materials
Article
Chemical Activation of Banana Peel Waste-Derived Biochar
Using KOH and Urea for CO2 Capture
Joanna Sreńscek-Nazzal 1 , Adrianna Kamińska 1 , Jarosław Serafin 2 and Beata Michalkiewicz 1, *
Citation: Sreńscek-Nazzal, J.;
Kamińska, A.; Serafin, J.;
Michalkiewicz, B. Chemical
Activation of Banana Peel
Waste-Derived Biochar Using KOH
and Urea for CO2 Capture. Materials
2024, 17, 872. https://doi.org/
10.3390/ma17040872
Academic Editor: Jon Alvarez
Received: 26 January 2024
Revised: 8 February 2024
Accepted: 12 February 2024
Published: 14 February 2024
Copyright: © 2024 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Materials 2024, 17, 872. https://doi.org/10.3390/ma17040872
1 Department of Catalytic and Sorbent Materials Engineering, Faculty of Chemical Technology and
Engineering, West Pomeranian University of Technology in Szczecin, Piastów Ave. 42,
71-065 Szczecin, Poland; joanna.srenscek@zut.edu.pl (J.S.-N.); kaminska.adrianna@zut.edu.pl (A.K.)
2 Department of Inorganic and Organic Chemistry, University of Barcelona, Martí i Franquès, 1-11,
08028 Barcelona, Spain; jaroslaw.serafin@qi.ub.es
* Correspondence: beata.michalkiewicz@zut.edu.pl
Abstract: This article describes the synthesis and characterization of porous carbon derived from
waste banana peels by chemical activation with KOH or by activation KOH and urea modification.
The as-synthesized samples were carefully characterized by various techniques. The prepared
carbonaceous materials possess highly developed micropore and mesopore structures and high
specific surface area (up to 2795 cm2 /g for materials synthetized with KOH and 2718 cm2 /g for
activated carbons prepared with KOH and urea). A series of KOH-activated samples showed CO2
adsorption at 1 bar to 5.75 mmol/g at 0 ◦ C and 3.74 mmol/g at 25 ◦ C. The incorporation of nitrogen
into the carbon sorbent structure increased the carbon uptake capacity of the resulting materials
at 1 bar to 6.28 mmol/g and to 3.86 mmol/g at 0 ◦ C and 25 ◦ C, respectively. It was demonstrated
that treatment with urea leads to a significant increase in nitrogen content and, consequently, CO2
adsorption, except for the material carbonized at 900 ◦ C. At such a high temperature, almost complete
decomposition of urea occurs. The results presented in this work could be used in the future for
utilization of biomass such as banana peels as a low-cost adsorbent for CO2 capture, which could
have a positive impact on the environment and human health protection.
Keywords: banana peels; urea; activated carbon; CO2 adsorption
1. Introduction
In recent years, there has been a significant increase in carbon dioxide emissions into
the atmosphere. It is widely believed that carbon dioxide (CO2 ) is the most dangerous
anthropogenic greenhouse gas. Emissions of this gas are related to the rapid development of
industrialization and technology that has taken place over the past 20 years [1]. This rapid
industrial development has contributed to the overconsumption of carbon-rich compounds,
such as fossil fuels, to meet energy needs, among other things. Therefore, research is being
conducted to minimize CO2 emissions. In this regard carbon-based systems are being
developed to capture carbon dioxide [2].
Activated carbons (ACs) are the most promising adsorbents proposed for CO2 cap-
ture due to their highly developed specific surface area and extensive pore system [3].
In addition, carbonaceous materials can be obtained from most elemental carbon-rich
materials by thermal decomposition [4]. Depending on the conditions of the activation and
carbonization process, as well as the type of raw material and activating agent used, the
resulting carbon adsorbents can have different properties. Commonly used raw materials
for industrial-scale production of activated carbon are wood, peat, bituminous coal and
lignite [5]. In recent years, raw materials of plant origin (biomass) have been gaining
importance as precursors for the synthesis of activated carbon. Banana peels are among
the agricultural biomass waste that has potential to be used as a raw material to produce
carbonaceous materials [6]. Banana peel waste is part of the solid waste generated during
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Materials 2024, 17, 872 2 of 15

the processing of this fruit and is mainly produced in homes, restaurants, and food outlets.
Unfortunately, this waste does not provide any economic advantages and, instead, is a
pollution source, leading to environmental issues, which makes this biomass troublesome
in terms of disposal and storage [7]. The application of banana peels as a precursor to
production activated carbons allows the use of raw materials that have not been used before
and represents a new way of utilizing these wastes.
The characteristic feature of activated carbon that makes it so widely used in many
chemical processes is the ability to modify the surface of the carbon to obtain, among other
things, a material with good adsorption properties. Not surprisingly, various modifications
of activated carbons are constantly being introduced to alter their acid–base, catalytic and
textural properties, which largely determine their suitability for adsorption processes [8].
The advantages of carbon-based sorbents, in addition to their high concentration of microp-
ores and large surface area, include the fact that the surface chemistry of activated carbon
can be readily modified by the incorporation of various functional groups, depending
on the specific requirements of the application. Additional properties, including pore
size, volume, surface area and distribution, can be easily adjusted by manipulating the
activation conditions and activating agents. Due to the increased availability of binding
sites resulting from micropores in activated carbon, the process of CO2 adsorption on
microporous materials is facilitated, which is another advantage of microporous adsorbents
worth highlighting [1].
In order to obtain activated carbons with new and broader properties, in addition
to appropriately selected chemical activation parameters, atoms of various elements are
introduced into the carbon matrix. Activated carbons doped with heteroatoms have gained
considerable attention due to their functionality and improvement of their remarkable
properties. Some key heteroatoms such as nitrogen (N), sulfur (S) and metal oxides (MgO,
CuO, etc.) are generally used to develop excellent CO2 adsorbents [9].
The physicochemical properties of nitrogen-modified activated carbons make the
development of new and efficient technologies to produce such materials a major focus of
functional carbon materials research at this time. From the results of studies described in
the literature, it appears that the ability of activated carbons to adsorb carbon dioxide, based
on the physical adsorption process, can be enhanced by incorporating nitrogen functional
groups into their structure [10,11].
In general, modifications of activated carbons to enrich these materials with nitro-
gen can be divided into two main methods: (1) impregnation of activated carbons with
nitrogen-containing compounds and (2) thermal treatment of the carbon precursor in the
presence of a nitrogen-containing agent [12]. The method of impregnating activated car-
bons with nitrogen compounds has been widely reported in the literature. This method
involves some problems related to the blocking of most of the pores present in structures
of activated carbons, causing a drastic deterioration of their textural parameters [13]. The
second way to synthesize nitrogen-modified carbons is to subject the precursor to thermal
decomposition in the presence of a so-called reagent-N, a compound containing nitrogen
atoms in its structure. The most common reagents used for this purpose are ammonia, urea,
melamine and nitric oxide. To a lesser extent, pyrrole, hydrogen cyanide, formamide, hy-
droxylamine, hydrazine, carbazole and acridine are also used [14]. Of note is the use of urea
to enrich activated carbon with nitrogen. This type of modification can be accomplished
by impregnating the carbon precursor with a urea solution or by mechanically mixing
the reactants in solid form. The reaction with urea allows the introduction of significant
amounts of nitrogen groups on the surface of activated carbons [15]. Depending on the
modification, the nitrogen content of the resulting materials is typically in the range of 4
to 9 wt.%. Activated carbons obtained by modifying the carbon precursor with urea prior
to the activation process are characterized by a much more strongly developed specific
surface area and a larger pore volume than analogous unmodified materials [16,17].
In this study, we report a facile strategy for synthesis of activated carbons and nitrogen-
doped activated carbon by using banana peels as a carbon source, KOH as the chemical
Materials 2024, 17, 872 3 of 15

agent and urea as an additional nitrogen source through one-staged chemical activation
with carbonization. It was demonstrated that treatment with urea leads to a significant
increase in nitrogen content and, consequently, CO2 adsorption, except for the material
carbonized at 900 ◦ C. At such a high temperature, almost complete decomposition of urea
occurs. Considering that the precursor was waste banana peels obtained as waste from
a local fresh fruit juice production facility, a low-cost carbon source was applied and a
value-added product was obtained. In addition, the use of biomass, which is difficult to
dispose of, and its conversion into functional carbonaceous materials that can be used as
CO2 sorbents, makes this waste management method environmentally friendly and in line
with the so-called ‘green chemistry’ trends.
The novelty of the study lies in the description of banana peel modification using
urea, which has not been previously documented. This modification resulted in increased
CO2 adsorption. It is worth emphasizing that urea modification, activation using KOH
and carbonization occurred simultaneously. CO2 adsorption was compared for materials
produced at five different temperatures, with urea-modified and unmodified materials
prepared for each temperature. This approach provided valuable insights into the nitro-
gen introduction capabilities using urea. Other authors typically compare urea-modified
materials with a single reference material that does not contain urea.

2. Materials and Methods

2.1. Chemicals and Materials
The raw material used in the work was waste banana peels obtained from a local fresh
fruit juice production point (Szczecin, Poland). The manufacturer’s stickers were removed
from the banana peels, then the biomass was cut into smaller pieces and air-dried at ambient
temperature for 48 h. In next step, the raw material was transferred to a laboratory dryer
(Alpina, Konin, Poland) and dried at 40 ◦ C for 24 h. The dried biomass was ground into
powder in a laboratory grinder (Chemland, Stargard, Poland).
In this study, the following reagents were used: HCl (Sigma-Aldrich, Burlington, MA,
USA), aqueous saturated KOH solution (Sigma-Aldrich, Burlington, MA, USA) and urea
(Sigma-Aldrich, Burlington, MA, USA).

2.2. Synthesis of Activated Carbons from Banana Peels

Banana peels were impregnated with saturated KOH solution (the ratio of biomass to
activator was 1:1) or with saturated KOH solution in the presence of urea (weight ratio 1:1)
and thoroughly mixed. Impregnation of the biomass took place at ambient temperature for
3 h. After this time, the materials were placed in a laboratory dryer at 200 ◦ C for 19 h.
The activated carbons obtained by this method were named B_KOH_x, where x
corresponds to the temperature at which the carbonization process was carried out. Simi-
larly, activated carbons obtained in the above-described method using urea were named
B_KOH_urea_x, (x—carbonization temperature).
After removal from the laboratory dryer, the impregnated materials were ground,
transferred to a quartz boat and placed in a tube furnace (Czylok, Jastrz˛ebie-Zdrój, Poland).
The thermal decomposition (simultaneous carbonization and activation process) of
biomass in the furnace was carried out in the temperature range of 700–900 ◦ C and in
an inert gas atmosphere (nitrogen, 18 L/h). The dwell time of the samples at the set
carbonization temperature was 1 h. After the carbonization and activation process, the
materials were ground again and washed with distilled water until the pH of the filtrate
was close to neutral. Then, 100 mL of HCl was added to the synthesized materials and
boiled. After cooling to room temperature, the samples were again washed with distilled
water. The synthesized activated carbons were dried in a laboratory dryer at 180 ◦ C.
This step was the same for the materials obtained by impregnation of biomass with
saturated KOH solution and by impregnation of biomass with saturated KOH solution in
the presence of urea.
The scheme of the preparation of activated carbons is shown in Figure 1.
 cooling to room temperature, the samples were again washed with distilled water. The
synthesized activated carbons were dried in a laboratory dryer at 180 °C.
This step was the same for the materials obtained by impregnation of biomass with
saturated KOH solution and by impregnation of biomass with saturated KOH solution in
Materials 2024, 17, 872 the presence of urea. 4 of 15
The scheme of the preparation of activated carbons is shown in Figure 1.

ambient temperature
grinding
3h

KOH
or
200 °C
KOH and CH₄N₂O 19h

activation
00 – 00 °C
with
carbonization 18 l/h N2

treatment
after distilled H2O
thermal decomposition
process pH ~ 7

Figure1.1. Schematic
Figure Schematicillustration
illustrationfor
forsynthesis
synthesisof
ofbanana-derived
banana-derivedporous
porouscarbons.
carbons.
2.3. Characterization the Obtained Activated Carbons
2.3. Characterization the Obtained Activated Carbons
Nitrogen sorption at −196 ◦ C and carbon dioxide at 0 ◦ C and 25 ◦ C was used to
Nitrogen sorption at −196 °C and
characterize textural parameters. Gas adsorption carbon dioxide at 0 °C and 25were
measurements °C was used to
carried char-
out on
aacterize textural parameters.
QUADRASORB evo™ volumetricGas adsorption
apparatus measurements
(Anton Paar, were carried out
St Albans, UK;on a QUAD-
previously
RASORB evo™
Quantachrome volumetric
Instruments, apparatus
Boynton Beach, (Anton Paar,
Activated carbon
USA, 2014). St adsorption
Before Albans, UK; previously
measurements
were taken, the samples were degassed for 19 h under vacuum at 250 C. Specificmeasure-
Quantachrome Instruments, Boynton Beach, USA, 2014). Before ◦
adsorption surface
ments
area were
was taken, the
calculated fromsamples were degassed for 19 h under
the Brunauer–Emmett–Teller (SBET )vacuum
equation. at 250
The°C.totalSpecific
pore
surface was
volume area determined
was calculated fromfrom
the the Brunauer–Emmett–Teller
maximum adsorption of nitrogen (SBET) vapor
equation.
at aThe total
relative
pore volume
pressure was The
of ~0.99. determined from the maximum
density functional theory (DFT) adsorption
method of wasnitrogen
used tovapor at a rela-
determine the
tive pressure
volume of ~0.99. The density functional theory (DFT) method was used to determine
of micropores.
the volume
The X-rayof micropores.
diffraction (XRD) analysis of the prepared activated carbons was recorded
by anTheX-rayX-ray diffraction (X’Pert–PRO,
diffractometer (XRD) analysis of the prepared
Panalytical, Almelo, activated carbons was
The Netherlands, recorded
2012) using
by Kα
Cu an X-ray diffractometer
radiation (λ = 0.154 nm) (X’Pert–PRO, Panalytical,
as the radiation sourceAlmelo, in the 2θThe Netherlands,
range ◦
of 10–100 2012)
. us-
ing Cu Kα radiation
Raman spectroscopy(λ = 0.154 nm) as
was used to the radiation
determine thesource
carbon inskeleton
the 2θ range of 10–100
structure of the°.ob-
tainedRaman
carbonspectroscopy
materials. The wasRaman
used analysis was recorded
to determine the carbon on skeleton
an InVia structure
Raman microscope
of the ob-
(Renishaw
tained carbonPLC, New Mills,
materials. TheWotton-under-Edge,
Raman analysis wasUK, 2007) at
recorded ona an
laser wavelength
InVia of 785 nm.
Raman microscope
The spectra PLC,
obtained inMills,
the Raman shift range fromUK, 500 cm −1 to 2000 cm−1 were analyzed.
(Renishaw New Wotton-under-Edge, 2007) at a laser wavelength of 785
After
nm. The spectra obtained in the Raman shift range from 500 cmand
normalizing the maximum of the G peak to 1, the intensity −1 toposition
2000 cmof−1 the
were G ana-
and
D peaks in each spectrum were read and the ratio of these intensities
lyzed. After normalizing the maximum of the G peak to 1, the intensity and position of was determined.
the G Toand
visualize
D peaks theinsurface structureswere
each spectrum of theread
synthesized
and the carbonaceous
ratio of these materials,
intensitiesthe wasSEM
de-
pictures
termined. were taken with a SU8020 Ultra-High Resolution Field Emission Scanning Electron
Microscope (Hitachi
To visualize theLtd., Tokyo,
surface Japan, 2012).
structures of the synthesized carbonaceous materials, the
The nitrogen content of carbonaceous
SEM pictures were taken with a SU8020 Ultra-High materials was tested
Resolution Field using
Emission a Leco
ScanningCN
628 elemental analyzer (LECO Corporation,
Electron Microscope (Hitachi Ltd., Tokyo, Japan, 2012). St. Joseph, MI, USA, 2011). The standard
curveThe wasnitrogen
determined contentusing an EDTA standard.
of carbonaceous materials Approximately
was tested using 0.035a g of sample
Leco CN 628was ele-
weighed for measurement.
mental analyzer (LECO Corporation, St. Joseph, MI, USA, 2011). The standard curve was
X-ray fluorescence
determined using an EDTA (XRF) and an Epsilon
standard. 3 spectrometer
Approximately 0.035 g of (Panalytical,
sample wasAlmelo,weighedThe for
Netherlands,
measurement. 2011) were utilized for elemental analysis.

3. Results and Discussion

Based on XRF research, it was determined that dried banana peels contain 16 wt.%
potassium and 2 wt.% chlorine. The nitrogen content, tested using a Leco CN 628 elemental
analyzer, was found to be 1 wt.%.
Table 1 shows the percentage yield of carbonaceous materials. The yield of activated
carbon decreases as the temperature of biomass carbonization increases.
Materials 2024, 17, 872 5 of 15

Table 1. Percentage yield of carbonaceous materials.

Sample Yield (%)

B_KOH_700 15
B_KOH_750 15
B_KOH_800 14
B_KOH_850 11
B_KOH_900 11
B_KOH_urea_700 19
B_KOH_urea_750 18
B_KOH_urea_800 15
B_KOH_urea_850 10
B_KOH_urea_900 10

Table 2 shows the textural characterization of the carbon materials. Based on the N2
adsorption data, the BET surface area (SBET ) and the pore and micropore volumes were
calculated for the two groups of activated carbons studied. For KOH-activated materials,
the size of the specific surface area is in the range of 1268–2795 m2 /g, and the pore volume
ranges from 0.547 to 1.652 cm3 /g. On the other hand, for materials obtained by chemical
activation with KOH in the presence of urea, the SBET parameter is in the range from 1653
to 2718 m2 /g and the total pore volume ranges from 0.718 to 1.487 cm3 /g.

Table 2. Values of the textural parameters of carbonaceous materials.

Sample SBET (m2 /g) Vtot (cm3 /g) Vmic (cm3 /g) N Content (wt.%)
B_KOH_700 1268 0.547 0.464 2.1
B_KOH_750 1623 0.669 0.582 1.5
B_KOH_800 1651 0.744 0.565 1.7
B_KOH_850 2598 1.361 0.680 1.7
B_KOH_900 2795 1.652 0.608 1.6
B_KOH_urea_700 1653 0.718 0.596 5.8
B_KOH_urea_750 2228 0.981 0.726 3.6
B_KOH_urea_800 2271 1.052 0.690 2.9
B_KOH_urea_850 2580 1.209 0.731 2.5
B_KOH_urea_900 2718 1.487 0.632 2.1

As can be seen, carbonaceous materials obtained from precursors that have been
modified with urea prior to the activation process show a much more strongly developed
specific surface area and a larger pore volume than analogous materials obtained from
precursors that have not been treated with urea [16,18].
The use of urea significantly influenced the development of the porous structure of
the tested carbon materials, as shown by the data presented in Table 1. This is particularly
evident in the case of carbon B_KOH_urea_750, whose specific surface area increased
by more than 600 m2 /g after the introduction of urea into the system compared to the
system without urea (B_KOH_750). In addition, for samples obtained at temperatures
above 800 ◦ C, no significant differences in textural parameters were observed, regardless of
the method used to prepare the carbonaceous materials.
Since we have examined the nitrogen content in dried banana peels (1.0 wt.%), we can
conclude that we are dealing with two nitrogen sources. The nitrogen content in materials
untreated with urea after the carbonization process was higher than in dry banana peels.
Therefore, from 0.5 to 1.1% of nitrogen was incorporated into the carbon due to contact
with gaseous nitrogen at high temperatures.
The nitrogen content in materials treated with nitrogen was significantly higher. The
increase in these values is attributed to nitrogen from urea. In samples treated with urea,
part of the nitrogen likely comes from gaseous nitrogen. However, it is not possible to
determine these proportions. Estimating this based on the difference in nitrogen content
 terials untreated with urea after the carbonization process was higher than in dry banana
peels. Therefore, from 0.5 to 1.1% of nitrogen was incorporated into the carbon due to
contact with gaseous nitrogen at high temperatures.
The nitrogen content in materials treated with nitrogen was significantly higher. The
Materials 2024, 17, 872 increase in these values is attributed to nitrogen from urea. In samples treated with urea, 6 of 15
part of the nitrogen likely comes from gaseous nitrogen. However, it is not possible to
determine these proportions. Estimating this based on the difference in nitrogen content
for samples carbonized at the the same
same temperature
temperature in thethe presence
presence or
or absence
absence of
of urea
urea would
would
be too much of a simplification.
The textural properties
propertiesof ofthe
thebiomass-based
biomass-basedactivated
activated carbons
carbons were
were determined
determined by2
by N
sorption
N at −
2 sorption at196 ◦ C.
−196 °C.NN adsorption–desorption
2 adsorption–desorption isotherms
isotherms for
for carbon
carbon materials activated
2
with KOH are shown in Figure 2a while those those for
for carbon
carbon materials
materials activated
activated with
with urea
urea are
are
shown in Figure 2b. As can be seen, both materials prepared with potassium
Figure 2b. As can be seen, both materials prepared with potassium hydroxidehydroxide as
thethe
as activating agent
activating agentand
andmaterials
materials with urea
with introduced
urea introduced areare
microporous
microporous with
withmoderate
moder-
development
ate developmentof mesoporosity.
of mesoporosity.

1100
1100
(a) 1000 (b)
1000

900
900
N2 adsorption (cm³/g )

800 800

N2 adsorption (cm³/g)
700 700

600 600

500 500
400 400
300 300
B_KOH_700
B_KOH_urea_700
200 B_KOH_750
200 B_KOH_urea_750
B_KOH_800
100 B_KOH_urea_800
B_KOH_850
100 B_KOH_urea_850
B_KOH_900
0 B_KOH_urea_900
0.0 0.2 0.4 0.6 0.8 1.0 0
0.0 0.2 0.4 0.6 0.8 1.0
P/P0 P/P0

Figure 2. Adsorption–desorption
Figure 2. Adsorption–desorptionisotherms
isothermsofof(a)
(a)samples
samplessynthesized
synthesized with
with KOH
KOH and
and (b)(b)
forfor sam-
samples
ples synthesized with KOH and
synthesized with KOH and urea. urea.

Isotherms
Isotherms obtained
obtained from N22 adsorption
adsorption for for materials
materials activated
activated with
with KOHKOH as as well
well as
KOH-activated
KOH-activated materials
materials inin the
the presence
presence of of urea
urea in temperature range of 700–800 ◦°C
in the temperature C
can
can be classified
classified asas Type I, while materials obtained at 850 ◦
°CC and 900 ◦
°C show mixed
C show mixed
features of Type I and IV isotherms, accordingaccording to to the
the UPAC
UPAC classification
classification [19].
[19].
The
The type
typeI Iisotherm
isothermisisassociated
associated with microporous
with microporous materials,
materials,while the type
while IV iso-
the type IV
isotherm
therm indicates
indicates mesoporous
mesoporous materials.
materials. TheThe initial
initial partofofthe
part theisotherm
isothermisistype
typeI Iwith
withsig-
sig-
nificant adsorption at low relative pressures
pressures (P/Po
(P/Po <<0.1),
0.1),which
whichcorresponds
corresponds to to adsorption
adsorption
micropores. At medium
in micropores. medium and and high
highrelative
relativepressures,
pressures,the theisotherm
isotherm is is
classified
classifiedas as
type IV
type
with an H4-type hysteresis loop, indicating that these are materials
IV with an H4-type hysteresis loop, indicating that these are materials containing bothcontaining both micro
and mesopores
micro in theirinstructure
and mesopores [19,20].[19,20].
their structure
N22 adsorption
adsorption increases
increasesasasthe activation
the activationtemperature
temperature of the of carbon materials
the carbon increases,
materials in-
indicating
creases, a gradual
indicating development
a gradual of the porous
development of thestructure, reachingreaching
porous structure, the highest thenitrogen
highest
uptake for
nitrogen samples
uptake for activated at a temperature
samples activated of 900 ◦ C.ofA900
at a temperature similar
°C. Arelationship has been
similar relationship
noted and described in the literature by other researchers [21,22].
has been noted and described in the literature by other researchers [21,22].
It can be concluded that the obtained activated carbons have both micropores and
mesopores, as confirmed by the distribution of pores shown in Figure 3a,b. Figure 3a,b
show the pore size distribution (PSD) of KOH-activated and KOH and urea-activated
carbon materials determined by DFT from N2 adsorption at liquid nitrogen temperature.
As shown in Figure 3, all carbon materials contained both micropores up to the 2 nm
range and mesopores in their structure. All materials, regardless of their heat treatment
temperature contained mesopores in the range of 2 nm to 5 nm. However, a significant
increase in the volume of mesopores in the range of 2.5–13 nm is observed for materials
activated with both KOH and KOH with urea at the two highest temperatures of 850 ◦ C
and 900 ◦ C.
 increase in the volume
As shown in Figureof3,mesopores
all carbon in the range
materials of 2.5–13
contained nmmicropores
both is observedup fortomaterials
the 2 nm
activated
range andwith both KOH
mesopores and KOH
in their withAll
structure. urea at the two
materials, highest temperatures
regardless of 850 °C
of their heat treatment
and 900 °C. contained mesopores in the range of 2 nm to 5 nm. However, a significant
temperature
When
increase in the
the activation
volume oftemperature
mesopores in wasthehigher
rangethan 800 °C,
of 2.5–13 nmthe
is development of meso-
observed for materials
Materials 2024, 17, 872 pores was more pronounced. It can be assumed that thermal degradation of the pore 7wall
of°C
15
activated with both KOH and KOH with urea at the two highest temperatures of 850
led
andto900
the°C.
expansion of micropores to mesopores [22].
When the activation temperature was higher than 800 °C, the development of meso-
0.6 0.8
pores was more pronounced. It can be assumed that thermal degradation of(b)
the pore wall
(a)
led to the expansion of micropores
0.7 to mesopores [22].
0.5
/g·nm) (cm³/g·nm)

/g·nm) (cm³/g·nm)
0.6 0.6
0.8
0.4 (a) (b)
0.5
0.7
Volume

Volume
0.5
0.3 0.4
0.6
(cm³

(cm³
VolumePore

VolumePore
0.4
0.3
0.5
0.2 B_KOH_700 B_KOH_urea_700
dV/dW Pore dV/dW

dV/dW Pore dV/dW

B_KOH_750 B_KOH_urea_750
0.3 0.2
0.4
B_KOH_800 B_KOH_urea_800
0.1 B_KOH_850 B_KOH_urea_850
B_KOH_900 0.1
0.3 B_KOH_urea_900
0.2 B_KOH_700 B_KOH_urea_700
0.0 B_KOH_750 0.0 B_KOH_urea_750
0.2
0 1 2 3 4 5 6 7 8 9 10 11 12B_KOH_800
13 14 15 0 1 2 3 4 5 6 7 8 9 10 11B_KOH_urea_800
12 13 14 15
0.1 B_KOH_850 B_KOH_urea_850
Pore Width (nm) B_KOH_900 0.1 Pore Width (nm)
B_KOH_urea_900

0.0
Figure
Figure 3.
3. Carbon
Carbon pore
pore size
size distribution
distribution0.0determined
determined by
by DFT
DFT method
method for
for (a)
(a) samples
samples synthesized
synthesized with
with
0 1 2 3 4 5 KOH
6 7and
8 (b)
9 samples
10 11 12 synthesized
13 14 15 with KOH
0 1 and
2 3urea.
4 5 6 7 8 9 10 11 12 13 14 15
KOH and (b) samples synthesized with KOH and urea.
Pore Width (nm) Pore Width (nm)
The
When pore
thesize distributions
activation shown
temperature in Figure
was higher 4athan
and ◦ C, determined
b were
800 for theofcarbon
Figure 3. Carbon pore size distribution determined by DFT method for the development
(a) samples synthesizedmeso-
with
materials
pores
KOH and using
was(b)
more DFT based
pronounced.
samples on
synthesized CO
It can
withbe
2 adsorption
assumed
KOH at 0 °C and confirmed the presence
that thermal degradation of the pore
and urea. ofwall
mi-
cropores
led to theinexpansion
all samples. The course of
of micropores to pore distribution
mesopores [22]. for KOH-activated carbons as well
as forThe
KOH-activated carbons with
pore size distributions urea addition
shown
shown Figureis4a
in Figure similar.
and b The
weresamples showed
determined forthree dom-
the carbon
inant diameter
materials using
using ranges:
DFT 0.3–0.4
DFTbased
based onnm,
on COCO0.4–0.7 nm and
adsorption
adsorption
2 2 at 0 ◦and
at 0.7–1
0 °C nm.
C and confirmed
confirmed the the presence
presence of
of mi-
micropores in all samples. The course of pore distribution for KOH-activated
cropores in all samples. The course of pore distribution for KOH-activated carbons as well carbons as
1.8 1.8
well
as forasKOH-activated
for KOH-activated carbons
carbons
B_KOH_700 with with urea addition
urea(b)addition is similar.
is similar. The samples
The samples showed showed
B_KOH_urea_700 three
three dom-
(a)
1.6 dominant diameter
inant diameter ranges:
B_KOH_750
ranges: 0.3–0.4
0.3–0.4 nm, 0.4–0.7
nm, 0.4–0.7
1.6 nm and nm0.7–1
and 0.7–1
nm. nm. B_KOH_urea_750
B_KOH_800 B_KOH_urea_800
/g·nm) (cm³/g·nm)
/g·nm) (cm³/g·nm)

1.4 B_KOH_850 1.4 B_KOH_urea_850

1.8 B_KOH_900 1.8 B_KOH_urea_900
B_KOH_700 B_KOH_urea_700
1.2 (a) 1.2 (b) B_KOH_urea_750
1.6 B_KOH_750 1.6
Volume

B_KOH_urea_800
Volume

1.0 B_KOH_800 1.0

1.4 B_KOH_850 1.4 B_KOH_urea_850
B_KOH_900 B_KOH_urea_900
0.8
(cm³
(cm³

0.8
VolumePore

1.2 1.2
VolumePore

0.6 0.6
dV/dW Pore dV/dW

1.0
dV/dW Pore dV/dW

1.0
0.4 0.4
0.8 0.8
0.2 0.2
0.6 0.6
0.0 0.0
0.40.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 0.40.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
Pore width (nm) 0.2
Pore width (nm)
0.2
Figure 4. Micropore size distribution 0.0 curves of activated carbons prepared (a) with KOH (b) with
0.0
0.0 0.2 0.4 KOH
0.6 and urea
0.8 calculated
1.0 1.2 on the
1.4 basis of0.0CO2 adsorption.
0.2 0.4 0.6 0.8 1.0 1.2 1.4
Pore width (nm) Pore width (nm)

Figure 4. Micropore size distribution curves of activated carbons prepared (a) with KOH (b) with
Figure 4. Micropore size distribution curves of activated carbons prepared (a) with KOH (b) with
KOH and urea calculated on the basis of CO2 adsorption.
KOH and urea calculated on the basis of CO2 adsorption.

Nitrogen, the source of which was urea, was characterized using tests with an ele-
mental analyzer. The results of the tests on the nitrogen content of the materials obtained
are shown in Table 1. For materials obtained without urea, nitrogen content varies from
1.6–2.0 wt.%. Trends were observed to decrease with increasing temperature. The highest ni-
trogen content (2.0 wt.%) was characterized by material synthetized at 700 ◦ C (B_KOH_700),
while for the sample prepared at 900 ◦ C (B_KOH_900), the value was 1.6%. The nitrogen
content of materials unmodified with urea is due to the fact that this element occurs nat-
urally in banana peels (the percentage of nitrogen in this biomass noted in the literature
is estimated at about 2% wt; [23]), and was not removed from the carbonaceous material
during the carbonization process.
 The nitrogen content of materials unmodified with urea is due to the fact that this element
occurs naturally in banana peels (the percentage of nitrogen in this biomass noted in the
literature is estimated at about 2% wt; [23]), and was not removed from the carbonaceous
Materials 2024, 17, 872 material during the carbonization process. 8 of 15
Much greater differences in nitrogen content were observed for urea-modified sam-
ples. The highest nitrogen content of 5.8 wt % was noted for activated carbon carbonized
at 700 °C (B_KOH_urea_700),
Much greater differences inwhile for content
nitrogen the sample prepared
were observed foraturea-modified
the highest samples.
temperature
(B_KOH_urea_900),
The highest nitrogen thecontent
value was
of 5.8only
wt.%2.0 wtnoted
was %. for activated carbon carbonized at
700 ◦ C (B_KOH_urea_700), while for the sample prepared at the highest temperature
From the data presented in Table 1, it can be concluded that the amount of nitrogen
(B_KOH_urea_900),
introduced depends on thethe
value was only 2.0temperature;
carbonization wt.%. more nitrogen was introduced into
From the data presented in Table 1, it can be concluded that the amount of nitrogen
activated carbons obtained at lower temperatures. Similar observations have been re-
introduced depends on the carbonization temperature; more nitrogen was introduced into
ported in the literature for orange peel carbons prepared with urea [24], for N-doped ac-
activated carbons obtained at lower temperatures. Similar observations have been reported
tivated
in thecarbons
literaturefrom bamboo
for orange peelcharcoal [25] andwith
carbons prepared forurea
commercial urea-modified
[24], for N-doped activatedactivated
car-
carbons [26]. The decrease in nitrogen content with increasing carbonization
bons from bamboo charcoal [25] and for commercial urea-modified activated carbons temperature
[26].
is due
The to the degradation
decrease in nitrogen of unstable
content withthermal nitrogen
increasing groupstemperature
carbonization at higher process
is due totempera-
the
tures [27].
degradation of unstable thermal nitrogen groups at higher process temperatures [27].
XRD XRD analysiswas
analysis wasemployed
employed toto characterize
characterizecrystallinity of the
crystallinity carbon
of the materials,
carbon and and
materials,
the obtained patterns are presented in Figure
the obtained patterns are presented in Figure 5a,b. 5a,b.

(a) B_KOH_700 B_KOH_urea_700

B_KOH_750
(b)
B_KOH_urea_750
B_KOH_800 B_KOH_urea_800
B_KOH_850 B_KOH_urea_850
B_KOH_900 B_KOH_urea_900
Intensity ( a. u)

Intensity (a. u)

(100) (1 0 0)

(002)

20 40 60 20 40 60
2 Theta 2 Theta

Figure 5. Diffraction
Figure 5. Diffractionpatterns
patternsof
of the activatedcarbons
the activated carbonssynthesized
synthesized from
from banana
banana withwith (a) KOH
(a) KOH and and
(b) (b)
KOH KOHwith urea
with ureaand
andcarbonized undervarious
carbonized under varioustemperatures.
temperatures.

XRDXRD profilesshow
profiles showthat
that all
all materials
materials are
arelow
lowcrystalline.
crystalline.The absence
The absenceof sharp diffrac-
of sharp diffrac-
tion peaks proves that there is no crystalline phase in the materials. Comparingdata
tion peaks proves that there is no crystalline phase in the materials. Comparing the the data
shown in Figure 5, no significant differences were found between the materials prepared
shown in Figure 5, no significant differences were found between the materials prepared
with KOH and those obtained with KOH in the presence of urea. Fr all carbons, the diffrac-
with KOH and those obtained with KOH in the presence of urea. Fr all carbons, the dif-
tion patterns show only relatively broad diffraction peaks at ~43◦ , and for the B_KOH
fraction patterns
samples, a smallshow
broadonly relatively
diffraction peakbroad diffraction
appeared peaks
at ~24◦ the at ~43
which °, and for
correspond the 100
to the B_KOH
samples, a small broad diffraction peak appeared at ~24 ° the which
◦ correspond
and 002 diffraction planes of carbon, respectively. The peak at ~24 for the other materials to the 100
anddisappeared
002 diffraction planes
(flattened ofThe
out). carbon, respectively.
low intensity The peak
of the peak at ~24 ° for
corresponding theplane
to the other(1materials
0 0)
disappeared 44◦ for activated
at approx. (flattened out). The low intensity
carbons of the
indicates that peak
these corresponding
materials to the plane (1 0
have an amorphous,
highly
0) at disordered
approx. 44 ° forstructure,
activated which is characteristic
carbons of carbon
indicates that thesematerials
materials[28].
haveSimilar diffrac-
an amorphous,
tograms of poorly available carbon materials were reported in [29,30], in which the authors
attributed them to amorphous carbons.
Structural properties of B_KOH and B_KOH_urea were also tested with Raman spectra.
Raman spectra for activated carbons synthesized at temperatures ranging from 700 ◦ C to
900 ◦ C are shown in Figure 6a,b.
 highly disordered structure, which is characteristic of carbon materials [28]. Similar dif-
fractograms of poorly available carbon materials were reported in [29,30], in which the
authors attributed them to amorphous carbons.
Structural properties of B_KOH and B_KOH_urea were also tested with Raman spec-
Materials 2024, 17, 872 9 of 15
tra. Raman spectra for activated carbons synthesized at temperatures ranging from 700 °C
to 900 °C are shown in Figure 6a,b.

D band B_KOH_700 D band B_KOH_urea_700

1.0 (a) B_KOH_750 1.0 (b) B_KOH_urea_750
B_KOH_800 B_KOH_urea_800
B_KOH_850 B_KOH_urea_850
B_KOH_900 B_KOH_urea_900
0.8 0.8

G band G band
IG/ID=0.693 IG/ID=0.730
Intensity

Intensity
0.6 IG/ID=0.663 0.6 IG/ID=0.686
IG/ID=0.658 IG/ID=0.677
IG/ID=0.645 IG/ID=0.663
0.4 IG/ID=0.624 0.4
IG/ID=0.656

0.2 0.2

0.0 0.0
1000 1500 2000 1000 1500 2000
Raman Shift [cm−1] Raman Shift [cm−1]

Figure 6. Raman
Figure 6. Ramanspectra
spectraofofactivated
activatedcarbon
carbonsamples
samples produced
produced from
from banana
banana peels
peels withwith (a) KOH
(a) KOH and
and (b) KOH und urea.
(b) KOH und urea.

The
The spectra were characterized
spectra were characterized by by two
two broad
broadbands:
bands: thethe DD band
bandlocated
locatedat at1300
1300cmcm−−11,,
attributed
attributed to to the
the disordered
disorderedphase,phase,and andthe theGGbandbandlocated
locatedatat1600
1600cm cm−
−1 , corresponding
1 , corresponding to
the crystalline phase. It was found that the D band was more intense
to the crystalline phase. It was found that the D band was more intense than the G band, than the G band,
indicating that the
indicating that thestructure
structureofofcarbon
carbonwas was significantly
significantly disordered
disordered andand associated
associated withwith
the
the presence
presence of numerous
of numerous defects
defects in thein structure
the structure [29].[29].
In addition, the
In addition, the IIG
G/I
/IDDratios
ratiosofofallallprepared
preparedactivated
activatedcarbons
carbonsare areshown
shownin inFigure
Figure 6.
6.
The ratio of thethe intensity
intensity ofof the
the G Gband
bandto tothe
theintensity
intensityofofthetheDDband
band(I(I G /ID
G /I D ) indicates the
degree of graphitization
graphitization of of carbon
carbon materials.
materials. An An increase
increasein inthe
theIG
I G/I
/IDD peak
peak intensity ratio
indicates a higher degree of graphitization (ordering) of of the
the carbonaceous
carbonaceous material.material.
Activated
Activated carbon
carbon samples
samplesshowedshowedsimilarsimilarIGI/I
GD/Iratios in the
D ratios range
in the range of 0.624–0.693
of 0.624–0.693for
materials
for materialsprepared withwith
prepared KOH KOHand and
in theinrange of 0.656–0.730
the range of 0.656–0.730for materials
for materials obtained with
obtained
KOHKOH
with and urea.
and According to the Ito
urea. According G/ID ratios,
the IG /Isample
D ratios, B_KOH_700 (IG/ID = 0.693)
sample B_KOH_700 (IG /Iand
D = sample
0.693)
B_KOH_urea_700 (IG/ID = 0.730)
and sample B_KOH_urea_700 (IGwere
/ID =more0.730)ordered
were morematerials
orderedthan sample B_KOH_900
materials than sample
(I G/ID = 0.624)(Iand
B_KOH_900 G /IDsample
= 0.624)B_KOH_urea_900
and sample B_KOH_urea_900(IG/ID = 0.656),(IG indicating
/ID = 0.656), thatindicating
the degreethat
of
the degreeofofthe
ordering ordering of the
materials materials
decreases asdecreases as the carbonization
the carbonization temperaturetemperature
increases. increases.
morphologyof
The morphology ofthethecarbon
carbonmaterials
materials waswas characterized
characterized by bySEM,SEM, as shown
as shown in in
Figure 7.
The activated carbons prepared from banana peel biomass showed a porous structure
with typical cavities. The SEM images show a disordered structure, which is typical of
activated carbons. The materials contain numerous large tunnels, holes and channels [31].
A similar morphology of activated carbons produced from biomass has been reported in
other studies [4,31].
The CO2 adsorption capacity of this series of sorbents was investigated under 1 bar at
0 ◦ C and at 25 ◦ C. Figure 8 shows the results of CO2 adsorption tests, and corresponding
numerical data are provided in Table 3.
As can be seen from the data presented in Table 3 and Figure 8 for all activated
carbons, regardless of the synthesis method, the CO2 adsorption decreased with increasing
carbonization temperature. In addition, for activated carbons activated with KOH and
urea, the CO2 adsorption was higher than for carbons activated only with KOH. Sorbents
activated only with KOH possessed CO2 uptake ranging from 2.64 to 3.71 mmol/g at
25 ◦ C and 5.06 to 5.75 mmol/g at 0 ◦ C under 1 bar. In contrast, nitrogen-doped carbon
materials showed CO2 adsorption in the range of 2.82 to 3.85 mmol/g at 25 ◦ C and from
4.77 mmol/g to 6.26 mmol/g at 0 ◦ C under 1 bar. Among all samples, B_KOH_urea_750
had the highest CO2 capture adsorption at 0 ◦ C and 25 ◦ C under 1 bar at 6.26 mmol/g and
3.85 mmol/g, respectively. The CO2 adsorption obtained on this material was significantly
higher compared to material prepared under the same conditions but without urea.
Materials 2024,
Materials 17,
2024, 17,872
x FOR PEER REVIEW 10 of 16 10 of 15

A1 A2

20μm 10μm

20μm
B1 B2

Materials 2024, 17, x FOR PEER REVIEW 11 of 16

°C and 5.06 to 5.75 mmol/g at 0 °C under 1 bar. In contrast, nitrogen-doped carbon mate-
rials showed CO2 adsorption in the range of 2.82 to 3.85 mmol/g at 25 °C and from 4.77
mmol/g to 6.26 mmol/g at 0 °C under 1 bar. Among all10μm
20μm samples, B_KOH_urea_750 had
the highest CO2 capture adsorption at 0 °C and 25 °C under 1 bar at 6.26 mmol/g and 3.85
Figure
Figure7.7.SEM
SEMmicrographs
micrographsof the
of activated carbons:
the activated (A1,A2) activated carbon from banana peels
mmol/g, respectively. The carbons: (A1,A2)
CO2 adsorption activated
obtained oncarbon from
this materialbanana peels
was significantly
prepared with KOH;
prepared with KOH; (B1,B2) activated
(B1,B2) carbon
activated from banana
carbon from peels
banana prepared
peels with KOH and urea.
higher compared to material prepared under theprepared with KOH
same conditions and urea.
but without urea.

6 The activated carbons prepared from banana peel 7 biomass showed a porous struc-
ture with
(a) typical cavities.
0 °CThe SEM images show a disordered
(b) structure,0which
o
C is typical
6
of activated
5 carbons. The materials contain numerous large tunnels, holes and channels
[31]. A similar morphology of activated carbons produced from biomass has been re-
CO2 adsorption (mmol/g)

CO2 adsorption (mmol/g)

5
ported
4 in other studies [4,31].
The CO2 adsorption capacity of this series of sorbents
4 was investigated under 1 bar
3
at 0 °C and at 25 °C. Figure 8 shows the results of CO2 adsorption tests, and corresponding
3
numerical data are provided in Table 3.
2
B_KOH_700 2 B_KOH_urea_700
Table 3. Results of the adsorption experiments B_KOH_urea_750
at CO2 pressure of 1 bar and at 0 °C and 25 °C.
B_KOH_750
1 B_KOH_800 B_KOH_urea_800
1 B_KOH_urea_850
B_KOH_850
CO2 B_KOH_900
Uptake (mmol/g) B_KOH_urea_900
0
0.0 0.2
Sample
0.4 0.6 0.8 1.0
at 00 0.0
°C 0.2 0.4
at 25 0.6
°C 0.8 1.0
B_KOH_700
Pressure (bar) 5.74 3.73
Pressure (bar)
4 B_KOH_750 5.75
5 3.74
(c) 25 °C (d) 25 ° C
B_KOH_800 5.29 3.25
B_KOH_850 5.06
4 3.01
CO2 adsorption (mmol/g)

3
CO2 adsorption (mmol/g)

B_KOH_900 5.40 3.21

B_KOH_urea_700 6.07
3 3.77
2 B_KOH_urea_750 6.26 3.85
B_KOH_urea_800 5.70
2 3.45
B_KOH_urea_850 5.50 3.32
1 B_KOH_700 B_KOH_urea_700
B_KOH_urea_900 B_KOH_750 4.77
1
2.82 B_KOH_urea_750
B_KOH_800 B_KOH_urea_800
B_KOH_850 B_KOH_urea_850
As can be seen from the data presented in Table 3 and Figure 8 for all activated car-
B_KOH_900 B_KOH_urea_900
0 0
bons,0.0regardless
0.2 of the
0.4 synthesis
0.6 method,
0.8 the1.0CO2 adsorption
0.0 0.2decreased
0.4 with0.6increasing
0.8 1.0
carbonization temperature. In addition, for activated carbons activated
Pressure (bar) with
Pressure (bar) KOH and
urea, the CO2 adsorption
Figurewas
8. CO higher than for carbons◦ activated
2 adsorption isotherms measured at 0only
°C forwith KOH. Sorbents
(a) B_KOH series and (b) B_KOH_urea
Figure 8. CO adsorption isotherms measured at 0 C for (a) B_KOH series and (b) B_KOH_urea
activated only2 with series
KOHofpossessed
carbons and CO 2 uptake
CO ranging
2 adsorption frommeasured
isotherms 2.64 to 3.71
at 25 mmol/g
°C for (c)at 25 series and (d)
B_KOH
series of carbons and CO adsorption isotherms measured at 25 ◦ C for (c) B_KOH series and
B_KOH_urea2 series.
(d) B_KOH_urea series.
Based on the results, it can be concluded that the use of urea in the synthesis of acti-
vated carbons contributes to an increase in the CO2 adsorption capacity of samples ob-
tained by this method, compared to samples obtained using only KOH as a chemical ac-
tivator (Figure 9). The exception is materials obtained at 900 °C. The adsorption of CO2 on
the activated carbon not treated with urea is higher. This can be explained by the higher
values of the textural parameters of this sample. It is clear that CO2 adsorption is affected
simultaneously by several parameters: nitrogen content and values of textural parameters.
The introduction of urea also affects the modification of textural parameters. For a given
temperature, it causes an increase in the volume of micropores and specific surface area
except at 900 °C for SBET. An increase in pore volume was observed only for samples ob-
Materials 2024, 17, 872 11 of 15

Table 3. Results of the adsorption experiments at CO2 pressure of 1 bar and at 0 ◦ C and 25 ◦ C.

CO2 Uptake (mmol/g)

Sample at 0 ◦ C at 25 ◦ C
B_KOH_700 5.74 3.73
B_KOH_750 5.75 3.74
B_KOH_800 5.29 3.25
B_KOH_850 5.06 3.01
B_KOH_900 5.40 3.21
B_KOH_urea_700 6.07 3.77
B_KOH_urea_750 6.26 3.85
B_KOH_urea_800 5.70 3.45
B_KOH_urea_850 5.50 3.32
B_KOH_urea_900 4.77 2.82

Based on the results, it can be concluded that the use of urea in the synthesis of
activated carbons contributes to an increase in the CO2 adsorption capacity of samples
obtained by this method, compared to samples obtained using only KOH as a chemical
activator (Figure 9). The exception is materials obtained at 900 ◦ C. The adsorption of CO2
on the activated carbon not treated with urea is higher. This can be explained by the higher
values of the textural parameters of this sample. It is clear that CO2 adsorption is affected
simultaneously by several parameters: nitrogen content and values of textural parameters.
The introduction of urea also affects the modification of textural parameters. For a given
temperature, it causes an increase in the volume of micropores and specific surface area
except at 900 ◦ C for SBET . An increase in pore volume was observed only for samples
obtained in the temperature range of 700–800 ◦ C. It is not possible to analyze the effect on
Materials 2024, 17, x FOR PEER REVIEW
adsorption based solely on nitrogen content or textural parameters alone. However, 12 ofthe
16
◦
figure clearly shows that at temperatures below 900 C, urea treatment is beneficial.

7
KOH
KOH&urea
6
CO2 adsorption (mmol/g)

0
700 750 800 850 900
Temperature (oC)

Figure 9.
Figure 9. CO
CO22 adsorption
adsorption isotherms
isotherms measured
measured at ◦ C and
at 00 °C and 11 bar.
bar.

Moreover,
Moreover,considering
consideringthat thatCO
CO 2 2isisan
anacidic
acidicgas,
gas,the inclusion
the inclusionof of
nitrogen
nitrogenin the carbon
in the car-
matrix promotes CO capture by imparting an alkaline character to the adsorbent
bon matrix promotes2CO2 capture by imparting an alkaline character to the adsorbent sur- surface.
The
face.increase in CO2 sorption
The increase in CO2capacity
sorption observed for N-doped
capacity observed materials (B_KOH_urea_x
for N-doped materials
series) is associated
(B_KOH_urea_x withisanassociated
series) increase in the an
with surface alkalinity
increase of activated
in the surface carbons
alkalinity obtained
of activated
by chemical
carbons activation
obtained with KOH
by chemical in the presence
activation with KOH ofinurea
the[32]. In theofliterature,
presence urea [32].urea is
In the
described
literature, as a source
urea of nitrogen,
is described the useofofnitrogen,
as a source which in the
the use
production
of which process
in the of activated
production
carbons
process of makes it possible
activated carbons tomakes
obtainitmaterials
possible towith the highest
obtain materialsCO 2 capture
with efficiency
the highest CO 2
(compared to adsorbents for which other nitrogen sources were used)
capture efficiency (compared to adsorbents for which other nitrogen sources were used)[32].
[32].
Many reports describing the use of activated carbon as a CO2 sorbent have been pub-
lished in the literature. Table 4 shows high CO2 adsorption at 1 bar on activated carbons
produced from biomass described by other authors. To summarize, these biomass-based
carbonaceous materials exhibit CO2 uptake ranging from 4.1 mmol/g to 7.3 mmol/g at 0
°C and from 0.5 mmol/g to 5.0 at 25 °C.
Materials 2024, 17, 872 12 of 15

Many reports describing the use of activated carbon as a CO2 sorbent have been
published in the literature. Table 4 shows high CO2 adsorption at 1 bar on activated carbons
produced from biomass described by other authors. To summarize, these biomass-based
carbonaceous materials exhibit CO2 uptake ranging from 4.1 mmol/g to 7.3 mmol/g at
0 ◦ C and from 0.5 mmol/g to 5.0 at 25 ◦ C.

Table 4. Reported CO2 capture results for activated carbons prepared from biomass by chemical
activation by KOH.

CO2 Adsorption
CO2 Adsorption at 0 ◦ C
Activated Carbon Precursor at 25 ◦ C References
[mmol/g]
[mmol/g]
Vine Shoots 5.4 - [33]
Arundo donax 4.1 3.2 [34]
Carrot Peels 5.6 4.2 [35]
Celtuce Leaves 6.0 4.4 [36]
Coffee Grounds 4.4 3.0 [37]
Lumpy Bracket 7.2 4.6 [38]
Peanut Shell 7.3 4.4 [39]
Pomegranate Peels 6.0 4.1 [35]
Sargassum - 1.1 [40]
Palm Shells 6.3 4.4 [41]
Fern Leaves 4.5 4.1 [35]
Enteromorpha - 0.5 [40]
Bee-Collected Pollen 5.6 4.2 [42]
Molasses 5.4 - [43]
Sawdust 6.6 4.3 [44]
Starch 5.6 3.5 [44]
Cellulose 5.8 3.5 [44]
Jujun Grass - 4.9 [45]
Wood of Camellia japonica - 5.0 [45]
Banana peels 5.75 3.74 This work

Considering the data in the Table 4, the CO2 adsorption values obtained in this work
on activated carbon from banana peel are not the highest values in compered to data
reported in the literature, but it should be noted that the values reported in this work are
among the highest for biomass-derived activated carbons.
The presence of heteroatoms, such as nitrogen, can also affect the adsorption capacity
of activated carbon, and this phenomenon has also been described in the literature. Table 5
shows the CO2 adsorption on activated carbons obtained by activation with KOH and
different N-reagents or activation with N-reagent only.

Table 5. Comparison of the CO2 adsorption for recent N-doped activated carbons obtained from
biomass-based materials.

Activation CO2
CO2
Activated Carbon with Activation with Adsorption
Adsorption at 25 ◦ C References
Precursor KOH and N-Reagent at 0 ◦ C
[mmol/g]
N-Reagent [mmol/g]
Coconut shell KOH + Urea - 7.00 5.00 [46]
Black locust KOH + Ammonia - - 5.05 [47]
Longan shell KOH+ Carbamide - 5.60 4.30 [48]
Walnut shell KOH + Urea - - 5.4 [49]
Chestnut tannin - NH3 activation 3.44 2.27 [50]
Corncob particles - NH3 activation 4.50 2.81 [51]
Banana peels KOH + Urea - 6.26 3.86 This work
Materials 2024, 17, 872 13 of 15

According to the data presented in the table, the activated carbon obtained by our
team (by activating KOH in the presence of urea as a nitrogen source) has a CO2 adsorption
value at a level comparable to, and in some cases greater than, the materials described in
other works and obtained by the same method.
In addition, the CO2 adsorption values for activated carbons obtained by activa-
tion with N-reagent without activating agent in the form of KOH are significantly lower
(3.4 mmol/g at 0 ◦ C and 2.3 mmol/g at 25 ◦ C) than the adsorption values obtained for
other carbon materials (6.3 mmol/g at 0 ◦ C and 3.9 mmol/g at 25 ◦ C), which proves that
the method chosen by our team to obtain activated carbons from biomass is the best way to
obtain materials that can be applied in carbon adsorption.

4. Conclusions
It has been demonstrated that waste obtained from a local juice production facility,
specifically banana peels, serves as a good precursor for the production of activated car-
bon intended for CO2 adsorption. It has been shown that the addition of urea enhances
CO2 adsorption. Simultaneous treatment of banana peels with KOH and urea leads to an
increased nitrogen content in the resulting product, which is activated carbon. Unques-
tionably, it has been demonstrated that the increase in nitrogen content correlates with an
elevation in CO2 adsorption. On the other hand, raising the carbonization temperature
causes the decomposition of nitrogen-containing groups on the surface of activated carbon.
We observed that the optimal temperature for producing activated carbon with an elevated
nitrogen content is 750 ◦ C. The highest CO2 adsorption under 1 bar pressure was achieved
with the B_KOH_urea_750 material, which reached 6.36 mmol/g at 0 ◦ C and 3.85 mmol/g
at 25 ◦ C.

Author Contributions: Conceptualization, J.S.-N., B.M. and A.K.; methodology, A.K. and J.S.-N.;
validation, J.S.-N.; formal analysis, J.S.-N. and A.K.; investigation, J.S.-N., A.K. and J.S.; data cu-
ration, J.S-N.; writing—original draft preparation, A.K., J.S.-N. and J.S.; visualization, J.S.-N. and
A.K.; supervision, B.M. and J.S.-N. All authors have read and agreed to the published version of
the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Data are available upon request to the corresponding author.
Conflicts of Interest: The authors declare no conflicts of interest.

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