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One pot production of 5-hydroxymethylfurfural with high yield from
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cellulose by a Brønsted–Lewis–surfactant-combined heteropolyacid
catalystw
Shun Zhao, Mingxing Cheng, Junzi Li, Juan Tian and Xiaohong Wang*
Received 16th October 2010, Accepted 6th December 2010
DOI: 10.1039/c0cc04444j
A Brønsted–Lewis–surfactant-combined heteropolyacid (HPA)
Cr[(DS)H2PW12O40]3 has been synthesized, and is used as
a heterogeneous catalyst for the conversion of cellulose to
5-hydroxymethylfurfural in one pot within 2 h at 150 1C with
77.1% conversion and 52.7% yield. This micellar HPA catalyst
shows stability and can be recycled by simple separation process.
The synthesis of fuels and chemicals from biomass is a
central and ongoing challenge for developing environmentally
sustainable processes because of the reduction of fossil resources
and environmental problems.1 Among current biofuel sources,
5-hydroymethylfurfural (HMF) converted from biomass is a
versatile and key intermediate that is attracting much attention
in biofuels chemistry and the petroleum industry.1,2 Prepara-
tion of HMF had been achieved by chemical catalysis using
edible starting materials,1,3 primarily fructose and glucose,
which are easy to convert into valuable chemicals. Inedible
lignocellulosic biomass represents a rich source of feedstock for
HMF,4 however, its recalcitrant and heterogeneous properties
make its conversion typically inefficient and difficult.5
Most cellulosic biomass is processed involving depolymeri-
zation of cellulose to form glucose, followed by conversion of
glucose to HMF. The combination of hydrolysis of cellulose
and dehydration of glucose in one pot is possible, because both
processes can be catalyzed by acids, which decreases the step
of the production of glucose and the corresponding cost. Thus
far, although some chemical catalysts have been developed for
hydrolysis of cellulose,6 they are not suitable for this hetero-
geneous system.7 Recently, new systems have been developed.
Zhang et al.8 reported that Lewis acids CuCl2 and CrCl2 in
ionic liquids (IL) catalyzed in a single-step process and
converted cellulose to HMF with 57.5% yield at 120 1C for
8 h. In addition, N,N-dimethylacetamide (DMA) containing
lithium chloride (LiCl) was reported to be a privileged solvent
that enables the hydrolysis of polysaccharides, including
Key Lab of Polyoxometalate Science of Ministry of Education,
Faculty of Chemistry, Northeast Normal University,
5268 Renmin Street, Changchun 130024, Jilin Province, PR China.
E-mail: wangxh665@nenu.edu.cn; Fax: +86 431-85099759
w Electronic supplementary information available: Experimental
methods (general information, preparation of Cr[(DS)H2PW12O40]3,
the surface acidity of Cr[(DS)H2PW12O40]3, typical procedures for
cellulose hydrolysis), and Fig. S1–S9. See DOI: 10.1039/c0cc04444j
2176 Chem. Commun., 2011, 47, 2176–2178
COMMUNICATION
lignocellulosic biomass, cellulose, glucose and fructose, into
HMF.5 In a DMA–LiCl/IL system, CrCl2 and HCl collectively
catalyzed conversion of cellulose into HMF with 54% yield at
140 1C for 2 h. In the above two processes, IL was used as a
solvent. However, the high cost of ionic liquids could limit
their large-scale applications.
Heteropolyacids (HPAs) are known to be efficient acidic
catalysts for various organic reactions.9 Recently, Shimizu
et al.10 investigated the effect of the Brønsted and Lewis
acidities of HPAs and salts on catalyzing hydrolysis of poly-
saccharides such as cellobiose and cellulose to glucose. Our
group recently reported the catalytic activity of H3PW12O40 on
the hydrolysis of cellulose into glucose.11 However, these two
reports did not achieve the conversion of cellulose to HMF.
The development of an efficient, easily handled catalytic
system for the combination of cellulose hydrolysis and glucose
dehydration in one pot under mild conditions is equally
desirable and challenging.
In this work, we report a new process of Brønsted–Lewis–
surfactant-combined HPA catalyst Cr[(DS)H2PW12O40]3
(DS represents OSO3C12H25 dodecyl sulfate) that enables
cellulose depolymerization and glucose conversion to HMF
in a single process under mild conditions. Its higher activity
stems from several sources. (1) The Brønsted–Lewis–surfactant-
combined HPA catalyst could assemble micelles in water
solutions. And this first micellar catalytic system owns double
Brønsted and Lewis acidities, confirming the conversion of
cellulose into sugar and dehydration of sugar into HMF in a
tandem reaction. (2) This system overcomes the diffusion
problem in this solid–solid reaction and promotes the reaction
rate by the HPA micellar catalyst. (3) This is the first example
of a highly efficient conversion of cellulose into HMF under
mild conditions using a micellar HPA system within a short
time. (4) This micellar HPA catalyst provides a hydrophobic
environment sufficient for protecting HMF from further
decomposition and decreasing the by-products. (5) It allows
easy handling of this catalyst. The leaching test showed that
Cr[(DS)H2PW12O40]3 had excellent stability and could be
reused approximately six times as a rapid heterogeneous
catalyst by a simple treatment.
In a typical reaction protocol, 200 mg of cellulose was mixed
with 4 mL of water in a Parr reactor, then 0.06 mmol of
Cr[(DS)H2PW12O40]3 was added as the catalyst. The Parr
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Fig. 1 The conversion of cellulose by different catalysts. Reaction
conditions: 0.2 g of cellulose, 0.06 mmol of catalyst, 4 mL of water and
150 1C for 2 h.
reactor was immersed and stirred in an oil bath at 150 1C for a
specified time. The reaction was stopped by rapidly cooling the
reactor in an ice bath at 0 1C.
Hydrolysis of cellulose to HMF with high efficiency was
achieved by the Cr[(DS)H2PW12O40]3 heterogeneous catalyst.
Fig. 1 shows that a high conversion of cellulose and high yield
for HMF can be obtained under Cr[(DS)H2PW12O40]3 within
2 h at 150 1C. The catalytic performance is comparable with
that of a range of other solid acids, including CrCl3, Cr(DS)3,
H3PW12O40, and Cr[(DS)H2PW12O40]3. The range of catalytic
activity is Cr[(DS)H2PW12O40]3 > Cr[H2PW12O40]3 >
Cr(DS)3 > CrCl3 > H3PW12O40. Here, Cr[(DS)H2PW12O40]3
showed superior performance compared to other catalysts,
achieving 77.1% hydrolysis of cellulose and 52.7% yield of
HMF within 2 h. Cr[H2PW12O40]3 gave a higher yield of
HMF (35.7%) than pure HPAs H3PW12O40 (B0%), which
is attributed to its double acidity. The coordination of a Lewis
acid to a Brønsted acid is known to significantly increase its
original acidity.12 The Lewis acidity of Cr[(DS)H2PW12O40]3
originates from the metal cation as an electron pair acceptor,
and Brønsted acidity is generated from some protons of HPA
molecules.12 The FTIR spectrum of adsorbed pyridine
determines Cr[(DS)H2PW12O40]3 owing Lewis and Brønsted
acidities (Fig. S1, ESIw). The synergistic effect of the Lewis and
Brønsted acid sites of Cr[(DS)H2PW12O40]3 enables its high
catalytic activity for the conversion of cellulose into HMF
in one pot. Lewis acidity favors the hydrolysis of cellulose
into a monosaccharide, whereas Brønsted acidity favors the
dehydration of the sugar into HMF.
Cr[(DS)H2PW12O40]3 exhibits the highest activity attri-
buted to its amphiphilic properties as compared with
Cr[H2PW12O40]3. Cr[(DS)H2PW12O40]3 is a amphiphilic
molecule consisting of a hydrophilic head group, CrH2PW12O40,
and a hydrophobic tail, OSO3C12H25. Therefore,
Cr[(DS)H2PW12O40]3 allows itself to exhibit amphiphilic
properties to assemble micelles in an aqueous solution.
The formation of Cr[(DS)H2PW12O40]3 micelles was studied
by cryo-TEM imaging (Fig. 2), which shows mostly
single 200–300 nm particles. In the Cr[H2PW12O40]3 catalytic
system, without OSO3C12H25, the homogeneous one cannot
absorb certain cellulose molecules. The highest activity
of Cr[(DS)H2PW12O40]3 is attributed to accumulation of
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Fig. 2 The cryo-TEM image of the HPA micellar catalyst.
cellulose on HPA micelles. The IR spectra of
Cr[(DS)H2PW12O40]3 and its adsorbed cellulose confirm
the absorption of cellulose on the part of the micellar
catalyst (Fig. S2, ESIw). Compared to the spectrum of
Cr[(DS)H2PW12O40]3, the W–Od vibration band shifts to a
higher frequency (980 cm 1), indicating that some interaction
occurs between the O atom from cellulose and the terminal
oxygen atom from the HPA molecules. Compared to the peak
of the original cellulose at 1165 cm 1,13 the C–O–C stretching
shifts to 1160 cm 1, being attributed to the interaction
between C–O–C and HPAs. In addition, the 31P MAS NMR
spectrum of Cr[(DS)H2PW12O40]3 shows a signal narrow peak
at d = 14.7 ppm which corresponds to the 31P NMR
chemical shift of the 12-phosphotungstic acid.14 When the
catalyst adsorbed cellulose, the peak shifted to 16.2 ppm,
which is attributed to the interaction between cellulose and the
catalyst (Fig. S3, ESIw). The 13C MAS NMR of the catalyst-
adsorbed cellulose gives the peaks at 105.2, 89.3, 74.9 and
65.2 ppm corresponding to 104.9 for C1 carbon, 88.6 for C4,
74.6 for C2,3,4, and 64.7 ppm for C6 of cellulose,15 respectively.
These changes confirm the interaction between the catalyst
and cellulose. The concentration of cellulose is accumulated
compared to the surrounding water phase through interactions
with the micelle surface or through insertion into the micelle
itself, overcoming the insolubility of cellulose in water. Therefore,
we suggest that three synergistic effects enable superior results:
the adsorption of cellulose onto the micellar HPA catalyst, the
conversion of cellulose into glucose by the Brønsted acid, and
the efficient conversion of glucose into HMF by the Lewis acid.
Moreover, these micellar droplets, although dispersed in water,
are sufficiently hydrophobic to protect HMF from further
decomposition, decreasing the by-products.16 The stability of
HMF in Cr[(DS)H2PW12O40]3 and Cr[H2PW12O40]3 catalysis
systems was tested as follows: 50 mg of HMF was added into a
4 mL solution containing 0.06 mmol of catalyst in a steel
autoclave and was heated at 150 1C for a specified amount
of time. The stability of HMF in Cr[(DS)H2PW12O40]3
and Cr[H2PW12O40]3 systems are given in Fig. S4 (ESIw),
which shows that HMF was decomposed into levulinic
acid and furfural more slowly in the Cr[(DS)H2PW12O40]3
system than in the Cr[H2PW12O40]3 system. This is attributed
to the hydrophobic environment of this micellar catalysis
system.
Chem. Commun., 2011, 47, 2176–2178 2177

The formation of HMF was monitored for different
reaction times (2 to 5 h) and temperatures (140–170 1C)
(Fig. S5, ESIw). The 100% conversion of cellulose and the
best HMF yield above 70% were found at 170 1C and at a 4 h
reaction time.
An interesting finding is that our Cr[(DS)H2PW12O40]3
micellar catalyst is available for the conversion of ligno-
cellulosic biomass. Efficient production of fuels or chemicals
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from crude biomass often requires pretreatment processes.17
However, using our method, HMF can be produced directly
and readily from untreated lignocellulosic biomasses such
as corn stover and husk of Xanthoceras sorbifolia Bunge
(XSB, an biomass energy tree found in China) (Fig. S6, ESIw).
At 150 1C for 2 h, 57.3 and 62.5% of dry weight of corn stover
and husk of XSB were transformed into 30.8% and 35.5%
HMF, respectively. Notably, the furfural is formed from these
biomasses under our reaction conditions in yields of 28.9%
and 30.7%, respectively, which are nearly similar to those
obtained in industrial processes (34%–50%).18 The by-products
were formic acid, acetic acid, and levulinic acid. These results
are close to those of ammonia fiber expansion pretreatment17
and the DMA–LiCl IL system.5
The stability of a catalyst is an important parameter for its
evaluation. This micellar catalyst enables easy separation from the
reaction mixture. Unreacted cellulose could decant down to the
bottom and be separated. HMF was extracted by methyliso-
butylketone (MIBK), because of the insolubility of the catalyst in
MIBK. During extraction, Cr[(DS)H2PW12O40]3 exists between
the water phase and organic phase as an emulsion,19 which could
be separated easily (Fig. S7, ESIw). This point confirms the
recovery of the solid catalyst. After performing the extraction
twice, the isolated yield of HMF was up to 90%. ICP analysis of
the solution phase shows that less than 0.8% of HPA leached into
the MIBK phase. The morphology of the catalyst did not change
during the reaction (Fig. S8, ESIw). The cellulose conversions and
HMF yields were maintained efficiently after six repeated experi-
ments, showing only a slight decrease in activity (Fig. S9, ESIw).
To test whether this micellar catalysis is homogeneous or
heterogeneous,20 the catalyst was separated hot by CH2Cl2
extraction after reaction for 2 h (ca. 77.1% of cellulose conversion
and 52.7% of HMF yield). The residue was allowed to react over
further 2 h at the same temperature of 150 1C. The conversion
and yield were 79.4% and 53.8%, respectively, which show a
slight increase of cellulose conversion and HMF yield. These
results confirm that a little catalyst leaches into the mixture and
the catalyst is heterogeneous.
In summary, our one-pot process represents a chemical
route from unpretreated lignocellulosic biomass to HMF.
Our chemical conversion uses simple, inexpensive catalysts
to transform lignocellulose into valuable products with an
2178 Chem. Commun., 2011, 47, 2176–2178
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acceptable conversion and yield. The higher catalytic activity
is attributed to double Brønsted and Lewis acidities, and
the micellar structure with hydrophobic groups. HMF and
furfural could be produced readily in one step from untreated
lignocellulosic biomass under mild conditions. Our process
could be competitive to the cellulosic ethanol technology,
enabling a conversion rate of 33.2% for dry weight of corn
stover into ethanol in a complex process involving multiple
chemical, biochemical, and microbiological steps.17b
This work was supported by the National Natural Science
Foundation of China (20871026). It was supported by the
National Innovation Experiment Program for Undergraduates
No.091020036.
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This journal is c The Royal Society of Chemistry 2011