Selective Catalytic Production of 5-Hydroxymethylfurfural
from Glucose by Adjusting Catalyst Wettability
Liang Wang,[a]Hong Wang,[b]Fujian Liu,[a]Anmin Zheng,[c]Jian Zhang,[a]Qi Sun,[a]
James P. Lewis,[b]Longfeng Zhu,[d]Xiangju Meng,[a]and Feng-Shou Xiao*[a]
The development of highly-efficient catalysts for conversion of
glucose and fructose to 5-hydroxymethylfurfural (HMF) is of
great importance. In this work, theoretical simulations form
the basis for rational design and synthesis of a superhydropho-
bic mesoporous acid, that can completely prevent HMF hydra-
tion, giving HMF as sole product from full conversion of fruc-
tose. Interestingly, the combined superhydrophobic solid acid
and superhydrophilic solid base catalysts are very efficient for
one-pot conversion of glucose to HMF, giving a yield as high
as 95.4 %. The excellent catalytic data in the conversion of glu-
cose to HMF is attributed to the unique wettabilities of the
solid acid and base catalysts.
Biomass, which is regarded as a renewable feedstock, has been
intensively investigated for the production of fine chemicals
and transportation fuels.[1–4]However, selective formation of
a sole valuable product from biomass is still a challenge, be-
cause these kinds of reactions are usually accompanied by
many side-reactions, producing various undesirable by-pro-
The conversion of glucose has been widely studied for the
production 5-hydroxymethylfurfural (HMF), a significant inter-
mediate in the synthesis of a wide variety of chemicals and al-
ternative fuels.[4d,5,6]During this process, base and acid cata-
lysts are generally required to catalyze the isomerization of
glucose to fructose, and dehydration of fructose to HMF, re-
spectively (Figure S1). In this process, the major side-reaction is
produced by acid-catalyzed hydration of HMF to levulinic acid
(LA) and formic acid (FA).[4d,5a,b,7]To stabilize HMF and inhibit
the side-reaction, Dumesic and co-workers successfully devel-
oped a two-phase reactor system to continuously extract the
HMF product from the aqueous phase, leading to high HMF
yield.[5a,6a]In addition, Zhang and co-workers showed that they
could significantly increase HMF yield by replacing acidic aque-
ous solutions with metal chlorides in ionic liquids.[5b]
Considering that the side-reaction of HMF hydration occurs
on acidic sites with water molecules, we hypothesize that the
hydration of HMF can be prevented by isolating the acidic
sites from water molecules. In this study, we investigate the
production of HMF over a series of solid acid and base cata-
lysts with different wettabilities. Our investigation was motivat-
ed by computational simulations and, as we demonstrate here,
a superhydrophobic mesoporous polymer acid catalyst (P-
SO3H-154) with strong wettability does prevent the side-reac-
tion of HMF hydration, yielding HMF as a sole product from
the conversion of fructose. Considering the strong wettability
of the glucose substrate by the base catalyst, we employed
a superhydrophilic mesoporous polymer solid base (P-VI-0). In
support of our hypothesis, we found that the combined cata-
lysts of the superhydrophobic acid and the superhydrophilic
base exhibit extremely high HMF yield (95.4%) in the one-pot
conversion of glucose.
Figure 1a shows the simulation model featuring one water
molecule attached to the H+acid site on the HMF molecule;
this species is considered to be an intermediate formed during
the hydration of HMF.Figure 1b shows the correlation of free
energy with the reaction distance between H+and the oxygen
atom of water molecule (d in Figure 1a). The energy potential
along the reaction distance d shows an energy barrier of
7.5 kcalmol?1at d=2.05 ?, indicating it is not an energetically
spontaneous process in terms of water moving close to the
HMF molecule. However, once the system passes this energy
barrier, the whole process of water moving closer to HMF and
resulting in the hydration of HMF seems to be energetically fa-
vorable. Thus, we defined the distance region shorter than
2.05 ? as the reaction zone, which means that the side-reac-
tion is more likely to occur within this zone. The distance
beyond this value (>2.05 ?), we consider as the non-reaction
zone. These results suggest that keeping water at the distance
of the non-reaction zone would effectively prevent the hydra-
tion of HMF.
Prompted by this theoretical simulation, we expected that
a superhydrophobic catalyst would keep water at the distance
of the non-reaction zone. Hence, we synthesized a series of
[a] Dr. L. Wang, F. Liu, J. Zhang, Q. Sun, X. Meng, Prof. F.-S. Xiao
Key Laboratory of Applied Chemistry of Zhejiang Province
Hangzhou 310028 (PR China)
[b] Dr. H. Wang, Dr. J. P. Lewis
Department of Physics
West Virginia University
Morgantown, WV 26506-6315 (USA)
[c] Prof. A. Zheng
State Key Laboratory of Magnetic Resonance and
Atomic and Molecular Physics and Mathematics
Wuhan Institute of Physics and Mathematics
Chinese Academy of Science
Wuhan 430071 (PR China)
[d] L. Zhu
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry
Changchun 130012 (PR China)
Supporting Information for this article is available on the WWW under
? 2014 Wiley-VCH Verlag GmbH&Co. KGaA, WeinheimChemSusChem 2014, 7, 402–406 402
mesoporous polymer acid catalysts (P-SO3H-x, x stands for the
water contact angle on the surface of solid catalyst) with differ-
ent water wettabilities, including the superhydrophobic P-
SO3H-154 (Figure 2a), hydrophobic P-SO3H-125, P-SO3H-105,
and hydrophilic P-SO3H-44 (Figure S2, Table S1).These sam-
ples have rich porosity, acidic sites, and high thermal stability
(Figures S3–S6, Table S1). For comparison, Amberlyst-15, a hy-
drophilic industrial acid catalyst
with water droplet contact angle
at about 108, was used as a refer-
Figure 2b shows the hydration
of HMF in the presence of water
and various solid acid catalysts
angles. Very interestingly, the
amount of HMF remains con-
stant on use of the superhydro-
phobic P-SO3H-154 catalyst re-
gardless of solvent, even for the
DMSO–water mixed solvent (Fig-
ure 2b, Figure S7). In contrast,
the other solid acids could cata-
lyze the hydration of HMF. For
example, the HMF amount sig-
nificantly reduces over Amber-
lyst-15 catalyst (Figure 2b, Fig-
ure S7). These results suggest that the superhydrophobic P-
SO3H-154 is favorable for isolation of water molecules from the
acidic sites (Figure S8), preventing the hydration of HMF, which
is in good agreement with the results of theoretical simulation
(Figure 1). In contrast, acidic sites in the hydrophilic Amberlyst-
15 easily contact water molecules, leading to the hydration of
HMF. Furthermore, these suggestions are confirmed by1H NMR
spectra of DMSO–water-treated Amberlyst-15 and P-SO3H-154
catalysts (Figures S9 and S10).The Amberlyst-15 shows a dis-
tinct peak at 6.6 ppm, indicating the presence of water. How-
ever, we cannot observe water signals in
P-SO3H-154 catalyst. Moreover, the adsorption kinetics of water
shows that P-SO3H-154 does not adsorb water, while Amber-
lyst-15 could effectively adsorb a large amount of water (Fig-
Based on the fact that HMF is highly stable in hydration
over P-SO3H-154, we applied P-SO3H-154 to catalyze the dehy-
1H NMR spectrum of
Figure 1. Data of theoretical simulations. A) Model for the theoretical simulation using local-orbital density func-
tional theory and umbrella sampling (d expresses the distance between proton (H+) and the oxygen atom of
water molecule), and B) the correlation of free energy along the reaction distance d. Inset: model of structure
a and structure b.
Figure 2. Water contact-angle and catalytic performance of various catalysts.
A) Photographs and contact angles of water droplets on the surface of P-
SO3H-154 and Amberlyst-15; B) Hydration of HMF over various catalysts with
different water contact angles in DMSO (&) and DMSO–water solvents (~).
Reaction conditions: 1 mmol of HMF, 5 g of DMSO (or DMSO–water with
weight ratio at 9:1), 50 mg of solid catalyst, 1008C for 5 h; C) Time-depend-
ence in catalytic conversion of fructose over P-SO3H-154 catalyst (yield of
HMF: &, yield of LA: &) and over Amberlyst-15 catalyst (yield of HMF: ~,
yield of LA: ~). Reaction conditions: 100 mg of fructose, 50 mg of solid cat-
alyst, 5 g of THF–DMSO solvent (weight ratio at 1.5), 1008C.
Table 1. Catalytic data in dehydration of fructose to HMF over various
EntryCatalyst Solvent HMF yield [%]
[a] Reaction conditions: 100 mg of fructose, 50 mg of solid catalyst, 5 g of
solvent (weight ratio of THF to DMSO in the mixed THF–DMSO solvent at
1.5) for 10 h at 1008C; the major by-products were LA and FA. [b] The
same number of acidic sites as in P-SO3H. [c] 4.5 g of THF–DMSO (weight
ratio at 1.5) and 0.5 g of water. [d] 150 mg of catalyst, 2.5 h reaction time.
? 2014 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim ChemSusChem 2014, 7, 402–406 403
dration of fructose to HMF, which is an important step in the
one-pot production of HMF from glucose (Figure S1).Table 1
presents the catalytic data for the conversion of fructose to
HMF over various catalysts. As expected, P-SO3H-154 catalyst
shows extraordinarily high yields of 99.0% HMF as a sole prod-
uct (entries 1&2 in Table 1), much higher than yields of 53.8–
62.0% over H2SO4(entries 3&4 in Table 1), 45.7–66.0% over
Amberlyst-15 (entries 5 and 6 in Table 1), and 53.3% over ben-
zene sulfonic acid (C6H5-SO3H, entry 7 in Table 1) under the
same reaction conditions. These results confirm the excellent
catalytic properties in the dehydration of fructose to HMF over
P-SO3H-154 catalyst.More importantly, even if the presence
of water is as high as 10 wt%, P-SO3H-154 still gives high HMF
yield (>99.0%, entry 8 in Table 1). In comparison, the other
solid acid catalysts, Amberlyst-15, P-SO3H-44, P-SO3H-105, and
P-SO3H-125, show relatively low HMF yield with LA as by-prod-
uct (entry 9 in Table 1, Figure S12).
To understand the large differences in catalytic properties
between P-SO3H-154 and Amberlyst-15, the dependences of
catalytic yields of HMF and LA on time over both catalysts
have been performed (Figure 2c, Figure S13). Notably, LA ap-
pears as a by-product at the beginning of the reaction over
Amberlyst-15 catalyst. After reaction for 5 h, LA yield reaches
11.2%, and the highest yield of HMF is obtained (64.1%).
When the reaction time is over 5 h, the HMF yield gradually
decreases with reaction time, accompanied by increasing LA
yield. A similar phenomenon has also been reported in the
H2SO4-catalyzed system.However, HMF appears as a sole
product in the reaction process over P-SO3H-154 catalyst, indi-
cating that the hydration of HMF does not occur (Figure S14).
In addition, the P-SO3H-154 catalyst, which was directly filtered
from the reaction system, did not show any signal associated
with water, as observed in the
This result indicates that P-SO3H-154 could isolate water mole-
cules produced from the dehydration of fructose, preventing
the hydration process and generating a high HMF yield (Fig-
ure S16). It is also noted that P-SO3H-154 show a relatively
slower reaction rate than the conventional acid catalysts such
as Amberlyst-15 and C6H5-SO3H, and increasing the fructose
concentration in the starting solution could not effectively
change the reaction rate (Figure S17). This phenomenon might
be because the sample superhydrophobicity strongly influen-
ces the interaction between the catalyst and polar fructose.
However, in our case, a sole product of HMF was formed in
the conversion of fructose over P-SO3H-154, while the by-prod-
uct of LA was formed from the further hydration of HMF over
Amberlyst-15 and C6H5-SO3H catalysts. Considering the great
importance of product selectivity in biomass conversion and
an acceptable reaction rate, the P-SO3H-154 catalyst was pre-
ferred as an acid catalyst for the conversion of fructose to
HMF, instead of the conventional solid acids such as Amber-
lyst-15 and C6H5-SO3H (Figures S18). Moreover, leaching of
acidic sites in P-SO3H-154 is almost negligible. For example,
after treating P-SO3H-154 in THF–DMSO solvent for 10 h at
1008C and filtering the solid catalyst, the liquor is inactive for
the dehydration of fructose. More importantly, we performed
the dehydration of fructose to HMF in a continuous fixed-bed
1H NMR spectrum (Figure S15).
reactor over P-SO3H-154 catalyst using a 2.0 wt% fructose solu-
tion as feed (Figure 3). In the catalytic tests, no obvious de-
crease in HMF yield (42.0–48.0%) was observed for a 45 h reac-
tion. We also applied the dehydration of fructose to produce
HMF in a 20 g scale over low loading of P-SO3H-154 catalyst
(0.9 g), resulting in a yet higher HMF yield of greater than
99.0%. These results confirm the good catalytic properties of
P-SO3H-154 for production of HMF from fructose.
To realize the one-pot conversion of glucose to HMF, com-
bined catalysts of both solid acid and solid base were em-
ployed.[12,14]The solid bases with controllable wettability (P-VI-
x) were synthesized from copolymerization of divinylbenzene,
1-vinylimidazole, and N,N-methylenediacrylamide (Figure S19,
Figure 3. Production of HMF in a continuous system: A) Scheme of the
fixed-bed reactor. B) Dependence of HMF yield on time in the fixed-bed re-
actor; dehydration of fructose to HMF over P-SO3H-154 catalyst (&). Reac-
tion conditions: reaction temperature at 1008C, reactor volume at 10 mL,
0.2 g of P-SO3H-154, 2.0 wt% fructose in THF–DMSO solution (weight ratio
of 1.5), reaction flux 0.2 mLmin?1. The HMF selectivity is over 99.0% during
the reaction process. One-pot conversion of glucose to HMF over the com-
bined P-SO3H-154 and P-VI-0 catalysts (~). Reaction conditions: reaction
temperature at 1008C, reactor volume at 10 mL, 0.3 g of P-VI-0 and 0.15 g of
P-SO3H-154, 5.0 wt% glucose in THF–DMSO solution (weight ratio of 1.5), re-
action flux 0.2 mLmin?1. The HMF selectivity is at about 94.0% during the
reaction process, with by-products of levoglucosan and some others.
Figure 4. A) Photograph of P-VI-0 dispersed in water; B) Contact angle of
a water droplet on the surface of P-VI-0.
? 2014 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim ChemSusChem 2014, 7, 402–406 404
Figure 4). These samples have rich porosity and basic sites
(Table S2, Figures S20–S22).
Table 2 shows the one-pot conversion of glucose to HMF
over various combined acid-base catalysts. Notably, the pure
base catalyst (P-VI-0) or pure acid catalyst (P-SO3H-154) is
almost inactive for the formation of HMF (entries 1 and 2 in
Table 2). However, the combined catalysts could efficiently cat-
alyze the conversion of glucose to HMF. In particular, the com-
bined catalysts of superhydrophobic P-SO3H-154 and superhy-
drophilic P-VI-0 generated a HMF yield as high as 95.4%
(entry 3 in Table 2, Figure S23). In contrast, the combined cata-
lysts of superhydrophobic P-SO3H-154 and superhydrophobic
P-VI-150 generated a HMF yield of 76.2% (entry 5 in Table 2).
This phenomenon might be a result of the higher activity of P-
VI-0 in isomerization of glucose to fructose than that of P-VI-
150, which results from the better wettability of glucose solu-
tion on P-VI-0 than on P-VI-150 (Figure S24). Notably, the com-
bined catalysts of superhydrophobic P-SO3H-154 and relatively
hydrophobic P-VI-108 generated a HMF yield of 94.0%, which
is only slightly lower than that over the combined catalyst of
P-SO3H-154 and P-VI-0 (95.4%, entry 4 in Table 2). However, the
combined catalysts of P-SO3H-154 and P-VI-0 catalysts were
still preferable for the reaction, because the P-SO3H-154 and P-
VI-0 catalysts could be easily separated from each other after
the catalytic reactions based on their quite different water
wettabilities. In contrast, the separation of superhydrophobic
P-SO3H-154 and hydrophobic P-VI-108 from each other is diffi-
cult (Figure S25). Additionally, when very low loading of P-
SO3H-154 and P-VI-0 catalysts was used, a high yield of HMF at
92.8% was still obtained after a relatively long reaction time
(entry 9 in Table 2). In contrast, the combined catalysts of P-VI-
0 and Amberlyst-15 exhibited a HMF yield of only 58.1%,
which is strongly related to the hydration of HMF in the pres-
ence of hydrophilic Amberlyst-15 (Figure S26).
More importantly, we performed the one-pot conversion of
glucose to HMF in a continuous fixed-bed reactor over the
combined catalysts of P-SO3H-154 and P-VI-0 using a 5.0 wt%
glucose solution as feed (Figure 3). In a 45 h time reaction, no
obvious decrease of HMF yield (34.1–38.9%) was observed, in-
dicating the high stability and good recyclability of the P-
SO3H-154 and P-VI-0 catalysts. Additionally, we applied the
combined catalysts of P-SO3H-154 and P-VI-0 to a 20 g-scale
production of HMF from glucose, resulting in a yield of 89.5%
over low loading of catalysts (0.45 g of P-SO3H-154 and 0.9 g
of P-VI-0). These results offer suggest that the combined super-
hydrophobic P-SO3H-154 and superhydrophilic P-VI-0 catalysts
are preferable in the conversion of glucose to HMF. Moreover,
the isolation of HMF from the reaction system is also impor-
tant. By means of carbon-black adsorption, the isolated HMF
yield could reach 76.0% in our case.[6f]Further conversion of
HMF to a low boiling point species might be helpful for the
product isolation,[7a]which is still under investigation.
In summary, we have rationally designed and successfully
synthesized a series of solid acid and base catalysts with differ-
ent wettabilities for the selective production of HMF. Nearly all
fructose is converted to HMF as a sole product using the su-
perhydrophobic acid P-SO3H-154 catalyst. The catalyst with su-
perhydrophobicity completely prevents hydration of HMF. Fur-
thermore, the combined catalysts of superhydrophobic acid P-
SO3H-154 and superhydrophilic base P-VI-0 efficiently catalyzed
the one-pot conversion of glucose to HMF, resulting in a yield
as high as 95.4%. The strategy of combined acid-base catalysts
with controllable wettability opens a door for designing and
developing novel catalysts with both high activities and strong
selectivities for conversion of biomass in the future.
Materials: DMSO, EtOH, THF, H2SO4, glycerol, DMF, acetone, fruc-
tose, benzenesulfonic acid, glucose, and ethylbenzene were ob-
tained from Beijing Chemical Agents Company. Sodium p-styrene
sulfonate, divinylbenzene, azobisisobutyronitrile, 1-vinylimidazole,
Amberlyst-15, and HMF were purchased from Sigma–Aldrich Co.
N,N-methylenediacrylamide was obtained from Tianjin Chemical
Agents Company. The water concentration in DMSO and THF sol-
vent without any treatment were both higher than 0.5 mmolmL?1.
The carbon black BP2000 was supplied from CABOT Company.
Computational method: The free energy simulations were per-
formed by using the FIREBALL package, which is mainly a density
functional theory (DFT) based approach.The umbrella sampling
module was implemented in FIREBALL package,[16c]which allowed
us to carry out the molecular dynamic simulation along certain re-
action distance as we desired. The detailed documentation of the
computational approach has been listed in the Supplementary In-
Synthesis of P-SO3H-x: P-SO3H-x samples were synthesized from
copolymerization of divinylbenzene and sodium p-styrene sulfo-
nate (Table S3), where x stands for water contact angles on the sur-
face of solids. By adjusting the sample composition, the P-SO3H-
x samples with controllable wettability were obtained. In a typical
run for the synthesis of P-SO3H-154, divinylbenzene (2.0 g) and azo-
bisisobutyronitrile (0.05 g) were added into the mixture of THF
(20 mL) and water (2 mL), then sodium p-styrene sulfonate (0.17 g)
was added. After stirring for 3 h at room temperature, the mixture
was transferred to autoclave and treated at 1008C for 24 h. After
evaporation of the solvent at room temperature for 2 days, the ob-
tained solid sample was dispersed in EtOH (10 mL) and ion-ex-
changed using H2SO4(1m) at room temperature for 24 h. Finally, P-
SO3H-154 was obtained. In comparison, P-SO3H-44 was synthesized
Table 2. The catalytic yields of HMF from the conversion of glucose over
HMF yield [%]
[a] Reaction conditions: 100 mg of glucose, 50 mg of solid acid catalyst,
100 mg of solid base catalyst, 5 g of THF–DMSO mixed solvent (weight
ratio at 1.5), 1008C for 10 h. The major by-products were levoglucosan,
LA, and FA; [b] 10 mg of solid acid, 20 mg of solid base in 26 h.
? 2014 Wiley-VCH Verlag GmbH&Co. KGaA, WeinheimChemSusChem 2014, 7, 402–406 405
from the sulfonation of porous polydivinylbenzene according to Download full-text
a previous report.
Synthesis of P-VI-x: P-VI-x samples were synthesized from copoly-
merization of divinylbenzene, 1-vinylimidazole, and N,N-methylene-
diacrylamide (Table S3, x stands for water contact angles on the
solid surface). By adjusting the sample composition, the P-VI-x sam-
ples with controllable wettability were obtained. In a typical run
for the synthesis of P-VI-150, divinylbenzene (2.0 g) and azobisiso-
butyronitrile (0.05 g) was introduced into ethyl acetate (20 mL), fol-
lowed by the addition of 1-vinylimidazolate (0.2 g). After stirring
for 3 h at room temperature, the mixture was transferred to auto-
clave and treated at 1008C for 24 h. After evaporation of the sol-
vent at room temperature for 2 days and washing with ethyl ace-
tate twice, the solid sample of P-VI-150 was finally obtained.
The details for the sample characterization and catalytic tests are
shown in the Supporting Information.
We thank Prof. Mark E. Davis for helpful discussion on sample
synthesis and catalytic data, and Prof. Tao Zhang for analyzing
the product. This work is supported by National Natural Science
Foundation of China (21273197, U1162201, and 21173255), Na-
tional High-Tech Research and Development program of China
(2013AA065301), and Fundamental Research Funds for the Cen-
tral Universities (2013XZZX001). We would like to acknowledge
support from the Petroleum Research Fund of the American
Chemical Society (Grant PRF51290-ND6) and from the Program
for Theoretical and Computational Chemistry, Basic Energy Scien-
ces in the Office of Science of the US Department of Energy (DE-
FG02-10ER16164). We also thank the West Virginia University
High Performance Computing Facility funded in part by the Na-
tional Science Foundation Research Infrastructure Improvement
cooperative agreement (EPS-1003907) for computational time.
Keywords: 5-hydroxymethylfurfural · biomass · fructose ·
glucose · superhydrophilic base
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Received: October 9, 2013
Revised: October 27, 2013
Published online on January 7, 2014
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