinite physiological processes present in plants, there is one particu-
larly interesting for us. Plant roots are continuously exuding several substances, inor-
ganic and organic, to the immediate environment. They regulate the surrounding’s
physicochemical properties affecting the soil components’ availability [55]. This
process is another variable when analyzing the biochar behavior in the soil ecosystem.
The effects observed on biochar might be lowering (or rupture) hetero-aggregation,
and erosion of the biochar surface [56, 57]. The disaggregation process, caused by
organic acids, resulted to be a positive effect as the specific available surface of the
biochar increases, augmenting its ability to immobilize heavy metals.
A similar effect was reported in the interaction of some microorganisms with
biochar. The secondary metabolites produced by microorganisms also affect biochar
behavior and availability [58]. Some authors affirm that microbial organic exudates
could cover the surface of the biochar interfering with its ability to fix heavy metals
[59]. Dimkpa et al. reported that the effect is similar to the one produced with the
roots. This means that microorganisms’ secondary metabolites, such as exopolysac-
charides, may lead to the disaggregation of biochar hetero-aggregates generating
a larger available surface. Moreover, the authors are working on an alternative,
attempting to achieve a nanoparticle surface capping with secondary metabolites
that would stabilize nanoparticles preventing their aggregation and erosion [14].
Finally, and developing a sort of circular behavior of the whole system, nano-
biochars can stimulate the growth of the soil-rhizosphere microbial community.
Along the bibliography, there are several alternative mechanisms that might explain
this fact: (1) an indirect reduction by biochar of substances that inhibit microbial
growth, (2) physical improvement of the soil, due to the available microsites in the
structure of the biochar, able to inhabit, and (3) the biochar as a nutritional source
[60–63].

4 Environmental Applications of Biochar–Mineral


Composites

As mentioned, efforts are made to take advantage of the raw material composition.
One of the alternatives consisted of combining specific biochars with metal ions or
minerals. In this sense, particular characteristics could be achieved such as a greater
ratio of cation exchange, improved buffer performance, and controlled mineral libera-
tion [64]. Recent findings have led researchers to focus on the enrichment of biochars
176 J. Sartuqui et al.

with mineral compounds as they seem to be one of the best cost-effective treat-
ments for heavy metals pollution and emerging organic contaminants [65–69]. In
this section, we will discuss novel publications about biochar minerals developed
to solve current environmental issues related to soil, and water remediation will be
discussed.

4.1 Inorganic Substance Remotion

Inorganic contaminants such as heavy metals cannot be degraded like other contam-
inants. Therefore, their removal is a matter of concern to solve important environ-
mental issues caused by rapid industrialization. Heavy metal persistent accumulation
in aquatic environments and soil can be transferred to plants, animals, and humans
through direct uptake or along the food chain [5]. These inorganic contaminants
are considered extremely dangerous, even at low concentrations, for human beings
due to their potential multiple organ damage induction. Moreover, the International
Agency for Research on Cancer [31] and the United States Environmental Protection
Agency classify them as potent human carcinogens [70].
The most popular technique applied for heavy metal remotion is adsorption
throughout in situ immobilization technology due to the low costs of applications.
On the other hand, clays and biochars are the most common adsorbents investigated
because most of them are common, economical, and can be easily obtained [5, 18].
Inorganic contaminants regularly tested for the study of adsorption on clay
biochars composites are Cr(VI), Cd, Cu(II), Pb(II), Ni(II), and As, among others [5,
71, 72]. In particular, hexavalent chromium ions Cr(VI), the most common oxida-
tion state of Chromium, have received continuous attention due to high solubility,
bioavailability, and mobility in biological systems, and their presence in aquatic
environments is due to the rapid growth of textile, electroplating, and pigment and
paints industries [72]. It is worth mentioning that hexavalent chromium commonly
exists in the environment as chromate oxyanion (CrO4 ) and has a similar structure
to sulfate oxyanion (SO4 ). Therefore, CrO4 utilizes sulfate transporters located on
the cell membranes to enter the cytoplasm [73].
Wang et al. carried out a study about the mechanisms of how different biochar–clay
composites decrease the migration of heavy metals. They compared soil properties
that affect Brassica chinensis growth. These studies suggested that biochar–clay
composites significantly reduce heavy metals in contaminated soil and, therefore,
the accumulation of heavy metals in B. chinensis decreased. Among the composites
studied, biochar–attapulgite significantly enhanced heavy metal immobilization and
had the highest performance in low concentrations [5]. Attapulgite was also studied
with a fibrous morphology, thus a large specific surface area, by Qhubu et al. They
reported that this biochar–attapulgite composite moderates cation exchange capacity,
being a suitable material for the caption of low concentrations of Cr(VI) in water
from industrial effluents [72].
8 New Trends in Biochar–Mineral Composites 177

Zhou et al. and Liu et al. studied iron(II) containing mineral–biochars composites
derived from clays. They investigated how the initial surface loading of iron-bearing
clay minerals affects the adsorption–reduction of Cr(VI) [51, 74]. Zhou et al. used an
iron–clay biochar composite prepared by infiltrating the biomass of Populus nigra
with bentonite clay and iron salts for Cr(VI) removal [74]. Moreover, Liu et al.
developed a biologically formed iron(II)-containing composite, obtained by micro-
bial reduction. Notably, both of them concluded that the composite improves Cr(VI)
adsorption–reduction efficiency, thus it is expected to be applied for contaminant
remotion in water [51, 74].
Another dangerous heavy metal studied is lead Pb(II), which not only is involved
in many human nervous system disorders, causing neurobehavioral and intelligence
deficits, but also affects the gastrointestinal tract, kidneys, and reproductive system
[75, 76]. Recent studies conducted by Liu et al. showed a new biochar composite
containing molybdenum trioxide (MoO3 ) that could effectively remove lead from
contaminated water [77].
Recently, the nuclear energy industry became a rapidly developed topic because of
its lower energy consumption and higher efficiency [78]. Unfortunately, it generates
large amounts of dangerous radionuclides such as Uranium. Therefore, the develop-
ment of new approaches for its remotion is imperative. As a contribution to solving
this environmental issue, Chen et al. developed a biochar supported by iron sulfide
(FeS) nanoparticles and chitosan. They take advantage of the reductive properties of
FeS nanoparticles added to the larger specific surface area of the nanoscale. More-
over, they have proven that chitosan improves the aggregation of the nanoparticles
and enhances their stability. This study suggests that these new biochar compos-
ites could be an attractive approach for uranium remotion due to their stability, low
replacement costs, and high Uranium uptake capacity [71].

4.2 Emerging Organic Substances Remotion

Antibiotics treat a wide range of microbial infections in humans and other organ-
isms. The human organism can only absorb around 30% to 90% of them, thus a
high amount is excreted into the environment and accumulated in water bodies,
wastewater, and agricultural effluents [79]. Residual antibiotics threaten human and
animal health; some of the consequences of their presence in the environment are the
generation of drug-resistant pathogens and biological growth inhibition [80]. There-
fore, increasing studies have focused on antibiotic remotion from water, adsorption,
oxidation, photocatalytic, and biodegradation being the most used methodologies
[81].
Among the most commonly consumed antibiotics worldwide are fluoroquinolones
due to their wide spectrum, and include ciprofloxacin, gemifloxacin, levofloxacin,
moxifloxacin, norfloxacin, and ofloxacin [82]. Recently, various approaches to
remove fluoroquinolones have been developed [83, 84]. That is the case of Liu
178 J. Sartuqui et al.

et al., which used ilmenite to improve biochar stability and ofloxacin chemisorption
capacity [84].
Continuing with the subject, antibacterial and antifungal agents, widely used
in personal care products, have similar environmental and health consequences as
antibiotics. Due to their improper discharge, they have been identified in water world-
wide. Generally, these organic residues have a low biodegradability and, thus, signif-
icant environmental toxicity [85]. Wei et al. have successfully obtained a bismuth
vanadate (BiVO4) composite loaded with nitrogen-doped biochar that could be
used for the photocatalytic detoxification of Triclosan, a common broad-spectrum
microbicide [86].
Biochar–mineral is also studied for the remotion of an emerging pollutant, the
antibiotic resistance genes (ARGs). This genetic material is produced by bacteria
after antibiotic exposure and is mainly found in wastewater treatment plant effluents.
ARGs are dangerous because they can be spread through vertical gene transmission,
thus, promoting the dissemination of antibiotic resistance in bacterial communities.
A recent study demonstrated that cerium-modified biochars have good adsorption
ability for ARGs. In this case, cerium was used as a promotor of free radicals’
formation, which is involved in the gene’s degradation by an oxidation process [87].
Two of the major challenges to overcome during organic residue capture are the
difficulty of entirely separating them from the aquatic environment, and the possi-
bility to reuse the adsorbent. In a study directed by Fu et al., they proposed the utiliza-
tion of a magnetic biochar modified by a quaternary phosphonium salt to control or
even eliminate ARGs from aquatic environments. This novel biochar mechanism
is based on the fact that gens adsorbed onto the material could be magnetically
separated due to its high saturation magnetization intensity [88]. Using a different
methodology, Hu et al. fabricated a renewable tri-metallic spinel-decorated biochar
adsorbent with a self-cleaning ability through a Fenton-like catalysis. This original
approach could be potentially used for organic pollutant treatment in pharmaceutical
wastewater [89].

5 Conclusion

We discussed the relationship between biochar, minerals, and other natural organ-
isms or circumstances. The application possibilities of biochar are wide, and it gets
wider and with more complex functions if we focus on the nanoscale. The inter-
action among the threesome biochar–mineral–microorganism is a relationship in
which the performances, regarding the remediation role of each component, seem
to improve in a synergic way. We compared pristine biochars with mineral-enriched
ones. Both combined with microorganisms’ activity aiming to solve the problem of
heavy metal pollution both in soil and water. Up to now, there have been promising
results indicating that the possibility to remove heavy metals depends on the metal,
the microorganism (if used), the mineral and the origin, and the final characteristics
of the biochar. When analyzing the whole ecosystem in a natural environment, the
8 New Trends in Biochar–Mineral Composites 179

situation gets more complex. We can observe this in the rhizosphere, the surrounding
space of the roots under their direct influence. Variables such as raw materials, the
synthesis treatment severity, the pollutants to adsorb, and the soil properties influ-
ence the grade of remediation achieved by biochar. Later, we have to consider the
interaction with the “living world”, the interaction with the roots and its exudates,
and the interaction with microorganisms and their products.
Throughout this chapter, we discussed only a portion of the efforts that the scien-
tific community made to find alternatives to solve current environmental issues. The
results are generally promising and improved when combining biochar and minerals.
However, much remains to be done to develop more general methods and materials
to help solve multiple problems simultaneously to save resources, effort, and time.

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Chapter 9
Magnetic Composites of Biochar and Its
Applications

Abhinay Thakur and Ashish Kumar

1 Introduction

There is a tremendous degree of concern regarding environmental contamination


on a worldwide basis, particularly owing to the rapid pace of urbanization and the
rising usage of chemicals. The amount of contaminants released to the ecosystem,
including heavy metals, dyes, and other organics, poses a serious risk to human
health as well as to agriculture, fisheries, and food hygiene [1–3]. For example,
even at modest concentrations, toxic heavy metals accumulate in the human body
and could result in diarrhoea, hypertension, central nervous malfunction, and red
blood cell degeneration. Dyes from factory effluent could harm the immunological
and fertility functions in humans and induce aneuploidy and gene abnormalities in
living organisms. Excessive consumption of untreated wastewater might potentially
cause chronic disorders in humans and livestock and increase microbial resistance
[4–6]. Thus, it has become important to build solutions that are practical for reducing
ecological contamination. Biochar has been widely used by the scientific commu-
nity for the remediation and management of such pollutants. A type of low-density
scorched carbon substance known as “biochar” is generated when biomass is ther-
mally decomposed in the existence or lack of oxygen. The permeable configura-
tion, substantial surface region, abundance of mineral constituents, and interfacial
functional units constitute biochar. Several different raw components can be used
to produce biochar, including cotton straws, giant reed, peanut husks , and water

A. Thakur
Department of Chemistry, Faculty of Technology and Science, Lovely Professional University,
Phagwara, Punjab 144411, India
A. Kumar (B)
NCE, Department of Science and Technology, Government of Bihar, Bihar Engineering
University, Bihar 803108, India
e-mail: thakurabhinay96@gmail.com

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2023 185
A. K. Nadda (ed.), Biochar and its Composites, Materials Horizons:
From Nature to Nanomaterials, https://doi.org/10.1007/978-981-99-5239-7_9
186 A. Thakur and A. Kumar

hyacinths. Biochar has several uses, but it is most commonly employed as an adsor-
bent to eliminate emerging pollutants (EPs) such as organic dyes, water pollutants,
and heavy metal ions including Cu, Cd, Pb, Zn, and As [7–9]. Numerous initia-
tives have indeed been implemented to optimize the sorption ability of biochar. The
segregation and regeneration of biochar upon adsorbing EPs, though, continues to be
among the key issues to be resolved owing to the minute particulate dimensions and
reduced volume [10]. By using both chemical co-precipitation or pyrolysis activa-
tion, magnetic media, Fe3 O4 /Fe2 O3 , and biochar are combined to generate magnetic
biochar (MB). Utilizing exogenous magnetism, MB may be readily extracted and
exhibits good efficacy in adsorbing contaminants from a variety of sources, including
wastewater. As a result, it has been used extensively as an adsorbent to remove various
EPs, and contaminated water, and dislodge particulates from water. To increase the
absorption of Cr(VI), Cui et al. [11] created pyrolyzed ferric-loaded magnetic burley
tobacco stem biochar (MBTS). According to the findings, the adsorption capability
of MBTS, which was 14.2 times greater than those of bare burley tobacco stem
biochar (3.84 mg/g), reached 54.92 mg for Cr(VI)/g. The results led to the develop-
ment of a three-phase procedure for the absorption of Cr(VI) by MBTS: (1) Cr(VI)
swapped using hydroxyl sites on MBTS, (2) Cr(VI) reduced to Cr(III) by oxygen-
comprising units, and (3) created Cr(III) chelated with amino units upon MBTS.
Additional analysis of the FTIR spectrum showed that the C = C and C-N, C-
H groups were crucial in the elimination of Cr(VI). The Cr(VI) sorption capability
increased via processing, attaining a 15-time greater capability than the bare tobacco
stem biochar in this research. Consequently, chromium-contaminated wastewater
might be treated using biochar produced from tobacco stems that have been changed
by Fe3 O4 magnetic particulates, accomplishing the goal of waste management and
proving more cost-effective (Fig. 1). This idea was in accord with the regenerative
economy’s notion of treating potentially metal-polluted wastewater.
Additionally, for removing the tetracycline and methylene blue from aqueous
media, Chen et al. [12] used K2 FeO4 as a predecessor and intrinsic oxidant to create
MB utilizing a ball-milled oxidative magnetic transformation of pure biochar. In
contrast to OMB, which had a flawless texture attributable to K2 FeO4 oxidation, PB
had irregularities and a packed texture as seen in SEM scans (Fig. 2a–d). A specific
amount of apertures were also seen on the OMB, which increased the PV. According
to the EDS spectrum, PB’s surface contained O, C , and K (Fig. 2e–h). Over the
OMB’s substrate, sheet-like coatings of O, K, C , and Fe were applied (Fig. 2i–m).
According to the elemental assessment, OMB had a much greater absolute oxygen
concentration than PB (18.93/32.21 vs. 31.15/64.72). Furthermore, K was added to
the OMB interface. It is important to note that by having it emerge in the forms of
and −OK and −COOK, OMB was able to obtain an elevated cation interchange
capability.
Also noticeably increased from 0.7 to 71.2 m2 /g and through 0.001–0.034 cm3 /
g, correspondingly, were particular surface regions and porous density. The MB
demonstrated that its TC and MB adsorption capabilities greatly outperformed those
of the pure biochar, measuring 58.34 and 133.76 mg/g, correspondingly. Oxygen-
comprising compounds and Iron species controlled its adsorption.
9 Magnetic Composites of Biochar and Its Applications 187

Fig. 1 The engineering implications of MBTS and its technique for removing Cr(VI). Reprinted
with permission from Ref. [11] under CCBY 4.0

Fig. 2 SEM scans (a–d) and EDS spectrum (e–m) of biochars. Reprinted with permission from
Ref. [12] under CCBY 4.0
188 A. Thakur and A. Kumar

Similarly, in order to effectively eliminate malachite green (MG), Wang et al.


[13] created a unique calcium-functionalized magnetic biochar (Ca/MBC) using a
two-phase pyrolysis procedure. Calcium markedly altered the morphological char-
acteristics of the substance and enhanced its adsorption efficiency, particularly the
chemotactic attachment capacity with MG, which was affirmed via XPS, FTIR ,
and adsorption experimental studies. Iron-comprising oxides offered the prospect’s
structures magnetic characteristics, particularly the chemotactic attachment capacity
to MG. The maximal theoretical sorption capability was up to 12,187.57 mg/g and
was primarily driven by ligand interchange, electrostatic adsorption and hydrogen
binding. Following five adsorption–desorption phases, the sorption capability and
sorption frequency of MG persisted at 1424.2 mg/g and 71.21%, demonstrating the
benefits of Ca/MBC in extracting MG. Ca/MBC also retained a greater adsorption
capability at pH = 4–12. According to this research, biochar could be enhanced using
a green manufacturing method to create calcium-functionalized MB with a superior
ability to remove MG. The synthesized substance may effectively remediate soil in
addition to removing contaminants from water.
As we observed, the carbonization process, biomass feedstock, level of pyrolysis,
stimulation, and functionalization processes have a significant impact on the physic-
ochemical attributes and fundamental constitution of BC. Using a variety of modifi-
cation processes and organic feedstocks, BC shows fractal permeable morphologies,
wide surface functional units, and significant surface regions. Additionally, natu-
rally occurring functional compounds and minerals makes BC a potentially useful
component for designing hetero structures and composite [14–18]. Due to improved
mobility to active regions, superior π–π interactions, large active surface region,
and improved charge transmit, BC is easily incorporated into gas activation, metal
impregnation, ionic liquid grafting, and sulfonation operations, which has several
benefits in catalytic activities. Section 2 discusses the generation method of magnetic
composites of biochar by utilizing several methods as mentioned.

2 Synthetic Methods of Magnetic Composites of Biochar

2.1 Impregnation-Pyrolysis

By inoculating biomass using a media including transition metal compounds,


extracting the solvent, and then pyrolyzing the desiccated remnant in a muffle oven
containing an oxygen-limited or inert environment, MB can be produced. As a result,
magnetization and pyrolysis are accomplished in a single process, allowing the oper-
ational factors (such as pyrolysis duration, inert gas, and pyrolysis temperature)
to precisely regulate the physicochemical characteristics and sorption capability of
the MB. In an experiment, without using any chemicals, Zheng et al. [19] created
sludge-based MB (SMB) by pyrolyzing sewage sludge and dewatering iron muck.
Following the adsorption operation, SMB might be isolated from the media using
9 Magnetic Composites of Biochar and Its Applications 189

a magnet, indicating that the saturated magnetization was 25.60 emu g1 and that
the saturation material constituted Fe3 O4 . The batch adsorption investigation with
MB adsorption revealed that the sorption capabilities of SMB reached 47.44, 39.35,
and 25.85 mg/L, correspondingly, at several temperatures including 298, 308, and
318 K. The product’s maximal adsorption capability was attained following one
restoration using HCl acid at 296.52 mg/g. Furthermore, it became clear from the
well-expressed adsorption kinetics represented by the pseudo-second phase frame-
work that intra-particle dispersion was not the only rate-regulating phase in the
adsorbate. This research provides a suitable reference for the dewatering of iron
muck and the remediation of sewerage muck. The commodity might be utilized as a
cheap adsorbent for the elimination of MB.
Similarly, by integrating the two impregnations of the corncob biochar using
the pyrolysis of oxalate, Zhao et al. [20] were able to produce a number of the
magnetic CuFe2 O4 -loaded corncob biochar (CuFe2 O4 @CCBC) components. The
pure corncob biochar (CCBC) and CuFe2 O4 @CCBC were both evaluated utilizing
pHZPC assays. The findings showed that CuFe2 O4 was uniformly covered over the
substrate of CCBC and formed a face-cantered cubic crystallographic structure. Satu-
rated magnetization upon CCBC and CuFe2 O4 @CCBC were examined, and the as-
fabricated CuFe2 O4 @CCBC (5%) showed a specified surface region of 74.98 m2 g1 .
The results showed that the pHZPC was 7.0 and the pseudo-second was 5.75 emu g
1
. The Pb(II) sorption by CuFe2 O4 @CCBC or CCBC was well-fit by the adsorption
kinetics and thermodynamic behaviour of the Pb(II) Langmuir and kinetic models.
CuFe2 O4 @CCBC(5%) demonstrated good efficiency in regard to processing rate
and adsorption capability against Pb(II) at 30 °C and pH = 5.0, wherein the theoret-
ical rate constant (k2 ) and significantly greater than CCBC (4.38 × 10−3 gmg1 min1
and 15.66 mgg1 ), respectively. Optimum adsorption capacities (qm) were 7.68 ×
10−3 gmg1 min1 and 132.10 mgg1 , respectively. The adsorption activity of the compo-
nents was thermally activated and entropy-induced, according to thermodynamic
studies. The elimination process might be mostly attributable to the substitution of
Pb2+ for H+ in −COOH and Fe/Cu-OH to produce the interior surface complex,
according to the FTIR and XPS findings. Generally, the utilization of magnetic
CuFe2 O4 -loaded biochar as an environmentally benign adsorbent to remove heavy
metals in industrial wastewater has a significant perspective.

2.2 Co-precipitation

In order to generate magnetic biochar via co-precipitation, biochar must first be


dispersed into a media comprising transition metals. Next, NaOH or ammonium
hydroxide media must be added at a specific temperature, and the combination
must then be stirred for a duration of intervals at pH 9–11. The remaining mate-
rial is subsequently rinsed, and dehydrated, and the supernatant is then separated
to produce magnetic biochar. The magnetic media may be securely attached to the
biochar matrices using this process, which is more complex than the impregnation
190 A. Thakur and A. Kumar

technique but more controlled. For instance, Su et al. [21] utilized Luffa leaf (LL)
as a biomass source of carbon for biochars. A magnetized lignocellulose-derived
hierarchy permeable biochar was produced following activation, carbonization , and
chemical co-precipitation processes. Having 2565.4 m2 /g of effective surface region
and 1.4643 cm3 /g of overall porous volumes, the substrate was highly functionalized
with oxygen and carbon. To investigate the capability to eliminate organic contam-
inants, the antibiotic tetracycline hydrochloride (TH) and textile dyes rhodamine
B (RhB) were chosen as example. In the introduction of OH, Fe2+ and Fe3+ with
N2 shielding produce fragile colloidal molecules (Fe(OH)2 and Fe(OH)3 ). Figure 3
shows the development of magnetic hierarchical porous biochar. These alternative
compounds undergo a transient reaction with H+ to produce FeOOH and magnetic
NPs. Excessive OH continued to engage in the process as the pH of the media rises,
ultimately generating Fe3 O4 .
TH and RhBhad maximal adsorption capabilities that were greater than those of
the majority of carbon-based adsorbents at 1755.9 and 1701.7 mg/g, respectively.
The elimination efficacy was consistently above 70% following 10 rounds of usage,
demonstrating excellent durability. This study offered an innovative viewpoint on
the removal of organic toxins from water efficaciously by demonstrating the practi-
cability of utilizing lignocellulose LL as a carbon source to generate biochar and by

Fig. 3 Illustration of the production of magnetic hierarchical permeable biochar. Reprinted with
permission from Ref. [21] under CCBY 4.0
9 Magnetic Composites of Biochar and Its Applications 191

developing a highly effective magnetic hierarchical permeable adsorbent that could


successfully treat RhB and TH.
A simple co-precipitation method was used by Teng et al. [22] to create a magnetic
adsorbent ATP/CoFe2 O4 having a significant capability for adsorbing tannic acid
(TA). To enable magnetic specificity, the preloaded CoFe2 O4 granules were incorpo-
rated into the adsorbent substrates. Its TA adsorption dynamics, isotherm behaviour,
and magnetism segregation effectiveness were documented for this substance. The
created magnetic composites exhibited an excellent magnetic segregation efficacy
of 80%, fast adsorption dynamics of 3 h, and a significant adsorption capability of
109.36 mg/g. NaOH was able to efficiently recover the utilized ATP/CoFe2 O4 so that
it could be utilized five more times without noticeably losing its ability to remove
TA and operate magnetically. The substrate functionalization and the creation of
intermolecular hydrogen bonds were shown to be the adsorption processes of TA by
ATP/CoFe2 O4 .

2.3 Hydrothermal Carbonization

At a lesser temperature (100–300 °C) as compared to pyrolysis and under pres-


sure produced by the process directly, hydrothermal carbonization is the heteroge-
neous reaction of biomass using a metallic ion media in a reactor. This produc-
tion is more appealing due to the gentler process environment than the other tech-
niques and the lack of an alkali or a potent reduction reaction. Utilizing FeSO4 .7H2 O
and Chlorella Vulgaris (Cv) as primary ingredients, Peng et al. [23] produced nano
iron oxide-altered biochar, and research was done on its sorption on Rhodamine B
(RhB) in aquatic medium. The nano iron oxide-modified biochar (CBC-Fe(II)) had a
significant magnetic saturating rate (13.7 emu/g) and a significant surface region
(527.6 m2 /g) to aid in magnetic sorting. Considering a maximal adsorption capa-
bility of 286.4 mg/g, CBC-Fe(II) demonstrated higher adsorption capability against
RhB in aquatic media when contrasted to CBC-Fe(III) and CBC. The pseudo-second-
order kinetic model and Langmuir isotherm provided effective descriptions of the
sorption of RhB over CBC-Fe(II), showing interfacial chemisorption behaviours for
the adsorber. At a CBC-Fe(II) concentration of 30 mg, a contact duration of 120 min,
and a temperature of 25 °C, the RhB was most effectively adsorbed. The sorption of
RhB over CBC-Fe(II) exhibited good compliance with both models. Additionally, the
intra-particle dispersion model’s suitable findings showed that inner substrate sorp-
tion and liquefied layer dispersion both had a role in influencing the adsorption rate,
therefore intra-particle dispersion was not the only factor. All of the findings demon-
strated the produced CBC-Fe(II) adsorbent’s strong capability for ecological dye
adsorption.
Ineffective physicochemical features including substrate region, surface-
oxygenated moieties, porous density, and thickness are also produced by traditional
pyrolysis in the form of BC. In terms of BC manufacturing parameters and physico-
chemical characteristics, distinct source materials vary. The existing −OH, C = O,
192 A. Thakur and A. Kumar

Fig. 4 Remodelling and categorization of engineered biochar. Reprinted with permission from Ref.
[24] under CCBY 4.0

and –COOH functional moieties, moreover, are essential in the removal of several
EPs. The functional moiety (type and class) contained over the BC substrate deter-
mines whether the surface has hydrophobic or hydrophilic qualities. Several tech-
niques have been used to enhance the plenteous BC characteristics, including inter-
calation, steam activation, thermal gradients, and chemical processing. Owing to its
physicochemical characteristics, BC functions as a photocatalyst when other cata-
lysts are present (improved surface region, charge segregation, active region, porous
density, stability, functional moieties, catalyzing capability , and re-coverability).
Furthermore, the generation of BC using photocatalysts requires to be improved. For
example, ZnO added to BC enhances the nanocomposite’s adsorption and photocat-
alytic properties. Figure 4 illustrates different types of designed BC remodelling and
categorization for wastewater dye treatment.

3 Utilization of Magnetic Composite of Biochar


for the Adsorption of Several EPs

Magnetic biochar has been utilized extensively to remove contaminants from various
sources, including heavy metals, dyes, pesticides, and organic dyes, treatment of
organic contaminants, and wastewater. According to research, about 20% of research
has utilized magnetic biochar to remove other organic contaminants like organochlo-
rides and phenols, while about 19% of research have utilized it to remove antibiotics
[25–31]. About 44% of research has outlined using it to remove other EPs such as
9 Magnetic Composites of Biochar and Its Applications 193

heavy metals from wastewater. The remediation of radioactive contaminants has also
been done using magnetic biochar, demonstrating the versatility of the material in
ecological treatment. Corresponding to this, certain scientists have used the magnetic
and adsorption abilities of magnetic biochar to catalytically break down organic
contaminants. The applications of magnetic biochar composites for the removal and
remediations of several types of EPs have been discussed in detail beneath.

3.1 Adsorption of Dye

Several dyes and pigments are currently widely used in commercial products
including fabrics, printing, paper, paint, laundromat, skincare, rubber, foodstuff,
and polymers. Each year, greater than 10,000 distinct varieties of synthetic and
natural dyes, comprising 7 × 105 tonstonnes, are generated worldwide. These dye-
pollute wastewater’s chemical intricacy, durability, and low biodegradability are of
the utmost concern and remain to constrain access to pure water supplies. Unin-
tended dye-polluted wastewater outflow into water channels is one of the negative
effects of the growing dye market; it primarily harms marine life and food replen-
ishment, as well as secondarily harming public health. Therefore, it is crucial to
create environmentally friendly treatment techniques to get rid of volatile dyes and
other impurities from water. For instance, Wang et al. [13] created a unique Ca-
functionalized magnetic biochar (Ca/MBC) using a dual-phase pyrolysis technique
to effectively adsorb and eliminate malachite green (MG) as illustrated in Fig. 5.
Figure 6a displays the XPS spectrum of Ca/MBC both prior and following MG
adsorption. N 1 s spike occurred upon MG sorption at an adhesion affinity of approxi-
mately 398.4 eV, demonstrating that MG was packed upon Ca/MBC. The Ca 2p spike
of Ca/MBC experienced a considerable movement to a greater binding potential but
experienced no discernible movement pre or post-MG adsorption, indicating that the

Fig. 5 The procedure and pathway of Ca/MBC subjected to MG. Reprinted with permission from
Ref. [13] under CCBY 4.0
194 A. Thakur and A. Kumar

Ca binding condition altered (Fig. 6b). The electron cloud distribution of the two
components was tilted towards the anions due to the initial high number of anions
in Ca/MBC forming bonds involving Ca2+ . The greater negative MG became when
it reacted to Ca2+ , increasing the binding affinity of Ca 2p. Following extensively
entrapping MG, the Fe 2p signal substantially changed to a greater binding value, in
agreement with the Ca 2p signal (Fig. 6c). Following MG sorption by Ca/MBC, the
maxima at 289 eV (O = C–O) and 285 eV (C–O) significantly diminished, showing
that MG substituted numerous carbonates throughout MG elimination (Fig. 6d).
Additional evidence suggests that ligand interaction took place involving MG and Ca/
MBC.
Hydroxyl oxygen (OH) and Lattice oxygen (OL) the two distinct types of oxida-
tions that correlate to Ca/MB prior and following MG adsorption are depicted in
Fig. 6e. Following adsorption, OH underwent a little alteration that was mostly
caused by Fe-OH and Ca-OH. However, upon MG sorption by Ca/MBC, a significant
amount of OL vanished, additionally proving that MG can cause lattice alterations
and showing that the adsorption mechanism was predominately chemisorption.
Similarly, Fatimah et al. [32] researched into the creation of a magnetic
nanocomposite photocatalyst using biochar-impregnated NiNPs (Ni/BC), agricul-
tural residues, and palm leaf. The nickel (II) chloride precursor-impregnated palm
leaves were directly pyrolyzed to create the nanocomposite. For the photocatalytic
oxidation of methyl violet (MV), the photocatalytic efficiency of Ni/BC was assessed.
Individual Ni NPs between 30 and 50 nm in size were found scattered on the
charcoal composition according to the findings of the TEM investigations. Biochar’s
BET-specified surface region improved due to the distributed Ni NPs from 3.89
to 73.45 m2 /g. Substantial MV elimination was achieved by the Ni/BC in 30 min
for concentrations varying from 10 to 80 mg/L, demonstrating its excellent photo-
catalytic efficiency. The Ni/BC also demonstrated pH 4–10 durability and renewa-
bility without performance modification till the fifth application. Mg of approxi-
mately 12.6 emu/g was associated with the separate photo catalyst. The findings
demonstrated biochar’s usefulness as a substrate for nickel as a photoactive substance.
Roy et al. [33] created biochar composites made from Moringa oleifera
(M. oleifera) seeds, such as Biochar-ZnO (BZ), Biochar-Chitosan (BC), and
Chitosan-ZnO. (CZ). The polymers were then used to adsorb methylene blue. Spec-
trometric examination of the biochar-relied composites showed that the biochar
substrate had been altered by ZnO and chitosan, introducing various active and func-
tional moieties. The ZnO treatment made the resulting biochar completely granular
and gave it more crystallinity. Regarding produced sorbents, the estimated surface
region ranged from 0.90 ± 0.00 to 14.48 ± 1.13 m2 g−1 , with BZ denoting the greatest
and BC denoting the least surface areas, correspondingly. BC was determined to have
the maximum sorption capability (around 170 mg/g). The ZnO and chitosan modifi-
cations resulted in a 75% improvement in extraction from the BC and a 16% reduction
from the BZ, accordingly. RSM optimization for BC produced outcomes that were
comparable to those of the analytical tests. The characterization and empirical find-
ings indicate that the essential characteristic of the adsorption mechanism will be the
chemical functionality rather than surface area.
9 Magnetic Composites of Biochar and Its Applications 195

Fig. 6 a XPS spectrum of Ca/MBC prior and following MG adsorption, b Ca 2p, c Fe 2p, d O 1 s,
e C 1 s. Reprinted with permission from Ref. [13] under CCBY 4.0
196 A. Thakur and A. Kumar

Citric acid was used in the procedure by Omri et al. [34] to investigate its effect
upon the topological and texture attributes of the biochar that supports the metallic
NPs. Unexpectedly, the production of flocculated or even raspberry-shaped bimetallic
Cu/Ni NPs was caused by citric acid. For B-CA@CuNi, massive 450–500 nm aggre-
gates of 80 nm bimetallic CuNi NPs were observed. Exceptional nano raspberries
(174 ± 8 nm in size) made of separate 10–20 nm CuNi10/1 NPs were generated by
the bimetallic NPs in biochar substance synthesized with a preliminary Cu/Ni = 10
molar ratio (B-CA@CuNi10/1), which is intriguing. Owing to the reduced Ni concen-
tration, B-CA@CuNi10/1 was unable to be magnetized by a magnet as effectively
as B-CA@CuNi and B-CA@Ni substances. Investigation of B-CA@CuNi as a cata-
lyst for the breakdown of methyl orange (MO). In comparison to an identical mate-
rial manufactured without CA, discoloration was noticed after 10 min, which was
substantially quicker. B-CA@CuNi was recyclable at least three times whilst main-
taining its ability to discolour quickly. As highlighted in this study, citric acid has a
key role in structuring bimetallic NPs that are deposited in vivo upon biochar during
the steady pyrolysis process and in facilitating quicker catalytic staining of organic
dye medium.
Zhang et al. [35] used an eco-friendly one-phase process to effectively create
a unique nano-β-FeOOH/Fe3 O4 /biochar composite having improved photocatalytic
activity and super paramagnetism. The existence of Fe–O–C bonds among biochar
and β-FeOOH, which facilitated the transmission of photo-generated electrons, was
verified by the XPS spectra of the composites as they were made. The presence of
an electron–hole linkage among biochar and β-FeOOH was established by UV–vis
spectra, and this facilitated the quick interfacial transmission of photo-generated
electrons from β-FeOOH to biochar. These innovative architectures might improve
biochar’s reaction, accelerating photoelectrons in visible light to produce more free
radicals. The photo degradation of MO using nano-β-FeOOH/Fe3 O4 /biochar used
•OH as the main active component, according to free radical quenching and electron
spin resonance tests. Compared to the standard biochar, the collaborative photocat-
alytic system’s −FeOOH/Fe3 O4 /biochar showed good catalytic efficiency for the
breakdown of the MO; 2.03 times greater. However, the surface region dropped from
1424.82 to 790.66 m2 g1 . As a result of its super paramagnetism, β-FeOOH/Fe3 O4 /
biochar also had a robust framework, at least 98% catalytic properties, and was
simple to segregate. This study demonstrates the improved photocatalytic activity of
a substance called β-FeOOH/Fe3 O4 /biochar that could be applied to the remediation
of azo dye in wastewater.

3.2 Adsorption of Heavy Metals

As heavy metals could go down the food chain and stack in species, there is a signif-
icant risk to organisms, particularly for Pb, Cu , and Zn. Presently, the effectiveness
of heavy metal elimination differs depending on the procedure, and the majority
of procedures are impractical owing to secondary pollutant generation, expensive
9 Magnetic Composites of Biochar and Its Applications 197

management and maintenance, etc. Therefore, suitable remediation techniques for


heavy metals must be sought out. While different heavy metal ions typically occur
in the real world, advances in adsorption provide a superior way for the removal of
heavy metals [36–45]. Consequently, effective remediation must take into account
the dynamic adsorption of existing metal ions in ecosystems. Using templates made
from sunflower straw biochar (SFBC) generated at various calcination temp. and
using various SFBC/Fe weight proportions, Zhao et al. [46] created a sophisticated
Fe3 O4 @SFBC (Fe3 O4 -sunflower straw biochar) adsorbent. Fe3 O4 @SFBC exhibits
extraction efficiencies of 95.94 and 86.43% for As(V) and As(III), correspondingly,
at pH 4 and 6, according to research on the ideal pH for As(III/V) elimination. By
conducting batch investigations, the casting and calcining effects upon the biochar-
bound Fe3 O4 produced at various temperatures and SFBC/Fe weight proportions
were examined. The findings demonstrate that when the SFBC was heated at 450 °C
using an SFBC/Fe weight proportions of 1:5, the significant levels of As(V) and
As(III) adsorption, 188.753 and 121.347 mg/g, correspondingly, were attained. The
substance exhibits superior magnetic characteristics (54.52 emu/g) and tiny particu-
lates having a size between 12 and 14 nm, making it appropriate for the elimination
of arsenic. Last but not least, the substance was put through five straight cycles of
adsorption–desorption trials without any discernible loss in removal efficacy. As a
result, the novel adsorbent Fe3 O4 @SFBC can be employed effectively to remove
arsenic from aqueous systems.
Alongside examining changes to its surface chemistry, Mortazavian et al. [47]
assessed the impact of two-phase alterations on improving BCs efficacy for removing
aq. hexavalent chromium (Cr(VI)). Thermal treatment in air at 300 °C was the initial
alteration stage, generating hydrophilic biochar (HBC). After that, zero-valent iron
NPs (nZVI) were injected into the resultant HBC to create an HBC/nZVI composite,
which offered the physical sorption process a chemical reduction capacity. Research
on the kinetics of Cr(VI) elimination showed that HBC has a four-times larger poten-
tial for sorption than BC. Unaltered BC had a quicker preliminary absorption of
Cr(VI), but it quickly degraded and began to desorb. The efficiency of HBC’s elimi-
nation of Cr(VI) improved by a ratio of 10 following nZVI copulation. It was demon-
strated that the carboxyl and carbonyl moieties involved in Cr(VI) adsorption by the
detection of Cr(III) oxide exclusively in the HBC/nZVI used in the FTIR examina-
tion of the biochars after Cr(VI) sorption. Altered biochars could be considered a
more affordable option than conventional methods.
After Pb2+ sorption, Xu et al. [48] effectively manufactured unique KMnO4 -
treated magnetic biochar (KFBC) by adding Fe(NO3 )3 and treating it with KMnO4
after carbonization. The improvement in adsorption was mostly brought about by the
enhanced functional sites on the biochar’s interface following KMnO4 alteration and
manganese oxide addition. Figure 7a depicts the modifications made to the oxygen-
containing functional moieties over the biochar’s substrate following adsorption. The
functional moieties over the substrate of the biochar were exhausted by adsorption,
as evidenced by the lessening of the functional moieties following adsorption and
the lowering of the strength of the carboxyl and hydroxyl maxima. No additional
maxima were seen upon the KFBC substrate when combined using XRD (Fig. 7e),
198 A. Thakur and A. Kumar

proving that precipitation had a negligible impact on the Pb2+ sorption on KFBC.
Figure 7c displays the precise spectrum of C1s following adsorption. The distinctive
spikes of the biochar’s C–O and C = O were relocated and their peak densities altered
following adsorption, according to the fitted findings of C1s, which was caused by
the participation of carboxyl and hydroxyl moieties over the biochar’s substrate in
the process. Figure 7d displays the precise spectrum of O1s following adsorption.
The distinctive lattice oxygen spike regions all more than increased from the pre-
adsorption phase, demonstrating the production of Pb–O over the biochar’s substrate.
Whereas the typical peak regions of C–OH all dropped, the region of the C = O spike
rose, indicating bidentate and monodentate chelation over the substrate of the biochar.
According to the findings of the IR spectrum, -OH was most likely engaged in the
biochar’s adsorption mechanism.
Deng et al. [49] employed altered corncob biochars generated by slow pyrolysis
and pretreated with various MgCl2 amounts to investigate the adsorption capac-
ities against heavy metals. Following alteration, MgO and Mg(OH)2 particulates
were primarily incorporated into the carbon substrate of the biochar. The optimum
weight percentage of Mg/feedback for altered biochar was 15, and 15% Mg-BC

Fig. 7 Contrasted characterization of KFBC following adsorption by a FTIR, b XPS, c C1s of


XPS, d O1s of XPS, e XRD. Reprinted with permission from Ref. [48] under CCBY 4.0
9 Magnetic Composites of Biochar and Its Applications 199

possesses a substantially greater metal adsorption capability than pure biochar (2.36–
9.34 times). According to batch adsorption tests, lead (Pb(II)) and cadmium (Cd(II))
adhere to an intra-particle model while copper (Cu(II)) and lead (Pb(II)) adhere
to a pseudo-second-order concept. Thus, metals were evaluated using analytical
screening equipment, such as XRD, FTIR , and XPS, following they had been
adsorbed over 15% Mg-BC in an attempt to comprehend the processes. Figures 8
and 9 display the outcomes. Figure 8a shows the FTIR spectrum for the sorption
over 15% Mg-BC. Following adsorbing Cu(II), Cd(II) and Pb(II), the maxima of
3696 (−OH), 3412 (−OH), and 1618 cm1 (C = O) diminish, indicating precip-
itation (which was supported by XRD investigations). During metal addition, the
bonding at 1440 cm−1 (C–H) moved to 1383 cm−1 , showing that the metals inter-
acted to carboxyl via interfacial complex formation and generated metal chelation
upon the Mg-modified biochar. In addition, XPS detected the ion transfer of metal
ions (Fig. 9a). Consequently, metals deposited upon adsorbents were identified by
their end products using the XRD spectrum (Fig. 8b). The calcite (CaCO3 ) peak’s
strength vanished once the heavy metals were absorbed, and the Mg(OH)2 peak’s
strength dropped sharply. These findings demonstrate that precipitation from the
interaction of Mg(OH), CaCO3 , and metallic ions had a significant effect on the
sorption by 15% Mg-BC. Additionally, additional peaks that were associated with
the crystals of Cu(OH), CdCO3 , Cu2 (OH)2 CO3 , and Pb3 (OH)2 (CO3 )2 emerged on
the spectra of metal-loaded biochar. Figure 9b–e displays the results of the XPS
examinations of the materials with metal loading. Ion transaction and dispersion
were thus confirmed as the adsorption process of altered biochar-eliminating metals.
The banding strengths of 285.47, 284.79, and 286.76 eV in 15% Mg-B, contributed
to the C-comprising functional moieties of C–O, C–C, and C = O, correspondingly,
were used to match the maxima for the spectrum of C 1 s (Fig. 9f–i). The equiv-
alent concentrations of C–C increased from 66.17% to 77.0, 83.42, and 83.29%,
correspondingly, following Cu(II), Cd(II), and Pb(II) adsorption. On the Cu(II)- and
Pb(II)-covered biochars, the functional moieties of C = O were substituted by O–C
= O (287.15 and 275.68 eV), and the groups of C = O transition for Cd(II) adsorp-
tion over improved biochar (289.29 eV). It suggests that these functional units might
control the sorption process via metallic substrate complexation.
For utilizing adsorbent to remove Cd (II) ions from water, Saeed et al. [50] focused
on the methodical creation of Kenaf fibre biochar. The physicochemical activation
approach, which involves pre-impregnation using nitrogen (N2 ) and NaOH pyrol-
ysis, was used to create activated biochar. As per the core composite structure,
a few quadratic correlation prototypes were created from the empirical observa-
tions. Each model successfully suited the experimental results. According to the
empirical findings, the primary variables that influenced the output of biochar and
showed a favourable impact upon the frequency of Cd (II) ion elimination and sorp-
tion capability were the heating duration and pyrolysis temperature. The effective
surface region of the biochar, extraction efficiency and Cd adsorption capability all
responded favourably to the impregnation proportion; however, the output of the
biochar was not significantly affected. The aforementioned circumstances led to the
best biochar-based adsorbent being produced: 180 min of heating duration, 1:1 NaOH
200 A. Thakur and A. Kumar

Fig. 8 FTIR spectrum a XRD spectrums b prior and following metal adsorption over 15% Mg-BC.
Reprinted with permission from Ref. [49] under CCBY 4.0

Fig. 9 XPS spectrum (a), 15%Mg-BC (b, f), and Cu- (c, g), Cd- (d, h) and Pb-covered BC (e, i).
Reprinted with permission from Ref. [49]
9 Magnetic Composites of Biochar and Its Applications 201

impregnation proportion and a pyrolysis temperature of 550 °C. The best adsorbent
produced 27.50% biochar, removed 70.83% of Cd (II) ions, had an adsorption ability
of 23.48 mg/g, and had a biochar-specific surface region of 160.44 m2 /g.
To eliminate heavy metals from the wastewater, Wu et al. [51] employed biochar,
wherein biochar (BC) and magnetic biochar (MBC) were made using pomelo peel at
various temperatures. The physicochemical parameters of the BC were then outlined,
and the Pb2+ , Cu2+ , and Zn2+ adsorption properties on the biochars in single, binary,
and ternary metal systems were examined. The outcomes demonstrated that the sorp-
tion capability of biochar might be influenced by both magnetization and pyrolysis
temperature. In the binary metal state, Pb2+ and Zn2+ adsorption isotherm kinds were
modified. Pb2+ > Cu2+ > Zn2+ was the dominant adsorption sequence of the three
heavy metal ions in ternary metal sorption. In the coexisting atmosphere, the MBC of
500 °C demonstrated an excellent capability for adsorption to Pb2+ , with a maximal
adsorption capability of 48.74 mmol/g. Additionally, this research offered scientific
evidence for the use of pomelo peel and its technological use.
Through sequential activation with ferrous chloride, potassium perman-
ganate, triethylenetetramine, and epichlorohydrin, Liang et al. [52] created Fe–Mn
binary oxide/mulberry stem biochar composite adsorbent (FM-MBC) using mulberry
stems. According to the findings, the FM-MBC possesses a higher permeable surface
than mulberry stem biochar (MBC), having a BET substrate region of 74.73 m2 /g,
and the substrate was packed by MnO2 and α-Fe2 O3 particles that have undergone
amorphization. Additionally, functional moieties for carbonyls, carboxylic acid, and
hydroxyl were also produced over the FM-MBC substrate. The maximal Cr(VI) sorp-
tion capability at the ideal pH 2.0 was computed using the Langmuir model and was
found to be 31.02, 28.31, and 37.14 mg/g at 25, 35, and 45 °C, correspondingly. The
primary functional moieties in the sorption of Cr (VI) were the carboxyl, aromatic,
and hydroxyl groups.

3.3 Adsorption of EPs for Wastewater Treatment

Although approximately 71% of the earth’s surface is procured by water, just 2.5%
of that water is potable [53, 54, 54]. Most regrettably, this small amount of fresh
water has been ruined and contaminated. Up to this moment, more than 2.3 billion
individuals globally have water-related illnesses, particularly those in underdevel-
oped nations. Among the impurities in water are dyes, heavy metals, and polyaro-
matic hydrocarbons, among others [55–57]. The drinking water becomes unfit for
consumption if these pollutants reach a specific level. To get rid of EPs in wastewater,
Chen et al. [58] developed a practical, reproducible process for creating magnetic
biochar with a distinctive 3D system topology. In summary, Fe3+ was introduced
to the culture procedure while using the microbial filamentous fungus Trichoderma
reesei as a template. This led to consistent reintegration via the bio-assembly char-
acteristic of fungal hyphae. Ultimately, by manipulating various heating parameters
in a higher temperature procedure, magnetic biochar (BMFH/Fe3 O4 ) was created.
202 A. Thakur and A. Kumar

MG and TH were used as paradigms for organic pollutants to study the sorption
and Fenton-like catalytic activity of BMFH/Fe3 O4 . According to the observations,
BMFH/Fe3 O4 had a sorption capability for TH and MG of 171.26 and 158.2 mg/
g, correspondingly. This value was greater than that of most biochar adsorbent
materials, and it also demonstrated superior Fenton-like catalytic decomposition
of organic contaminants compared to typical catalysts. This work offers magnetic
biochar having outstanding efficiency, but more significantly, the technique adopted
could be successful in enhancing biochar’s effectiveness for improved management
of organic contaminants.
Phuong et al. [59] examined the effectiveness of rice straw-derived biochar and
magnetic biochar for the sorption of Safranin O (SO) from an aqueous medium. While
magnetic rice straw biochar (MRSB) was created through the chemical coagulation
of Fe3+ and Fe2+ , rice straw biochar (RSB) was created through pyrolysis in an oven
at 500 °C for 2 h in an oxygen-restricted condition. MRSB was reported to have a
maximal SO sorption capability of 41.59 mg/g, whereas RSB had a max SO sorption
capability of 29.07 mg/g. The intra-particle dispersion paradigm suggested that it
might not be the primary rate-limiting process. The sorption of SO particles using
MRSB and RSB adsorbents is explained by the integration of chemical and physical
mechanisms. The acquired findings showed that the magnetic biochar could readily
be extracted from the media utilizing an external magnet and could substantially
increase the SO adsorption capability of its predecessor biochar.
In a creative way, Liu et al. [60] created magnetic biochar (MBC) and utilized it
to improve sustained phosphorus extraction as vivianite. Utilizing batch studies and
a refined progressive P recovery methodology, the impacts of anaerobic digestion
(AD) duration, MBC dosage, and hydrothermal preprocessing temperature over the
production of vivianite were examined. According to the P separation data, sheer
vivianite-bound P (Fe(II)-P) content peaked on the tenth day of AD intervention
before rapidly declining as a consequence of vivianite oxidation and P restraint.
Vivianite production was decreased by HT preprocessing performed at moderately
elevated temperatures (135 and 185 °C); this detrimental impact of HT prepro-
cessing was significantly overcome with MBC replenishment. With expanding doses
of MBC from 0 to 12.5 g/L, the ratio of Fe(II)-P in the solid stage of sludge enhanced
significantly, rising to 57.1% from 8.3 to 17.4%. This indicates that MBC seemed
to significantly augmented impact on the composition of vivianite; this might be
related to the MBC-enhanced Fe(II) manufacturing, as demonstrated by the inflated
percentage of Fe(II) in Fe2p XPS. Additionally, the MBC inclusion reduced the
amount of water-extractable P through adsorption and encouraged organic P degrada-
tion, which aided in the synthesis of vivianite. These results provide a novel approach
to improve P extraction from HT-preprocessed AD muck.
The magnetic Fe-Cu bimetallic NMs (designated as MBC) were effectively
manufactured by Liu et al. [61] using a pyrolysis and co-precipitation process. It
worked well in removing ciprofloxacin (CIP) from aquatic media by activating
H2 O2 . Both catalytic efficiency and conformational integrity were quite excellent
in this substance. It also possessed strong magnetic qualities that made it simple to
segregate from media. The removal effectiveness of CIP in MBC/H2 O2 was 93.6% in
9 Magnetic Composites of Biochar and Its Applications 203

360 min under ideal reaction circumstances. Similar conditions led to a 51.0% trans-
formation of total organic carbon (TOC). To analyse the produced MBC’s catalytic
efficiency, the elimination effects across various conditions were examined. With just
H2 O2 , a maximum of 12.4% of CIP was removed from the operating unit (Fig. 10a).
H2 O2 self-degradation generated hydroxyl radicals, which were responsible for a
minor portion of the elimination. MBC separately was able to soak 59.3% of CIP,
compared to Fe-Cu or BC which were merely able to adsorb 12.9 and 50.6% of
CIP, correspondingly. MBC exhibited a greater ability for adsorption, which might
be because of its dense porous geometry. It was evident that the MBC/H2 O2 signif-
icantly increased the breakdown efficacy of CIP, as 93.6% of CIP was transformed
in 360 min, compared to 85% eradication for Fe-Cu/H2 O2 and only 19.9% eradica-
tion for BC/H2 O2 . The combinatorial interaction among the carbon framework and
metal, which expedited the breakdown of H2 O2 , led to the creation of the hydroxyl
radical (OH), that degraded CIP, which was primarily responsible for the consid-
erable enhancement in the eradication efficacy. Additionally, the TOC transition
efficacy in MBC/H2 O2 was 51% within 360 min (Fig. 10b). The elimination efficacy
of TOC steadily increased as CIP elimination effectiveness increased. As a result, it
demonstrates that the MBC has outstanding CIP mineralization efficacy.
In order to eliminate Bisphenol A (BPA) from marine environments, Katibi et al.
[62] concentrated over the formation of clean and magnetic biochar (BC) as a
greener and reasonably priced adsorbent. Utilizing the palm kernel husk as a cata-
lyst, ferrous chloride, and ferric chloride were effectively combined to generate inno-
vative magnetic biochar utilizing the chemical co-precipitation method. Herein, the
effects of functioning variables including contact moment (20–240 min), adsorbent
quantity (0.2–0.8 g), pH (3.0–12.0) , and preliminary dosage of BPA (8.0–150 ppm)
were investigated in the removal of BPA throughout batch adsorption framework
utilizing clean biochar and BC. With a 94.2% higher BPA extraction efficiency than
clean charcoal, it was discovered that the magnetically infused BC was superior. The

Fig. 10 a Elimination of CIP in distinct systems. b The elimination efficacy of TOC in the MBC/
H2 O2 . Reaction variables: preliminary CIP, 10 mg/L; pH: 6.4; catalyst quantity, 0.6 g/L; 10 mM,
H2 O2 . Reprinted with permission from Ref. [61] under CCBY 4.0
204 A. Thakur and A. Kumar

empirical results showed that the Freundlich paradigm might match the adsorption
isotherm more accurately than the pseudo-second-degree approach might regulate
the adsorption kinetic parameters. The BC as it was synthesized also showed strong
magnetic properties for easy recuperation, outstanding recycled content, great speci-
ficity, and eco-benign. It was discovered that adsorbent dosage, contact duration, and
pH have a significant impact on BPA elimination. The highest BPA sorption for MBC
occurs at pH 6, and the BPA adsorption increased with pH lowering. According to
a thermodynamic analysis, BPA adsorption upon MBC is an endothermic reaction
and spontaneously as a result of −ΔG and +ΔH, correspondingly. Hydrophobic and
electrostatic interaction and H-bonding were the primary pathways for BPA sorption
upon the synthesized BC. Thus, it could be concluded from this investigation that
innovative MBC is effective and useful for removing BPA from marine mediums
while also having the advantages of having ecological and widely accessible.

4 Adsorption Mechanism

For effective use of magnetic biochar in EPs and water remediation, it is crucial
to comprehend the adsorption process of the compound. The ways that pollutants
are attracted to magnetic biochar for adsorption include coordinate reactions, ion
transfer, hydrogen linkages, substrate complexation, electrostatic interaction, co-
precipitation, and more [63–66]. The porous geometry, functional moieties, and
chemical bonding upon the substrate of the magnetic biochar have an impact on the
adsorption process, which varies with the contaminants and is affected. The properties
of magnetic biochar and the ways that contaminants are absorbed are related. After
examining the literature, it could be argued that the main processes for the sorption
of EPs over magnetic biochars include substrate complexation, electrostatic interac-
tion, ion transfer , and O-comprising moieties. To explain the mechanism well, Chen
et al. [58] developed a practical, reproducible process for creating magnetic biochar
featuring a distinctive 3D system topology. In essence, Fe3+ was introduced to the
culture stage while using a template comprised of the microbiological filamentous
fungus Trichoderma reesei. This led to consistent reintegration via the bio-assembly
characteristic of fungal hyphae. Thus, the potential processes may be separated into
two steps: the adsorption technique and the catalytic reactivity process. In this inves-
tigation, BMFH/Fe3 O4 eliminates organic contaminants (TH and MG) via sorption
and the Fenton-like catalytic approach (Fig. 11). H-bond and Electrostatic interac-
tions, and π-π engagement are a few potential adsorption mechanisms. BMFH/Fe3 O4
and Organic contaminants have a significant electrostatic association that might be
advantageous for adsorption in an ecosystem having increased pH levels. The find-
ings of XPS and FT-IR spectrometric tests show that the texture of BMFH/Fe3 O4
contains a variety of functional moieties that are suitable for adsorption. For instance,
an H-bond might indeed construct by the C–O moiety with the C-H moiety in organic
contaminants, and the same performs with −O− and N+ by the O–H moiety. The
9 Magnetic Composites of Biochar and Its Applications 205

Fig. 11 Potential TH and MG elimination pathways of BMFH/Fe3 O4 through adsorption and


Fenton-like catalysis. Reprinted with permission from Ref. [58] under CCBY 4.0

aromatic rings in organic contaminants might engage with the π-π existing aromatic
rings in BMFH/Fe3 O4 , increasing the adsorption capability.

5 Conclusion and Future Perspectives

In this discussion, the utilization of several types of magnetic biochar for the
extraction of several EPs has been described, and the synthesis processes for
magnetic biochar are also briefly addressed. Magnetic biochar provides a superior
EPs removal effectiveness in contrast to biochar. The assessment was performed
on the magnetic biochar’s EP removal adsorption methods. For instance, by devel-
oping and using sophisticated Fe3 O4 @SFBC (Fe3 O4 -sunflower straw biochar) adsor-
bent. Fe3 O4 @SFBC exhibited extraction efficiencies of 95.94 and 86.43% for As(V)
and As(III), correspondingly, at pH 4 and 6, according to research on the ideal
pH for As(III/V) elimination. Additionally, the highest levels of As(V) and As(III)
adsorption, 188.753 and 121.347 mg/g, respectively, were reached when the SFBC
biochar was subjected to heat at 450 °C with an SFBC/Fe weight ratio of 1:5. The
substance exhibits superior magnetic characteristics (54.52 emu/g) and tiny partic-
ulates having a size between 12 and 14 nm, making it appropriate for the elimina-
tion of arsenic. These investigations indicate the efficacy of magnetic composites of
biochar for the removal of EPs. However, additional research must be done on using
magnetic biochar to remove more emerging pollutants such as antibiotics, phar-
maceutical waste, and organic contaminants. The extraction of toxic material and
inorganic/organic compounds by magnetic biochar as well as the biosorption and
removal process of organic material requires to be thoroughly researched, and inves-
tigation on interacting with the hazardous aquifer could be done in the coming years
206 A. Thakur and A. Kumar

by analysing the impact of additives on the physicochemical attributes of magnetic


biochar. In the nearish term, magnetic biochar is anticipated to attract more scientific
attention and endure increased advancement.

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of bronopol on aluminium in 0.5 M HCl solution: insights from experimental and quantum
chemical studies. Surf Interfaces 20:100542. https://doi.org/10.1016/j.surfin.2020.100542
29. Thakur A, Kaya S, Kumar A (2021) Recent innovations in nano container-based self-healing
coatings in the construction industry. Curr Nanosci 18:203–216. https://doi.org/10.2174/157
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and alloys. Eur J Mol Clin Med 07:49–67. https://doi.org/10.1007/978-3-030-35106-9_3
31. Thakur A, Kumar A, Kaya S, Marzouki R, Zhang F, Guo L (2022) Recent advancements in
surface modification, characterization and functionalization for enhancing the biocompatibility
and corrosion resistance of biomedical implants. Coatings 12:1459. https://doi.org/10.3390/coa
tings12101459
32. Fatimah I, WIjayanti HK, Ramanda GD, Tamyiz M, Doong R, Sagadevan S (2022) Nanocom-
posite of nickel nanoparticles-impregnated biochar from palm leaves as highly active and
magnetic photocatalyst for methyl violet photocatalytic oxidation. Molecules 27:6871
33. Roy H, Islam MS, Arifin MT, Firoz SH (2022) Synthesis, characterization and sorption proper-
ties of biochar, chitosan and ZnO-based binary composites towards a cationic dye. Sustainability
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208 A. Thakur and A. Kumar

34. Omiri J, Snoussi Y, Bhakta AK, Truong S, Ammar S, Khalil AM, Jouini M, Chehimi MM (2022)
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for dye degradation. Colloids Interfaces 6. https://doi.org/10.3390/colloids6020018
35. Zhang Z, Wang G, Li W, Zhang L, Guo B, Ding L, Li X (2021) Photocatalytic activity of
magnetic nano-β-feooh/fe3o4/ biochar composites for the enhanced degradation of methyl
orange under visible light. Nanomaterials 11:1–17. https://doi.org/10.3390/nano11020526
36. Kumar A, Thakur A (2020) Encapsulated nanoparticles in organic polymers for corrosion
inhibition. Elsevier Inc
37. Thakur A, Kaya S, Abousalem AS, Kumar A (2022) Experimental, DFT and MC simulation
analysis of Vicia Sativa weed aerial extract as sustainable and eco-benign corrosion inhibitor
for mild steel in acidic environment. Sustain Chem Pharm 29:100785. https://doi.org/10.1016/
j.scp.2022.100785
38. Thakur A, Kaya S, Abousalem AS, Sharma S, Ganjoo R, Assad H, Kumar A (2022) Compu-
tational and experimental studies on the corrosion inhibition performance of an aerial extract
of Cnicus Benedictus weed on the acidic corrosion of mild steel. Process Saf Environ Prot
161:801–818. https://doi.org/10.1016/j.psep.2022.03.082
39. Thakur A, Kumar A (2019) Nanotechnology and its significance in food industries: an overview.
J Emerg Technol Innov Res 6:344–348
40. Thakur A, Kumar A (2019) Potential of natural product extract as green corrosion inhibitors
for steel—a review. J Gujarat Res Soc 21:200–212
41. Thakur A, Kumar A (2019) Corrosion inhibition activity of Pyrazole derivatives on metals and
alloys in acidic environment: a review. J Emerg Technol Innov Res 6:339–343
42. Thakur A, Kumar A (2021) Sustainable inhibitors for corrosion mitigation in aggressive corro-
sive media: a comprehensive study. J Bio- Tribo-Corrosion 7:1–48. https://doi.org/10.1007/s40
735-021-00501-y
43. Thakur A, Kumar A (2022) Recent advances on rapid detection and remediation of environ-
mental pollutants utilizing nanomaterials-based (bio)sensors. Sci Total Environ 834:155219.
https://doi.org/10.1016/j.scitotenv.2022.155219
44. Thakur A, Kumar A, Kaya S, Vo DVN, Sharma A (2022) Suppressing inhibitory compounds
by nanomaterials for highly efficient biofuel production: a review. Fuel 312:122934. https://
doi.org/10.1016/j.fuel.2021.122934
45. Thakur A, Kumar A, Sharma S, Ganjoo R, Assad H (2022) Materials today: proceedings
computational and experimental studies on the efficiency of Sonchus arvensis as green corrosion
inhibitor for mild steel in 0. 5 M HCl solution. Mater Today Proc 66:609–621. https://doi.org/
10.1016/j.matpr.2022.06.479
46. Zhao Y, Shi H, Tang X, Kuang D, Zhou J, Yang F (2022) Performance and mechanism of As(III/
V) removal from aqueous solution by Fe3O4-sunflower straw biochar. Toxics 10. https://doi.
org/10.3390/toxics10090534
47. Mortazavian S, Murph SEH, Moon J (2022) Biochar nanocomposite as an inexpensive and
highly efficient carbonaceous adsorbent for hexavalent chromium removal. Materials (Basel)
15. https://doi.org/10.3390/ma15176055
48. Xu Y, Qu Y, Yang Y, Qu B, Shan R, Yuan H, Sun Y (2022) Study on efficient adsorption
mechanism of Pb2+ by magnetic coconut biochar. Int J Mol Sci 23. https://doi.org/10.3390/
ijms232214053
49. Deng Y, Li X, Ni F, Liu Q, Yang Y, Wang M, Ao T, Chen W (2021) Synthesis of magnesium
modified biochar for removing copper, lead and cadmium in single and binary systems from
aqueous solutions: adsorption mechanism. Water (Switzerland) 13. https://doi.org/10.3390/
w13050599
50. Saeed AAH, Harun NY, Sufian S, Bilad MR, Nufida BA, Ismail NM, Zakaria ZY, Jagaba
AH, Ghaleb AAS, Al-Dhawi BNS (2021) Modeling and optimization of biochar based adsor-
bent derived from Kenaf using response surface methodology on adsorption of CD2+. Water
(Switzerland) 13. doi: https://doi.org/10.3390/w13070999
51. Wu Q, Dong S, Wang L, Li X (2021) Single and competitive adsorption behaviors of cu2+,
pb2+ and zn2+ on the biochar and magnetic biochar of pomelo peel in aqueous solution. Water
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9 Magnetic Composites of Biochar and Its Applications 209

52. Liang M, Xu S, Zhu Y, Chen X, Deng Z, Yan L, He H (2020) Preparation and characterization
of fe-mn binary oxide/mulberry stem biochar composite adsorbent and adsorption of cr(Vi)
from aqueous solution. Int J Environ Res Public Health 17. https://doi.org/10.3390/ijerph170
30676
53. Dong L, Shan C, Liu Y, Sun H, Yao B, Gong G, Jin X, Wang S (2022) Characterization and
mechanistic study of heavy metal adsorption by facile synthesized magnetic xanthate-modified
chitosan/polyacrylic acid hydrogels. Int J Environ Res Public Health 19. doi: https://doi.org/
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54. Sun P, Hui C, Khan RA, Du J, Zhang Q, Zhao YH (2015) Efficient removal of crystal violet
using Fe3O4-coated biochar: the role of the Fe3O4 nanoparticles and modeling study their
adsorption behavior. Sci Rep 5:1–12. https://doi.org/10.1038/srep12638
55. Parveen G, Bashir S, Thakur A, Saha SK, Banerjee P, Kumar A (2020) Experimental and compu-
tational studies of imidazolium based ionic liquid 1-methyl- 3-propylimidazolium iodide on
mild steel corrosion in acidic solution Experimental and computational studies of imidazolium
based ionic liquid 1-methyl- 3-propylimidazolium. Mater Res Express 7:016510. https://doi.
org/10.1088/2053-1591/ab5c6a
56. Thakur A, Sharma S, Ganjoo R, Assad H, Kumar A (2022) Anti-corrosive potential of the
sustainable corrosion inhibitors based on biomass waste: a review on preceding and perspective
research. J Phys Conf Ser 2267:012079. https://doi.org/10.1088/1742-6596/2267/1/012079
57. Thakur A, Sharma S, Kumar A (2021) Preparation of composite metal-organic frameworks
58. Chen X, Lin J, Su Y, Tang S (2022) One-step carbonization synthesis of magnetic biochar with
3D network structure and its application in organic pollutant control. Int J Mol Sci 23. https://
doi.org/10.3390/ijms232012579
59. Phuong DTM, Loc NX (2022) Rice straw biochar and magnetic rice straw biochar for safranin
O adsorption from aqueous solution. Water (Switzerland) 14:1–14. https://doi.org/10.3390/
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60. Liu Y, Jin J, Li J, Zou Z, Lei R, Sun J, Xia J (2022) Enhanced phosphorus recovery as vivianite
from anaerobically digested sewage sludge with magnetic biochar addition. Sustain 14. https://
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61. Liu H, Liu Y, Li X, Zheng X, Feng X, Yu A (2022) Adsorption and Fenton-like degradation
of ciprofloxacin using corncob biochar-based magnetic iron–copper bimetallic nanomaterial
in aqueous solutions. Nanomaterials 12. https://doi.org/10.3390/nano12040579
62. Katibi KK, Yunos KF, Man HC, Aris AZ, Nor MZM, Azis RS (2021) An insight into a sustain-
able removal of bisphenol a from aqueous solution by novel palm kernel shell magnetically
induced biochar: synthesis, characterization, kinetic, and thermodynamic studies. Polymers
(Basel) 13. https://doi.org/10.3390/polym13213781
63. Abd El-Monaem EM, Omer AM, El-Subruiti GM, Mohy-Eldin MS, Eltaweil AS (2022)
Zero-valent iron supported-lemon derived biochar for ultra-fast adsorption of methylene blue.
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64. Santhosh C, Daneshvar E, Tripathi KM, Baltrėnas P, Kim TY, Baltrėnaitė E, Bhatnagar A (2020)
Synthesis and characterization of magnetic biochar adsorbents for the removal of Cr(VI) and
Acid orange 7 dye from aqueous solution. Environ Sci Pollut Res 27:32874–32887. https://
doi.org/10.1007/s11356-020-09275-1
65. Yang L, Gao J, Liu Y, Zhang Z, Zou M, Liao Q, Shang J (2018) Removal of Methyl orange
from water using sulfur-modified nZVI supported on biochar composite. Water Air Soil Pollut
229. https://doi.org/10.1007/s11270-018-3992-x
66. Zheng X, Zheng H, Xiong Z, Zhao R, Liu Y, Zhao C, Zheng C (2020) Novel anionic
polyacrylamide-modify-chitosan magnetic composite nanoparticles with excellent adsorption
capacity for cationic dyes and pH-independent adsorption capability for metal ions. Chem Eng
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Chapter 10
Biochar Composites for Environmental
and Energy Applications

Khaled Zoroufchi Benis, Kerry N. McPhedran, and Jafar Soltan

1 Introduction

Economic growth and improvements in agriculture productivity and practices have


resulted in an increasing trend in produced renewable biomasses such as agricul-
tural residues. For example, more than 3.5 billion people worldwide rely on wheat
as their primary food source, resulting in the annual production of over 850 million
tons of wheat straw [1]. Composting and open burning are common techniques for
disposing of agricultural residues. However, these have the disadvantages of emitting
air pollutants and greenhouse gases during combustion and losing the opportunity
of converting biomasses to value-added products [2, 3]. Recently, exploiting renew-
able biomasses to produce biofuel via environmentally acceptable processes such as
pyrolysis has attracted considerable interest.
Pyrolysis is the thermal degradation of biomass at high temperatures (300–900 °C)
in the absence of oxygen to produce syngas, bio-oil, and biochar [4]. From the energy
balance point of view, only 10–25% of the energy generated during pyrolysis is
consumed to run the process. The resulting bio-oil and syngas can be converted to the
biofuel or can be used as a feedstock to produce a wide range of value-added chemi-
cals [5]. Biochar can also be produced using conventional energy-intensive methods,
but it might not be economically viable on a large scale compared to bio-energy
biochar [5–7]. The method employed to create biochar (Fig. 1) can significantly

K. Zoroufchi Benis · J. Soltan


Department of Chemical and Biological Engineering, University of Saskatchewan, Saskatoon,
Canada
K. N. McPhedran (B)
Department of Civil, Geological & Environmental Engineering, University of Saskatchewan,
Saskatoon, Canada
e-mail: kerry.mcphedran@usask.ca
K. Zoroufchi Benis · K. N. McPhedran · J. Soltan
Global Institute for Water Security, University of Saskatchewan, Saskatoon, Canada

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2023 211
A. K. Nadda (ed.), Biochar and its Composites, Materials Horizons:
From Nature to Nanomaterials, https://doi.org/10.1007/978-981-99-5239-7_10
212 K. Zoroufchi Benis et al.

Fig. 1 Biochar production methods

impact its final chemical and physical characteristics. For instance, the creation of
biochar is favored by slow pyrolysis, while bio-oil, gasification, and syngas are the
results of fast pyrolysis. The amount of biochar produced during pyrolysis reduces
as the temperature rises, but the biochar’s aromatic condensation and carbon content
both improve.
The bio-energy or conventional biochars are carbon-rich organic materials that
have shown high potential in environmental remediation [8, 9]. Biochar is regarded
as an adsorbent for treating contaminated air and water, CO2 capture, and soil reme-
diation due to its pore characteristics, large surface area, and presence of active sites
and diverse functional groups on its surface [8, 10–12].
Despite the biochar’s unique characteristics that make it a potent material for envi-
ronmental remediation, significant interest has been shown in optimizing the pyrol-
ysis conditions or modifying biochar properties to improve its efficiency. Biochar
activation can be done via chemical and physical methods. Generally, alkaline and/or
acid treatment is used for chemical activation, whereas steam treatment is the most
common procedure for physical activation. The biochar treated with an alkaline or
acid solution, or a physical method, is called activated biochar. Additionally, biochar
composites, also called engineered biochars, are produced by impregnating biochar
with modifying agents such as metal oxides to promote the physicochemical char-
acteristics and enhance the adsorption capacity towards the target contaminant [13].
These treatments, including activated biochar and biochar composites, enhance the
functionality of the biochars and broaden their applicability for the adsorption of a
wider range of contaminants and other environmental applications. Biochar can be
modified using either pre-pyrolysis or post-pyrolysis processes. Pre-pyrolysis treat-
ment is done by treatment of raw biomass feedstock before the pyrolysis process,
whereas post-pyrolysis treatment is the preparation of biochar composite after pyrol-
ysis of the raw bio-waste [4]. For making a biochar composite, pristine biochar can
10 Biochar Composites for Environmental and Energy Applications 213

Fig. 2 Pre-pyrolysis and post-pyrolysis treatments for preparing biochar composites

be chemically or physically activated to improve its porosity and surface area, which
is typically done before the preparation of the composite [14].
Figure 2 shows the schematics of pre- or post-pyrolysis treatments for making
engineered biochar. Pre-pyrolysis treatments modify the raw biomass before it is
pyrolyzed into biochar, whereas post-pyrolysis treatments modify the biochar that
has already been formed. Feedstock and pyrolysis/modification variables such as
heating rate, temperature, and the type of applied chemical affect the composite
features and the efficiency of the treatment.
The current chapter aims to provide a foundation for comprehending how different
techniques of preparing biochar composites can alter their physiochemical proper-
ties and, in turn, their performance for environmental remediation. Section 2 briefly
overviews the common biochar activation techniques including chemical and phys-
ical methods. Section 3 categorizes and describes the methods that are used for
preparing biochar composites. Section 4 highlights the environmental applications
of biochar composites. Finally, Sect. 5 summarizes the future research directions and
Sect. 6 includes the conclusions of the chapter.

2 Biochar Activation

Different factors affect the physicochemical properties of biochar such as the biomass
feedstock and pyrolysis conditions. For instance, a high pyrolysis temperature elim-
inates more oxygenated functional groups, such as carbonyl and carboxyl groups,
resulting in a higher point of zero charge (PZC). However, raising the pyrolysis
temperature also raises the costs and reduces biochar yield [15]. Additionally, the
temperature of the pyrolysis process influences the surface area, pore characteris-
tics, and mineral content of a biochar. Therefore, optimizing the pyrolysis condition
to develop a biochar with desired properties for adsorption of a target contaminant
is crucial. Various functional groups on the biochar surface, including hydroxyl,
carboxy, carbonyl, amine, ether, amide, alkyl, and alkyne, play a crucial role in the
214 K. Zoroufchi Benis et al.

Fig. 3 Biochar activation methods

adsorption of contaminants. Physical and chemical activation can be used to enhance


these functional groups. Moreover, the activation of the biochar can enhance surface
features such as pore characteristics and surface area. Considering that activated
biochars can also be used for preparing biochar composites, this section overviews the
common chemical and physical activation techniques. The activation techniques and
their main characteristics are summarized in Fig. 3 and discussed further throughout
this section.

2.1 Physical Activation

Physical activation, also known as gas activation, involves using gases such as CO2
and steam [16]. The activation is done following the carbonization process and
usually requires high temperature (600–900 °C) [17]. Compared to chemical acti-
vation, the primary benefit of physical activation is that it prevents the inclusion
of impurities originating from the applied activating agent [18]. However, physical
activation techniques are often less efficient than chemical activation techniques,
but they are simpler and less expensive to implement. Physical activation enhances
biochar’s physicochemical characteristics by oxidizing the carbonaceous structure
and eliminating the by-products of incomplete combustion [19].
Steam activation is a commonly used physical activation technique that improves
the properties of pristine biochar by enhancing pore characteristics, polarity, and
porosity while decreasing the aromaticity. The steam activation process creates pores
in biochars a result of eliminating trapped volatile gases or particles and converting
the volatile materials and carbon content into CO and CO2 [20]. Steam activa-
tion is conducted after primary pyrolysis by contacting the pristine biochar with
steam for 0.5–3 h [17, 21]. The higher adsorption performance of steam-activated
biochar is due to the improved surface area, higher micropore volume, and higher
amount of oxygenated functional groups. For example, the sulfamethazine adsorption
capacity of a pristine biochar prepared from an invasive plant increased by 55% after
steam activation at 700 °C, which was attributed to enhanced pore characteristics
10 Biochar Composites for Environmental and Energy Applications 215

and surface area of the activated biochar [22]. Alternatively, activating wood apple-
derived biochar with superheated steam at 800 °C for 1.5 h enhanced its ibuprofen
adsorption capability by 5% [23].
CO2 activation is another common physical activation technique that can result in
improved surface area, pore volume, and a higher amount of active sites on biochar
surfaces [24]. The interaction of CO2 with biochar during CO2 activation results
in the formation of CO (i.e., hot corrosion) and the development of a microporous
structure [25]. For example, the surface of a corncob-biochar increased from 57 to
755 m2 /g after CO2 activation [24]. In a comparative study, the micropore volume
and surface area of CO2 -activated barley straw-biochar were 0.327 cm3 /g and 789
m2 /g, while those for the steam-activated biochar were 0.230 cm3 /g and 552 m2 /g,
respectively [26]. In another study, the amount of Ca and Na in biochar was found to
be higher after purging with CO2 at a high temperature as compared to N2 purging.
As a result, CO2 activation may be utilized to modify the characteristics of biochars
in various applications, such as the treatment of water and wastewater, where alkali
metals (e.g., Ca and Na) can induce cation exchange [17].
Air activation is not recommended in most circumstances since the reaction
occurs quickly, and the carbonaceous material burns up irrepressibly. However, the
air-activated biochar may have improved pore characteristics that make it useful for
the adsorption of non-charged or non-polar organic contaminants [20]. For example,
a significant change were observed in the external/internal surfaces and porosity
of grape seed-biochar [27], as were the formation of a considerable fraction of
micropores on olive-tree-biochar during an air activation process [18].
Overall, the benefit of physical activation techniques is the simplicity of the acti-
vation process. However, they result in biochars that are typically less efficient as
compared to chemical activation techniques. Accordingly, several chemical acti-
vation agents and techniques have been developed and used to enhance biochar
characteristics that are discussed in the following section.

2.2 Chemical Activation

The most frequent approach to biochar activation is chemical activation which


involves mixing biomass (pre-pyrolysis treatment) or pristine biochar (post-pyrolysis
treatment) with an activation agent. The most widely used activation agents can
be categorized into acids and oxidizers, and alkaline solutions. These agents are
presented in the following three sections.

2.2.1 Acids and Oxidizers

Treatment of a biochar with acids or oxidizers can improve its porosity and surface
area, eliminate metallic impurities, introduce acidic functional groups, and alter the
PZC of biochar [4]. Moreover, chemical activation alters the oxygen-containing
216 K. Zoroufchi Benis et al.

functional groups such as COOH, and O–H, C O, which play a crucial part role in
the adsorption capacity of biochars. The hydrophilicity and functionality of a biochar
in the liquid phase can be enhanced by introducing oxygen-containing functional
groups to its surface [28, 29].
H3 PO4 , HNO3 , HCl, H2 SO4 , C6 H8 O7 , C2 H2 O4 , and H2 O2 are widely used
acids and oxidizers for biochar activation [30]. For example, the raw biomass BET
(Brunauer, Emmett and Teller) surface area of 2 m2 /g dramatically increased to
1,452 m2 /g after mixing with H3 PO4 solution and microwave pyrolysis [31]. In other
studies, HCl-activated biochars showed enhanced adsorption capacity toward organic
compounds that can be attributed to the formed carboxylic, phenolic, carbonyl, and
lactonic groups on the biochar surface, decreased ash content, removal of impurities,
and formation of hydrophobic active sites [32, 33]. HNO3 and H2 O2 activation of
biochar resulted in the introduction of acid-binding sites, such as carbonyl, phenolic,
and carboxylic, which enhanced its surface acidity and porosity [34]. H2 O2 activa-
tion of a peanut-hull biochar improved the oxygenic active sites, such as carboxylic
groups, leading to a 20-fold higher Pb(II) adsorption [35]. Activation of eucalyptus
saw dust biochar using acetic acid, citric acid, and tartaric acid resulted in a lower
BET surface area than the pristine biochar. However, activated biochar had a higher
methylene blue adsorption capacity that was due to the introduced carboxyl group on
the surface of biochar [36]. It is important to note that the disposal of waste media of
strong acids after the activation process may cause secondary pollution. Therefore,
despite the weak activation capability of organic acids, their easier disposal can be
considered as their main advantage over strong acids.

2.2.2 Alkali Treatment

Alkali treatment can improve the surface area, porosity, surface basicity, and the
number of oxygenated functional groups of a biochar. The degree to which alka-
line activation improves biochar characteristics may vary depending on the type of
base employed. KOH and NaOH are the commonly used bases in biochar activa-
tion [4, 14]. For instance, high BET surface areas of 2,825 and1,156 m2 /g were
reported for a NaOH-activated coconut shell biochar [37] and a KOH-activated
wakame biochar [38], respectively. The cadmium adsorption capacity of a biochar
increased 2–3 times after KOH activation, which was due to the increased amount
of oxygenated, aromatic, and carboxyl functional groups [39]. Moreover, the PZC
of biochar increases by alkaline activation that can be favorable in the adsorption
of anions [40]. For example, the higher arsenate (As(V)) adsorption performance of
a KOH-activated biochar compared to H2 O2 -activated biochar was attributed to its
more favorable PZC [41].
Overall, different activation agents introduce a variety of functional groups to
biochar surfaces. For example, alkaline activation may introduce hydroxyl groups,
whereas oxidizing agents may form carboxylic groups. Therefore, it is important
to choose an appropriate activation agent based on the characteristics of the target
contaminants. A combination of two activation processes (e.g., acid and alkaline
10 Biochar Composites for Environmental and Energy Applications 217

treatments) may also be beneficial by introducing multiple functional groups to the


biochar surface.

3 Biochar Composites

Introducing external components into the biochar matrix is a relatively recent method
for integrating multifunctional features into a hybrid composite material. Therefore,
biochar composites benefit from the advantages of both incorporated components
and biochar matrix. In certain instances, pristine biochar may not have an affinity for
a target contaminant, but it serves as a scaffold with a large surface area to support
the external components that will serve as adsorption sites. Biochar composites are
usually prepared by impregnating biochar with clays, metals, carbonaceous materials,
or microorganisms [4, 14]. Typically, biochar composites are prepared by mixing the
feedstock (pre-pyrolysis) or produced biochar (post-pyrolysis) with modification
agents such as metal salts and clays. The following sections present the features of
different biochar composites, and some examples are provided for their application.

3.1 Clay-Biochar Composites

Clay minerals such as bentonite, biotite, pyrite, and kaolinite are natural and low-
cost materials with a layered structure, high ion exchange capacity, and surface
area that show a high capacity to adsorb different contaminants. However, they are
generally tiny particles and may swell in water thereby hindering their application
in systems such as fixed-bed adsorption [42]. Clay-biochar composites can over-
come the drawbacks of the clays and benefit from the advantages of both materials.
For example, a clay-biochar composite prepared by combining bentonite clay and
municipal solid waste showed 40% higher ciprofloxacin adsorption capacity than
pristine biochar. The higher adsorption performance of the composite was because
of enhanced porosity and intercalation of ciprofloxacin in the bentonite layers and
electrostatic interactions between the composite surface and the adsorbate [43].
Pyrolysis of a mixture of bamboo biochar and montmorillonite facilitated the
conversion of bamboo powder to biochar, and the resulting composite success-
fully adsorbed NH4 + and PO4 3− [44]. An attapulgite-biochar composite created
by pyrolysis of zinc chloride–treated rice straw biomass and attapulgite showed
higher surface area, pore volume, cation exchange capacity, and oxygenated func-
tional groups compared to pristine biochar. The performance of the composite
was considerably higher than pristine biochar in the reduction of the bioavailable
portion of cadmium and arsenic in the river sediment [45]. The nutrient release cycle
from a struvite-biochar composite was significantly longer than that of conventional
chemical fertilizers [46], and also had higher Cu immobilization ability [47].
218 K. Zoroufchi Benis et al.

3.2 Metal-Biochar Composites

Biochar can be modified with different metals such as Fe, Al, Mn, and Zn to improve
its adsorption capacity for organic chemicals and heavy metals and for immobiliza-
tion through enhanced electrostatic interactions, precipitation, and surface complex-
ation [4]. Metal-biochar composites are generally produced by mixing feedstock
or pristine biochar with metal chloride or nitrate salt solutions. Typically, biochar
has a negative charge that makes it an excellent adsorbent for positively charged
contaminants but a poor adsorbent for negatively charged contaminants such as Cl− ,
PO4 3− and NO3 − . Metal-biochar composites with a positive charge will have a higher
affinity towards negatively charged contaminants [14, 48].
Fe-biochar composites with various types of deposited iron oxides, such as
FeOOH, Fe2 O3 , and Fe3 O4, are widely reported in the literature. For instance,
the arsenic adsorption capacity of a corncob biochar increased 20-fold after treat-
ment with Fe(NO3 )3 and pyrolysis. However, the modification did not enhance the
adsorption of cationic lanthanide [49]. Electrochemical deposition of iron oxide on
the biochar matrix improved its arsenic adsorption capacity from 25 to 922 μg/
g, which was attributed to the formation of inner-sphere complexes among arsenic
oxyanions and the deposited iron oxides on the biochar surface [50]. Multiple iron
species can coexist in Fe-biochar composites that increase the biochar performance
through a variety of mechanisms. For instance, it was observed that Fe(II) on the
surface of FeCl3 -modified biochar reduced Cr(VI) into Cr(III), and then insoluble
Cr(III)–Fe(III) precipitates were formed [51].
The redox reaction of zero-valent iron (ZVI)-modified biochar has been reported
frequently in the literature [52–54]. For example, it was reported that the removal
of Pb(II) onto ZVI-modified biochar occurs in two steps. First, Pb(II) is adsorbed
onto active sites of the modified biochar, followed by the reduction of adsorbed Pb2+
to Pb0 by the metallic Fe [52]. Similarly, the adsorbed CrO4 2− onto the surface of
ZVI-modified biocharis reduced to Cr(III) by oxidation of Fe0 to Fe2+ and Fe3+ [55].
Magnetic biochar has received a lot of attention in recent years due to the ease
with which spent biochar can be separated from treated water using a magnetic field.
Moreover, the deposited iron oxides on the biochar surface act as adsorption sites.
Co-precipitation of ferric and ferrous oxides onto biomass followed by pyrolysis
(pre-pyrolysis) [56] or after pyrolysis (post-pyrolysis) [57] leads to the formation
of magnetic biochar. It is important to note that magnetite formation on the biochar
surface may block biochar pores and reduce the surface area [58]. Yet, a higher surface
area was obtained for a magnetic biochar. This was attributed to the evaporation of
FeCl3 -derived chemicals from cavities and pores during the modification process
leading to the creation of new spaces [59]. In a comparative study, a magnetic biochar
developed by the pre-pyrolysis process showed higher arsenic adsorption capacity
than that of magnetic biochar developed by the post-pyrolysis process [60]. Similarly,
magnetic chestnut shell-biochar showed three times higher adsorption capacity than
pristine biochar [61]. Overall, the magnetic properties and adsorption capacities
depend on modification conditions. For example, increasing Fe concentration during
10 Biochar Composites for Environmental and Energy Applications 219

the modification process led to reducing Cu(II) adsorption performance of a magnetic


biochar [62].
An Al-biochar composite with high arsenic and phosphorus adsorption capacity
was prepared by soaking feedstock biomass in an AlCl3 solution before the pyrolysis
process [63]. A composite prepared using the same method showed higher NO3 −
and PO4 3− adsorption capacity compared to pristine biochar, which was because of
its higher surface area and the functional groups created on the biochar surface [64].
Similarly, an Al-biochar composite derived from bamboo biomass showed higher
sulfamethoxazole and sulfapyridine removal efficiencies in both batch and column
adsorption tests [65].
Mn-biochar composites are usually produced by mixing biomass or biochar
with Mn salts such as KMnO4 solution. A MnO2 -modified biochar was prepared
by mixing biochar particles with KMnO4 solution followed by dropwise addition of
Mn(II) acetate solution. The modified biochar had high efficiency in removing Cd
and Pb from water [66]. Similarly, an Mn oxide-loaded biochar prepared through
soaking with biochar KMnO4 successfully immobilized soil arsenic by oxidation
of As(III) to As(V) [67]. In another study, aMnO2 /Mn3 O4 -modifed biochar was
made by mixing the biomass with KMnO4 solution before pyrolysis. The higher
Pb(II), Cu(II), and Cd(II) adsorption performance of the modified biochar than that
of unmodified biochar was attributed to the deposited MnOx particles and higher
surface area and more oxygenated functional groups [68].
Zn-biochar composites have shown high adsorption capacities for both inorganic
and organic contaminants. A Zn-biochar composite derived from glue residue modi-
fied by ZnCl2 showed higher Cr(VI) adsorption capacity than HCl and KOH-activated
biochars. It was reported that deposited ZnO improved the adsorption of Cr(VI) by ion
exchange and electrostatic interaction [69]. In a similar study, Zn(NO3 )2 -pretreated
biomass was pyrolyzed to obtain a Zn-biochar composite and successfully removed
Cr(VI) from water by ion exchange and electrostatic interaction [70]. A Zn-biochar
composite with a high surface area of 1,556 m2 /g showed high adsorption capaci-
ties for tetracycline, chlortetracycline, and oxytetracycline. Hydrogen bonding and
electrostatic interaction were reported as the major mechanisms of adsorption [71].
In another study, Zn-loaded biochars were prepared at various pyrolysis tempera-
tures using a pre-pyrolysis modification method. The largest surface area was attained
at the higher pyrolysis temperature; however, the As(V) adsorption capacity reduced
at higher pyrolysis temperature [72]. It was discovered that the higher zinc content
of the composite prepared at 400 °C was responsible for its higher As(V) adsorption
capacity, suggesting that the adsorbent’s surface chemistry was crucial to the As
adsorption [72].
Ternary and quaternary biochar composites consisting of more than one
metal(oxide)have been developed to benefit from the advantages and adsorption
capabilities of different metals. For example, a sawdust-based biochar composite with
the addition of iron and zinc chloride salts was prepared. Zn-biochar and Fe-biochar
had tetracycline adsorption capacities that were three times higher than unmodi-
fied biochar, however, the Zn-Fe-biochar had a four-fold greater adsorption capacity
[73]. Microwave pyrolysis followed by an electrochemical treatment was utilized to
220 K. Zoroufchi Benis et al.

prepare two biochar composites impregnated with Al and Zn oxides (AlZn-biochar)


[74], and Fe and Mn oxides (FeMn-biochar) [13]. Both the ternary biochar compos-
ites showed higher arsenic adsorption capacities compared to the binary biochar
composites (with single metal oxide). In addition to the synergetic effect of the two
metal oxides in enhancing the adsorption capacity, Zn oxides in AlZn-biochar and
Mn oxides in FeMn-biochar acted as oxidizers to oxidize highly toxic As(III) to less
toxic As(V) throughout the adsorption process.
In another study, a magnetic biochar composite modified by Fe3 O4 and MnOx
was prepared under anoxic conditions using potato leaves and stems. The composite
possessed a higher pore volume and surface area than pristine biochar. Compared
to pristine biochar, the adsorption capacity of the composite was 1.2, 1.5, and 1.6
times higher for norfloxacin, ciprofloxacin, and enrofloxacin, respectively [75].
A CuZnFe2 O4 –biochar composite successfully adsorbed sulfamethoxazole and
bisphenol A by hydrogen bonding, π-π Electron Donor − Acceptor (EDA) interac-
tions, and hydrophobic interactions [76]. A FeMnCe-biochar composite was synthe-
sized using KMnO4 , Ce2 (CO3 )3 , and Fe(NO3 )3 . The deposited metal oxides on the
biochar surface allowed oxidation of As(III) to As(V) and complexation of arsenic
ions with hydroxyl groups [77].
Layered double hydroxides (LDHs)-biochar composites have been reported
as a ‘win–win’approach for both biochar and LDHs in improving their char-
acteristics. LDHs are bimetallic hydroxide clays with layered structures and
exchangeable interlayer anions. The formula of LDHs could be described as
[M1−x 2+ Mx 3+ (OH)2 ]x+ (An– )x/n ·mH2 O, where M2+ and M3+ are divalent and trivalent
cations (e.g., Mg–Al, Zn–Al, Mg–Fe, Ni–Fe, Ca–Al), respectively, An− represents
an interlayer anion, x is the M3+ /(M2+ + M3+ ) ratio, and the charge of the layer
depends on the M2+ /M3+ ratio [78, 79]. LDH-biochar composites have been success-
fully utilized to remove inorganic and organic contaminants from water, and there
have been few studies investigating their Advanced Oxidation Processes (AOP) catal-
ysis performance. However, further research is required to determine the viability
of LDH-biochar composites for soil remediation [79]. LDH-biochar composites can
simultaneously improve nutrient retention and also immobilize metals because of
several improvement mechanisms. They have a high anion exchange capacity, which
makes them ideal for the adsorption of anions such as nitrate [80], phosphate [81],
and arsenic [82]. Additionally, hydrogen bonding, pore-filling, and π–π EDA inter-
actions allow LDH-biochar composites to be employed for the removal of organic
chemicals [83].
Overall, different techniques have been used to combine biochar and metal(oxides)
to make biochar-metal composites. The composites have shown high efficiencies in
the adsorption of organic and inorganic chemicals from contaminated water and soil.
However, their preparation costs and metal releasing potential should be considered
prior to their consideration for use in real-world applications.
10 Biochar Composites for Environmental and Energy Applications 221

3.3 Carbonaceous Material-Biochar Composites

Graphene and carbon nanotubes (CNTs) are highly effective at removing organic and
inorganic impurities in various matrices. However, high preparation costs limit their
application. Using carbon graphene or nanotubes to modify biochar can improve the
surface area and pore characteristics of the biochar while decreasing the necessary
concentrations of graphene or carbon nanotubes, hence reducing the cost of prepara-
tion [84]. Composites of graphene-biocharor CNTs-biochar can be very effective at
removing organic pollutants because of the abundance of oxygenated groups (e.g.,
carboxyl and phenolic hydroxyl groups) and π electrons in their structure. A CNTs-
biochar composite (1% carbon nanotube) showed higher methylene blue adsorption
capacity because of its higher surface of 390 m2 /g than that of 9 m2 /g for pristine
biochar [85]. Similarly, the surface area of pristine biochar increased from 261 to
468 m2 /g after coating with graphene, which led to higher phenol and methyl blue
adsorption performance of the composite compared to pristine biochar. The π–π
EDA interactions were observed as the main adsorption mechanism [86]. Adsorp-
tion of sulfamethazine was enhanced in graphene oxide-biochar (GO) composites
mostly by π–π EDA interactions; however, pore-filling, hydrogen bonding, and ion
exchange also played important roles [87].
Metals-contaminated soil and water have also been treated with carbonaceous
material-biochar composites. GO-biochar composites are usually produced through
pre-pyrolysis impregnation of feedstock with a suspension of graphene oxide that
improves surface area and often produces more oxygenated functional groups than
the pristine biochar because of the integration of the graphene into the composite
[14]. For example, in addition to a threefold increase in the specific surface area of
GO-biochar composite compared to unmodified biochar, Fourier-transform infrared
spectroscopy (FTIR) spectra revealed an increase in the intensity of single –OH,
O–C–O, C–O, and C = Cpeaks by 550%, 200%, 100%, and 100% respectively. The
Hg(II) adsorption capacity of the composite increased due to complexation with the
abundant oxygenated groups on the composite surface [88].
Another study reported that the GO-biochar composite had significantly better
effectiveness at removing Cr(VI) from an aqueous solution than pristine biochar.
The authors hypothesized that the electrostatic attraction of Cr(VI), together with
the reduction of Cr(VI) to Cr(III) and complexation of Cr(III), led to the adsorp-
tion of Cr(VI) onto the composite [89]. Pb and sulphapyridine were removed from
water using a CNT-biochar composite. Hydrogen bonding and π-π EDA interactions
enhanced the adsorption of organic contaminants, and Pb was removed via surface
complexation with oxygenated functional groups [90].
222 K. Zoroufchi Benis et al.

3.4 Microorganism–Biochar Composites

Microbial communities are often essential for eliminating pollutants from the envi-
ronment. The microbial methods are widely used in wastewater treatment and decom-
posing organic contaminants due to low cost and environmental friendliness [91, 92].
However, the microbial methods still have several drawbacks, including the loss or
reduction of microbial activity and the challenging separation and recovery following
treatment [93]. The microscopic size of microorganisms enables them to penetrate
tiny pores and establish a biofilm, a solid structure that can withstand washout [94].
Biochar is an inert material with a high surface area that promotes the colonization
and growth of biofilms with favorable features. Therefore, microorganism–biochar
composites have the benefits of stable and high biomass that is not easily washed
out, rapid reaction speed, high toxin resistance, and simple separation [95, 96].
The efficacy of biodegradation is enhanced when microorganisms with strong
organic contaminant degradation capacities are immobilized on the biochar. In addi-
tion, microorganism-biochar composites can be effective at immobilizing metals
in soil due to the complexation of metals with various oxygen- and nitrogen-
containing groups on microbial cells. For example, a microorganism–biochar
composite degraded naphthenic acids while simultaneously adsorbing the metals
from oil sands process water [97]. They found a sevenfold increase in the composite’s
adsorption capacity for As(V) compared to pure biochar. In another study, polycyclic
aromatic hydrocarbon (PAH)-degrading microbes were immobilized on a biochar
that showed higher degradation capacity for fluoranthene, phenanthrene, and pyrene
in soil compared to pristine biochar. It was proposed that biochar aided the PAH
mass transfer from the soil to the biochar, and subsequently, PAHs were degraded by
the immobilized microbes [98]. Additionally, soil fertility can be increased with the
help of microorganism-biochar composites because of the microorganisms’ capacity
to fix nitrogen and release phosphate [99].

3.5 Summary of Biochar Composites

Biochar composites have been the subject of many studies in recent years because
of their ease of synthesis, the possibility of modifying physicochemical properties,
and the development of new functionalities. Metal-biochar composites are widely
studied, among which Fe-biochar composites gained more recent attention because
of the different functionalities of various types of deposited iron oxides such as
FeOOH, Fe2 O3 , and Fe3 O4 .Water treatment has been the primary focus of the
studies undertaken on the biochar-composites. The following section summarizes
the demonstrated performances of biochar composites in different environmental
applications.
10 Biochar Composites for Environmental and Energy Applications 223

4 Environmental Application of Biochar Composites

Demand for sustainable materials necessitates that engineers and scientists look
for new sources of these materials. The exploitation of renewable resources is
increasing in popularity as a result of environmental awareness, economic concerns,
and substantial technology breakthroughs. There is a growing interest worldwide
in finding ways to convert renewable and abundant natural resources like agricul-
tural wastes into value-added products. Biochar composites with unique properties
have shown high potential for different environmental applications. The following
sections highlight the trending applications of biochar composites.

4.1 Water and Wastewater Treatment

The worldwide water scarcity crisis is becoming increasingly dire as a result of the
rising population, rising water demand, and diminishing water resources. In addition,
safeguarding our water resources and the environment, while also meeting the needs
of an expanding global population, is a major challenge for humanity. Different
inorganic and organic contaminants present in water and wastewater pose a significant
risk to environmental and human health. Therefore, there is a pressing demand for
promising and cost-effective techniques to eliminate these contaminants. Different
methods have been developed to treat various contaminated water matrices such as
membrane separation, coagulation, reverse osmosis, precipitation, and adsorption.
In particular, adsorption has attracted a lot of attention as a treatment technology
because of its potential for reduced costs and easier operations compared to other
methods [42].
Several adsorbents have been utilized to adsorb contaminants from water including
modified activated carbons, metal oxides, and resins [100–102]. Coupled with the
relatively low cost of implementation of adsorption processes as compared to other
treatment methods, biochars can be used to further reduce costs given they are inex-
pensive and eco-friendly alternatives to more expensive commercial adsorbents [4,
11]. Additionally, biochar composites can be prepared focusing on the target applica-
tion. For example, Fig. 4 presents the schematic diagram of the municipal wastewater
treatment process combined with a filtration column packed with biochar compos-
ites. As a final barrier, this column can be filled by biochar composites capable of
capturing the contaminants that were not removed in previous steps of the process.
The adsorption efficiency is primarily dependent on the characteristics of the
targeted contaminant and the biochar. Various biochar composites have shown
higher adsorption performance compared to pristine biochar in removing inorganic
and organic contaminants such as nutrients, heavy metals, dyes, pesticides, antibi-
otics, phenolics oils, persistent organic compounds, and polynuclear aromatics. For
example, the Pb(II) adsorption capacity of a biochar increased from 6.4 to 98.9% after
modification with magnesium oxide, showing a significantly higher performance
224 K. Zoroufchi Benis et al.

Fig. 4 Schematic diagram of municipal wastewater treatment process combined with a filtration
column packed with biochar composites

of biochar composite [103]. Similarly, pristine biochar could only remove 10% of
phosphate, but MgO-biochar was able to remove 67% [104]. Effective elimination
of biological water contaminants can also be achieved with modified biochars. For
example, compared to pristine charcoal, H2 SO4 -treated biochar was more effective
at removing Escherichia coli from stormwater [105].
Despite the mentioned advantages of the adsorption process over other treatment
methods, managing the spent (exhausted) adsorbent can be challenging. Exhausted
adsorbents are either regenerated or disposed of in landfills or incinerators, depending
on the cost of the adsorbent and the type of captured contaminants [106]. Typically,
the adsorption process is reversible which is especially the case for physical adsorp-
tion. Therefore, there is an added cost and potential for environmental damage (such
as contamination of soil, groundwater, and surface water) when the contaminant-
loaded adsorbent is disposed of in a landfill [107]. On the other hand, exhausted
adsorbents that are incinerated may release harmful gases and produce ash that may
include dangerous elements [108].
Exhausted adsorbents can be regenerated and reused to reduce the amount of
disposed waste and the cost. Depending on the type of loaded contaminants the
exhausted biochar can be regenerated by heating, microwave irradiation, chemical
regeneration using organic or inorganic solvents, and supercritical fluid regenera-
tion [109]. However, in non-thermal procedures that occur in solution, the adsor-
bates, such as heavy metals, are desorbed without decomposing; thus, the removal of
adsorbate-laden solution poses an additional challenge [106]. Another challenge of
the regeneration/reuse of an adsorbent is that the regeneration process may impact the
biochar properties, alter its structure and porosity, and damage the functional groups
and adsorption sites. The damaged biochar may lose its adsorption functionality and
usefulness. Therefore, the regeneration process should be optimized to recover the
adsorbent with a minimum damage to the biochar.
10 Biochar Composites for Environmental and Energy Applications 225

4.2 Soil Remediation

Soil health has recently become the most commonly recognized notion in terms of
sustainable use and management of soil resources, leading to the global develop-
ment of traditional soil management and use practices [110]. The residence time
of biochar in soils is estimated to be in the range of 10 to 1,000 years, making its
lifespan around 10 to 1000 times longer than that of most soil organic materials
[111]. Biochar composites can improve soil health by enhancement of the physical
structure, immobilization of metals, degradation/retention of organic contaminants,
retention of nutrients and water, adaptation of salinity, suppression of antibiotic resis-
tance genes, and assisting the soil’s living system [112]. There are a few reports on
the effect of biochar composites on the soil’s physical structure. However, it has been
reported that pristine biochar can decrease soil bulk density by 3–11% and enhance
porosity by 14–64%[112]. A Fe-biochar composite resulted in a positive stabilization
mechanism of soil organic carbon by improving the soil aggregate stability and the
amount of organic carbon included in large aggregates [113].
Biochar has been shown to be an effective substance for removing a wide range
of contaminants from soil environments depending on the soil and biochar charac-
teristics. The effectiveness of biochar in soil remediation results from its carbon-
rich composition, wide range of functional groups, high surface area, porous struc-
ture, high chemical and microbiological stability, and high cation exchange capacity
[114]. In addition, the biochar’s heterogeneous structure with acidic and basic, and
hydrophobic and hydrophilic functional groups allows it to react strongly with a wide
variety of soil components [115]. Therefore, the biochar has been identified as an
excellent adsorbing matrix for numerous soil contaminants [114]. There are several
reports on higher heavy metals immobilization of biochar composites compared to
unmodified biochar including a Mg-biochar composite for Cd [116], a Fe-biochar
composite for Pb and Sb [117], and a ZVI-biochar composite for Cd and As [118].
In addition to immobilizing metals, innovative biochar composites have success-
fully been utilized to remove organic contaminants. For instance, a microorganism-
biochar composite enhanced the biological degradation of dibutyl phthalate while
preventing plant uptake of the compound [119]. Another combination of microor-
ganisms and biochar aided in the mass transfer and biodegradation of PAHs in the
soil [98]. Metal-biochar composites have also been successfully utilized in the reme-
diation of organic chemicals. For example, a MoS2 -biochar composite adsorbed
ciprofloxacin from a soil more effectively than pristine biochar [120]. In another
study, a Fe-biochar composite was observed to be more efficient than pristine biochar
in reducing pesticide uptake due to high adsorption ability and increasing plant root
iron plaque [121].
Biochar composites have shown better efficiency in nutrient retention compared
to pristine biochar. For example, a Fe–Mg LDH-biochar composite improved the
retention of NH4 + (through hydrogen bonding) and NO3 ¯ (by anion exchange) and
immobilized hazardous metal ions [122]. A Fe-K-biochar composite increased the
available amount of K, Ca, NO3 ¯, and PO4 + for plants and decreased the leaching of
226 K. Zoroufchi Benis et al.

PO4 + and NO3 ¯. The composite had the potential to be utilized as a fertilizer due to
its capacity to both slow the leaching of soil nutrients and boosting the bioavailability
of minerals [123].
Salt toxicity is a significant factor in limiting crop yield. It was observed that a Mn-
biochar composite reduced sodium accumulation and improved safflower growth and
salinity adaptability [124]. Carbon sequestration is another possible environmental
application of the biochar and biochar composite. The global carbon cycle depends
heavily on soils as a carbon sink and directly impacts climate change. It has been
suggested that biochar [125] and its composites [126] may positively affect soil
carbon sequestration. However, further research should be done to study the effect
of feedstock types, in addition to pyrolysis and modification conditions of biochar,
on enhancing the carbon sequestration capacity of the soil.
Despite the benefits of employing biochar composites for soil remediation, safety
considerations must be taken into account when applying them. The principal prob-
lems of employing biochar composites for soil remediation are the potential for
release of hazardous PAHs and metals and the remobilization of soil pollutants due
to the facilitation of transport by biochar colloids [127]. For example, it was specu-
lated that released CNT or nano-sized graphene particles on the biochar composites
may harm living organisms [128]. It is also possible that the immobilized microor-
ganisms on microorganism-biochar composites may act as invasive species thereby
leading to ecological disasters [129]. These safety considerations must be given
special attention before the application of biochar composites.

4.3 Catalyst and Activator

Biochar has exceptional characteristics that make it a suitable catalyst or catalyst


carrier including chemical stability, diversity of surface functional groups, and high
porosity and surface area, [130]. For example, a variety of biochars have been used
as catalysts for biodiesel production [131, 132]. In a study, vegetable oils were trans-
esterified, and free fatty acids were esterified using sulfuric acid-treated biochars as
a catalyst [131]. In another study, a sulfonated biochar showed high activity in ester-
ification and reducing free fatty acids [132]. Similarly, a hydrophobic sulfonic acid
functional biochar was highly selective and active in the alkylation of 2-methylfuran
using cyclopentanone for biofuel production [133].
Biochars also served as carriers of catalysts. For example, the transesterification
of vegetable oil with methanol was catalyzed using CaO-based catalysts supported
on a biochar [134]. An aluminum-biochar composite was used as a catalyst for
the isomerization of glucose to fructose [135]. Recently, the biochar was used in
sulfate radical-based AOPs to degrade emerging contaminants [136]. It was found
that biochars modified by metals and phenolic compounds had higher concentrations
of persistent free radicals that facilitated the degradation of polychlorinated biphenyls
by activating persulfate to create sulfate radicals [137].
10 Biochar Composites for Environmental and Energy Applications 227

4.4 Supercapacitor

In recent years, there has been a surge of international interest in studying sustainable
and renewable energy sources. Numerous studies have focused on supercapacitors
because of their numerous beneficial properties, including high power density, cycle
stability, and rapid charge–discharge capability [138]. Electrode materials for super-
capacitors should ideally have high pore characteristics to supply sufficient active
sites for electrochemical reactions [139]. The application of common carbonaceous
materials, such as CNT, graphite granules, and granular activated carbon, is limited
because of their high cost. Recently, biochars with high porosity and surface area
have been used as electrodes in a supercapacitor [138]. For example, after being acti-
vated by nitric acid, the biochar’s specific capacitance rose from 14 to 115 F/g. The
pristine and activated biochars had a lifetime of over 5,000 cycles [140]. Similarly,
a Mn-biochar composite had a specific capacitance of 493 F/g that reduced by about
22% after 5,000 cycles [141]. Similarly, a KOH and FeSO4 -modified biochar showed
a specific capacitance of 256 F/g [142]. Although introducing different functional
groups can further enhance a biochar’s capacitance capability, the modification cost
should be considered to make biochar-based electrodes economically feasible.

4.5 Fuel Cell

Microbial fuel cells (MFCs) are gaining popularity as viable technologies for wastew-
ater treatment and energy recovery. Generally, MFCs consist of two compartments
containing a cathode and an anode, respectively, that are separated by a membrane
[143]. Biochars can be used in different parts of an MFC including the anode, cathode,
and membrane. For example, a KOH-modified biochar was utilized as both anode and
cathode showing a higher power generation and dye removal compared to carbon felt.
This was attributed to the biochar’s high concentration of oxidizing substances [144].
In another study, a biochar was treated with nickel ferrite and nanorod/poly(3,4-
ethylenedioxythiophene) and was successfully employed as an anode in an MFC
[145]. Similarly, KOH, Fe, and Zn-modified biochars were used as cathode mate-
rials for an MFC equipped with a KOH-modified biochar. This cathode showed a high
power density of 1,329 mW/m2 , which was comparable to that of Pt nanoparticles
supported on carbon of 1,337 mW/m2 [146].
An ideal membrane for MFC (usually a proton exchange membrane) is cheap and
has high proton conduction, a low rate of biofouling, and low oxygen and substrate
crossover [147]. Depending on the pyrolysis condition, feedstock type, and modi-
fication conditions, biochar composites may be used as a membrane in MFC. For
example, the proton conductivity per unit cost of a sulfonated biochar was 32 times
higher than the Nafion membrane [148].
Biochar and biochar composites have recently been shown to have promising
MFC applications. However, there are still many unanswered questions that need
228 K. Zoroufchi Benis et al.

to be addressed before the technology can be widely adopted, including the need
for a cost analysis for mass production, standardization in the preparation process,
practical properties, and performance compared to standard materials.

5 Future Directions

Many studies have been completed on biochar composites for application in environ-
mental remediation, however, there are still many unanswered research questions.
The stability of the biochar is a key factor to nsider when using it for water treatment
and soil remediation. There has been a report of dissolving the organic material of
the biochar during the complexation with heavy metals, indicating that biochar’s
instability may cause the leaching of dissolved organic matter into solution [149].
Additionally, there is the possibility of leaching of metals or toxic compounds from
modified biochars into water or soil leading to secondary pollution. The potential
toxicity of biochar composites to microorganisms is another factor that should also
be considered. The biochar’s toxicity may rise as a result of the chemical and physical
changes due to the modification or activation process (reactivity, presence of metals
nanoparticles, etc.).For example, the cytotoxic effect of a Fe-biochar composite was
reported in the treatment of real river sediments [150].
Most studies on biochar and biochar composites have only been conducted in
lab settings; thus, it is crucial to examine biochar’s efficacy and sustainability on a
larger scale in natural ecosystems. Improper disposal of biochar might cause envi-
ronmental damage. Therefore, it is critical to develop improved methods for dealing
with the management of contaminant-laden biochars. Additionally, there is a dearth
of information regarding the large-scale production of biochar composites. Modi-
fying the biochar will increase manufacturing costs; thus, it is important to weigh the
benefits of employing modified biochars as adsorbents against those of alternative
materials like activated carbon. Overall, further investigations are needed to establish
the applications of biochar composites in the real-world.

6 Conclusion

In recent years, biochar composites have garnered considerable interest due to their
promising potential for environmental remediation. Incorporating external compo-
nents into the biochar matrix is a technique for merging multifunctional character-
istics into a hybrid composite material. Biochar composites are mainly prepared by
impregnating the biochar with clays, metals, carbonaceous materials, or microor-
ganisms. Biochar composites with distinctive characteristics have demonstrated
promising potential for environmental applications such as the treatment of water
and wastewater, soil remediation, catalysis, supercapacitors, and fuel cells. However,
10 Biochar Composites for Environmental and Energy Applications 229

further research should focus on investigating the stability, toxicity, economic


feasibility, and regeneration/reuse of biochar composites.

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