Catalysis Reviews

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Emerging role of nanobiocatalysts in hydrolysis

of lignocellulosic biomass leading to sustainable
bioethanol production

Mahendra Rai, Avinash P. Ingle, Raksha Pandit, Priti Paralikar, Jayanta

Kumar Biswas & Silvio Silverio da Silva

To cite this article: Mahendra Rai, Avinash P. Ingle, Raksha Pandit, Priti Paralikar, Jayanta
Kumar Biswas & Silvio Silverio da Silva (2018): Emerging role of nanobiocatalysts in hydrolysis
of lignocellulosic biomass leading to sustainable bioethanol production, Catalysis Reviews, DOI:
10.1080/01614940.2018.1479503

To link to this article: https://doi.org/10.1080/01614940.2018.1479503

Published online: 11 Jun 2018.

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CATALYSIS REVIEWS
https://doi.org/10.1080/01614940.2018.1479503

Emerging role of nanobiocatalysts in hydrolysis of

lignocellulosic biomass leading to sustainable bioethanol
production
Mahendra Raia, Avinash P. Ingleb, Raksha Pandita, Priti Paralikara,
Jayanta Kumar Biswasc, and Silvio Silverio da Silvab
a
Nanotechnology Lab., Department of Biotechnology, SGB Amravati University, Amravati, Maharashtra,
India; bDepartment of Biotechnology, Engineering School of Lorena, University of Sao Paulo, Lorena,
Sao Paulo, Brazil; cEnviromicrobiology, Ecotoxicology and Ecotechnology Research Laboratory,
Department of Ecological Studies, University of Kalyani, Nadia, Kalyani 741235, West Bengal, India

ABSTRACT ARTICLE HISTORY

Catalytic conversion (hydrolysis) of carbohydrate polymers pre- Received 18 April 2018
Accepted 18 May 2018
sent in the lignocellulosic biomass into fermentable sugars is a
key step in the production of bioethanol. Although, acid and KEYWORDS
enzymatic catalysts are conventionally used for the catalysis of Acid catalyst; bioethanol;
various lignocellulosic biomass, recently application of immobi- enzyme; hydrolysis;
lized enzymes (biocatalysts) have been considered as the most Lignocellulosic biomass;
promising approach. Immobilization of different biocatalysts nanocellulose;
such as cellulase, β-glucosidase, cellobiose, xylanase, laccase, nanofiltration;
nanomaterials;
etc. on support materials including nanomaterials to form nano- nanotechnology
biocatalyst increases catalytic efficacy and stability of enzymes.
Moreover, immobilization of biocatalysts on magnetic nanopar-
ticles (magnetic nanobiocatalysts) facilitates easy recovery and
reuse of biocatalysts. Therefore, utilization of nanobiocatalysts
for catalysis of lignocellulosic biomass is helpful for the devel-
opment of cost-effective and ecofriendly approach. In this
review, we have discussed various conventional methods of
hydrolysis and their limitations. Special emphasis has been
made on nanobiocatalysts used for hydrolysis of lignocellulosic
biomass. Moreover, the other most important aspects, like nano-
filtration of biomass, conversion of lignocellulose to nanocellu-
lose, and toxicological issues associated with application of
nanomaterials are also discussed.

Introduction
Hydrolysis of lignocellulosic biomass is considered as the second most impor-
tant step in the process of bioethanol production, which is generally employed
for the degradation of released carbohydrates (cellulose and hemicellulose) into
simple fermentable sugars.[1,2] However, the first step is pretreatment, in which
complex structure of lignocellulosic biomass is disrupted to release the carbohy-
drate polymers.[3] There are several pretreatment methods such as physical

CONTACT Mahendra Rai mahendrai7@gmail.com; pmkrai@hotmail.com Department of Biotechnology,

S.G.B. Amravati University, Amravati, 444 602 Maharashtra, India
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lctr.
© 2018 Taylor & Francis
2 M. RAI ET AL.

pretreatment (grinding and milling, microwave, extrusion, freeze pretreatment,

hydrodynamic cavitation, etc.),[4–6] chemical pretreatment (alkali, acid, organo-
solv, ozonolysis, and ionic liquid),[7–9] physicochemical pretreatment (steam
explosion, liquid hot water, ammonia fiber explosion, ammonia recycle percola-
tion, wet oxidation, CO2 explosion, etc.),[10,11] biological pretreatment (use of
various microorganisms and their products, i.e. enzymes)[12–14], and combina-
tion pretreatment methods are available and routinely in practice for the
disruption of lignocellulosic biomass into carbohydrates.[15–18]
However, hydrolysis of lignocellulosic biomass determines the overall
efficiency of the process and conventionally it is achieved by chemical
degradation and enzymatic catalysis (biocatalyst). Chemical hydrolysis meth-
ods employed the application of various acids catalysts like sulfuric and
hydrochloric acid for hydrolysis of a variety of lignocellulosic biomass.[19]
But these acid catalysts are reported to have lower efficacy toward the
formation of hexoses (sugars) at moderate operational conditions.[20] The
lower efficacy of hydrolysis was mainly due to decomposition of the sugars
into undesirable compounds during hydrolysis. These compounds include
furfural and hydroxymethylfurfural (HMF), the products of the dehydration
of pentoses and hexoses, respectively.[21–23]
The limitations associated with acid catalysis, such as less specificity,
generation of toxic inhibitors, neutralization or removal of unreacted acid,
etc., have necessitated the development of novel, green, and sustainable
approach for the disruption of lignocellulosic biomass.[22,23] Considering
the high specificity, selectivity, and potential catalytic activity of enzymes,
they have become the foremost choice being the most promising biocatalysts
for effective and ecofriendly degradation of lignocellulosic biomass into
simple sugars.[24] Although, the application of biocatalysts promotes green
approach due to noninvolvement of chemicals and non-generation of any
toxic inhibitors, the high operational costs owing to low stability and reusa-
bility of the enzymes is a major concern associated with utilization of
biocatalysts in the hydrolysis of lignocellulosic biomass.[25] However, immo-
bilization of enzymes on support materials by physical adsorption, covalent
bonds, cross-linkages, or specific ligands has been gaining a great deal of
attention in recent years.[26] Immobilization of enzyme on support materials
provides stability to enzymes against chemical and environmental attacks and
also enhances its catalytic efficacy.
Considering the recent path-breaking developments in nanotechnology, it
is assumed to provide a wealth of diverse nanomaterials, which can be used
for immobilization of enzymes. It is widely accepted that immobilization of
enzymes on nanoscale materials is a novel and promising approach, which
enhances the catalytic efficacy of enzyme.[27–29] The nanoparticle-based
immobilized enzymes are collectively known as ‘nanobiocatalyst’. The devel-
opment of nanobiocatalyst is an example of emerging and innovative
 CATALYSIS REVIEWS 3

breakthroughs of nanotechnology and biotechnology.[30–32] The formation of

nanobiocatalyst includes the conjugation of enzyme on the various nanoma-
terials using cross-linking molecules which favors desirable chemical kinetics
and selectivity for substrates.[33,34] Actually, immobilization of enzyme using
cross-linking molecule provides a spacer, which minimizes steric hindrance
between enzyme and the solid supports leading to increase in the flexibility of
immobilized enzyme.[35]
Although different approaches have been reported for immobilization of
biocatalysts, in-depth literature is not available on involvement of active sites
of the enzyme during immobilization on nanomaterials. It is demonstrated
that orientation of enzyme (active site) during immobilization is a random
process, which plays an important role in the resulting activity of the
immobilized biocatalyst. However, it depends greatly on the nature of bio-
catalyst, the physical properties of the solid support, and approach used for
immobilization.[27] Moreover, to avoid the blocking of active sites of the
biocatalyst, it is proposed that different inhibitors can be used which has
ability to form a complex with the enzyme during immobilization and can be
easily dissociated after the immobilization.[36]
The reports available suggested that the large surface areas of nanoscale
materials allow a higher enzyme loading and reduce mass transfer resis-
tance for substrates which is considered as very important requirement for
the development of nanobiocatalysts.[33] Moreover, the fabrication of
magnetic nanobiocatalysts by immobilization of enzyme on magnetic
nanoparticles is because such nanobiocatalysts can be easily recovered
and reused in a large-scale continuous process. It significantly increases
the life of the biocatalyst, hence reducing the cost of the biocatalytic
process.[34,37]
This article aims to review the recent developments and application of
nanobiocatalysts in hydrolysis of lignocellulosic biomass. In addition, brief
overview on conventional approaches available for hydrolysis of lignocellu-
losic biomass, their advantages, and disadvantages have also been high-
lighted. Moreover, certain other aspects like nanofiltration (NF) of biomass,
conversion of lignocellulose to nanocellulose, and toxicity concerns of nano-
materials are also discussed.

Conventional hydrolysis methods

The conventional methods available for the hydrolysis of lignocellulosic
biomass mainly include the utilization of acid catalysts and biocatalysts
(enzyme). All these methods are briefly described here.
4 M. RAI ET AL.

Acid catalysis
Acid catalysis (hydrolysis) is the first and older approach which has been
studied for the last 100 years because it has potential to act on a variety of
lignocellulosic materials. This method is also useful at industrial scale due to
their low cost. Both concentrated and dilute acids can be effectively used as
catalysts for the hydrolysis of lignocellulosic biomass because these acids have
ability to breakdown the cellulose and hemicellulose polymers of lignocellu-
losic biomass to form individual sugar molecules which can be fermented
into ethanol. It is important to note that hemicellulose is more easily hydro-
lyzed than cellulose.[38,39] This approach is known as ‘liquid acid hydrolysis’;
however, another approach called as ‘solid acid hydrolysis’ is attracting a
great deal of attention from researchers due to their various advantages over
liquid hydrolysis catalysts.[40]

Liquid acid catalysts

In dilute acid catalysis, lignocellulosic biomass is treated with various mineral
acids such as sulfuric, hydrochloric, or phosphoric acid having concentra-
tions in between 1%–10% at moderate temperature (i.e. 100°C–150°C).[41]
This method is most effective in the removal and recovery of the hemicellu-
lose as dissolved sugars. It is proposed that glucose yields from cellulose
increase with hemicellulose removal to almost 100%.[42] Recently, Sritrakul
et al.[43] demonstrated the efficacy of dilute sulfuric acid as a catalyst in the
hydrolysis of sugarcane bagasse pith and concluded that dilute acid hydro-
lysis effectively coverts carbohydrate polymers of sugarcane bagasse pith in
various fermentable sugars like glucose, xylose, galactose, and arabinose.
Dilute acids efficiently hydrolyzed cellulosic materials into sugar; however,
dilute acids further degrade the sugars and forms many other toxic inhibitory
compounds like furfural, 5-HMF furans and phenols which inhibit the
growth of microbes used for fermentation.[44,45]
Moreover, in the case of concentrated acid hydrolysis, the lignocellulosic
biomass is treated with acid catalysts mentioned earlier having concentration
up to 70% at low temperature (37°C) and low pressure. In this approach, the
conversion rate of cellulose to glucose is comparatively higher (90%) than
with dilute acid hydrolysis. The treatment at low temperature and pressure
helps to minimize the degradation of sugars.[42] Concentrated sulfuric acid is
considered to be most efficient.[46] Jung et al.[46] demonstrated the two-step
hydrolysis of waste paper using concentrated sulfuric acid. In the first step,
the biomass was treated with 60%–80% (w/w) of sulfuric acid at 30°C for
1–5 h. Moreover, in the second step, the reaction mixture was diluted to 4%
(w/w) sulfuric acid and autoclaved at 121°C for 1 h. After completion of the
reaction, the solids parts were separated from aqueous solution by filtration.
 CATALYSIS REVIEWS 5

The filtrate was analyzed for glucose which showed significant conversion of
cellulose to glucose.
Having various advantages such as rapid, efficient, and low cost, dilute
acid hydrolysis also has some disadvantages. One of the major disadvantages
of dilute acid hydrolysis is associated with corrosion issues, which mandatory
require utilization of expensive materials for the construction and operation
of equipment.[47,48] In addition, generation of toxic inhibitory compounds as
mentioned earlier is also restrict the use of this approach in some cases.[49,50]
However, in the case of concentrated acid hydrolysis, the conversion rate is
very high, operation of process at low temperatures and pressures require
low-cost materials, such as fiberglass tanks and piping for construction of
equipment.[51] On the contrary, the conversion rate is comparatively slow
and needs additional step for acid neutralization using higher amount of lime
if acid is not removed properly by washing, it may increase the process
cost.[42]
The mechanism of acid hydrolysis involves the depolymerization of com-
plex carbohydrates of lignocellulosic biomass into monosaccharides through
solvolytic homogenous or heterogeneous reactions. The treatment of ligno-
cellulosic biomass with dilute acid leads to cleavage of glycosidic linkages
which results in breaking down of polysaccharides into monomers. In actual,
the protons released from the dissociation of acids in aqueous solution
migrate to the reactive sites of lignocellulose and disrupts the structure at a
molecular structure.[52,53]

Solid acid catalysts

In recent past, application of solid acid catalysts for hydrolysis of cellulose
into sugars has received a great deal of attention. Actually, solid acid catalyst
is defined as solid which can donate protons or accept electrons during
reactions. The catalytic efficacy of a solid acid catalyst mainly depends on
its acidic centers present on its surface. Therefore, solid acids with Brønsted
acid sites can catalyze biomass hydrolysis very efficiently.[54] These catalysts
possess numerous advantages over liquid acid hydrolysis which mainly
includes easy separation of product, recycling and reuse of catalyst, less
damage to the reactor, etc. In addition, utilization of solid acid catalysts is
considered as ecofriendly approach which has negligible impact on the
environment. The role of solid acid catalysts has been extensively studied
for the hydrolysis of a variety of lignocellulosic biomass. The important solid
acid catalysts commonly used include transition-metal oxides, zeolites,
cation-exchange resins, heteropoly acids, magnetic solid acids, etc..[40,54]
In addition, supported acid catalysts have been found to be very promising
for the hydrolysis of lignocellulosic polymer like cellulose as they possess
considerably large acidic species on their surface compared with zeolites and
transition-metal oxides.[40] Some commonly used supports for solid acid
6 M. RAI ET AL.

catalysts include silica,[55] polymer resins,[56] porous coordination polymers,[57]

and amorphous carbons (metal oxides and zeolites). Among these, metal
oxides are most preferably used as supports for solid acid catalyst because of
their thermal and mechanical stability, high specific surface area, and large
pore size. Various sulfonated metal oxides have the ability to supply many
acidic species. Similarly, supported carbonaceous solid acids are also consid-
ered as most effective catalysts for the conversion of cellulose into biofuels.
Moreover, Maggi et al.[58] demonstrated that application of silica as a support
for sulfonic acid makes it very active heterogeneous catalyst for the selective
esterification of levulinic acid with stoichiometric amount of alcohols.
Due to abovementioned properties, solid acid catalysts showed enhanced effi-
cacy than liquid acid catalyst.[42] Out of the abovementioned solid acid catalysts,
magnetic solid acids are considered as most promising because it is possible to
recycle and reuse the catalyst due to their strong magnetic properties.[59] In
addition, carbon-based solid acids bearing –SO3H, –COOH, and –OH groups
have strong affinity to cellulose chain and make the acid sites closer to the β-1,4-
glycosidic bonds.[42]

Enzymatic catalysis
Enzymatic catalysis (hydrolysis) of lignocellulosic biomass is comparatively
new and considered as more efficient approach than acid hydrolysis. Usually,
it involves the use of various biocatalysts like cellulase enzymes which are
highly specific. Depending on their mode of action, cellulases are categorized
into three major classes – first is endoglucanase, which attacks low crystal-
linity regions by endoaction present in the cellulose fiber and creates free
chain-ends. The second class is known as exoglucanases or cellobiohydrolases
which hydrolyze the 1–4 glycosidic linkages to form cellobiose and the third
is β-glucosidase which converts cello-oligosaccharides and disaccharide cel-
lobiose into glucose residues. Apart from these, there are a number of other
biocatalysts viz. glucuronide, acetylesterase, xylanase, β-xylosidase, galacto-
mannase, and glucomannase that disrupts hemicelluloses. The combination
of these biocatalysts can be used for the hydrolysis of both cellulose and
hemicellulose.[60] Although biocatalyst-mediated hydrolysis of lignocellulosic
biomass is mostly the preferred approach, the high cost of such biocatalysts
makes the process very expensive.
Both bacteria and fungi having ability to produce cellulases are commonly used
for the hydrolysis of lignocellulosic materials.[61] Among bacteria, different mem-
bers of genera Clostridium, Bacillus, Thermomonospora, Caldicellulosiruptor,
Butyrivibrio, Cellulomonas, Erwinia, Thermobifida, Fibrobacter, Cytophaga,
Sporocytophaga, Cellulomonas, Ruminococcus, Bacteriodes, Erwinia, Acetovibrio,
Microbispora, and Streptomyces showed potential in the hydrolysis of different
kinds of lignocellulosic biomass.[30,31,62] Bacterial degradation of lignocellulosic
 CATALYSIS REVIEWS 7

biomass is more restricted to materials containing low amounts of lignin, because

bacteria are very poor producers of lignin degrading enzymes (lignanases).[62]
Among the fungi, white-rot, brown-rot, and soft-rot fungi are most pre-
ferably used for the hydrolysis of lignocellulosic biomass.[30,63] The mode of
action of each fungus depends on the type of lignocellulosic biomass. White-
rot and soft-rot fungi effectively degrade the lignin because these fungi
produce various lignin-degrading enzymes such as lignin peroxidases, man-
ganese-dependent peroxidases, polyphenol oxidases, and laccases. However,
brown-rot fungi mainly attack cellulose components.[64,65] In addition, var-
ious species of Trichoderma, Aspergillus, Schizophyllum and Penicillium gen-
era are also commonly used in hydrolysis.[66] There are a few reports
regarding the direct use of standard enzymes in pure form, that is, cellulase
(available with commercial companies) for the hydrolysis of lignocellulosic
biomass.[7,67]
Enzyme catalysis has many advantages over acid hydrolysis – the actual
cost required for equipment construction is very low because it does not have
corrosion problem due to operation of process at mild conditions (pH 4.8
and temperature 45°C–50°C), but the higher cost of enzyme increases the
overall cost of process and this is major disadvantage of enzymatic hydro-
lysis. In addition, due to the very specific action of biocatalysts, there is no
generation of toxic inhibitors.

Role of nanobiocatalysts in hydrolysis

The major disadvantages particularly associated with the cost of biocatalyst
have been overcome by the fabrication of nanobiocatalysts. As mentioned
earlier, various physical and chemical approaches are proposed for the
immobilization of biocatalyst on different carriers like nanomaterials.
Depending on the type of enzyme attachment, the approaches are mainly
classified as physical adsorption, entrapment, encapsulation, covalent attach-
ments, cross-linking, and bioaffinity interactions[68,69] (Figure 1). Among
these approaches, covalent binding is considered as the most promising
approach because it involves formation of strong complex through the
covalent bonds between enzyme and nanoparticles.[70] In addition, combina-
tion approaches can also be used, for example, immobilization of enzyme by
adsorption followed by cross-linking or covalent bonding for better binding
efficacy.
Application of nanobiocatalysts in the process of lignocellulosic biomass
hydrolysis holds great promise to revolutionize the entire scenario.[6]
Recently, various nanomaterials are used as a support for the immobilization
enzyme which mainly includes magnetic nanomaterials, silica nanoparticle,
nickel nanoparticles, carbon nanotubes, oxide nanoparticles, etc.
Nanomaterials can potentially increase the efficiency of immobilized enzyme
8 M. RAI ET AL.

Figure 1. Illustration of various approaches available for immobilization of enzyme (adapted

from Lee and Duong[69] with copyright permission from John Wiley and Sons Publisher).

because it provides large surface area for enzyme attachment, which helps in
higher enzyme loading per unit mass of particles.[71,72] Immobilization of
biocatalyst on magnetic nanomaterials allows the repeated use of same
biocatalyst for more than one cycle of catalysis due to its easy recovery by
applying simple magnetic field. According to the reports summarized in this
review, there is possibility to use magnetic nanobiocatalyst for more than 15
cycles of lignocellulosic biomass hydrolysis, which means there is no need of
addition of biocatalyst (enzyme) for catalysis each time. Therefore, repeated
use of highly expensive biocatalyst in immobilized form ultimately reduces
the cost involved in the process and makes the process cost-effective and
sustainable.

Magnetic nanobiocatalysts
Immobilization of various enzymes on magnetic nanoparticles and their use
as magnetic nanobiocatalysts has attracted the attention of researchers from
all over the world as a novel approach for the degradation of lignocellulosic
biomass and hydrolysis of various components of lignocellulosic biomass.
The easy recovery of enzyme by applying magnetic field and its reuse is
helpful in the reduction of cost involved. The immobilization of cellulolytic
 CATALYSIS REVIEWS 9

enzymes on nanosupport helps to minimize the problem of steric hindrances

between enzyme and carrier, as it has been frequently observed in case of
enzymes immobilized on the surface of bulk supports.[69,73]
The production of sugars and biofuels from lignocellulosic biomass
through the nanoparticles-mediated enzyme hydrolysis (immobilization of
enzymes like cellulases and hemicellulases on magnetic nanoparticles) can be
effectively achieved. Moreover, in this approach, immobilized enzymes can
be magnetically recovered and recycled for further use.[74] Immobilization of
enzymes on magnetic nanomaterials has currently attracted attention of
many researchers because it offers many advantages such as the high specific
surface area, high stability, low toxicity, low resistance to mass transfer, and
biocompatibility.[75] It was demonstrated that immobilization of enzymes on
solid supports like magnetic nanoparticles increase their thermostability as
compared to free enzymes.[74,76]
It was demonstrated that immobilization of β-glucosidase on polymer magnetic
nanofibers by entrapment method efficiently hydrolyzed cellobiose into glucose,
which can be further used for the production of bioethanol. The immobilization of
β-glucosidase on magnetic nanofibers provides stability to the enzyme and its
magnetic nature increases possibility of repeated use by separating immobilized
enzyme by applying magnetic field.[77] Similarly, β-glucosidase (isolated from
fungus) immobilized on magnetic nanoparticles was used as nanobiocatalyst for
hydrolysis of cellobiose. The immobilization of enzyme achieved very high binding
efficiency (93%). Moreover, about 50% of catalytic activity of immobilized enzyme
at 16th cycle confirmed the higher stability of enzyme after immobilization.[78]
Immobilized cellulase on magnetic Fe3O4 nanoparticles using carbodiimide as
linking polymer is efficiently used for the hydrolysis of microcrystalline cellulose.
Due to the magnetic nature of nanoparticles, the enzyme could be recovered easily
and recycled for six times.[79] In another study, combination of cellulase and β-
cyclodextrin was used for the hydrolysis of rice straw. The combination is prepared
by immobilization of cellulase isolated from Aspergillus niger onto β-cyclodextrin-
conjugated magnetic particles using silanization and reductive amidation pro-
cesses. It was reported that the catalytic activity of immobilized cellulase was
reported to enhance due to synergistic effect of β-cyclodextrin and as compared
to free cellulase, magnetized cellulase showed ability to hydrolyze rice straw
continuously.[80] Recently, Sanchez-Ramirez et al.[75] covalently immobilized cel-
lulase recovered from Trichoderma reesei on chitosan-coated magnetic nanopar-
ticles using glutaraldehyde as a coupling molecule. It was observed that
immobilized enzyme can retain about 80% of its activity even after 15 cycles of
repeated use in the hydrolysis of carboxymethylcellulose. Zang et al.[81] synthesized
magnetic chitosan (Fe3O4-chitosan) nanoparticles and used as a support for the
immobilization of cellulase through covalent bonding using gluteraldehyde as a
coupling agent. The maximum hydrolysis of lignocellulosic biomass was reported
at pH 5 and 50°C. In addition, it was observed that immobilization of cellulase
10 M. RAI ET AL.

enzyme on zinc ferrite nanoparticles significantly increases enzymatic hydrolysis of

ultrasound-assisted alkaline pretreated Crotalaria iuncea biomass. Maximum 74%
binding efficacy of enzyme was reported when immobilization of cellulase was
carried out on activated ferrite nanoparticles at pH 5 and temperature 60°C using
glutaraldehyde as a crosslinker. Moreover, it was observed that the immobilized
enzyme was stable at 60°C while retaining its activity up to 3 recycles and showed
53% hydrolysis yield on pretreated biomass.[82] Moreover, in another attempt,
holocellulase recovered from A. niger was immobilized on magnetic iron oxide
(Fe2O3) nanoparticles for the efficient hydrolysis of pretreated paddy straw. The
immobilization was achieved by both physical adsorption and covalent coupling.
The comparative study on saccharification using immobilized and free cellulase
showed that immobilized enzyme showed 52%, whereas, free enzyme showed 47%
saccharification efficiency.[83] On contrary, in the comparative evaluation of free
and immobilized cellulase on magnetic nanoparticles for enzymatic hydrolysis of
lignocellulosic biomass for sustainable bioethanol production, it was demonstrated
that free enzyme showed more conversion of cellulose to glucose (78%) than
immobilized cellulase (72%) in the first cycle. But, in case of immobilized enzymes,
it can be used in the second and third cycle after recovery which showed conver-
sion of 68% and 52%, respectively.[7]

Silica nanoparticles
Apart from magnetic nanoparticles, silica nanoparticles are also effectively
used for the immobilization of lignocellulolytic enzyme such as cellulase.
Lupoi and Smith[84] demonstrated the catalytic activity of cellulase immobi-
lized on silica nanoparticles in simultaneous saccharification and fermentation
(SSF) reactions for improved ethanol production from lignocellulosic materi-
als. It was observed that silica nanoparticles showed better affinity towards the
adsorption of cellulase. The immobilized cellulase produced 1.6 times more
glucose from cellulose than free cellulase enzyme. Moreover, SSF reactions deal
with the simultaneous hydrolysis of cellulose to glucose by cellulase, while
yeast ferments glucose to ethanol at the same time. In addition, it was reported
that the yield of ethanol was found to be increased by 2.1 to 2.3 times due to
application of SSF approach. Similarly, Chang et al.[85] demonstrated the
immobilization of two mesoporous silica nanoparticles having different parti-
cle size, pore size, and surface area by physical adsorption and chemical
binding. Further, it was reported that cellulase immobilized on mesoporous
silica nanoparticles having large pore size by chemical binding showed effective
cellulose-to-glucose conversion exceeding 80% yield and excellent stability.
 CATALYSIS REVIEWS 11

Nickel nanoparticles
Catalytic conversion of lignocellulose into cellulose and conversion of cellulose
into sugar is essential for nurturing society. Metal such as nickel can be used in
the process of hydrogenation, i.e. conversion of glucose to sorbitol.[86] Nickel
can be used in the degradation of lignocellulosic material into hemicellulose.[87]
Catalytic cracking or reforming is the effective way, which can be used in the
hydrolysis of lignocellulosic material into biomass or into biofuel.
Nanomaterials act as catalyst in the pretreatment of lignocellulosic material.
Nanoparticles have many special attributes as large surface area to the volume
ratio, high catalytic activity, high surface reactivity, and strong adsorption
capacity. Nanoparticles of nickel act as catalyst in the conversion of lignocellu-
losic material into biofuel.[88] Biomass gasification is the most promising way for
the pretreatment of lignocellulosic biomass to synthesis gas (syngas), which is a
mixture of carbon monoxide and hydrogen. Syngas can be used as fuel or as an
intermediate in the production of liquid fluid. Costly and tedious hydrolysis
processes can be deducted by using nickel nanoparticles. Generally, high tem-
perature is required for the catalytic processes, which can be minimized by using
nickel nanoparticles. Nanocrystalline nickel nanoparticles act as catalyst in
hydrogen and tar production from lignocellulosic material.[89]
Stability of enzyme is a very crucial step at the time of hydrolysis of
lignocellulosic material. Hence, the stability of cellulases can be improved by
using nanomaterials. Srivastava et al.[90] reported the synthesis of nickel-cobal-
tite nanoparticles and evaluated their effect on the production of cellulases at
different concentrations of synthesized nanoparticles. The study demonstrated
that concentration of nanoparticles at 1 mM concentration showed maximum
production of cellulose, whereas as the concentration of nanoparticles was
increased it reduces the production of cellulases. Nickel-cobaltatite nanoparti-
cles have influence on the thermostability of the cellulase enzyme; at 1 mM
concentration, nanoparticles showed stability of enzyme at 80°C for 8 h,
whereas the stability of enzyme was less in absence of nanoparticles. Hence,
these nanoparticles demonstrated better thermostability of enzyme as com-
pared without nanoparticles, which indicates that it can help in the cost-
effective production of cellulases enzyme from less expensive substrate.[88]

Carbon nanotubes
Unlike other nanomaterials, carbon nanotubes (CNTs) also attracted great deal of
attention due to their most fascinating electrical, properties, thermal properties,
and high mechanical strength.[91–93] Among the single-walled carbon nanotubes
(SWCNTs) and multi-walled carbon nanotubes (MWCNTs), MWCNTs was
preferably used for immobilization enzymes because of their structural arrange-
ments, which provide it enhanced electronic properties, a large edge to basal plane
12 M. RAI ET AL.

ratio and rapid electrode kinetics.[93] Reports suggested that functionalized

MWCNTs can be more promising in holding the enzymes and naked.
MWCNTs functionalized with carboxylic acid groups showed significant
immobilization, that is, 98% of cellulase were produced by the fermentation
of sewage treatment plant sludge using Trichoderma reesei RUT C-30 via
covalent linkage.[94] Similarly, Mubarak et al.[91] demonstrated the immobiliza-
tion of cellulase on functionalized MWCNTs with its various concentrations;
however, maximum 97% binding efficacy was reported at the enzyme concen-
tration of 4 mg/mL. Moreover, it was reported that catalytic activity of immo-
bilized enzyme remains about 52% even after six cycles of hydrolysis.
Recently, cellulase recovered from Aspergillus niger was immobilized on
the functionalized MWCNTs through carbodiimide coupling. Thus, immo-
bilization cellulase via covalent linking was found to be effective in hydrolysis
of cellulose with 85% binding efficacy. Moreover, the studies on reusability of
immobilized enzyme suggested that it can be reused multiple times without
much loss in enzyme activity because immobilized enzyme retained 75% of
its original activity after sixth cycle.[93]

Other oxide nanomaterials

In addition to abovementioned nanomaterials, some other nanomaterials can
also be used for immobilization of cellulase-like oxide nanomaterials. It was
claimed that MnO2 nanoparticles synthesized from Aspergillus fumigatus can
act as superior support for the immobilization of cellulase for enhanced
efficacy. The immobilization increases the thermostability of cellulase (70°C
for 2 h). Moreover, it was reported that immobilized cellulase can retain 60%
activity even after five cycles of hydrolysis.[76] Moreover, immobilization of
cellulase recovered from A. niger on TiO2-lignin hybrid support using phy-
sical interactions also showed promising catalytic activity even after tenth
cycle of its reuse.[95]
All these studies confirmed that immobilization of enzymes on various
nanomaterials and their use as nanobiocatalysts would be a novel and
economical viable alternative for the hydrolysis of lignocellulosic biomass.
Table 1 summarizes the various nanomaterials used for the immobiliza-
tion of different enzymes and their binding and catalytic efficacy after
reuse.[7,75,76,78,79,82,91,93–100] However, Figure 2 illustrated the schematic
representation of enzyme immobilization on magnetic nanomaterials and
their application in hydrolysis of lignocellulosic biomass.

NF of biomass
Biomass processing of cellulosic material results in the conversion of cellu-
lose into its constituent sugar molecules (i.e. glucose). A conventional
Table 1. Various nanomaterials used for the immobilization of different enzymes and their binding and catalytic efficacy after reuse.
Immobilization Binding
Nanomaterials Enzyme immobilized approach efficiency Catalytic efficiency after reuse References
[7]
Magnetic iron oxide nanoparticles Cellulase Covalent 98% 52% after 3rd cycle
bonding
[76]
MnO2 nanoparticles Cellulase Covalent 75% 60% after 5th cycles
bonding
[78]
Magnetic iron oxide nanoparticles β-glucosidase Covalent 93% 50% up to 16th cycle
bonding
[79]
Magnetic (Fe3O4) nanoparticles Cellulase Covalent 90% 10% after 6 cycles
bonding
[82]
Zinc ferrite nanoparticles Cellulase Covalent 53% **
bonding
[91]
Functionalized MWCNTs Cellulase Physical 97% 52% after 6th cycles
adsorption
[93]
MWCNTs functionalized with N-ethyl-N-(3-dimethylaminopropyl) Cellulase Covalent 85% 75% after 6th cycles
carbodiimide hydrochloride bonding
[94]
MWCNTs functionalized with carboxylic acid Cellulase Covalent 98% **
bonding
[95]
TiO2-lignin hybrid support. Cellulase Physical 80% 90% after 10th cycle
interactions
[96]
Superparamagnetic nanoparticles β-glucosidase A and Covalent 100% 85% after 3rd cycle and 43%
Cellobiohydrolase D bonding after 10th cycle
[75]
Chitosan-coated magnetic nanoparticles Cellulase Covalent 100% 80% after 15th cycle
bonding
[97]
Magneto-responsive graphene nanosupports Cellulase Covalent ** 55% after 4 cycles
bonding
[98]
Mesoporous silica functionalized with vinyl and amino group Cellulase Physical ** 78%–100% and 72%–91% after
adsorption first cycle
[99]
Fe3O4 nanoparticles and Fe3O4/Alginate nanocomposites Cellulase Physical ** 56% after 1 cycle
adsorption
CATALYSIS REVIEWS

[100]
Silver and gold nanoparticle Cellulase Physical ** 73% and 78% after 6 cycles
adsorption
**Details not available/not mentioned.
13
14 M. RAI ET AL.

Figure 2. Schematic representation of enzyme immobilization on magnetic nanomaterials and

their application in hydrolysis of lignocellulosic biomass.

technique of biomass processing involves the process of acid hydrolysis,

which converts lignocellulosic biomass into sugars along with the acid.[101]
The typical combination of sugar–acid can be separated by chromatographic
separation technique and the separated sugar can be utilized for the produc-
tion of biofuels. The chromatographic separation technique is not perfect, as
the proper recovery of acid and sugar is not possible and it results in acid–
sugar contamination. Hence, the only solution, which can solve the issue of
sugar and acid separation is NF. NF assembly contains nanofilter membrane,
which processes sugar contaminated acid. The acid is passed through nano-
filter membrane, whereas sugar is rejected and the sugar molecule can be
separated, which can be further utilized for biofuel production.[102]
NF is a unique filtration process, which is an intermediate between ultrafil-
tration and osmosis. It is designed to achieve separation of low-molecular-
weight compounds such as sugars, dissolved minerals, and salts.[103,104] NF
membrane modules available for filtration of biomass are GEsepa, SU- 210,
SU-600, NF-45, NF-90, etc. GEsepa is commercially available from GE
Osmonics which is cellulose acetate-based NF membrane. NF-45, NF-99HF,
and NF-200 are available from Filmtech cooperation.[105] Lyu et al.[106] proposed
two-stage NF assembly for recovering a large number of chemicals and sugars
such as cyclopentenones, glucose, acetic acid, and monophenols from lignocel-
lulose of rice straw by the process of hydrothermal liquefaction. Hydrothermal
liquefaction is a chemical process used for the transformation of biomass to high
product yield, with very less energy consumption. For achieving high amount of
sugars and chemicals, initially ultrafiltration assembly was used as the
 CATALYSIS REVIEWS 15

pretreatment of lignocellulosic material and afterward it was passed through NF

assembly. MW GE, DL, and DK nanomembrane filters were used for the
separation of biomass. It was found that DL + DK two-stage NF can be used
for the separation of glucose, acetic acid, and monophenols.
Ranney[102] designed the NF assembly for the filtration of cellulosic bio-
mass. NF assembly composed of an input chamber, which contains a mixture
of water, acid, and sugar. The chromatographic unit is being configured to
perform a partial separation of acid and sugars. The chromatographic cham-
bers have two outlet chambers, first output is to supply the separation of
sugars and a second output chamber is to supply sugar contaminated acid
mixture. The filtration chamber has an input and outlet connection, an input
line is coupled to the chromatographic unit. Second outlet line of filtration
and input connection of chromatographic assembly are coupled together. A
nanomembrane is fixed or positioned within the filtration chamber. One side
of the membrane has input connection and it received acid-sugar contami-
nants. The nanomembrane allows the passage of the acid, but blocks the
passage of sugars present in the mixture of acid and sugars. An evaporative
acid processor is coupled to the output line of the nanomembrane so that
evaporative acid processor receives the dilute acid via output line and it is re-
concentrated by evaporation. The removal of sugar from the mixture helps in
the proper separation of acid from the sugar. There is one feedback line from
NF membrane filtration assembly, which helps in the passage of separated
sugar back into the chromatographic chamber. Again sugar is filtered
through the chromatographic chamber and collected in the separate outlet.
After the complete recovery process of sugar, the chamber in which sugar is
collected is coupled with the sugar processing unit, where the process of
distillation takes place. The sugar processing unit results in the formation of
the ethanol. Hence, NF membrane can be used in the recovery of the
bioethanol and the acid can be separated from acid–sugar mixture.[102,107,108]

Lignocellulose to nanocellulose
Conversion of lignocellulosic biomass into glucose, lignin, cellulose, and
hemicellulose is a tedious process. The main focus of overall world toward
lignocellulose is not only limited to biofuel production[109,110] but also
involved the synthesis of nanocellulose.[111,112] Nanocellulose is single crys-
talline cellulose needle-like structure with 1–100 nm in diameter. The ratio of
degree of crystallinity and geometrical aspects plays a very important role in
controlling the properties of nanocellulose.[111,113] Different sources such as
cotton, palm, cellulose, saccharin, wood, and wheat straw are used for the
production of nanocellulose.[114,115]
Now-a-days, global focus is directed toward conversion of lignocellulosic
biomass to nanocellulose for biofuel production. Nanocellulose can be of two
16 M. RAI ET AL.

types on the basis of morphological differences namely, cellulose nanocrystals

and cellulose nanofibrils.[116,117] These forms of nanocellulose exhibit novel
attractive properties such as high specific surface area, high aspect ratio,
nontoxic, low thermal expansion, and apart from these, they are having
low cost, come from natural and abundant sources and has ability to replace
synthetic fibers.[116,118,119] Nanocellulose has potential applications in tissue
engineering scaffolds, regenerative medicine, textiles, food packing, catalysis,
drug delivery, fabrication of optically transparent film, etc.[120,121]
The lignocellulose to nanocellulose conversion includes pretreatment of
lignocellulosic biomass to separate out cellulose and some fractions of
hemicellulose and lignin. Different strategies like variation in terms of
temperature, pH, treatment time, and types of catalyst involved have been
used in pretreatment of lignocellulosic biomass.[111,122] Chemical treat-
ment method is most popular technique often used for isolation of
nanocellulose from cellulose fibers. In acid hydrolysis process, hydronic
bond breakdown and attack on inter- and intramolecular bonds among
cellulose in biomass. Different concentration and dilutions of acid solu-
tion are involved in acid hydrolysis treatment.[123,124] Recalcitrance is the
major obstacle in separation of cellulose, hemicellulose, and lignin, and
the main goal of pretreatment is to break lignocellulosic biomass to
solubilize noncellulosic contents namely hemicellulose and lignin.[125]
The top down destructive approach has been used for conversion of
cellulosic biomass to nanocellulose by mechanical, chemical, and biologi-
cal reactions.[113,119,126,127] The 2,2,6,6-tetramethylpiperidinyl-1-oxyl
(TEMPO) radicals have been applied for the disintegration of cellulose
into nanocellulose in cellulose depolymerization treatment method. In
TEMPO-mediated oxidation method, outside facing primary hydroxyl
group of cellulose fibril have been oxidized to carboxylate group leading
to production of nanosized particles of cellulose.[128,129]
The conventional methods based on chemical processes like acid hydro-
lysis and thermal hydrolysis have been employed for conversion of cellu-
lose to nanocellulose till date. The chemical process involves fabrication of
cellulose by alkaline treatment followed by acid depolymerization for
production of nanocellulose. However, during these processes, the huge
amount of toxic wastes are emitted, which generates environmental
problems.

Toxicity of nanoparticles: a major concern

As described in the previous section, nanoparticles have facilitated many
technological advances in various fields, but there are concerns regarding
their toxicity and safety toward human and environment.[130] The envir-
onmental and toxicological aspects of nanoparticles used for hydrolysis of
 CATALYSIS REVIEWS 17

lignocellulosic biomass are not extensively studied. There are only a few
reports available, which suggests the toxicity of nanoparticles used in the
pretreatment and hydrolysis of lignocellulosic biomass. However, knowing
the hazardous effect of nanomaterials, it is necessary to develop the safe
manufacturing protocol and products. There are possibilities of the release
of nanoparticles used for enzyme immobilization into environment leading
to harmful effects. For instance, magnetic nanoparticles used for hydrolysis
of lignocellulosic biomass have shown to exert harmful effect on biological
systems. It is reported that the toxicity of surface-coated magnetic nano-
particles results from the biodegradation of metabolites that generate
reactive oxygen species (ROS) such as hydrogen peroxide and hydroxyl
radicals. ROS generation causes damage to cells by peroxidizing lipids,
disrupting DNA, modifying gene transcription, and varying proteins col-
lectively leading to cell death through apoptosis.[131] Whereas, the
uncoated magnetic nanoparticles were reported to be cytotoxic above the
concentration of 100 µg/mL.[132]
Silica nanoparticles have been reported to greatly enhance nuclear
protein aggregation and fibrilization. The protein aggregation subsequently
leads to the formation of inclusion bodies, contributing the neurodegen-
erative processes.[133] In general, nanoparticles reduce the cell viability and
proteasome activity, increase levels of lactate dehydrogenase, induce ROS
and apoptosis, disturb cell cycle and activate p53-mediated signaling path-
way in vitro.[130,133,134] However, the scarce studies on hydrolysis of lig-
nocellulose necessitate further extensive studies to understand toxicity
issues.

Conclusions
Hydrolysis of lignocellulosic biomass is a crucial step in the process of
biofuel production. Generation of toxic inhibitors due to acid hydrolysis
methods leads to tedious downstream processing. Enzymatic hydrolysis
approach is very specific and ecofriendly, but high-cost enzymes make
the process expensive. In this context, applications of various nanomater-
ials for the immobilization of various hydrolytic enzymes increase the
efficiency and stability of enzymes. In addition, immobilization of enzymes
on magnetic nanomaterials leading to the development of nanobiocatalysts
is considered as most promising and widely accepted for the hydrolysis of
various lignocellulosic biomass. Due to magnetic nature, such nanobioca-
talysts can be easily recovered by applying a magnetic field and reuse for
more than one cycle of hydrolysis. Reuse of immobilized enzyme will help
to make the process economically viable. Moreover, the techniques like NF
are very useful for the filtration of various treated biomass. Thus, use of
nanotechnology can be recommended for the effective, ecofriendly, and
18 M. RAI ET AL.

economically viable hydrolysis of lignocellulosic biomass. Moreover, look-

ing at the toxicological concerns associated with some nanomaterials, there
is a need to perform extensive studies on evaluation of toxicity of such
nanomaterials and also consider safety issues regarding the environment
and human being.

Acknowledgments
MR is grateful to University Grants Commission, New Delhi, India for proving financial
assistance in the form of Basic Science Research Faculty Fellowship. API is highly thankful to
Research Council for the State of Sao Paulo [Fundação de Amparo à Pesquisa do Estado de
São Paulo (FAPESP)], Brazil, for providing financial assistance (Process Number- 2016/
22086-2) in the form of Post-Doctoral Fellowship. SSS is thankful to Brazilian National
Council for Scientific and Technological Development (CNPq) (Process No. 401308/2014-6
and 150745/2015-0) for research grants.

Funding
This work was supported by the University Grants Commission, New Delhi, India; Research
Council for the State of Sao Paulo (FAPESP); [2016/22086-2]; Brazilian National Council for
Scientific and Technological Development (CNPq) [401308/2014-6] and [150745/2015-0].

Conflict of interest
Authors have no conflict of interest to declare.

References
[1] Lukajtis, R.; Kucharska, K.; Hołowacz, I.; Rybarczyk, P.; Wychodnik, K.; Słupek, E.;
Nowak, P.; Kaminski, M. Comparison and Optimization of Saccharification Conditions
of Alkaline Pre-Treated Triticale Straw for Acid and Enzymatic Hydrolysis Followed by
Ethanol Fermentation. Energies 2018, 11, 639, DOI:10.3390/en11030639.
[2] Ciolacu, D. E.; Biochemical Modification of Lignocellulosic Biomass. In Biomass as
Renewable Raw Material to Obtain Bioproducts of High-Tech Value; Popa, V. I., Volf, I.,
Eds.; Elsevier: Amsterdam, Netherlands, 2018. pp 315–350.
[3] Jonsson, L. J.; Martín, C. Pretreatment of Lignocellulose: Formation of Inhibitory By-
Products and Strategies for Minimizing Their Effects. Bioresour. Technol. 2016, 199, 103–
112.
[4] Kumar, A. K.; Sharma, S. Recent Updates on Different Methods of Pretreatment of
Lignocellulosic Feedstocks: A Review. Bioresour. Bioprocess. 2017, 4, 7. DOI: 10.1186/
s40643-017-0137-9.
[5] Taherzadeh, M. J.; Karimi, K. Pretreatment of Lignocellulosic Wastes to Improve
Ethanol and Biogas Production: A Review. Int. J. Mol. Sci. 2008, 9, 1621–1651.
[6] Teran-Hilares, R.; de Almeida, G. F.; Ahmed, M. A.; Antunes, F. A. F.; Da Silva, S. S.;
Han, J. I.; Santos, J. C. D. Hydrodynamic Cavitation as an Efficient Pretreatment
 CATALYSIS REVIEWS 19

Method for Lignocellulosic Biomass: A Parametric Study. Bioresour. Technol. 2017,

235, 301–308.
[7] Yang, B.; Wyman, C. E. Effect of Xylan and Lignin Removal by Batch and Flow
through Pretreatment on the Enzymatic Digestibility of Corn Stover Cellulose.
Biotechnol. Bioeng. 2004, 86, 88–95.
[8] Ichwan, M.; Son, T. W. Study on Organosolv Pulping Methods of Oil Palm Biomass.
Proceedings of the International Seminar on Chemistry, Jatinangor, Indonesia, 2011,
364–370.
[9] Zheng, Q.; Zhou, T.; Wang, Y.; Cao, X.; Wu, S.; Zhao, M.; Wang, H.; Xu, M.; Zheng, B.;
Zheng, J.; Guan, X. Pretreatment of Wheat Straw Leads to Structural Changes and
Improved Enzymatic Hydrolysis. Sci. Reports. 2018, 8, 1321. DOI: 10.1038/s41598-018-
19517-5.
[10] Rabemanolontsoa, H.; Saka, S. Various Pretreatments of Lignocellulosics. Bioresour.
Technol. 2016, 199, 83–91.
[11] Kim, D. Physico-Chemical Conversion of Lignocellulose: Inhibitor Effects and
Detoxification Strategies: A Mini Review. Molecules. 2018, 23, 309. DOI: 10.3390/
molecules23020309.
[12] Vats, S.; Maurya, D. P.; Shaimoon, M.; Agarwal, A.; Negi, S. Development of a
Microbial Consortium for the Production of Blend Enzymes for the Hydrolysis of
Agricultural Waste into Sugars. J. Sci. Ind. Res. 2013, 72, 585–590.
[13] Akhtar, N.; Gupta, K.; Goyal, D.; Goyal, A. Recent Advances in Pretreatment
Technologies for Efficient Hydrolysis of Lignocellulosic Biomass. Environ. Prog.
Sustain. Energy. 2016, 35, 489–511.
[14] Paye, J. M. D.; Guseva, A.; Hammer, S. K.; Gjersing, E.; Davis, M. F.; Davison, B. H.;
Olstad, J.; Donohoe, B. S.; Nguyen, T. Y.; Wyman, C. E.; Pattathil, S.; Hahn, M. G.;
Lynd, L. R. Biological Lignocellulose Solubilization: Comparative Evaluation of
Biocatalysts and Enhancement via Co-Treatment. Biotechnol. Biofuels 2016, 9, (8).
DOI:10.1186/s13068-015-0412-y.
[15] Brodeur, G.; Yau, E.; Badal, K.; Collier, J.; Ramachandran, K. B.; Ramakrishnan, S.
Chemical and Physicochemical Pretreatment of Lignocellulosic Biomass: A Review.
Enzyme Res 2011, 2011, Article ID 787532. DOI:10.4061/2011/787532.
[16] Mood, S. H.; Golfeshan, A. H.; Tabatabaei, M.; Jouzani, G. S.; Najafi, G. M.; Gholami,
M.; Ardjmand, M. Lignocellulosic Biomass to Bioethanol: A Comprehensive Review
with a Focus on Pretreatment. Renew. Sustain. Energy Rev. 2013, 27, 77–93.
[17] Sindhu, R.; Binod, P.; Pandey, A. Biological Pretreatment of Lignocellulosic Biomass –
An Overview. Bioresour. Technol. 2016, 199, 76–82.
[18] Mulat, D. G.; Huerta, S. G.; Kalyani, D.; Horn, S. J. Enhancing Methane Production
from Lignocellulosic Biomass by Combined Steam-Explosion Pretreatment and
Bioaugmentation with Cellulolytic Bacterium Caldicellulosiruptor bescii. Biotechnol
Biofuels. (2018), 11, 19. DOI: 10.1186/s13068-018-1025-z.
[19] Lenihan, P.; Orozco, A.; O’Neill, E.; Ahmad, M. N. M.; Rooney, D. W.; Mangwandi, C.;
Walker, G. M. Kinetic Modelling of Dilute Acid Hydrolysis of Lignocellulosic Biomass.
In Biofuel Production: Recent Developments and Prospects; Bernardes, M. A. D. S., Ed.;
Intech Open Publisher, London, UK, 2011.
[20] Gámez, S.; González-Cabriales, J. J.; Ramírez, J. A.; Garrote, G.; Vázquez, M. Study of the
Hydrolysis of Sugar Cane Bagasse Using Phosphoric Acid. J. Food Eng. 2006, 74, 78–88.
[21] Mittal, A.; Black, S. K.; Vinzant, T. B.; O’Brien, M.; Tucker, M. P.; Johnson, D. K.
Production of Furfural from Process-Relevant Biomass-Derived Pentoses in a Biphasic
Reaction System. ACS Sustainable Chem. Eng. 2017, 5, 5694–5701.
20 M. RAI ET AL.

[22] Perna, M. D. S. C.; Bastos, R. G.; Ceccato-Antonini, S. R. Single and Combined Effects
of Acetic Acid, Furfural, and Sugars on the Growth of the Pentose-Fermenting Yeast
Meyerozyma guilliermondii. 3 Biotech. 2018, 8, 119. DOI:10.1007/s13205-018-1143-0.
[23] De Souza, R. L.; Yu, H.; Rataboul, F.; Essayem, N. 5-Hydroxymethylfurfural (5-HMF)
Production from Hexoses: Limits of Heterogeneous Catalysis in Hydrothermal
Conditions and Potential of Concentrated Aqueous Organic Acids as Reactive
Solvent System. Challenges 2012, 3, 212–232.
[24] Reynaldo, P. B.; Adriano, E.; Marcelo, M.; Silvia, N. Enzymatic Hydrolysis of Sugarcane
Biomass and Heat Integration as Enhancers of Ethanol Production. J. Renew. Mater.
2018, 6, 183–194.
[25] Chen, H. Z.; Liu, Z. H. Enzymatic Hydrolysis of Lignocellulosic Biomass from Low to
High Solids Loading. Eng. Life Sci. 2016, 00, 1–11.
[26] Datta, S.; Christena, L. R.; Rajaram, Y. R. S. Enzyme Immobilization: An Overview on
Techniques and Support Materials. 3 Biotech. 2013, 3, 1–9.
[27] Zdarta, J.; Meyer, A. S.; Jesionowski, T.; Pinelo, M. A General Overview of Support
Materials for Enzyme Immobilization: Characteristics, Properties, Practical Utility.
Catalysts. (2018), 8, 92. DOI: 10.3390/catal8020092.
[28] Ramakrishna, T. R. B.; Nalder, T. D.; Yang, W.; Marshall, S. N.; Barrow, C. J.
Controlling Enzyme Function through Immobilization on Graphene, Graphene
Derivatives and Other Two Dimensional Nanomaterials. J. Mater. Chem. B. 2018.
DOI: 10.1039/C8TB00313K.
[29] Song, J.; Lei, T.; Yang, Y.; Wu, N.; Su, P.; Yang, Y. Attachment of Enzymes to
Hydrophilic Magnetic Nanoparticles through DNA-Directed Immobilization with
Enhanced Stability and Catalytic Activity. New J. Chem. 2018. DOI: 10.1039/
C8NJ00426A.
[30] Budarin, V.; Shuttleworth, P. S.; Lanigan, B.; Clark, J. H. Nanocatalysts for Biofuels. In
Nanocatalysis Synthesis and Applications; Polshettiwar, V., Asefa, T., Eds.; Wiley:
Hoboken, NJ, USA, 2013. pp 595–614.
[31] Mohamad, N. R.; Marzuki, N. H. C.; Buang, N. A.; Huyop, F.; Wahab, R. A. An Overview
of Technologies for Immobilization of Enzymes and Surface Analysis Techniques for
Immobilized Enzymes. Biotechnol. Biotechnol. Equip. 2015, 29, 205–220.
[32] Misson, M.; Zhang, H.; Jin, B. Nanobiocatalyst Advancements and Bioprocessing
Applications. J. R. Soc. Interface 2015, 12, 20140891.
[33] Husain, Q.; Ansari, S. A.; Alam, F.; Azam, A. Immobilization of Aspergillus oryzae Beta
Galactosidase on Zinc Oxide Nanoparticles via Simple Adsorption Mechanism. Int. J.
Biol. Macromol. 2011, 49, 37–43.
[34] Ingle, A. P.; Rathod, J.; Pandit, R.; da Silva, S. S.; Rai, M. Comparative Evaluation of
Free and Immobilized Cellulase for Enzymatic Hydrolysis of Lignocellulosic Biomass
for Sustainable Bioethanol Production. Cellulose 2017, 24, 5529–5540.
[35] Basso, A.; Braiuca, P.; Cantone, S.; Ebert, C.; Linda, P.; Spizzo, P.; Caimi, P.; Hanefeld,
U.; Degrassi, G.; Gardossia, L. In Silico Analysis of Enzyme Surface and Glycosylation
Effect as a Tool for Efficient Covalent Immobilisation of CalB and PGA on Sepabeads®.
Adv. Synth. Catal. 2007, 349, 877–886.
[36] Lee, S. Y.; Lee, J.; Chang, J. H.; Lee, J. H. Inorganic Nanomaterial-Based Biocatalysts.
BMB Rep. 2011, 77–86. DOI:10.5483/BMBRep.2011.44.2.77.
[37] Rai, M.; dos Santos, J. C.; Soler, M. F.; Marcelino, P. R. F.; Brumano, L. P.; Ingle, A. P.;
Gaikwad, S.; Gade, A.; da Silva, S. S. Strategic Role of Nanotechnology for Production
of Bioethanol and Biodiesel. Nanotechnol. Rev. 2016, 5, 231–250.
[38] Taherzadeh, M. J.; Karimi, K. Acid Based Hydrolysis Processes for Ethanol from
Lignocellulosic Materials: A Review. BioResources. 2007, 2, 472–499.
 CATALYSIS REVIEWS 21

[39] Lenihan, P.; Orozco, A.; O’Neill, E.; Ahmad, M. N. M.; Rooney, D. W.; Walker, G. M.
Dilute Acid Hydrolysis of Lignocellulosic Biomass. Chem. Eng. J. 2010, 156, 395–403.
[40] Huang, Y. B.; Fu, Y. Hydrolysis of Cellulose to Glucose by Solid Acid Catalysts. Green
Chem 2013, 15, 1095.
[41] Xu, Z.; Huang, F. Pretreatment Methods for Bioethanol Production. Appl. Biochem.
Biotechnol. 2014, 174, 43–62.
[42] Shahbaz, A.; Zhang, B. Dilute and Concentrated Acid Hydrolysis of Lignocellulosic
Biomass. In Bioalcohol Production; Waldron, K., Ed.; Woodhead Publishing Limited
and CRC Press: USA, 2010. pp 143–158.
[43] Sritrakul, N.; Nitisinprasert, S.; Keawsompong, S. Evaluation of Dilute Acid
Pretreatment for Bioethanol Fermentation from Sugarcane Bagasse Pith. Agri. Nat.
Resour. 2018. DOI: 10.1016/j.anres.2017.12.006.
[44] Baadhe, R. R.; Potumarthi, R.; Mekala, N. K. Influence of Dilute Acid and Alkali
Pretreatment on Reducing Sugar Production from Corncobs by Crude Enzymatic
Method: A Comparative Study. Bioresour. Technol. 2014, 162, 213–217.
[45] Castro, E.; Nieves, I. U.; Mullinnix, M. T. Optimization of Dilute-Phosphoric-Acid Steam
Pretreatment of Eucalyptus benthamii for Biofuel Production. Appl. Energy 2014, 125,
76–83.
[46] Jung, J. Y.; Choi, M. S.; Yang, J. K. Optimization of Concentrated Acid Hydrolysis of Waste
Paper Using Response Surface Methodology. J. Korean Wood Sci. Tech. 2013, 41, 87–99.
[47] Mosier, N.; Wyman, C.; Dale, B.; Elander, R.; Lee, Y. Y.; Holtzapple, M.; Ladisch, M.
Features of Promising Technologies for Pretreatment of Lignocellulosic Biomass.
Bioresour. Technol. 2005, 96, 673–686.
[48] Zheng, Y.; Pan, Z.; Zhang, R. Overview of Biomass Pretreatment for Cellulosic Ethanol
Production. Int. J. Agri. Biol. Eng. 2009, 2, 51–68.
[49] Jennings, E. W.; Schell, D. J. Conditioning of Dilute-Acid Pretreated Corn Stover
Hydrolysate Liquors by Treatment with Lime or Ammonium Hydroxide to Improve
Conversion of Sugars to Ethanol. Bioresour. Technol. 2011, 102, 1240–1245.
[50] Rajan, K.; Carrier, D. J. Effect of Dilute Acid Pretreatment Conditions and Washing on
the Production of Inhibitors and on Recovery of Sugars during Wheat Straw Enzymatic
Hydrolysis. Biomass Bioenergy 2014, 62, 222–227.
[51] Wijaya, Y. P.; Putra, R. D. D.; Widyaya, V. T.; Ha, J. M.; Suh, D. J.; Kim, C. S.
Comparative Study on Two-Step Concentrated Acid Hydrolysis for the Extraction of
Sugars from Lignocellulosic Biomass. Bioresour. Technol. 2014, 164, 221–231.
[52] Harmsen, P. F. H.; Hujigen, W. J. J.; Lopez, L. M. B.; Bakker, R. R. C. Literature Review
of Physical and Chemical Pretreatment Processes for Lignocellulosic Biomass.
Biosynergy. 2018. available at https://www.ecn.nl/docs/library/report/2010/e10013.pdf.
accessed on April 7, 2018.
[53] Loow, Y. L.; Wu, T. Y.; Jahim, J. M.; Mohammad, A. W.; Teoh, W. H. Typical
Conversion of Lignocellulosic Biomass into Reducing Sugars Using Dilute Acid
Hydrolysis and Alkaline Pretreatment. Cellulose. 2016, 23, 1491–1520.
[54] Guo, F.; Fang, Z.; Xu, C. C.; Smith, R. L., Jr. Solid Acid Mediated Hydrolysis of Biomass
for Producing Biofuels. Prog. Energy Combust. Sci. 2012, 38, 672–690.
[55] Bootsma, J. A.; Shanks, B. H. Cellobiose Hydrolysis Using Organic–Inorganic Hybrid
Mesoporous Silica Catalysts. Appl. Catal. A-Gen. 2007, 327, 44–51.
[56] Hegner, J.; Pereira, K. C.; DeBoef, B.; Lucht, B. L. Conversion of Cellulose to Glucose and
Levulinic Acid via Solid-Supported Acid Catalysis. Tetrahedron. Lett. 2010, 51, 2356–
2358.
22 M. RAI ET AL.

[57] Akiyama, G.; Matsuda, R.; Sato, H.; Takata, M.; Kitagawa, S. Cellulose Hydrolysis by a
New Porous Coordination Polymer Decorated with Sulfonic Acid Functional Groups.
Adv. Mater. 2011, 23, 3294–3297.
[58] Maggi, R.; Shiju, N. R.; Santacroce, V.; Maestri, G.; Bigi, F.; Rothenberg, G. Silica-
Supported Sulfonic Acids as Recyclable Catalyst for Esterification of Levulinic
Acid with Stoichiometric Amounts of Alcohols. Beilstein J. Org. Chem. 2016, 12,
2173–2180.
[59] Atsushi, A.; Masatoshi, N.; Shun, N.; Kohki, E. Hydrolysis of Sugars Using Magnetic
Silica Nanoparticles with Sulfonic Acid Groups. Chem. Lett. 2011, 40, 1195–1197.
[60] Verardi, A.; De Bari, I.; Ricca, E.; Calabrò, V. Hydrolysis of Lignocellulosic Biomass:
Current Status of Processes and Technologies and Future Perspectives. In Bioethanol;
Lima, M. A. P., Natalense, A. P. P., Eds.; InTech publisher, London, UK, 2012; p. 302.
[61] Rozenfelde, L.; Puíe, M.; Krûma, I.; Poppele, I.; Matjuðkova, N.; Vederòikovs, N.;
Rapoport, A. Enzymatic Hydrolysis of Lignocellulose for Bioethanol Production.
Proc. Latvian Acad. Sciences. Section B. 2017, 71, 275–279.
[62] De Souza, W. R.; Microbial Degradation of Lignocellulosic Biomass. In Sustainable
Degradation of Lignocellulosic Biomass: Techniques, Applications and
Commercialization; Chandel, A. K., Da Silva, S. S., Eds.; InTech Publisher: Rijeka,
Croatia, 2012.
[63] Du, W.; Yu, H.; Song, L.; Zhang, J.; Weng, C.; Ma, F.; Zhang, X. The Promising Effects
of By-Products from Irpex lacteus on Subsequent Enzymatic Hydrolysis of Bio-
Pretreated Corn Stalks. Biotechnol. Biofuels 2011, 4, 37.
[64] Sánchez, C. Lignocellulosic Residues: Biodegradation and Bioconversion by Fungi.
Biotechnol. Adv. 2009, 64, 185–194.
[65] Tayyab, M.; Noman, A.; Islam, W.; Waheed, S.; Arafat, Y.; Ali, F.; Zaynab, M.; Lin, S.;
Zhang, H.; Lin, W. Bioethanol Production from Lignocellulosic Biomass by
Environment-Friendly Pretreatment Methods: A Review. Appl. Ecol. Environ. Res.
2018, 16, 225–249.
[66] Li, Y. H.; Zhang, X. Y.; Zhang, F.; Peng, L. C.; Zhang, D. B.; Kondo, A.; Bai, F. W.;
Zhao, X. Q. Optimization of Cellulolytic Enzyme Components through Engineering
Trichoderma reesei and On-Site Fermentation Using the Soluble Inducer for Cellulosic
Ethanol Production from Corn Stover. Biotechnol Biofuels. 2018, 11, 49. DOI: 10.1186/
s13068-018-1048-5.
[67] Victoria, J.; Odaneth, A.; Lali, A. Importance of Cellulase Cocktails Favoring
Hydrolysis of Cellulose. Preparative Biochem. Biotechnol. 2017, 47, 547–553.
[68] Hanefeld, U.; Gardossi, L.; Magner, E. Understanding Enzyme Immobilization. Chem.
Soc. Rev. 2009, 453–468.
[69] Lee, C. K.; Duong, A. N. Enzyme Immobilization on Nanoparticles: Recent
Applications. In Emerging Areas in Bioengineering, 1st edn.; Chang, H. N., Ed.;
Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, Germany, 2018; pp. 67–80.
[70] Abraham, R. E.; Verma, M. L.; Barrow, K. J.; Puri, M. Suitability of Magnetic Nanoparticle
Immobilised Cellulases in Enhancing Enzymatic Saccharification of Pretreated Hemp
Biomass. Biotechnol. Biofuels. 2014, 7, 90. DOI: 10.1186/1754-6834-7-90.
[71] Grewal, J.; Ahmad, R.; Khare, S. K. Development of Cellulase-Nanoconjugates with
Enhanced Ionic Liquid and Thermal Stability for in Situ Lignocellulose
Saccharification. Bioresour. Technol. 2017, 242, 236–243.
[72] Perwez, M.; Ahmad, R.; Sardar, M. A Reusable Multipurpose Magnetic Nanobiocatalyst
for Industrial Applications. Int. J. Biol. Macromol. 2017, 103, 16–24.
[73] Husain, Q. Nanomaterials Immobilized Cellulolytic Enzymes and Their Industrial
Applications: A Literature Review. JSM Biochem. Mol. Biol. 2017, 4, 1029.
 CATALYSIS REVIEWS 23

[74] Kim, K. H.; Lee, O. K.; Lee, E. Y. Nano-Immobilized Biocatalysts for Biodiesel
Production from Renewable and Sustainable Resources. Catalysts. (2018), 8, 68. DOI:
10.3390/catal8020068.
[75] Sánchez-Ramírez, J.; Martínez-Hernández, J. L.; Segura-Ceniceros, P.; López, G.; Saade,
H.; Medina-Morales, M. A.; Ramos-González, R.; Aguilar, C. N.; Ilyina, A. Cellulases
Immobilization on Chitosan-Coated Magnetic Nanoparticles: Application for Agave
atrovirens Lignocellulosic Biomass Hydrolysis. Bioprocess Biosys. Eng. 2017, 40, 9–22.
[76] Cherian, E.; Dharmendirakumar, M.; Baskar, G. Immobilization of Cellulase onto
MnO2 Nanoparticles for Bioethanol Production by Enhanced Hydrolysis of
Agricultural Waste. Chin. J. Catal. 2015, 36, 1223–1229.
[77] Lee, S.; Jin, L. H.; Kim, J. H.; Han, S. O.; Na, H. B.; Hyeon, T.; Koo, Y. M.; Kim, J.; Lee,
J. H. β-Glucosidase Coating on Polymer Nanofibers for Improved Cellulosic Ethanol
Production. Bioprocess Biosyst. Eng 2010, 33, 141–147.
[78] Verma, M. L.; Chaudhary, R.; Tsuzuki, T.; Barrow, C. J.; Puri, M. Immobilization of β-
glucosidase on a Magnetic Nanoparticle Improves Thermostability: Application in
Cellobiose Hydrolysis. Bioresour. Technol. 2013, 135, 2–6.
[79] Jordan, J.; Kumar, C. S. S.; Theegala, C. Preparation and Characterization of Cellulase-
Bound Magnetite Nanoparticles. J. Mol. Catal. B. Enzymol. 2011, 68, 139–146.
[80] Huang, P. J.; Chang, K. L.; Hsieh, J. F.; Chen, S. T. Catalysis of Rice Straw Hydrolysis by
the Combination of Immobilized Cellulase from Aspergillus niger on β-cyclodextrin-
Fe3O4 Nanoparticles and Ionic Liquid. BioMed Res. Int 2015, 2015, Article ID 409103.
DOI:10.1155/2015/409103.
[81] Zang, L.; Qiu, J.; Wu, X.; Zhang, W.; Sakai, E.; Wei, Y. Preparation of Magnetic
Chitosan Nanoparticles as Support for Cellulase Immobilization. Ind. Eng. Chem.
Res. 2014, 53, 3448–3454.
[82] Manasa, P.; Saroj, P.; Korrapati, N. Immobilization of Cellulase Enzyme on Zinc Ferrite
Nanoparticles in Increasing Enzymatic Hydrolysis on Ultrasound-Assisted Alkaline
Pretreated Crotalaria juncea Biomass. Indian J. Sci. Technol. 2017, 10, 1–7.
[83] Kumar, A.; Singh, S.; Tiwari, R.; Goel, R.; Nain, L. Immobilization of Indigenous
Holocellulase on Iron Oxide (Fe2O3) Nanoparticles Enhanced Hydrolysis of Alkali
Pretreated Paddy Straw. Int. J. Biol. Macromol. 2017, 96, 538–549.
[84] Lupoi, J. S.; Smith, E. A. Evaluation of Nanoparticle-Immobilized Cellulase for
Improved Yield in Simultaneous Saccharification and Fermentation Reactions.
Biotechnol. Bioeng. 2011, 108, 2835–2843.
[85] Chang, R. H. Y.; Jang, J.; Wu, K. C. W. Cellulase Immobilized Mesoporous Silica
Nanocatalysts for Efficient Cellulose-to-Glucose Conversion. Green Chem 2011, 13, 2844–
2850.
[86] Kobayashi, H.; Hosaka, Y.; Hara, K.; Feng, B.; Hirosakia, Y.; Fukuoka, A. Control of
Selectivity, Activity and Durability of Simple Supported Nickel Catalysts for Hydrolytic
Hydrogenation of Cellulose. Green Chem. (2014), 16, 637. DOI: 10.1039/c3gc41357h.
[87] Chandel, A.; Da Silva, S. S.; Singh, O. V. Detoxification of Lignocellulosic Hydrolysates
for Improved Bioethanol Production. In Biofuel Production-Recent Developments and
Prospects; Dos Santos Bernardes, M. A., Ed.; In tech: Croatia, 2011. pp 225–246.
[88] Srivastava, N.; Srivastava, M.; Manikanta, A.; Singh, P.; Ramteke, P. W. Mishra
Nanomaterials for Biofuel Production Using Lignocellulosic Waste. Environ. Chem.
Lett. 2017, 15, 179–184.
[89] Richardson, Y.; Blina, J.; Vollea, G.; Motuzas, J.; Julbe, A. In Situ Generation of Ni
Metal Nanoparticles as Catalyst for H2-Rich Syngas Production from Biomass
Gasification. Appl. Catal. A 2010, 15, 220–230.
24 M. RAI ET AL.

[90] Srivastava, N.; Rawat, R.; Sharma, R.; Oberoi, H. S.; Srivastava, M.; Singh, J. Effect of
Nickel-Cobaltite Nanoparticles on Production and Thermostability of Cellulases from
Newly Isolated Thermotolerant Eurotiyomycetes sp. NS Appl. Biochem. Biotechnol.
2014, 174, 1092–1103.
[91] Mubarak, N. M.; Wong, J. R.; Tan, K. W.; Sahu, J. N.; Abdullah, E. C.; Jayakumar, N. S.;
Ganesan, P. Immobilization of Cellulase Enzyme on Functionalized Multiwall Carbon
Nanotubes. J. Mol. Catal. B Enzym. 2017, 107, 124–131.
[92] Piccinino, D.; Delfino, M.; Botta, G.; Crucianelli, M.; Grossi, V.; Passacantando, M.;
Antiochia, R.; Favero, G.; Saladino, R. Highly Efficient Synthesis of Aldehydes by Layer
by Layer Multi-Walled Carbon Nanotubes (MWCNTS) Laccase Mediator Systems.
Appl. Catal. A: Gen 2015, 77–88.
[93] Ahmad, R.; Khare, S. K. Immobilization of Aspergillus niger Cellulase on Multiwall
Carbon Nanotubes for Cellulose Hydrolysis. Bioresour. Technol. 2018, 252, 72–75.
[94] Mohammed-Abd, R.; Nour, A. H. Optimization of Immobilized Cellulase onto Carbon
Nanotubes Using Response Surface Methodology. Int. J. Phys. Sci. 2012, 7, 841–849.
[95] Zdarta, J.; Jedrzak, A.; Klapiszewski, L.; Jesionowski, T. Immobilization of Cellulase on
a Functional Inorganic–Organic Hybrid Support: Stability and Kinetic Study. Catalysts.
2017, 7, 374. DOI: 10.3390/catal7120374.
[96] Song, Q.; Mao, Y.; Wilkins, M.; Segato, F.; Prade, R. Cellulase Immobilization on
Superparamagnetic Nanoparticles for Reuse in Cellulosic Biomass Conversion. AIMS
Bioeng. 2016, 3, 264–276.
[97] Gokhale, A. A.; Lu, J.; Lee, I. Immobilization of Cellulase on Magnetoresponsive
Graphene Nano-Supports. J Mol. Catal. B Enzym. 2013, 90, 76–86.
[98] Hartono, S. B.; Qiao, S. Z.; Liu, J.; Jack, K.; Ladewig, B. P.; Hao, Z.; Lu, G. Q. M.
Functionalized Mesoporous Silica with Very Large Pores for Cellulase Immobilization.
J. Phys. Chem. C. 2010, 114, 8353–8362.
[99] Srivastava, N.; Singh, J.; Ramteke, P. W.; Mishra, P. K.; Srivastava, M. Improved
Production of Reducing Sugars from Rice Straw Using Crude Cellulase Activated
with Fe3O4/Alginate Nanocomposite. Bioresour. Technol. 2015, 183, 262–266.
[100] Mishra, A.; Sardar, M. Cellulase Assisted Synthesis of Nano-Silver and Gold: Application
as Immobilization Matrix for Biocatalysis. Int. J. Biol. Macromol. 2015, 77, 105–113.
[101] Qi, B.; Luo, J.; Chen, X.; Hang, X.; Wan, Y. Separation of Furfural from
Monosaccharides by Nanofiltration. Bioresour. Technol. 2011, 102, 7111–7118.
[102] Ranney, J. T.; Nanofilter System and Method of Use. US patent No. 7,077,953 B2, 2006.
[103] Kumar, A.; Gayakwad, A.; Nagal, B. D. A Review: Nano Membrane and Application.
Int. J. Innovative Res. Sci., Eng. Technol. 2014, 3, 8373–98381.
[104] Qi, B.; Luo, J.; Chen, G.; Chen, X.; Wan, Y. Application of Ultrafiltration and
Nanofiltration for Recycling Cellulase and Concentrating Glucose from Enzymatic
Hydrolyzate of Steam Exploded Wheat Straw. Bioresour. Technol. 2012, 104, 466–472.
[105] Niwa, M.; Shindo, S.; Nishida, T.; Kishimoto, J.; Minamino, A.; Kurihara, H.; Yamada,
K. Method for Producing Sugar Solution, and Method for Producing Ethanol. Patent
No. EP 2816124 A1. 2014.
[106] Lyu, H.; Chen, K.; Yang, X.; Younas, R.; Zhu, X.; Luo, G.; Zhang, S.; Chen, J. Two-Stage
Nanofiltration Process for High-Value Chemical Production from Hydrolysates of
Lignocellulosic Biomass through Hydrothermal Liquefaction. Sep. Puri. Technol.
2015, 147, 276–283.
[107] Ramli, S. N. B. A Thesis on Fabrication of Nanofiltration Hollow Fiber Membrane for the
Separation of Xylose-Glucose; Faculty of Chemical & Natural Resources Engineering
Ijniversiti Malaysia Pahang, Pahang, Malaysia, 2014.
 CATALYSIS REVIEWS 25

[108] Xiong, B.; The Development of Carboxylic Acid Separation by Nanofiltration

Membrane for Carboxylate Platform Using Lignocellulosic Biomass. Department of
Agricultural and Biological Engineering. Ph.D. Thesis submitted to The Pennsylvania
State University. 2014.
[109] Gullon, P.; Conde, E.; Moure, A.; Domınguez, H.; Parajo, J. C. Selected Process
Alternatives for Biomass Refining: A Review. The Open Agri. J. 2010, 4, 135–144.
[110] Lange, J. P.; Lewandowski, I.; Ayoub, P. M. Cellulosic Biofuels: A Sustainable Option
for Transportation. Sustainable Development in the Process Industries; Harmsen, J.;
Powell, J. B.; Eds., John Wiley & Sons: New York, NY, USA, 2010; pp 171–198.
[111] Lee, H. V.; Hamid, S. B. A.; Zain, S. K. Conversion of Lignocellulosic Biomass to
Nanocellulose: Structure and Chemical Process. The Sci. World J 2014, Article ID
631013. DOI:10.1155/2014/631013.
[112] Siro, I.; Plackett, D. Microfibrillated Cellulose and New Nanocomposite Materials: A
Review. Cellulose 2010, 17, 459–494.
[113] Lavoine, N.; Desloges, I.; Dufresne, A.; Bras, J. Microfibrillated Cellulose Its Barrier
Properties and Applications in Cellulosic Materials: A Review. Carbohydr. Poly. 2012,
90, 735–764.
[114] Oksman, K.; Etang, J. A.; Mathew, A. P.; Jonoobi, M. Cellulose Nanowhiskers Separated
from a Bio-Residue from Wood Bioethanol Production. Biomass Bioenergy. 2011, 35,
146–152.
[115] De Oliveira, J. A. R.; Da Silva Martins, L. H.; Komesu, A.; Neto, J. M. Nanotechnology
Applications on Lignocellulosic Biomass Pretreatment. In Nanotechnology for Bioenergy
and Biofuel Production; Rai, M. K., Silverio Ds Silva, S., Eds.; Springer International
Publishing: Switzerland, 2017. pp 19–37.
[116] Abdul-Khalil, H. P. S.; Davoudpour, Y.; Islam, M. N.; Mustapha, A.; Sudesh, K.;
Dungani, R.; Jawaid, M. Production and Modification of Nanofibrillated Cellulose
Using Various Mechanical Processes: A Review. Carbohydr. Polym. 2014, 99, 649–665.
[117] Xu, X.; Liu, F.; Jiang, L.; Zhu, J. Y.; Haagenson, D.; Wiesenborn, D. P. Cellulose
Nanocrystals vs Cellulose Nanofibrils: A Comparative Study on Their
Microstructures and Effects as Polymer Reinforcing Agents. ACS Appl. Mater.
Interfaces 2013, 5, 2999–3009.
[118] Deepa, B.; Abraham, E.; Cordeiro, N.; Mozetic, M.; Mathew, A. P.; Oksman, K.; Faria,
M.; Thomas, S.; Pothan, L. A. Utilization of Various Lignocellulosic Biomass for the
Production of Nanocellulose: A Comparative Study. Cellulose 2015, 22, 1075–1090.
[119] Jiang, F.; Hsieh, Y. L. Chemically and Mechanically Isolated Nanocellulose and Their
Self-Assembled Structures. Carbohydr. Polym. 2013, 95, 32–40.
[120] Fukuzumi, H.; Saito, T.; Isogai, A. Influence of TEMPO Oxidized Cellulose Nanofibril
Length on Film Properties. Carbohydr. Polym. 2013, 93, 172–177.
[121] Sacui, I. A.; Nieuwendaal, R. C.; Burnett, D. J.; Stranick, S. J.; Jorfi, M.; Weder, C.;
Foster, E. J.; Olsson, R. T.; Gilman, J. W. Comparison of the Properties of Cellulose
Nanocrystals and Cellulose Nanofibrils Isolated from Bacteria, Tunicate, and Wood
Processed Using Acid, Enzymatic, Mechanical, and Oxidative Methods. ACS Appl.
Mater. Interfaces 2014, 6, 6127–6138.
[122] Pedersen, M.; Meyer, A. S. Lignocellulose Pretreatment Severity Relating pH to
Biomatrix Opening. New Biotechnol. 2010, 27, 739–750.
[123] Hendriks, A. T. W. M.; Zeeman, G. Pretreatments to Enhance the Digestibility of
Lignocellulosic Biomass. Bioresour. Technol. 2009, 100, 10–18.
[124] Wulandari, W. T.; Rochliadi, A.; Arcana, I. M. Nanocellulose Prepared by Acid
Hydrolysis of Isolated Cellulose from Sugarcane Bagasse. IOP Conf. Ser. Mater. Sci.
Eng. 2016, 107, 012045.
26 M. RAI ET AL.

[125] Karimi, K.; Shafiei, M.; Kumar, R. Progress in Physical and Chemical Pretreatment of
Lignocellulosic Biomass. In Biofuel Technologies; Gupta, V. K., Tuohy, M. G., Eds.;
Springer Publisher: Germany, 2013. pp 53–96.
[126] Brinchi, L.; Cotana, F.; Fortunati, E.; Kenny, J. M. Production of Nanocrystalline
Cellulose from Lignocellulosic Biomass: Technology and Applications. Carbohydr.
Poly. 2013, 94, 154–169.
[127] Zhou, C.; Xia, X.; Lin, C.; Tong, D.; Beltramini, J. Catalytic Conversion of
Lignocellulosic Biomass to Fine Chemicals and Fuels. Chem. Soc. Rev. 2011, 40,
5588–5617.
[128] Peyre, J.; Pääkkönen, T.; Reza, M.; Kontturi, E. Simultaneous Preparation of Cellulose
Nanocrystals and Micron-Sized Porous Colloidal Particles of Cellulose by TEMPO-
mediated Oxidation. Green Chem 2015, 17, 808–811.
[129] Salminen, R.; Reza, M.; Pääkkönen, T.; Peyre, J.; Kontturi, E. TEMPO-mediated
Oxidation of Microcrystalline Cellulose: Limiting Factors for Cellulose Nanocrystal
Yield. Cellulose 2017, 24, 1657–1667.
[130] Gupta, I.; Duran, N.; Rai, M. Nano-Silver Toxicity: Emerging Concerns and
Consequences in Human Health. In Nano-Antimicrobials: Progress and Prospects; Rai,
M., Cioffi, N., Eds.; Springer Verlag: Germany, 2012. pp 525–548.
[131] Liu, G.; Gao, J. H.; Ai, H.; Chen, X. Y. Applications and Potential Toxicity of Magnetic
Iron Oxide Nanoparticles. Small 2013, 9, 1533–1545.
[132] Mou, X. B.; Ali, Z. S.; Li, S.; He, N. Y. Applications of Magnetic Nanoparticles in
Targeted Drug Delivery System. J. Nanosci. Nanotechnol. 2015, 15, 54–62.
[133] Phukan, G.; Shin, T. H.; Shim, J. S.; Paik, M. J.; Lee, J. K.; Choi, S.; Kim, Y. M.; Kang, S.
H.; Kim, S.; Kang, Y.; Lee, S. H.; Mouradian, M. M.; Lee, G. Silica-Coated Magnetic
Nanoparticles Impair Proteasome Activity and Increase the Formation of Cytoplasmic
Inclusion Bodies in Vitro. Sci. Reports 2016, 6. DOI:10.1038/srep29095.
[134] Wu, J.; Wang, C.; Sun, J.; Xue, Y. Neurotoxicity of Silica Nanoparticles: Brain Localization
and Dopaminergic Neurons Damage Pathways. ACS Nano 2011, 5, 4476–4489.