Vous êtes sur la page 1sur 17

Green Chemistry

View Article Online


TUTORIAL REVIEW View Journal | View Issue

Hydrolysis of cellulose to glucose by solid acid catalysts


Cite this: Green Chem., 2013, 15, 1095 Yao-Bing Huang and Yao Fu*

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
Downloaded by University of Oxford on 30/04/2013 15:22:23.

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.

1. Introduction regarding the existing energy systems based on fossil


resources. To solve this problem, people are forced to explore
The discovery and utilization of fossil resources has changed renewable resources to substitute the fossil resources in order
the energy supplement of the whole world. Current energy to meet increasing energy demands.14 Until now, various
systems are mainly based on these fossil resources such as forms of energy systems have been developed as excellent
coal, petroleum and natural gas. However, the rapid consump- alternatives such as solar, wind, biomass, hydroelectric and
tion of these resources, together with the resulting global geothermal.5,6 Among these new forms of energy sources,
warming caused by CO2 emissions, raises sustainability issues biomass is the only sustainable source of organic carbon on
Earth, which is considered as one part of the solution for pro-
ducing fuels and chemicals.79
Department of Chemistry, Anhui Province Key Laboratory of Biomass Clean Energy,
Biomass can be obtained all over the world and it generally
University of Science and Technology of China, Hefei 230026, P. R. China. occurs in the form of organic materials such as grass, wood,
E-mail: fuyao@ustc.edu.cn agricultural crops and their residues and waste. These

Yao-Bing Huang has studied at Dr Yao Fu obtained his PhD


the University of Science of Tech- degree from the Department of
nology of China (USTC) since Chemistry at USTC in 2005. He
2004. After obtaining his Bache- then began his academic career
lors Degree in 2008, he contin- at the Anhui Province Key Lab-
ued to study green organic oratory of Biomass Clean Energy.
synthesis under the supervision He is presently a professor of
of Prof. Qiang-Xiang Guo and organic chemistry at USTC. His
Yao Fu. Now, he works on the research interests cover tran-
development of ecient hetero- sition-metal catalyzed organic
geneous catalysts for organic reactions, the synthesis of hetero-
reactions and biomass conver- geneous catalysts for green chem-
Yao-Bing Huang sion. Yao Fu istry processes and the selective
conversion of biomass derived
compounds into value-added chemicals and biofuels.

This journal is The Royal Society of Chemistry 2013 Green Chem., 2013, 15, 10951111 | 1095
View Article Online

Tutorial Review Green Chemistry

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-
Downloaded by University of Oxford on 30/04/2013 15:22:23.

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

Scheme 1 Utilization of lignocelluloses to produce chemicals and fuels.

1096 | Green Chem., 2013, 15, 10951111 This journal is The Royal Society of Chemistry 2013
View Article Online

Green Chemistry Tutorial Review

Table 1 Dierent performances of solid acid catalysts in the hydrolysis of cellulose

Acidity Pretreatment Assistance Temp. Time Glucose and


Catalyst (mmol g1) method Solvents method (K) (h) TRSa yield/% Ref.

HNbMoO6 1.90 H2O 403 12 8.5 63


ZnCaFe H2O 433 20 29 64
Amberlyst-15 [BMIm]Cl/H2O 373 5 11 68
CPSO3H 0.067 H2O 393 10 93 74
Nafion NR50 [BMIm]Cl H2O 403 2 35 76
Nafion SAC50 H2O 463 24 11 77
PCPsSO3H 1.80 H2O 393 3 5.3 78
ACSO3H 1.90 H2O 373 3 64 75
BCSO3H 1.98 H2O Microwave 363 1 19.8 83
CSASO3Hb 1.76 Milled/sieved H2O Microwave 403 1 34.6 84
SCSO3H 2.15 [BMIm]Cl/H2O 383 4 63 85
Published on 28 February 2013 on http://pubs.rsc.org | doi:10.1039/C3GC40136G

ACNSO3H-250 2.23 Milled H2O 423 24 62.6 86


CMK-3-SO3H 2.39 Milled H2O 423 24 74.5 86
SimCnSO3H 0.37 Milled H2O 423 24 50.4 87
H3PW12O40 Milled H2O 423 2 18 97
H3PW12O40 H2O 453 2 50.5 98
Downloaded by University of Oxford on 30/04/2013 15:22:23.

H5BW12O40 H2O 333 6 77 99


H3PW12O40 Milled H2O Microwave 363 3 75.6 100
Micellar HPA H2O 443 8 39.3 101
[MIMPSH]nH3nPW H2O/MIBK 413 5 36 102
CsH2PW12O40 H2O 433 6 27 103
H-beta 1.05 Milled H2O 423 24 12 105
HY zeolite Milled [C4mim]Cl/H2O Microwave 373 0.13 37 106
HY zeolite 1.36 [BMIm]Cl/H2O 403 2 50 107
Fe3O4SBASO3H 1.09 H2O 423 3 26 108
Fe3O4SBASO3H 1.09 Solvent activation H2O 423 3 50 108
MNPs@SiO2SO3H 0.5 H2O 423 3 30.2 112
Ru/CMK-3 Milled H2O 503 24 34.2 116
CaFe2O4 0.068 Milled H2O 423 24 36 117
HTOHCa 1.17 Milled H2O 423 24 40.7 118
a
TRS: total reducing sugars. b Corncob was used as the starting material.

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

3. Hydrolysis of cellulose by liquid acids


The hydrolysis of cellulose is a process to break the -1,4-glyco-
sidic bonds of the polymer which is an essential step for the
conversion of cellulose and opens the possibility of sub-
sequent catalytic transformations. Direct hydrolysis of ligno-
Scheme 2 Structure of cellulose (degree of polymerization n = DP). cellulosic biomass with acids goes back to the early 19th century

This journal is The Royal Society of Chemistry 2013 Green Chem., 2013, 15, 10951111 | 1097
View Article Online

Tutorial Review Green Chemistry

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
Downloaded by University of Oxford on 30/04/2013 15:22:23.

properties that mineral acids do not possess.


eective in the hydrolysis of cellulose in the presence of CaCl2
and LiCl as the additives.51 The results showed that the salts
had a swelling eect by increasing the hydrolysis rate, leading 4. Hydrolysis of cellulose by solid acids
to an 85% yield of glucose at 90 C. Additionally, concentrated
acids had an apparent swelling eect on cellulose. Cellulose The hydrolysis of cellulose into sugars with solid acids has
swells when the sulfuric acid concentration is above 50%.52 received increasing attention. Solid acid catalysts have various
Camacho et al.53 studied the eect of H2SO4 concentration advantages over liquid acid catalysts: ease of product separ-
(from 31%70%, (w/v)) on the solubilization rate of microcrys- ation, recyclability, less damage to the reactor. Besides, the use
talline cellulose, revealing that acid promoted the total solubil- of solid acid catalysts can reduce the pollutants which will
ization of cellulose when the concentration was above 62%. have a minimal impact on the environment. Up till now,
Although hydrolysis with concentrated acids operates at low numerous reviews have been published on the transformation
temperature and atmospheric pressure, these processes had of cellulose with solid acids.2528 Herein, we would like to sum-
strict requirements on water content and displayed severe marize the recent advances in this subject. Several types of
corrosion.50 solid acids are included in the following part and their cata-
Hydrolysis of cellulose with dilute acid usually requires lytic performance is summarized in Table 1.
high temperature. Madison et al.54 reported a treating process
in which wood was treated with 0.5 wt% H2SO4 in a continu- 4.1 Metal oxides
ous reaction. The degradation of products was minimized for Metal oxides are a type of solid catalyst with many Lewis acid
the short residence time of cellulose in the reactor. Another sites. Metal oxides are always prepared with high specific
successful process using an isothermal plug flow reactor was surface and pore sizes which are easy for the reactants to
reported by Grethlein and Thompson.55 They used 1 wt% access and contact with the active sites inside the metal oxide
H2SO4 in the continuous process at 240 C with a short resi- pores. These metal oxides can be used for the hydrolysis of
dence time of 0.22 min; 50% glucose was obtained at last. A sucrose, cellobiose and even cellulose.
few years later, Harris et al.56 used a two stage system contain- As a type of strong solid acid, mesoporous transition-metal
ing dilute H2SO4 in the saccharification of wood. After the oxides have been prepared and used in organic chemical trans-
hemicellulose was extracted, cellulose was transferred for formations.61 Recently, Domen et al.62 reported that meso-
hydrolysis and a high purity of glucose was obtained. porous NbW oxide could be used as a solid catalyst for the
The hydrolysis of cellulose was achieved with gaseous HCl hydrolysis of sucrose and cellobiose. The rate of glucose pro-
as reported by the Wilke group.57 The HCl stream was duction and the turnover frequency (TOF) for the hydrolysis of
adsorbed on the dried wood particles and initiated the sucrose were higher than those of other solid acids (i.e. Amber-
hydrolysis of hemicelluloses. After extraction of the hemicellu- lyst-15, Nb2O5). The acid strength increased gradually with the
lose sugars, the residue was dried and mixed with HCl gas at addition of W, reaching the highest reaction rate with meso-
45 C, achieving 90% conversion of the available carbohydrate porous Nb3W7 oxide. The high catalytic performance of Nb3W7
content of wood to sugars. High pressure HCl systems were oxide was attributed to the high surface area mesoporous
also reported for the hydrolysis reaction.57,58 Apart from structure and strong acid sites. However, the NbW oxide cata-
gaseous HCl, anhydrous HF was employed in the hydrolysis of lyst had a lower activity for the cellobiose hydrolysis due to the
cellulose. The main advantage of using anhydrous HF is its low Brnsted acid sites.
low boiling point (19.5 C) which facilitated the acid recovery. In order to solve the problem, Domen et al. also reported
The yield of sugars was about 45% at 0 C.59 The recovery a layered transition-metal oxide HNbMoO6 that exhibited

1098 | Green Chem., 2013, 15, 10951111 This journal is The Royal Society of Chemistry 2013
View Article Online

Green Chemistry Tutorial Review

remarkable catalytic performance for the hydrolysis of sucrose,


cellobiose, starch and cellulose (Scheme 3).63 For the hydro-
lysis of sucrose and cellobiose, the layered HNbMoO6 catalyst
exhibited the highest activity, producing glucose at twice the
rate of Amberlyst-15 (Fig. 1). The high activity of HNbMoO6 in
these reactions was attributed to its strong acidity, water-toler-
ance and intercalation ability. The XRD patterns and FT-IR
spectrum of HNbMoO6, immersed with glucose, sucrose and
cellobiose, revealed that the saccharide was successfully inter-
calated into the interlayer gallery. However, the total yield of
the products (glucose and cellobiose) was only 8.5% in the Fig. 2 Hydrolysis of starch and cellulose with HNbMoO6 and Amberlyst-15.
hydrolysis of cellulose (Fig. 2). Thus, increasing the acid site (Adapted from ref. 63.)
Published on 28 February 2013 on http://pubs.rsc.org | doi:10.1039/C3GC40136G

density and the surface area of a layered transition-metal oxide


is necessary for the full conversion of cellulose to sugars.
divinylbenzene resins with sulfonic groups (SO3H) are one of
In addition, nanoscale metal oxide catalysts have the poten-
these polymer based acids, known as Amberlyst. They are com-
tial to improve the catalytic performance of the hydrolysis reac-
mercially available, inexpensive and stable in most solvents.
Downloaded by University of Oxford on 30/04/2013 15:22:23.

tion. Fang et al.64 used nano ZnCaFe oxide as the catalyst in


The macroporous structures of these acids allow small mole-
the crystalline cellulose hydrolysis reaction. The catalyst exhibi-
cules to enter into the pores and interact with more active acid
ted good catalytic activities. The cellulose conversion and the
sites.
glucose selectivity were 42.6% and 69.2%, respectively. Nano
Recent pioneering work on the hydrolysis of microcrystal-
ZnCaFe oxide gave better performances with respect to
line cellulose and -cellulose with Amberlyst 15DRY resin was
hydrolysis rates and glucose yields than fine particle ZnCaFe.
reported by Schth et al.68 Purified cellulosic substrates were
Besides, the paramagnetic nature of Fe oxides made it easy
dissolved in 1-butyl-3-methylimidazolium chloride ([BMIm]Cl)
to separate the nano ZnCaFe oxide from the reaction
in order to increase their solubility and make the transport of
mixture by simple magnetic filtration techniques.
cellulose chains to the acid sites a highly demanding process.
After hydrolysis with Amberlyst 15DRY, cellulosic materials
4.2 Polymer based acids were selectively converted to cello-oligomers or sugars. As the
reaction proceeded, the hydrolysis performances using Amber-
Polymer based acids with Brnsted acid sites have been used
lyst 15DRY showed an induction period of about 1.5 h (Fig. 3).
as eective solid catalysts for many organic reactions
However, when soluble p-toluenesulfonic acid ( p-TSA) was
including hydrolysis reactions.6567 Macroreticulated styrene-
used, resembling the acid sites of Amberlyst 15DRY, no induc-
tion period was given during the first 1.5 h. HPLC analysis of
the reducing sugars showed that almost no mono- and di-
saccharides were produced during the initial 1.5 h, while the
production of small sugars was detected for the reaction catalyzed
by p-TSA. The dierence of the two systems was investigated by

Scheme 3 Hydrolysis of cellulose to glucose with HNbMoO6. (Reproduced


from ref. 63.)

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.)

This journal is The Royal Society of Chemistry 2013 Green Chem., 2013, 15, 10951111 | 1099
View Article Online

Tutorial Review Green Chemistry

Fig. 4 Hydrolysis of microcrystalline cellulose. Appearance of cellulose recov-


ered from [BMIm]Cl by addition of water after the reaction times indicated. The
values between parentheses represent the percentage of isolated cellulose.
(Adapted from ref. 68 with permission from Wiley-VCH.)

the visual appearance of isolated cellulose suspensions and


Published on 28 February 2013 on http://pubs.rsc.org | doi:10.1039/C3GC40136G

degree of polymerization (DP) analysis. The recovered cellulose


from the ionic liquid appeared in dierent forms with the Fig. 5 Depolymerization of cellulose over Amberlyst 15 DRY: Eect of the
reaction variation (Fig. 4). The isolated cellulose became amount of catalyst on the yield of glucose. (Adapted from ref. 69 with per-
smaller with increasing reaction time, giving a colloidal dis- mission from Wiley-VCH.)
Downloaded by University of Oxford on 30/04/2013 15:22:23.

persion after 5 h of reaction. The figure shows that there were


substantial changes in the cellulose structure. The degree of
polymerization (DP) analysis of cellulose at dierent recovered Compared to the enzymatic hydrolysis of cellulose, the
times also demonstrated that cellulose was eectively depoly- solid or liquid acid catalyzed depolymerization of cellulose
merized in the presence of Amberlyst 15DRY. It was worth always requires higher temperature due to its higher reaction
noting that cello-oligomers with a DP of around 30 were found activation energy. It was reported that the activation energy for
after 1.5 h of hydrolysis of microcrystalline cellulose and could cellulose hydrolysis with dilute acid is 170180 kJ mol1 (no
be precipitated in 90% yield. No fermentable sugars were matter what temperature and acid concentration are used).70
detected during the first 1.5 h which was in accordance with On the other hand, the activation energy for enzymatic
the induction time observed in Fig. 4. Since the high solubility hydrolysis is only 350 kJ mol1, resulting in the hydrolysis
of sugars in ionic-liquid made the sugar extraction and ionic reaction being conducted at the low temperature of 50 C.7173
liquid recovery very dicult, the route gave a cello-oligomer An ideal cellulose-mimetic catalyst consisting of a cellulose-
production method instead of total hydrolysis into ferment- binding domain and a catalytic domain was developed for
able sugars which was an advantage of this process. Further cellulose hydrolysis by Pans research group.74 The catalyst
extension of the reaction time led to the production of sugars contained a chlorine (Cl) group which plays the cellulose-
and some dehydration products. The most appealing part of binding role by forming hydrogen bonds, and sulfonic acid
the route was that it can selectively convert cellulose or even groups (SO3H) functioning as the hydrolytic domains. Chloro-
wood into cello-oligomers, which could be further broken methyl polystyrene (CP) resin with Cl groups was chosen as
down into sugars. The hydrolysis reaction proceeded in the the catalyst support. The SO3H groups were introduced by
cellulose cello-oligomers sugars dehydration products partially substituting Cl groups with sulfanilic acid. The
series, and if the process was properly terminated at dierent proposed mechanism of cellulose hydrolysis is shown in
times, cellulose fragments or sugars could be selectively Scheme 4. The catalyst was firstly applied to the hydrolysis of
obtained for dierent use in biorefineries. cellobiose. It was completely hydrolyzed to glucose at 120 C
In order to gain more insight into the controlling factors in over 2 h, while only 8% of cellobiose was obtained with sulfu-
hydrolysis reactions, Rinaldi and Schth et al.69 investigated ric acid under the same conditions. Adsorption experiments
the eect of dierent parameters on the hydrolysis of cellulose showed that CPSO3H adsorbed both glucose and cellobiose
in [BMIm]Cl with Amberlyst 15DRY such as acid amount, reac- through hydrogen binding between the chloride groups on the
tion temperature and impurities. They found that depolymeri- catalyst and the hydroxyl groups of the sugars (Fig. 6). The pre-
zation is a first-order reaction with respect to catalyst ferable adsorption of cellobiose over glucose is critical for cel-
concentration. Particularly, they discovered that the induction lobiose hydrolysis to proceed which ensures the desorption of
period depends heavily on the amount of acid used for the glucose product from the catalyst. CPSO3H showed excellent
reaction (Fig. 5). Increase of catalyst concentration from 0.46 catalytic performance for the hydrolysis of crystalline cellulose
to 6.9 mmol of H3O+ decreased the induction time from 1.9 h (Avicel). The best yield of glucose from CPSO3H was up to
to less than 5 min. This means that the acid concentration played 93%, while almost no Avicel was hydrolyzed on using sulfuric
an important role in the hydrolysis reaction, and the use of a acid. The activation energy of cellulose hydrolysis catalyzed by
larger amount of Amberlyst 15DRY resembling the use of a CPSO3H was 83 kJ mol1 at 373413 K and is much lower
soluble strong acid showed no induction period for the pro- than that of sulfuric acid (170 kJ mol1) or sulfonated active
duction of glucose. The activation energy for the depolymeriza- carbon (ACSO3H) (110 kJ mol1).75 This was the key point as
tion of cellulose is 108 kJ mol1, which is relatively lower than to why the hydrolysis reaction could be conducted at lower
that with liquid acid (i.e. H2SO4 170 kJ mol1). temperature.

1100 | Green Chem., 2013, 15, 10951111 This journal is The Royal Society of Chemistry 2013
View Article Online

Green Chemistry Tutorial Review

Scheme 4 Hydrolysis mechanism of a cellulase-mimetic solid catalyst. (Repro-


duced from ref. 74.)
Published on 28 February 2013 on http://pubs.rsc.org | doi:10.1039/C3GC40136G
Downloaded by University of Oxford on 30/04/2013 15:22:23.

Scheme 5 Schematic representation of the structure of PCPsSO3H. (Adapted


from ref. 78 with permission from Wiley-VCH.)

and 1.2% yields of xylose, glucose and cellobiose, respectively.


By increasing the reaction time, the yields of these sugars
increased. The merit of this new catalyst is that it prevents the
Fig. 6 Adsorption curve of glucose and cellobiose onto resins in aqueous solu- formation of side-products such as 5-hydroxymethylfurfural or
tion (a) glucose on Amberlyst-15; (b) cellobiose on Amberlyst-15; (c) glucose on levulinic acid which are normally found in the hydrolysis of
CPSO3H; and (d) cellobiose on CPSO3H. (Adapted from ref. 74.)
cellulose under strong acidic conditions. However, it was hard
for cellulose to diuse deep inside the porous solid due to the
Apart from the Amberlyst-type resins, Nafion (sulfonated large size of cellulose. Since cellulose is a crystal and insoluble
tetrafluoroethylene based fluoropolymer-copolymer) was in water, it is assumed that only one end of the cellulose chain
another type of eective solid acid for the hydrolysis of cellu- diused into the pores and had contact with the acidic sites,
lose. Suh et al.76 developed a cellulose pretreatment process leading to a clean cut of the chain. The reuse experiments of
using [BMIm]Cl before the subsequent hydrolysis over Nafion the PCPs catalyst showed no decrease in the catalytic activity
NR50. The pretreatment step was to decrease the crystallinity after testing 13 times, indicating that it was a highly stable
of cellulose. The hydrolysis of regenerated cellulose (from the catalyst for the hydrolysis reaction.
pretreatment of cellulose with [BMIm]Cl) yielded 35% glucose.
Moreover, Lucht et al.77 reported the hydrolysis of cellulose by 4.3 Sulfonated carbonaceous based acids
a Nafion supported on amorphous silica (Nafion SAC 13) cata- Among various types of solid acid for the hydrolysis of cellu-
lyst under mild conditions. The catalyst had the potential to lose, carbonaceous solid acids have superior catalytic activities.
be recycled or applied in a continuous flow reactor. It showed The good recyclability and cheap naturally occurring raw
excellent performance in the hydrolysis of cellobiose; 100% materials of these carbonaceous acids make them better candi-
glucose was obtained at 130 C over 24 h. The hydrolysis of dates for the production of biofuel precursors. The first carb-
cellulose needed a higher temperature (190 C); the yield of onaceous acids from sulfonated D-glucose/sucrose materials
glucose was 11% for the first time. The catalyst provided 8% were reported by Hara et al.79 D-Glucose and sucrose were
and 7% yields of glucose for the second and third reaction incompletely carbonized at low temperature to form small
runs, which suggested it to be a recyclable catalyst for the con- polycyclic aromatic carbon rings and subsequently sulfonated
version of cellulose into useful chemicals in the future. with sulfuric acid to introduce sulfonic groups (SO3H). They
Porous coordination polymers (PCPs) are a new class of used the carbonaceous acids for the transesterification of veg-
porous solids with a large variety of pore surfaces and pore etable oils to biofuels. After their work, much attention was
structures. Recently, it was demonstrated by Akiyama et al.78 paid to these new types of amorphous solid acid which could
that PCPs decorated with sulfonic acid groups could be used be used as catalysts for the cellulose hydrolysis reaction.
as catalysts for cellulose hydrolysis. MIL-101, composed of a Carbon-based solid acids were prepared by sulfonation of
chromium oxide cluster and terephthalate ligand, was chosen incompletely carbonized natural polymers, such as sugars, cel-
as the platform to introduce the SO3H groups, and the BET lulose and starch or by incomplete carbonization of sulfopoly-
surface area was 1915 m2 g1 (Scheme 5). The hydrolysis reac- cyclic aromatic compounds in conc. H2SO4. Hara et al.75,8082
tion was carried out at 393 K over 3 h and produced 2.6% 1.4% reported the preparation method of carbon material bearing

This journal is The Royal Society of Chemistry 2013 Green Chem., 2013, 15, 10951111 | 1101
View Article Online

Tutorial Review Green Chemistry

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,
Downloaded by University of Oxford on 30/04/2013 15:22:23.

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

Table 2 Hydrolysis of crystalline cellulose by various acid catalysts (ref. 75)a

Functional Density Max. acidity Surface area


Catalyst groups (mmol g1) H0 (m2 g1) Yields of hydrolysis products

H2SO4 20.4 11 Glucose: 10%, -1,4-glucan: 38%


Niobic acid Acidic OH 0.4 5.6 90
H-mordenite Acidic OH 1.4 5.6 480
Nafion SO3H 0.9 11 to 13 <1
Amberlyst-15 SO3H 4.8 2.2 50
Carbon material (CH0.62O0.54S0.05) SO3H 1.9 8 to 11 2 Glucose: 4%, -1,4-glucan: 64%
COOH 0.4
Phenolic OH 2.0
a
Conditions: catalyst 0.3 g, cellulose 25 mg, H2O 0.7 g, 3 h.

1102 | Green Chem., 2013, 15, 10951111 This journal is The Royal Society of Chemistry 2013
View Article Online

Green Chemistry Tutorial Review

further increasing the temperature. The hydrolysis of ball-


milled cellulose was conducted at 150 C over these solid acids
and the ACNSO3H sulfonated at 250 C gave the best per-
formance; the cellulose conversion and glucose yield were
74.3% and 62.6%, respectively. Apart from the sulfonation con-
ditions, the carbon sources were also evaluated. Among the
tested carbons, CMK-3, a type of ordered mesoporous material,
gave the best performance with a cellulose conversion of
Scheme 7 Procedure for corncob hydrolysis by CSA derived from the hydrolysis 94.4% and a glucose yield of 74.5% which is the highest
residue. (Reproduced from ref. 83.) glucose yield achieved via catalysis by carbon based solid acids
until now. The sulfonated CMK-3 material has a higher acid
density and surface area (412 m2 g1); both parameters are
Published on 28 February 2013 on http://pubs.rsc.org | doi:10.1039/C3GC40136G

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
Downloaded by University of Oxford on 30/04/2013 15:22:23.

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

Fig. 7 Hydrolytic conversion of cellulose over heterogeneous acids. Reaction


conditions: cellulose pretreated by ball-milling 0.05 g, catalyst 0.05 g, water
Scheme 8 Hydrolysis of cellulose with glucose derived sulfonated carbon acid. 5 mL, reaction time 24 h, temperature 423 K. (Adapted from ref. 87.)

This journal is The Royal Society of Chemistry 2013 Green Chem., 2013, 15, 10951111 | 1103
View Article Online

Tutorial Review Green Chemistry

have potential for the selective hydrolysis of cellulose to


glucose.

4.4 Heteropoly acids


Heteropoly acids (HPAs) are a type of solid acid, consisting of
early transition metaloxygen anion clusters, and they are
usually used as a recyclable acid in chemical transform-
ations.88,89 The most common and widely used heteropoly
acids are Keggin type acids with the formula [XYxM(12x)O40]n
(X is the heteroatom and M and Y are addendum atoms).
Heteropoly acids have received much attention due to their
fascinating architectures and excellent physicochemical pro-
Published on 28 February 2013 on http://pubs.rsc.org | doi:10.1039/C3GC40136G

perties such as Brnsted acidity, high proton mobility and good


stability.9093 They dissolve in polar solvents and release H+,
whose acidic strength is stronger than typical mineral acids
such as sulfuric acid.94 However, the Keggin type acids cannot
Downloaded by University of Oxford on 30/04/2013 15:22:23.

be used as heterogeneous catalysts in polar solvents. The sub-


stitution of protons with larger monovalent cations such as
Cs+ gives solid catalysts that are insoluble in water and other
polar solvents.95 For example, CsxH3xPW12O40 was used as a
heterogeneous catalyst with strong acidity and large surface
area. Heteropoly acids have been widely used in catalytic Fig. 8 Eect of deprotonation enthalpy of acid catalyst on () TRS yield and
systems for biomass conversion.96 Recently, they exhibited () cellulose conversion, for cellulose hydrolysis at 423 K over 2 h. (Reproduced
from ref. 97.)
excellent performances in the hydrolysis of cellulose to
glucose. After extraction with organic solvents, the heteropoly
acids could be separated from the homogeneous solution and The total loss of catalyst after six runs was 8.8% of the starting
dried for the next use. amount of H3PW12O40.
Shimizu et al.97 reported heteropoly acid (H3PW12O40 and Apart from the heteropoly acids mentioned above, many
HSiW12O40) and metal salt (M3(PW12O40)n, M = cation) cata- other heteropoly acids have also been developed to catalyze the
lysts for the hydrolysis of cellobiose and ball-milled cellulose hydrolysis reaction. Mizuno et al.99 reported that highly nega-
into glucose or sugars. Comparison experiments on the tively charged heteropoly acids, particularly H5BW12O40, have
hydrolysis of cellulose with dierent acids (heteropoly acids stronger acidity than H3PW12O40 for the hydrolysis of non-pre-
and mineral acids) revealed that the heteropoly acids show treated crystalline cellulose into saccharides under mild
better hydrolysis activity eects than mineral acids. The total reaction conditions. The HPAs, H5BW12O40, H5AlW12O40 and
reducing sugars yield decreased in the following order: H5GaW12O40, gave dierent performances and aorded water-
H3PW12O40 > HSiW12O40 > HClO4 > H2SO4 > H3PO4. The soluble saccharides such as glucose and cellobiose (Table 3).
hydrolysis reaction using H3PW12O40 provided TRS and Among these HPAs, H5BW12O40 gave the highest glucose yield
glucose in 18% and 15% yields, respectively. The conversion of of 77%. The hydrolysis activities of these HPAs were better
cellulose, and TRS yield correspond well to the deprotonation than Keggin type acids and conventionally utilized H2SO4 and
enthalpy (DEP) of these Brnsted acids, such that a stronger HCl. It was worth mentioning that the highly negatively
Brnsted acid is more favorable for the hydrolysis of -1,4-glyco- charged heteropoly acid solution was a better cellulose-
sidic bonds in cellulose (Fig. 8). They also used salts of solvent with strong hydrogen-bond accepting abilities due to
PW12O403 (Ag+, Ca2+, Co2+, Y3+, Sn4+, Sc3+, Ru3+, Fe3+, Hf 4+, the external metaloxygen clusters from the anions. When the
Ga3+ and Al3+) for the hydrolysis of cellulose. The turnover fre- crystalline cellulose was immersed in an aqueous solution of
quencies (TOFs) for cellulose conversion and TRS formation Na5BW12O40 at room temperature for 72 h, the crystallinity of
first increased with the e/r values (ratio of charge and ionic cellulose decreased. The crystalline peaks almost disappeared
radius) and then decreased. Maximum TOFs for both cellulose after crystalline cellulose was immersed in an aqueous solu-
conversion and TRS formation were achieved with moderate tion of H5BW12O40 at 20 C for 24 h, while not much change
Lewis acidity (e/r values) such as for Sn0.75PW12O40. was found in the crystallinity on treatment with H2SO4 and
Wang et al.98 reported the optimization of the hydrolysis HCl solutions. These results show that the hydrogen bond
reaction conditions with the H3PW12O40 catalyst such as reac- accepting ability of H5BW12O40 leading to a decrease in the
tion time, temperature and the amount of cellulose. Microcrys- crystallinity of cellulose is another factor in the high catalytic
talline cellulose was selected as the starting material. A higher performance beyond the strong acidity. H5BW12O40 was also
glucose yield of >50% was obtained with a selectivity of >90% used for the hydrolysis of natural lignocellulosic biomass such
at 453 K over 2 h. In their recycling experiments, the as rice plant and Japanese cedar and a mixture of saccharides
H3PW12O40 was extracted from the solution with diethyl ether. with high yields (>77%) was obtained.

1104 | Green Chem., 2013, 15, 10951111 This journal is The Royal Society of Chemistry 2013
View Article Online

Green Chemistry Tutorial Review

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
Published on 28 February 2013 on http://pubs.rsc.org | doi:10.1039/C3GC40136G

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
Downloaded by University of Oxford on 30/04/2013 15:22:23.

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

This journal is The Royal Society of Chemistry 2013 Green Chem., 2013, 15, 10951111 | 1105
View Article Online

Tutorial Review Green Chemistry

Table 4 The results of the solid acid-catalyzed hydrolysis of Avicel cellulosea


(ref. 106)

Entry Catalyst Time/min Yield of glucose Yields of TRS

1b HY 600 2.1 7.1


2c HY 4 20.8 23.4
3 HY 8 36.9 47.5
4d HY 15 24.2 34.8
5 HZSM-5a 9.5 35.2 42.9
6 HZSM-5b 9.5 33.7 45.3
7 H-beta 8.5 29.6 41.1
8 NKC-9 3.3 26.9 38.4
9e HY 8 4.5 12.7
10 8 7.1 18.8
Published on 28 February 2013 on http://pubs.rsc.org | doi:10.1039/C3GC40136G

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.
Downloaded by University of Oxford on 30/04/2013 15:22:23.

Table 5 Results of HY zeolite-catalyzed hydrolysis of dierent cellulose


samples (ref. 106)a

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

1106 | Green Chem., 2013, 15, 10951111 This journal is The Royal Society of Chemistry 2013
View Article Online

Green Chemistry Tutorial Review

Scheme 11 Catalyst separation from the reaction mixture. (Adapted from ref.
108.)

Table 6 Hydrolysis of cellulose with MNPs@SiO2SO3Ha


Scheme 10 Preparation of Fe3O4 SBASO3H. (Reproduced from ref. 108.)
Published on 28 February 2013 on http://pubs.rsc.org | doi:10.1039/C3GC40136G

area. Also, when corncob was used as lignocellulose biomass


for a hydrolysis reaction, the total reducing sugar (TRS) yield
Downloaded by University of Oxford on 30/04/2013 15:22:23.

was 45% (Fig. 9). Acid amount/ Yield of Yield of


Catalyst mmol g1 TRS glucose TON
The catalyst separation is presented in Scheme 11. The
used Fe3O4SBASO3H can be easily separated from the reac- MNPs@SiO2SO3H 0.5 30.2 7.0 3.8
tion mixture by using a permanent magnet. The recycled cata- Amberlyst-15 4.8 29.3 6.2 0.4
lyst was washed with 1 M H2SO4 and water/ethanol, and dried a
Conditions: cellulose 0.15 g, catalyst 0.15 g, H2O 1.5 ml, 423 K.
at 80 C for the next use without deactivation. TEM, XRD and
BET analysis of the used catalyst revealed that the mesoporous
structure is retained and the Fe3O4SBASO3H is robust in the using the MNPs@SiO2SO3H catalyst was much higher than
hydrothermal conditions. that using Amberlyst-15 (3.8 vs. 0.4) (Table 6).
Another appealing work based on a magnetic solid acid was
reported by Ebitani et al.112 The catalyst was prepared by using 4.7 Supported metal catalysts
CoFe2O4 as the magnetic core and embedded with silica, fol-
Supported metal catalysts have been widely used in biomass
lowed by oxidation of thiol groups to SO3H groups. It was a
conversion due to their excellent hydrogenation activities.
highly active catalyst for the hydrolysis of disaccharides and
Numerous works have focused on the conversion of cellulose
polysaccharides. The use of nanoparticles was expected to
into sugar alcohols with supported metal catalysts in the pres-
overcome the diculty of the solidsolid reaction and they
ence of acids.113115 Cellulose was hydrolyzed to sugars over
were well dispersed in water solution. By introducing magnetic
acid and then hydrogenated into the sugar alcohols by sup-
parts in the catalyst, it can be easily separated from solution.
ported metal catalysts under H2 pressure. However, the
The hydrolysis of cellulose was conducted at 423 K in water
hydrolysis of cellulose to glucose is rarely catalyzed solely by
and the glucose yield was 7%; the TRS yield was 30% which
supported metal catalysts. Recently, Fukuoka et al.116 success-
was similar to that using Amberlyst-15. But the TON number
fully converted cellulose to glucose by using a supported Ru
catalyst. Various supported materials, including mesoporous
carbon materials (CMKs), carbon black (XC-72), activated
carbon (AC) and C60 were tested and the CMK supported Ru
catalyst (Ru/CMK-3) showed the best performance (the glucose
yield was 34% and the oligosaccharide yield 5%). The loading
amount of Ru on the catalyst had an apparent eect on the
product distribution. When the Ru loading ranged from 2% to
10%, the glucose yield increased from 28% to 34% while the
oligosaccharides decreased from 22% to 5%. The yield of total
reducing sugars was ca. 40% regardless of the Ru loading.
Besides, CMK-3 itself catalyzed the hydrolysis of cellulose in
water at 503 K and gave a 21% yield of glucose and 22% yield
of oligosaccharides (total 43%). The above results show that
CMK-3 is able to convert cellulose into oligosaccharides and
sugars, and Ru plays a very important role in the conversion of
Fig. 9 Hydrolysis of macrocrystalline cellulose by dierent solid acids (1.5 g
oligosaccharides into glucose. Further experiments on the
solid acid catalyst, 1.5 g cellulose, 15 ml H2O, at 150 C for 3 h). (Reproduced hydrolysis of cellobiose with CMK-3 and Ru/CMK-3 confirmed
from ref. 108.) the suspicion. The hydrolysis of cellobiose with Ru/CMK-3

This journal is The Royal Society of Chemistry 2013 Green Chem., 2013, 15, 10951111 | 1107
View Article Online

Tutorial Review Green Chemistry

above were aimed at overcoming these limitations. Solid acids


have many advantages over conventional liquid acids, in separ-
ation, recycling and being environmental benign. However, the
mass transfer limitations between the insoluble polymers and
heterogeneous catalysts are bottlenecks for the hydrolysis
system. Conceptually, solid acids having higher specific
surface areas, pore sizes/volume and strong acid sites are
prone to exhibit better performances in the reaction. The
number of Brnsted acid sites, anity with the substrates and
catalyst stability are all key factors in the hydrolysis reaction.
Among the mentioned solid catalysts, carbon-based solid acids
Scheme 12 Hydrolysis of cellulose by Ru/CMK-3.
bearing SO3H, COOH and OH groups and cellulose-
Published on 28 February 2013 on http://pubs.rsc.org | doi:10.1039/C3GC40136G

mimetic catalysts have strong anity to the cellulose chain


under the optimized conditions yielded 25% glucose, while and make the acid sites closer to the -1,4-glycosidic bonds.
the CMK-3 support gave a similar performance to the blank Magnetic solid acids are promising materials for the reaction
test (6.5% and 7.9% yield of glucose), which meant that the due to their easier separation and recyclability. Heteropoly
Downloaded by University of Oxford on 30/04/2013 15:22:23.

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.

5. Summary and outlook


The hydrolysis of cellulose to glucose is a critical step for the
production of cellulosic bioethanol and many other value- Notes and references
added molecules. So far, the hydrolysis process cannot be
amplified to industrial scale production due to its low 1 W. P. Nel and C. J. Cooper, Energy Policy, 2009, 37, 166.
economy and eciency. The catalytic systems mentioned 2 S. Shafiee and E. Topal, Energy Policy, 2009, 37, 181.

1108 | Green Chem., 2013, 15, 10951111 This journal is The Royal Society of Chemistry 2013
View Article Online

Green Chemistry Tutorial Review

3 R. Luque, L. Herrero-Davila, J. M. Campelo, J. H. Clark, 32 J. Zhang, B. Zhang, J. Zhang, L. Lin, S. Liu and P. Ouyang,
J. M. Hidalgo, D. Luna, J. M. Marinas and A. A. Romero, Biotechnol. Adv., 2010, 28, 613.
Energy Environ. Sci., 2008, 1, 542. 33 T. H. Kim and Y. Y. Lee, Bioresour. Technol., 2005, 96,
4 R. Henry, Plant Biotechnol. J., 2010, 8, 288. 2007.
5 F. Kreith and D. Y. Goswami, in Handbook of Energy 34 M. Benoit, A. Rodrigues, Q. Zhang, E. Fourre,
Eciency and Renewable Energy, CRC Press: Taylor and K. D. Oliveira Vigier, J. Tatibouet and F. Jerome, Angew.
Francis Group, Boca Raton, FL, 2007. Chem., Int. Ed., 2011, 50, 8964.
6 M. Graziani and P. Fornasiero, in Renewable Resources and 35 J. Xue, H. Chen and Z. Kadar, Biomass Bioenergy, 2011, 35,
Renewable Energy: A Global Challenge, CRC Press: Taylor 3859.
and Francis Group, Boca Raton, FL, 2007. 36 S. Zhu, Y. Wu, Z. Yu, J. Liao and Y. Zhang, Process
7 D. L. Klass, Biomass for Renewable Energy, Fuels, and Biochem., 2005, 40, 3082.
Chemicals, Academic Press, San Diego, 1998. 37 H. Ma, W. Liu, Y. Wu and Z. Yu, Bioresour. Technol., 2009,
Published on 28 February 2013 on http://pubs.rsc.org | doi:10.1039/C3GC40136G

8 J.-P. Lange, E. Heide, J. Buijtenen and R. Price, Chem- 100, 1279.


SusChem, 2012, 5, 150. 38 A. Payen, C. R. Hebd. Seances Acad. Sci., 1838, 7, 1052.
9 D. Hayes, Catal. Today, 2009, 145, 138. 39 A. Brogniart, A. B. Pelonze and R. Dumas, C. R. Chim.,
10 J. C. Serrano-Ruiz, R. Luque and A. Sepu lveda-Escribanoa, 1839, 8, 51.
Downloaded by University of Oxford on 30/04/2013 15:22:23.

Chem. Soc. Rev., 2011, 40, 5266. 40 H. Staudinger, Ber. Dtsch. Chem. Ges., 1920, 53, 1073.
11 D. M. Alonso, J. Q. Bond and J. A. Dumesic, Green Chem., 41 D. Klemm, B. Heublein, H.-P. Fink and A. Bohn, Angew.
2010, 12, 1493. Chem., Int. Ed., 2005, 44, 3358.
12 W. Torres, S. S. Pansare and J. G. Goodwin, Catal. Rev. Sci. 42 M. E. Himmel, S. Y. Ding, D. K. Johnson, W. S. Adney,
Eng., 2007, 49, 407. M. R. Nimlos, J. W. Brady and T. D. Foust, Science, 2007,
13 H. de Lasa, E. Salaices, J. Mazumder and R. Lucky, Chem. 315, 804.
Rev., 2011, 111, 5404. 43 A. C. OSullivan, Cellulose, 1997, 4, 173.
14 G. Huber, S. Iborra and A. Corma, Chem. Rev., 2006, 106, 44 M. Jarvis, Nature, 2003, 426, 611.
4044. 45 Y. Nishiyama, J. Sugiyama, H. Chanzy and P. Langan,
15 P. Maki-Arvela, B. Holmbom, T. Salmi and D. Murzin, J. Am. Chem. Soc., 2003, 125, 14300.
Catal. Rev. Sci. Eng., 2007, 49, 197. 46 M. Wada, Y. Nishiyama, H. Chanzy, T. Forsyth and
16 C. E. Wyman, B. E. Dale, R. T. Elander, M. Holtzapple, P. Langan, Powder Dir., 2008, 23, 92.
M. R. Ladisch and Y. Y. Lee, Bioresour. Technol., 2005, 96, 47 R. Palkovits, K. Tajvidi, J. Procelewska, R. Rinaldi and
1959. A. Rupper, Green Chem., 2010, 12, 972.
17 Y. H. P. Zhang and L. R. Lynd, Biotechnol. Bioeng., 2004, 48 Nanjing Forestry Institute, Plant Hydrolysis Technology,
88, 797. Agricultural Press, Beijing, 1st edn, 1961.
18 J. A. Geboers, S. Van de Vyver, R. Ooms, B. Op de Beeck, 49 W. L. Faith, Ind. Eng. Chem., 1923, 37, 9.
P. A. Jacobs and B. F. Sels, Catal. Sci. Technol., 2011, 1, 714. 50 F. Bergius, Ind. Eng. Chem., 1937, 29, 247.
19 J. R. Regalbuto, Science, 2009, 325, 822. 51 P. L. Ragg, P. R. Fields and P. B. Tinker, Philos.
20 Y. P. Zhang and L. R. Lynd, Biotechnol. Bioeng., 2004, 88, Trans. R. Soc. London, Ser. A, 1987, 321, 537.
797. 52 J. F. Saeman, J. L. Bubl and E. E. Harris, Ind. Eng. Chem.,
21 P. Engel, R. Mladenov, H. Wulfhorst, G. Jager and Anal. Ed., 1945, 17, 35.
A. C. Spiess, Green Chem., 2010, 12, 1959. 53 F. Camacho, P. Gonzalez-Tello, E. Jurado and A. Robles,
22 A. C. Salvador, M. C. Santos and J. A. Saraiva, Green J. Chem. Technol. Biotechnol., 1996, 67, 350.
Chem., 2010, 12, 632. 54 E. E. Harris and E. Beglinger, The Madison Wood-Sugar
23 J. F. Saeman, Ind. Eng. Chem., 1945, 37, 43. Process, Report no. R1617, US Department of Agriculture,
24 R. W. Torget, J. S. Kim and Y. Y. Lee, Ind. Eng. Chem. Res., Forest Service, Forest Products Laboratory, Madison, WI,
2000, 39, 2817. 1946.
25 F. Guo, Z. Fang, C. C. Xu and R. L. Smith Jr., Prog. Energy 55 D. R. Thompson and H. E. Grethlein, Ind. Eng. Chem.
Combust. Sci., 2012, 38, 672. Prod. Res. Dev., 1979, 18, 166.
26 K. D. O. Vigier and F. Jrme, Top. Curr. Chem., 2010, 295, 56 J. F. Harris, A. J. Baker, A.H. Conner, T. W. Jeries,
63. J. L. Minor, R. C. Pettersen, R. W. Scott, E. L. Springer,
27 K. Shimizu and A. Satsum, Energy Environ. Sci., 2011, 4, T. H. Wegner and J. I. Zerbe, in Two-stage Dilute Sulfuric
3140. Acid Hydrolysis of Wood: An Investigation of Fundamentals,
28 P. L. Dhepe and A. Fukuoka, ChemSusChem, 2008, 1, 969. Gen. Tech. Rep., FPl-45, U. S. Department of Agriculture,
29 D. Sidiras and E. Koukios, Biomass, 1989, 19, 289. Forest Service, Forest Products Laboratory, Madison, WI,
30 T. Tassinari, C. Macy and L. Spano, Biotechnol. Bioeng., 1985, p. 73.
1980, 22, 1689. 57 R. A. Antonoplis, H. W. Blanch, R. P. Freitas,
31 R. P. Swatloski, S. K. Spear, J. D. Holbrey and R. D. Rogers, A. F. Sciamanna and C. R. Wilke, Biotechnol. Bioeng., 1983,
J. Am. Chem. Soc., 2002, 124, 4974. 25, 2757.

This journal is The Royal Society of Chemistry 2013 Green Chem., 2013, 15, 10951111 | 1109
View Article Online

Tutorial Review Green Chemistry

58 P. E. Linnett, J. P. M. Sanders, US Pat., 4677198, 1987. 84 Y. Jiang, X. Li, X. Wang, L. Meng, H. Wang, G. Peng,
59 R. Erckel, R. Franz, R. Woernle and T. Riehm, US Pat., X. Wang and X. Mu, Green Chem., 2012, 14, 2162.
4556431, 1985. 85 H. Guo, X. Qi, L. Li and R. L. Smith Jr., Bioresour. Technol.,
60 M. R. Ladisch, Process Biochem., 1979, 14, 21. 2012, 116, 355.
61 C. Tagusagawa, A. Takagaki, A. Iguchi, K. Takanabe, 86 J. Pang, A. Wang, M. Zheng and T. Zhang, Chem.
J. N. Kondo, K. Ebitani, T. Tatsumi and K. Domen, Chem. Commun., 2010, 46, 6935.
Mater., 2010, 22, 2035. 87 S. V. de Vyver, L. Peng, J. Geboers, H. Schepers, F. de
62 C. Tagusagawa, A. Takagaki, A. Iguchi, K. Takanabe, Clippel, C. J. Gommes, B. Goderis, P. A. Jacobs and
J. N. Kondo, K. Ebitani, S. Hayashi, T. Tatsumi and B. F. Sels, Green Chem., 2010, 12, 1560.
K. Domen, Angew. Chem., Int. Ed., 2010, 49, 1128. 88 I. V. Kozhevnikov, Chem. Rev., 1998, 98, 171.
63 A. Takagaki, C. Tagusagawa and K. Domen, Chem. 89 N. Mizuno and M. Misono, Chem. Rev., 1998, 98, 199.
Commun., 2008, 5363. 90 C. L. Hill, J. Mol. Catal. A: Chem., 2007, 262, 2.
Published on 28 February 2013 on http://pubs.rsc.org | doi:10.1039/C3GC40136G

64 F. Zhang, X. Deng, Z. Fang, H. Zeng, X. Tian and 91 I. V. Kozhevnikov, J. Mol. Catal. A: Chem., 2007, 262, 86.
J. Kozinski, Petrochem. Technol., 2011, 40, 43. 92 I. V. Kozhevnikov, J. Mol. Catal. A: Chem., 2009, 305, 104.
65 Y. Uozumi and K. Shibatiomi, J. Am. Chem. Soc., 2001, 93 N. Mizuno, K. Yamaguchi and K. Kamata, Coord. Chem.
123, 2919. Rev., 2005, 249, 1944.
Downloaded by University of Oxford on 30/04/2013 15:22:23.

66 X. Qi, M. Watanabe, T. M. Aida and R. Lee Smith Jr., Green 94 J. Macht, M. J. Janik, M. Neurock and E. Iglesia, Angew.
Chem., 2008, 10, 799. Chem., Int. Ed., 2007, 46, 7864.
67 M. T. Sanz, R. Murga, S. Beltran and J. L. Cabezas, Ind. 95 T. Okuhara, Chem. Rev., 2002, 102, 3641.
Eng. Chem. Res., 2002, 41, 512. 96 W. Deng, Q. Zhang and Y. Wang, Dalton Trans., 2012, 41,
68 R. Rinaldi, R. Palkovits and F. Schth, Angew. Chem., Int. 9817.
Ed., 2008, 47, 8047. 97 K. Shimizu, H. Furukawa, N. Kobayashi, Y. Itayab and
69 R. Rinaldi, N. Meine, J. vom Stein, R. Palkovits and A. Satsuma, Green Chem., 2009, 11, 1627.
F. Schth, ChemSusChem, 2010, 3, 266. 98 J. Tian, J. Wang, S. Zhao, C. Jiang, X. Zhang and X. Wang,
70 H. J. Heeres, B. Girisuta and L. P. B. M. Janssen, Ind. Eng. Cellulose, 2010, 17, 587.
Chem. Res., 2007, 46, 1696. 99 Y. Ogasawara, S. Itagaki, K. Yamaguchi and N. Mizuno,
71 V. Bravo, M. P. Paez, M. Aoulad and A. Reyes, Enzyme ChemSusChem, 2011, 4, 519.
Microb. Technol., 2000, 26, 614. 100 X. Li, Y. Jiang, L. Wang, L. Meng, W. Wang and X. Mu,
72 C. A. Schall, A. P. Dadi and S. Varanasi, Biotechnol. RSC Adv., 2012, 2, 6921.
Bioeng., 2006, 95, 904. 101 M. Chenga, T. Shia, H. Guana, S. Wang, X. Wang and
73 L. Shuai, Q. Yang, J. Y. Zhu, F. C. Lu, P. J. Weimer, Z. Jiang, Appl. Catal., B, 2011, 107, 104.
J. Ralph and X. J. Pan, Bioresour. Technol., 2010, 101, 3106. 102 Z. Sun, M. Cheng, H. Li, T. Shi, M. Yuan, X. Wang and
74 L. Shuai and X. Pan, Energy Environ. Sci., 2012, 5, 6889. Z. Jiang, RSC Adv., 2012, 2, 9058.
75 S. Suganuma, K. Nakajima, M. Kitano, D. Yamaguchi, 103 J. Tian, C. Fan, M. Cheng and X. Wang, Chem. Eng.
H. Kato, S. Hayashi and M. Hara, J. Am. Chem. Soc., 2008, Technol., 2011, 34, 482.
130, 12787. 104 N. Salman, C. H. Rscher, J. C. Buhl, W. Lutz, H. Toufar
76 S. Kim, A. A. Dwiatmoko, J. W. Choi, Y. Suh, D. J. Suh and and M. Stcker, Microporous Mesoporous Mater., 2006, 90,
M. Oh, Bioresour. Technol., 2010, 101, 8273. 339.
77 J. Hegner, K. C. Pereira, B. DeBoef and B. L. Lucht, Tetra- 105 A. Onda, T. Ochi and K. Yanagisawa, Green Chem., 2008,
hedron Lett., 2010, 51, 2356. 10, 1033.
78 G. Akiyama, R. Matsuda, H. Sato, M. Takata and 106 Z. Zhang and Z. K. Zhao, Carbohydr. Res., 2009, 344, 2069.
S. Kitagawa, Adv. Mater., 2011, 23, 3294. 107 H. Caia, C. Li, A. Wang, G. Xua and T. Zhang, Appl. Catal.,
79 M. Toda1, A. Takagaki1, M. Okamura1, J. N. Kondo, B, 2012, 123124, 333.
S. Hayashi, K. Domen and M. Hara, Nature, 2005, 438, 108 D. Lai, L. Deng, Q. Guo and Y. Fu, Energy Environ. Sci.,
178. 2011, 4, 3552.
80 M. Kitano, D. Yamaguchi, S. Suganuma, K. Nakajima, 109 D. Lai, L. Deng, J. Li, B. Liao, Q. Guo and Y. Fu, Chem-
H. Kato, S. Hayashi and M. Hara, Langmuir, 2009, 25, SusChem, 2011, 4, 55.
5068. 110 D. Margolese, J. A. Melero, S. C. Christiansen,
81 K. Fukuhara, K. Nakajima, M. Kitano, H. Kato, S. Hayashi B. F. Chmelka and G. D. Stucky, Chem. Mater., 2000, 12,
and M. Hara, ChemSusChem, 2011, 4, 778. 2448.
82 (a) M. Hara, Energy Environ. Sci., 2010, 3, 601; 111 C. S. Gill, B. A. Price and C. W. Jones, J. Catal., 2007, 251,
(b) S. Suganuma, K. Nakajima, M. Kitano, D. Yamaguchi, 145.
H. Kato, S. Hayashi and M. Hara, Solid State Sci., 2010, 12, 112 A. Takagaki, M. Nishimura, S. Nishimura and K. Ebitani,
1029. Chem. Lett., 2011, 40, 1195.
83 Y. Wu, Z. Fu, D. Yin, Q. Xu, F. Liu, C. Lu and L. Mao, 113 H. Kobayashi, H. Ohta and A. Fukuoka, Catal. Sci.
Green Chem., 2010, 12, 696. Technol., 2012, 2, 869.

1110 | Green Chem., 2013, 15, 10951111 This journal is The Royal Society of Chemistry 2013
View Article Online

Green Chemistry Tutorial Review

114 R. Palkovits, K. Tajvidi, A. M. Ruppertc and 117 T. Komanoya, H. Kobayashi, K. Hara, W. J. Chun and
J. Procelewska, Chem. Commun., 2011, 47, 576. A. Fukuoka, Appl. Catal., A, 2011, 407, 188.
115 C. Luo, S. Wang and H. Liu, Angew. Chem., Int. Ed., 2007, 118 F. Zhang and Z. Fang, Bioresour. Technol., 2012, 124,
46, 7636. 440.
116 H. Kobayashi, T. Komanoya, K. Hara and A. Fukuoka, 119 Z. Fang, F. Zhang, H. Zeng and F. Guo, Bioresour. Technol.,
ChemSusChem, 2010, 3, 440. 2011, 102, 8017.
Published on 28 February 2013 on http://pubs.rsc.org | doi:10.1039/C3GC40136G
Downloaded by University of Oxford on 30/04/2013 15:22:23.

This journal is The Royal Society of Chemistry 2013 Green Chem., 2013, 15, 10951111 | 1111