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As the main component of lignocelluloses, cellulose is a biopolymer consisting of many glucose units
Published on 28 February 2013 on http://pubs.rsc.org | doi:10.1039/C3GC40136G
connected through -1,4-glycosidic bonds. Breakage of the -1,4-glycosidic bonds by acids leads to the
hydrolysis of cellulose polymers, resulting in the sugar molecule glucose or oligosaccharides. Mineral
acids, such as HCl and H2SO4, have been used in the hydrolysis of cellulose. However, they suer from
problems of product separation, reactor corrosion, poor catalyst recyclability and the need for treatment
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of waste euent. The use of heterogeneous solid acids can solve some of these problems through the
ease of product separation and good catalyst recyclability. This review summarizes recent advances in the
hydrolysis of cellulose by dierent types of solid acids, such as sulfonated carbonaceous based acids,
Received 18th January 2013,
polymer based acids and magnetic solid acids. The acid strength, acid site density, adsorption of the sub-
Accepted 28th February 2013
stance and micropores of the solid material are all key factors for eective hydrolysis processes. Methods
DOI: 10.1039/c3gc40136g
used to promote reaction eciency such as the pretreatment of cellulose to reduce its crystallinity and
www.rsc.org/greenchem the use of ionic liquids or microwave irradiation to improve the reaction rate are also discussed.
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materials come from biological photosynthesis from CO2, problems such as reactor corrosion, catalyst recovery and
water and sunlight, thus making them sustainable and green requires treatment of the acid residue, producing lots of
feedstocks with zero carbon emission.10 The first generation of waste.23,24 From the industrial point of view, the above limit-
biofuels are mainly bioethanol and biodiesel which are pro- ations must be taken into account when designing production
duced from sugars, starches and vegetable oils. However, con- processes. In addition, several aspects also need to be of
cerns were raised that the utilization of these materials concern such as economy, simplicity, eciency and environ-
competed with food for feedstocks.11 Moreover, their potential mental friendliness.
availability is limited by the amount of fertile soil.11 The utilization of heterogeneous acids has the potential to
Due to the above limitations, the second generation of bio- overcome some of the above limitations due to the ease of sep-
fuels has mainly concentrated on the utilization of lignocellu- aration of catalysts. Significant development of this transform-
losic biomass. Lignocellulose can be grown in combination ation has been made by using various types of catalysts with
with food or on barren land. Every year, sees the formation of large pore size and strong acid strength.2528 Associated with
Published on 28 February 2013 on http://pubs.rsc.org | doi:10.1039/C3GC40136G
about 220 billion dry tons of available biomass (ca. 45 EJ of these solid acids, many pretreatment technologies have also
energy content),12,13 and lignocellulose forms about 7095% been developed to reduce the crystallinity of cellulose and
of it.14 Lignocelluloses are composed of mainly three com- increase its surface area in order to improve the reaction
ponents, cellulose (4050%), hemicelluloses (2535%) and eciency and selectivity, for example, ball-milling,29,30 solubil-
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lignin (1520%) ( percentages of the components vary from ization/precipitation in ionic liquids,31 liquid acids/alkaline
dierent biomass resources).15,16 A schematic biorefinery for solutions,32,33 the non-thermal atmospheric plasma method34
the utilization of lignocellulose is shown in Scheme 1.17 and so on. It is worth noting that most hydrolysis processes
Among these biopolymers, cellulose is the most valuable one with solid acids require the pretreatment of cellulose as shown
which can be converted into glucose and subsequently fermen- in Table 1. Apart from that, microwave irradiation induced
ted into bioethanol or dehydrated into platform molecules.18 assistance of the hydrolysis of cellulose is an eective heating
Besides, cellulosic biofuels have been considered as the most method compared to conventional oil heating.3537
promising candidates for the replacement of current pet- In this review, we summarize the recent advances in the
roleum based fuels.19 hydrolysis of cellulose into glucose with solid acids. The review
The first step for cellulose utilization is to depolymerize it is divided into the following parts: (1) structure of cellulose;
into soluble oligosaccharides and glucose. However, the (2) hydrolysis of cellulose by liquid acids; (3) hydrolysis of cel-
natural polymer forms a robust crystal structure with high lulose by solid acids. The final part of this review presents an
chemical stability, thus making the depolymerization pro- outlook of the future of this domain.
cesses more dicult. The established methods for cellulose
hydrolysis are known to be catalyzed by cellulose enzymes. But
limitations of the enzymes systems are obvious in that the pro- 2. Structure of cellulose
cesses are always low eciency and have a high enzyme
cost.2022 At the same time, much work has been concentrated Early exploration work on the structure of cellulose was carried
on the hydrolysis of cellulose to glucose with mineral acids. out by Anseleme Payen.38 He obtained a resistant fibrous solid
Sulfuric acid is known as a typical acid for this reaction. material with the formula C6H10O5 after the treatment of
However, the large-scale use of acid suers from several various plant tissues with acids and ammonia. It was the
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earliest cellulose.39 The structure of cellulose was elucidated occur in the state of I, I. They can be found in the same
in 1920 by Hermann Staudinger.40 He found that cellulose was material from almost every biomass source. The ratio of the
composed of D-glucose units, linked to each other to form long two crystalline forms depends on the source of cellulose. Gen-
chains (Scheme 2). The structure of cellulose was made up of erally, cellulose I is rich in the cell walls of algae and bacterial
many glucose moieties linked in the form of -D-anhydrogluco- cellulose while cellulose I is abundant in cotton, wood and
pyranose units (AGUs). The AGUs are linked to each other tunicate cellulose.45 Cellulose I, is thermodynamically not
through glycosidic bridges on the C1 and C4 carbon atoms.41 the most stable form in nature.46 When cellulose I swells in
The number of repeating AGUs is defined as the degree of concentrated sodium hydroxide, it easily forms the thermody-
polymerization (DP) of cellulose. Generally, the DP of cellulose namically more stable cellulose II after the removal of the swel-
varies according to the original type of materials, for example, ling agent.42,43 Cellulose III can be obtained by treatment of
the common range of DP for wood pulp is about 3001700 and cellulose I, I with the ammonia fiber explosion process. Cel-
is 80010 000 for cotton or other plant fibers.41 Due to the lulose IV can be obtained by treating cellulose III with glycerol
huge number of hydroxyl groups and linkage of -1,4-glyco- at 206 C.42,43 However, cellulose III, IV are not common and
sidic bonds, it is easy to form intra- and intermolecule hydrogen are thus ignored in our discussion. The more generally known
bonds which make the cellulose resistant during chemical and and discussed forms of cellulose are microcrystalline Avicel
biological treatment and make it highly insoluble in common cellulose and -cellulose which come from pure bacterial cellu-
solvents.42 lose and the treatment of wood with alkali extraction.47
According to the crystal features, cellulose has at least seven
forms, I, I, II, IIII, IIIII, IVI, IVII.43,44 In nature, most cellulose
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and several processes were reported to be eective in the 20th experiment showed that only 0.050.1% of HF remained in the
century.48 The first technology for the acid hydrolysis of cellu- system, opening the possibility of reusing mineral acids in the
lose was developed by Faith in 1923.49 In the process, sulfuric hydrolysis of cellulose.57
acid solution (0.5 wt%) was used to treat wood waste in brick- Current strategies for the hydrolysis of cellulose with acids
lined percolators. After about 45 min at 170 C, a dilute sugar are mainly accomplished with the acids mentioned above.
solution was obtained. The solution was transferred for fermen- Although homogeneous-based processes are ecient, the
tation after neutralization. A 50% yield of sugars was obtained mineral acid systems still suer from major problems in
according to the theoretical yield of fermentable sugars. product/catalyst separation, reactor corrosion, catalyst recy-
After the work, many processes were reported to be eective cling and the treatment of waste euent. For example, in the
in the hydrolysis of cellulose. They used dierent kinds of H2SO4 based system, the acid in the reaction mixture has to be
acids such as HCl, H2SO4, HF and organic acids (oxalic, neutralized with a mixture of CaO/CaSO4 which forms lots of
maleic, furmaric). In 1937, Bergius reported the hydrolysis of gypsum as waste.56 For the HCl system it is dicult to reuse
cellulose with 40 wt% HCl (ca. 12 mol L1) at room temp-
Published on 28 February 2013 on http://pubs.rsc.org | doi:10.1039/C3GC40136G
the liquid acid while the HF system is very toxic when utilized
erature.50 Cellulose was solubilized in concentrated acid together in large-scale processes.57,60 In the search for greener pro-
with hemicelluloses, leaving insoluble lignin. The hydrolysis cesses for hydrolyzing cellulose, solid acids were developed to
products were glucose and oligosaccharides without dehy- address some of the problems and have some unique catalytic
dration products. Concentrated HCl (67 mol L1) was also
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Fig. 3 (A) Total release of reducing sugars from -cellulose (using p-TSA),
microcrystalline cellulose, wood (spruce), -cellulose (using Amberlyst
15DRY), determined by 3,5-dinitrosalicylic acid (DNS) assay. (B) Production of
mono- and disaccharides, monitored by HPLC, for the hydrolysis of -cellulose
catalyzed by p-TSA and by Amberlyst 15DRY. Reaction conditions: cellulose
(5 g) dissolved in 100 g [BMIm]Cl, Amberlyst 15DRY (1.00 g, 4.6 mmol H+) or
p-TSA (4.6 mmol), water (111 mmol), 373 K. (Reproduced from ref. 68 with
Fig. 1 Hydrolysis of sucrose with dierent solid acids. (Adapted from ref. 63.) permission from Wiley-VCH.)
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SO3H groups from microcrystalline cellulose at 723 K overr showed that the strong interactions (hydrogen bonds to oxygen
5 h under N2 flow. The black powder was then boiled in 15 wt% atoms in glycosidic bonds) between the phenolic OH groups
H2SO4 at 353 K under N2 for 10 h; after filtration and and the glycosidic bonds in -1,4-glucan led to higher catalytic
washing with hot water, carbon based acid was obtained. activities. Such hydrogen bonds were expected to bind cellu-
Characterization of this solid acid showed that the carbon lose to the surface of the catalysts, making it easier for the
material is composed of uniform functionalized graphene hydrolysis to proceed. The activation energy for cellulose
sheets, bearing SO3H, COOH and phenolic OH groups hydrolysis with this carbon based acid was 110 kJ mol1 which
which are dierent to conventional solid acids with single was lower than that with sulfuric acid (170 kJ mol1). The
functional groups (Scheme 6). The eective surface area of the amorphous carbon acid was recovered from the reaction
carbon material during hydrolysis was about 560 m2 g1, mixture and reused at least 25 times without decrease in
larger than the BET surface area after hydrolysis (only activity. Elemental analysis and ion chromatography revealed
2 m2 g1). The H2O vapor adsorptiondesorption isotherm that only 1% SO3H groups leached into the solution during
Published on 28 February 2013 on http://pubs.rsc.org | doi:10.1039/C3GC40136G
showed that a larger amount of water was incorporated into the first reaction and no further leaching was detected in sub-
the bulk of the catalyst. The incorporation ability of hydro- sequent reactions. The excellent performance of the carbon
philic molecules made it easy for a cellulose chain in solution based catalyst opens the possibility of converting cellulose into
to be in contact with the SO3H groups in the carbon material, value-added molecules with cheap and ecient solid acids,
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which gave rise to high catalytic performance. which has the potential for use in industrial production in the
Comparable experiments for the hydrolysis of cellulose with future.
dierent solid acids revealed that carbon-based acids exhibit A mild process for the hydrolysis of cellulose to reducing
remarkable hydrolysis performances (Table 2). After reacting sugars under microwave irradiation was developed by Fu and
for 3 h, 68% of cellulose was hydrolyzed to glucose (4% yield) Yin et al.83 They used carbon sulfuric acids (BCSO3H) derived
and soluble -1,4-glucan (64% yield), the liquid acid H2SO4 from bamboo, cotton and starch as catalysts. The introduction
also has a high activity for the hydrolysis of cellulose (10% of microwave irradiation greatly accelerated the rate of the
glucose and 38% -1,4-glucan). The enhanced hydrolytic cata- hydrolysis reaction. Comparison of hydrolysis results between
lysis of the amorphous carbon with SO3H, OH and COOH the two heating methods over BCSO3H revealed that the accel-
and was further investigated via an adsorption experiment erating eect of microwave irradiation on the reaction was
with cellobiose, a short -1,4-glucan of cellulose. The results evident. The hydrolysis reaction operated at a lower temp-
erature of 70100 C and the yield of reducing sugars was higher
than that using conventional heating. The yields of hydrolysis
products were dierent with the dierent types of carbon
acids. The correlation between the hydrolysis product yields
and adsorption values confirmed the results from Haras work
that the adsorption of the phenolic OH groups of BCSO3H to
the oxygen atoms in the -1,4-glycosidic bonds was responsible
for the high catalytic activities of these carbon-based solid
acids when hydrolyzing cellulose to glucose.
Carbonaceous solid acid (CSA) can also be applied to real
biomass substrates under microwave irradiation. The Jiang
and Mu research group84 illustrated that lignocellulosic
biomass (e.g. corncob) can be well hydrolyzed by self-derived
Scheme 6 Schematic structure of the carbon-based solid acid. (Reproduced CSA under microwave irradiation. The CSA was prepared from
from ref. 82a.) hydrolyzed corncob residue and was used for the hydrolysis of
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corncob (Scheme 7). In this way, the whole corncob could be important for cellulose conversion.
utilized in the process and two products were obtained that A new class of sulfonated silica/carbon nanocomposite cata-
were sugars (from the cellulose and hemicelluloses part) and lyst was reported by Jacobs and Sels et al. for the hydrolysis of
CSA (from the unconverted solid residue). The hydrolysis reac- ball-milled cellulose to sugars.87 The sample was prepared by
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tions produced 78% yield of xylose and arabinose at 403 K. evaporation of a sucrose/TEOS/F127 solution (carbon source/
The eective utilization of the hydrolyzed residues reduces the silica precursor/structure-directing amphiphilic surfactant)
cost of the catalysts and pollution. and followed by carbonization in N2 to decompose F127 and
Apart from microwave irradiation, ionic liquids were also convert the sucrose into carbon residues. The resulting hybrid
investigated as eective solvents for the hydrolysis of cellulose materials were finally treated with sulfuric acid to obtain sulfo-
with glucose derived sulfonated carbon acid, reported by Qi nated silica/carbon nanocomposites. As the carbonization
et al. (Scheme 8).85 Cellulose has good solubility in the ionic temperature varied, the ratio of the Si and C in the samples
liquid which enables easier contact with more acid sites. changed, denoted as SimCn-T-SO3H (m, n are the weight percen-
When the reaction was conducted at 110 C, the total reducing tages of silica and carbon, T is the carbonization temperature).
sugars yield was up to 72.7%. Further increase in the reaction The catalysts exhibited good performances in the hydrolysis
temperature led to an increase reaction rates but decreased the reaction. The Si33C66-823-SO3H catalyst resulted in the highest
TRS yield, due to the rapid decomposition of the formed glucose yield of 50% (Fig. 7). The hybrid surface structure
sugars at higher temperature. facilitated the adsorption of -1,4-glucan on the solid acid, and
Whereas much eort has been invested in the optimization together with the strong accessible Brnsted acid sites
of the hydrolysis reaction conditions of cellulose over carbon- suggested that the sulfonated silica/carbon nanocomposites
based solid acids, the sulfonation conditions have rarely been
considered. Recently, Zhang et al.86 reported that by changing
the sulfonation temperature of the active carbon (AC), the cata-
lyst exhibited dierent catalytic activities in the hydrolysis reac-
tion. The active carbon was treated with/without nitric acid
and sulfonated at dierent temperature ranging from
150300 C. With the increase of the sulfonation temperature,
the acid density of the sulfonated carbon increased. The
specific areas of the samples were increased when the temp-
erature was increased from 150 to 250 C, but decreased on
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Table 3 Saccharication of crystalline cellulose in aqueous acidic mediaa (ref. recovery of the heterogeneous catalyst was easier than that of
99) conventional heteropoly acids.
Concentration 4.5 H-form zeolites
[mol L1] Yield [%]
Zeolites are microporous, aluminosilicate minerals that are
Entry Acid Anion Proton Glucose Cellobiose commonly used in petrochemistry. They are non-toxic and easy
1 H3PW12O40 0.70 2.1 8 2 to recover from solution. They have porous structure that can
2b H3PW12O40 0.60c 3.5 18 2 accommodate a wide variety of cations, such as H+, Na+, K+,
3 H4SiW12O40 0.70 2.8 37 2 Mg2+. These cations are loosely bonded to the zeolite surface
4b H4SiW12O40 0.70 3.5 61 5
5 H5BW12O40 0.70 3.5 77 5 and can be released into solution to exhibit dierent catalytic
6 H5BW12O40 0.40 2.0 4 <1 activities. H-form zeolites are widely used acid catalysts due to
7 H5AlW12O40 0.70 3.5 68 3 their shape-selective properties in chemical reactions. The
8 H5GaW12O40 0.70 3.5 62 3
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9 H6CoW12O40 0.70 4.2 59 5 acidity is related to the atomic ratio of Si/Al; the amount of Al
10 H2SO4 1.75 3.5 <1 nd atoms is proportional to the amount of Brnsted acid sites,
11 HCl 3.5 3.5 4 nd the higher the ratio of Al/Si, the higher the acidity of the
a
Reaction conditions: crystalline cellulose (100 mg), aqueous acidic catalyst.104
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solution (2 mL), 60 C. Crystalline cellulose was immersed in the Onda et al.105 reported the hydrolysis of cellulose with
solution at room temperature for 24 h, and then the mixture was
dierent types of solid acids in water. H-form zeolites with
heated at 60 C for 48 h. Yields are based on the glucose unit in
cellulose used. b The proton concentration was adjusted using H2SO4. various structures and Si/Al ratios were included. However, the
c
Saturated concentration. zeolite catalysts with high Si/Al ratio, such as H-beta (75) and
H-ZSM (45), showed higher activities than those with lower Si/
Al ratio such as H-beta (13) and H-mordenite (10) for glucose,
As is known, the hydrolysis of cellulose is always restricted which was in contrast to the acidity density of zeolites. This
by the poor contact between a catalyst and cellulose. The may due to the highly hydrophobic character of zeolites with
hydrolysis reactions always require higher catalyst/substrate high Si/Al ratios. The glucose yield was relatively low compared
mass ratios, higher temperature and longer reaction times to to ACSO3H which was about 12%. It may due to the small
achieve maximum conversion, but lead to a lower selectivity to pore diameters of zeolites that limited the accessibility and
glucose and lots of side products. Much work has focused on their weak and less acidic sites. In order to further improve the
developing eective approaches or technologies for the catalytic activities of zeolites under milder conditions, Zhao
hydrolysis of cellulose. By using heteropoly acids under micro- and Zhang106 proposed a new route by using an ionic liquid as
wave irradiation, reported by the Mu research group,100 cellu- the solvent to increase the solubility of cellulose, improving
lose was completely converted with a high selectivity to the contact between cellulose and zeolites. Besides, microwave
glucose at lower temperature (80100 C). The best result for irradiation (MI) was used to accelerate the hydrolysis rates.
glucose (75.6%) was obtained by using 88% of H3PW12O40 Among the tested zeolites, HY zeolite, with the lowest Si/Al
solution as a catalyst at 90 C for 3 h. Furthermore, the system molar ratio, showed the best hydrolysis performance at 240 W
could be applied to the hydrolysis of real lignocellulosic in 8 min (TRS yield was 47.5% with a glucose yield of 36.9%)
biomass such as corncob, corn stover and bagasse; 37.2%, (Table 4). The higher MI power led to the formation of
43.3% and 27.8% yields of glucose were obtained, respectively. 5-hydroxymethylfurfural (HMF) (49% yield under MI power
Another appealing route was the development of micellar hetero- of 400 W) through consecutive elimination of water during the
poly acid catalyst [C16H33N(CH3)3]H2PW12O40 with a surfac- hydrolysis of cellulose. Compared with the conventional
tant group.101 The catalyst greatly improved the solubility of heating manner in an oil bath, the TRS yield using microwave
cellulose in water, and thereby promoted the hydrolysis of cel- irradiation heating was almost four times that obtained using
lulose. Following the work, a series of HPA ionic liquids oil bath heating. The results strengthened the evidence that
[C4H6N2(CH2)3SO3H]nH3nPW12O40 was prepared for the con- proper solvents and heating methods could greatly improve
version of cellulose to glucose under mild conditions.102 The the reaction eciency over solid acids. Finally, application of
catalyst was demonstrated to be eective, and the conversion this method to other cellulose samples with dierent origins
of cellulose was 55.1% with a 36% yield of glucose in a water or with dierent degrees of polymerization (DP) also suc-
MIBK (methyl isobutyl ketone) biphasic system. The catalyst ceeded (Table 5). The higher the DP value of cellulose, the
could be separated and recovered from the reaction mixture longer the microwave heating time that was required to reach
and reused six times without appreciable loss of activity. the maximal TRS yield. When the DP value increased, the
The substitution of H+ by larger monovalent Cs+ leads to yields of TRS and glucose dropped slightly.
insoluble CsxH3xPW12O40 which shows easier catalyst separ- Further insight into the mutual behavior of zeolites in ionic
ation. Wang et al.103 reported the hydrolysis of microcrystalline liquids was gained by Zhang et al.107 By using XRD charac-
cellulose to reducing sugars and glucose. The highest selectiv- terization, they found that the framework structure of a zeolite
ity for glucose was 84% with Cs2.2H0.8PW12O40, while the is stable while the enlargement of cell parameters takes place
highest yield (27%) was obtained over CsH2PW12O40. The due to the dilatation eect of an ionic liquid. [BMIm]Cl
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a
Conditions: cellulose 100 mg, [C4mim]Cl 2.0 g, H2O 10 ml, catalyst
10 mg, MI at 240 W. b Heated with an oil bath at 100 C. c With MI at
400 W. d With MI at 80 W. e Heated with an oil bath at 180 C.
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Glucose TRS
Entry Cellulose type DP Time/min yield yields Scheme 9 Proposed reaction pathway and recovery of HY. (Adapted from ref.
107 with permission from Elsevier). The released H+ can also catalyze the side
1 -Cellulose 100 7 34.9 46.5 reaction, dehydrating glucose into HMF. The recovered catalyst could be reused
2 Avicel cellulose 220 8 36.9 47.5 by simple calcination.
3 Spruce cellulose 275 9 34.5 44.4
4 Sigmacell cellulose 450 9.5 32.5 42.4
5b Cellulose 1440 12.5
a (SBA-15), which can be successfully separated from the reac-
Conditions: cellulose 100 mg in [C4mim]Cl (2.0 g), H2O 10 mg, HY
zeolite 10 mg, heated with MI at 240 W. b Milled cellulose 45 mg, tion system with a permanent magnet, in our recent
H-form zeolite catalyst (HZSM-5 or H-beta) 50 mg, H2O 5 ml, heated work.108,109
using an oil bath at 150 C for 24 h. The magnetic solid acid was prepared by a surfactant-tem-
plated solgel method similar to reported methods.110,111
Fe3O4 magnetic nanoparticles were dispersed in the block
entered into the HY channels and filled the channel space. copolymer P123 for the co-condensation of tetraethoxysilane
FT-IR results showed that H+ cations generated in situ from the (TEOS). After assembly, 3-(mercaptopropyl)trimethoxysilane
Brnsted acid sites of the zeolites were the key active species MPTMS was added to introduce mercapto groups. H2O2 was
for the hydrolysis of cellulose. According to the charac- used to oxidize the mercapto groups into sulfonic acid groups
terization, the authors proposed a reaction pathway for HY cata- inside the pores of the mesoporous silica. X-Ray photoelectron
lyzed cellulose hydrolysis in IL (Scheme 9). First, the [BMIM]+ spectroscopy (XPS) analysis of the sample showed that there
of the IL enters into the channels of zeolite HY and reacts with was only one peak (169.01 eV) between 158177 eV in binding
the acidic sites to replace the H+. After that, the released H+ energy, demonstrating that the sulfur element in the catalyst
moves to the surface of cellulose and hydrolysis occurs. was completely in the form of sulfonic acid groups
(Scheme 10).
Experiments on the hydrolysis of cellobiose with Fe3O4
4.6 Magnetic solid acids SBASO3H showed that the magnetic solid acid gave an even
As for the real biomass feedstock and practical process for the better performance than sulfuric acid. A proposed explanation
hydrolysis of cellulose to glucose, a challenge still exists with was that the channels in the magnetic solid acid contain con-
respect to the transformation system. Solid catalysts cannot be centrated acid sites and the uniform channels allow the reac-
directly separated when solid residues are formed during the tants to easily enter and interact with these acid sites. Further
hydrolysis process. Although cellulose can be degraded into hydrolysis of amorphous cellulose ( pretreated with 1-butyl-3-
soluble sugars, the lignin components of the actual cellulosic methylimidazolium chloride) with Fe3O4SBASO3H gave a
biomass cannot be converted and humins sometimes form as 50% yield of glucose. The protons diused from the SBA-15
solid residues, both of which are dicult to separate from the channels on the surface of cellulose undergo hydrolysis reac-
recovered solid catalysts. Additionally, the separation of cata- tion. When the magnetic solid acid was used for the hydrolysis
lysts from the hydrolysis solid residue is important for of microcrystalline cellulose, the yield of glucose decreased to
the analysis of the recovered catalyst which may be related to 26%. Comparative studies revealed that Fe3O4SBASO3H
the explanation of the catalytic mechanism. To address the exhibited an even better hydrolysis performance than AC
problem, we developed magnetic sulfonated mesoporous silica SO3H and Amberlyst-15, presumably due to its higher surface
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Scheme 11 Catalyst separation from the reaction mixture. (Adapted from ref.
108.)
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support had no activity in the hydrolysis and the Ru species acids have been proven to be active catalysts for cellulose con-
played the role of hydrolyzing the -1,4-glycosidic bonds version, but their water solubility limits their large-scale appli-
(Scheme 12). Later work showed that the active Ru species was cation. Incorporation of HPAs into supports or the use of
RuO2H2O which was proposed to desorb the hydrated water to insoluble salts of HPAs may solve the problem and require
give a Lewis acid site that can depolymerize cellulose to further investigation.
glucose.117 Another hypothesis was that the Ru species worked Recent advances in the introduction of ionic liquids, micro-
as a Brnsted acid by the heterolysis of water molecules on Ru wave irradiation, supercritical water and nanoparticles to the
which had a low pKa. The new method for the hydrolysis of cel- cellulose hydrolysis system may allow the reaction to proceed
lulose without acids has a bright future for the development of more easily under milder conditions. Besides, cellulose pre-
new metal catalysts in the hydrolysis field. treatment can reduce the degree of polymerization of cellulose
and increase the surface area which would significantly
4.8 Others improve the reaction eciency and reduce the operation cost.
Recently, many new catalysts have emerged as powerful tools All these technologies help to overcome the recalcitrance of
for the hydrolysis of cellulose to sugars. Zhang and Fang118 cellulose and depolymerize it to a certain extent. Pretreatment
reported the eective use of ferrate CaFe2O4 as a hetero- is also the first step in the conversion of lignocellulosic
geneous catalyst for cellulose hydrolysis. In their work, an biomass to chemicals, thus more convenient and ecient pre-
ionic liquid was used for pretreatment to reduce the crystalli- treatment methods, reaction media and advanced heating
nity. The reaction was carried out at 423 K over 24 h. The best methods should be considered in the hydrolysis of cellulose.
yield of glucose was achieved with fresh CaFe2O4 catalyst on Although cellulose hydrolysis has been developed with
hydrolyzing the pretreated cellulose; the glucose yield was 37% solid acids toward the greener synthesis of sugars, the reaction
and the selectivity was 74%. The catalyst could be reused eciency and selectivity still need to be improved. The devel-
several times without much drop in the activity. opment of highly acidic catalysts with nanometre size, good
Hydrotalcite [Mg4Al2(OH)12CO34H2O], activated by satu- substrate anity and thermal stability is a challenge towards
rated Ca(OH)2, was used as an inorganic catalyst for the practical systems. The production of fuels and chemicals from
hydrolysis of cellulose, as reported by Fang et al.119 The reac- biomass requires multidisciplinary collaboration of research-
tion was carried out at 423 K over 24 h with ball-milled cellu- ers from enzymatic, homogeneous, and heterogeneous cata-
lose; the conversion and glucose selectivity were 46.6% and lysis and the bio-/chemical engineering research areas.
85.3%, respectively. The catalyst could be reused 4 times and Economic, environmental, and sustainable aspects should all
the catalytic activity remained. Compared with carbon-based be considered when designing new catalytic systems.
solid acids, the activated hydrotalcite catalyst is more stable We thank the 973 Program (2012CB215305,
and can be separated more easily from the reaction mixture. 2012CB215306), NSFC (21172209) and CAS (KJCX2-EW-J02) for
financial support.
1108 | Green Chem., 2013, 15, 10951111 This journal is The Royal Society of Chemistry 2013
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