Chemocatalytic Conversion of Cellulosic Biomass to Methyl Glycolate, Ethylene Glycol, and Ethanol

Article abstract of DOI:10.1002/cssc.201601714

Production of chemicals and fuels from renewable cellulosic biomass is important for the creation of a sustainable society, and it critically relies on the development of new and efficient transformation routes starting from cellulose. Here, a chemocatalytic conversion route from cellulosic biomass to methyl glycolate (MG), ethylene glycol (EG), and ethanol (EtOH) is reported. By using a tungsten-based catalyst, cellulose is converted into MG with a yield as high as 57.7 C % in a one-pot reaction in methanol at 240 °C and 1 MPa O₂, and the obtained MG can be easily separated by distillation. Afterwards, it can be nearly quantitatively converted to EG at 200 °C and to EtOH at 280 °C with a selectivity of 50 % through hydrogenation over a Cu/SiO₂ catalyst. By this approach, the fine chemical MG, the bulk chemical EG, and the fuel additive EtOH can all be efficiently produced from renewable cellulosic materials, thus providing a new pathway towards mitigating the dependence on fossil resources.

Full text of DOI:10.1002/cssc.201601714

Accepted Article
Title: Chemocatalytic Conversion of Cellulosic Biomass to Methyl
Glycolate, Ethylene Glycol and Ethanol
Authors: Gang Xu, Aiqin Wang, Jifeng Pang, Xiaochen Zhao, Jinming
Xu, Nian Lei, Jia Wang, Mingyuan Zheng, Jianzhong Yin, and
Tao Zhang
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: ChemSusChem 10.1002/cssc.201601714
Link to VoR: http://dx.doi.org/10.1002/cssc.201601714
A Journal of
www.chemsuschem.org

ChemSusChem
10.1002/cssc.201601714
COMMUNICATION
Chemocatalytic Conversion of Cellulosic Biomass to Methyl
Glycolate, Ethylene Glycol and Ethanol
Gang Xu,[a,b] Aiqin Wang,* Jifeng Pang, Xiaochen Zhao, Jinming Xu, Nian Lei, Jia Wang,
[a]
[a]
[a]
[a]
[a]
[a]
[
a]
[b]
[a]
Mingyuan Zheng, Jianzhong Yin and Tao Zhang*
Dedication ((optional))
Abstract: Production of chemicals and fuels from renewable
cellulosic biomass is important to construction of a sustainable
society, and it critically relies on the development of new and
efficient transformation route starting from cellulose. Here we report
a chemocatalytic conversion route from cellulosic biomass to methyl
glycolate (MG), ethylene glycol (EG) and ethanol (EtOH). Under the
catalysis of tungsten-based catalyst, cellulose is converted into MG
hydrothermal stability of the catalysts. The latter concern
necessitates the employment of more durable yet expensive
noble metal catalysts to replace nickel.[
11a]
Considering that
glycolaldehyde is a key intermediate in the EG formation from
cellulose (Scheme 1a),[11] and it is highly reactive towards
alcohols to form esters,[12] we envisage that by coupling the two
reactions in one pot, i.e., cellulose conversion to glycolaldehyde
and esterification of glycolaldehyde with methanol, methyl
glycolate (MG) would be produced directly from cellulose
(Scheme 1b).
with a yield as high as 57.7 C% in one-pot reaction in methanol at
o
2
40 C and 1 MPa oxygen, and the obtained MG can be easily
separated by distillation and then nearly quantitatively converted to
o
o
EG at 200 C and to EtOH at 280 C with a selectivity of 50%
through hydrogenation over Cu/SiO catalyst. By this approach, fine
2
chemical MG, bulk chemical EG, and fuel additive EtOH can all be
efficiently produced from renewable cellulosic materials, thus
providing a new avenue to mitigating the dependence on fossil
resources.
The high demand for energy and the increasing concerns
over global climate change have motivated great interest in
utilization of lignocellulosic biomass, a renewable, abundant and
nonedible carbon source, as an alternative to fossil resources for
production of fuels and chemicals.[1] The recalcitrance of
cellulose, however, presents great challenges in oriented
depolymerization under mild and environmentally benign
conditions. Traditional mineral acid-catalyzed hydrolysis of
cellulose suffers from serious environmental issues while the
emerging enzymatic hydrolysis is still a costly and low-efficiency
method.[ Chemocatalytic approach, on the other hand, offers
new opportunities in one-pot conversion of cellulose to
chemicals, especially when a multi-functional catalyst is used to
promote a series of cascade reactions towards the target
product meanwhile minimizing side reactions arising from
unstable intermediates.[3-9] Previously, we reported the one-pot
conversion of cellulose to ethylene glycol (EG) in water with Ni-
Scheme 1. Chemocatalytic conversion of cellulose via intermediate
glycolaldehyde. (a) One-pot conversion of cellulose to ethylene glycol; (b) one-
pot conversion of cellulose to methyl glycolate; (c) Methyl glycolate conversion
to ethylene glycol and ethanol via hydrogenation.
2]
MG is not only an important intermediate widely used in
synthesis of biodegradable polymers;[12a] more importantly, it can
be regarded as a platform molecule for production of EG and
ethanol (EtOH),[13] as shown in Scheme 1c. Currently, the
production of MG relies exclusively on fossil resources and
involves multi-step reactions and complicated separation
processes. We conceive that once MG can be produced from
renewable lignocellulose, a new chemocatalytic, nonenzymatic
route for the production of cellulosic EtOH will be available, that
is highly desirable and even competitive to the current high-cost
enzyme-catalyzed cellulosic EtOH. The key to this route is the
one-pot conversion of cellulose to MG in methanol.
W
2
C/AC catalyst.[10] In spite of a high yield of EG obtained, the
employment of water media not only adds more cost to the
separation and purification of the polyols due to the formation of
azeotropic mixtures, but also presents greater challenges to the
[
a]
Dr. G. Xu, Prof. Dr. A. Q. Wang, Dr. J. F. Pang, Dr. X. C. Zhao, Dr.
J. M. Xu, Mr. N. Lei, Dr. J. Wang, Dr. M. Y. Zheng, Prof. Dr. T.
Zhang
Depolymerization of cellulose in methanol has been reported
to proceed smoothly in methanol, producing methyl glucoside,
methyl levulinate, as well as methyl lactate, and the
predominance of one specific ester was strongly dependent on
the catalyst as well as the reaction temperature.[14] Generally,
glucoside and levulinate are formed at relatively milder reaction
State Key Laboratory of Catalysis, iChEM (Collaborative Innovation
Center of Chemistry for Energy Materials)
Dalian Institute of Chemical Physics, Chinese Academy of Sciences
457 Zhongshan Road, Dalian 116023, China
E-mail: aqwang@dicp.ac.cn
taozhang@dicp.ac.cn
[
b]
Dr. G. Xu and Prof. Dr. J. Z. Yin
State Key Laboratory of Fine Chemicals, School of Chemical
Machinery, Dalian University of Technology
Dalian 116024, China
[14a,b]
conditions with the promotion of Brønsted acid catalysts,
while the lactate requires a higher reaction temperature due to
the involvement of C-C bond cleavage and it is usually catalyzed
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
This article is protected by copyright. All rights reserved.

ChemSusChem
10.1002/cssc.201601714
COMMUNICATION
by Lewis acid such as Sn-substituted zeolites, mixed
Bronsted/Lewis acid such as Sn-triflate catalyst, or basic
catalysts.[14c-e] In comparison with these three esters, MG has
never been reported to yield in an appreciable amount from
cellulose although glycolic acid was reported to produce from
cellulose or bio-oil.[15] We suppose that the challenge for the
selective transformation of cellulose to MG lies in the kinetic
manipulation, which should enable the selective C-C cleavage of
cellulose-derived sugars and the subsequent conversion of
glycolaldehyde to proceed in such a manner that their reaction
rates match well with each other; otherwise, side reactions will
rapidly occur due to extremely unstable glycolaldehyde. In our
earlier studies, we found that W-containing compounds were a
type of highly active and selective catalyst for the C-C cleavage
of cellulose to produce glycolaldehyde,[11] and that a higher
activation energy required for the C-C cleavage (140-150
kJ/mol) allowed the reaction to proceed more selectively at
elevated temperatures (above 200 oC).[16] The knowledge
established on the cellulose conversion to EG leads us to
believe that the same catalysts would be effective for the
selective formation of MG directly from cellulose as long as the
solvent is changed from water to methanol.
To our delight, in O
2
atmosphere all the W-containing catalysts
behaved selective towards MG (Fig. 1b); the best result was
obtained with a physical mixture of WO and CMK-3 (noted as
WO +CMK-3 wherein CMK-3 is a mesoporous carbon material
) as the catalyst which afforded MG yield as high as 57.7 C%.
Following the WO +CMK-3 catalyst, pure WO as well as the
supported W C/CMK-3 also gave excellent MG yields (> 50 C%),
almost doubled that in N . Even those heteropoly acid catalysts
(HPW and HSiW), which were selective for methyl levulinate in
due to their strong Brønsted acidity, evolved to become
selective for MG in Of particular interest is the
disappearance of 1,1,2-trimethoxyethane in elevated
pressure while it was the major product in either N or air
x
x
[
17]
x
x
2
2
N
2
2
O .
O
2
2
atmosphere (Table S1). These results demonstrate that oxygen
atmosphere play an important role in directing the reaction
towards MG, either by manipulating the reaction kinetics or by
changing the catalyst property or both. In addition to oxygen
pressure, other operation parameters also affected the MG
selectivity; slightly lower reaction temperature (e.g., 220 oC) or
reduced amount of catalyst appeared to favor methyl lactate
while the presence of water in methanol solvent decreased the
MG selectivity by forming more methyl acetate (Figs. S5-S7).
To clarify the reaction pathway from cellulose to MG as well
as the key role of O
2
, we then studied the reaction kinetics over
a
90
b
90
80
70
60
50
40
30
20
10
0
Methyl acetate
1,1,2-Trimethoxyethane
Methyl lactate
Methyl glycolate
Methyl 2-hydroxybutanoate
Methyl levulinate
Methyl acetate
Methyl lactate
Methyl glycolate
Methyl levulinate
WO catalyst in N and O , respectively. Comparing the products
x
2
2
80
70
60
50
40
30
20
10
0
profiles with the reaction temperature and time in different
atmospheres (Figs. 1c, 1d), one can clearly see the following
differences: (i) (hemi)acetalization products of glycolaldehyde
such as 2,2-dimethoxyethanol and1,1,2-trimethoxyethane were
absent in O
2
while they were formed in significant amounts in N
2
,
x
4
T
W
iW
3
x
4
T
3
WO
2WO
AM
HP
HS
WO
WO
2WO
H
A
M
HP
W
HSiW
WO
H
x+CMK-3
2
C/CMK-3
W2C/CMK-3
suggesting that they could be converted into MG in O
2
, and this
W
WO
c
d
assumption was proved by control experiments (Table S2); (ii)
60
50
40
30
20
10
0
60
50
40
30
20
10
0
2
40
00
240
200
160
120
80
Methyl glycolate
Methyl lactate
2
the reaction rate in O is two orders of magnitude faster than in
2
1
,1,2-Trimethoxyethane
Methyl glycolate
Methyl lactate
1,1,2-Trimethoxyethane
Methyl acetate
Methyl levulinate
α-D-Methyl glucoside
Methyl acetate
Methyl levulinate
α-D-Methyl glucoside
160
120
80
40
0
2 W 2 W 2
N (7.7 mmol/mol .s in O vs. 0.07 mmol/mol .s in N ),
demonstrating that oxygen accelerates the whole reaction, not
merely the final oxidation step; (iii) the MG selectivity is greatly
enhanced in O via suppressing a variety of side reactions,
2
particularly the formation of 1,1,2-trimethoxyethane, 2,2-
dimethoxyethanol and methyl 2-hydroxybutanoate; (iv) when the
Methyl 2-hydroxybutanoate
,2-Dimethoxyethanol
2
40
0
20
40 60 80 100 120 140 160 180 200 220 240
Time (min)
20 40 60 80 100 120 140 160 180 200 220 240
Time (min)
Figure 1. Catalytic performances of various W-based catalysts (a, b) and the
evolution of products with the reaction time (c, d) under N (a, c) and O (b, d)
: 0.5 g cellulose, 4×10-4 mol W, 50 mL
. Reaction conditions in O : 0.5 g
2
reaction proceeds in N , the concurrent increase of 1,1,2-
trimethoxyethane and MG in almost equal amounts with the
temperature rise indicates the former cannot transform into the
latter in the absence of O . Moreover, methyl glucoside was
2
detected while glucose was not irrespective of atmosphere,
indicating the former is more stable than the latter. [18] Our
2
2
atmosphere. Reaction conditions in N
2
o
methanol, 260 C, 2 h, 800 r/min, 2 MPa N
2
2
cellulose, 4×10 mol W, 50 mL methanol, 240 oC, 2 h, 800 r/min, 1 MPa O
AMT, HPW and HSiW are abbreviations of ammonium metatungstate,
40 and H SiW12 40, respectively. The yield in Y axis is based on
carbon (C%)
-
4
2
.
H
3
PW12O
4
O
control experiments with glucose and methyl glycoside
respectively as the substrates showed that both of them could
be transformed into MG, in almost identical yields (Table S2).
Taking these results together, we propose the reaction pathway
from cellulose to MG shown in Scheme S1. It consists of three
tandem reactions: (1) methanolysis of cellulose to glucose and
glycoside, and the latter can transform to the former reversably,
Our practice began with the reaction of cellulose in methanol
in N atmosphere with various tungstic compounds as the
catalysts. However, the MG yield was not satisfactory (< 30 C%)
although the catalysts and reaction conditions were optimized
2
(
Fig. 1a, and Figs. S1-S3). Meanwhile, the formation of an
(
2) C-C cleavage of glucose via retro-aldol condensation to
appreciable amount of 1,1,2-trimethoxyethane suggests that the
MG formation reaction proceed too slowly to match with the
preceding C-C cleavage reaction. Considering that oxygen could
greatly accelerate the transformation of glycolaldehyde to MG
even without any catalyst (Fig. S4), we consequently turn to
conducting the reaction of cellulose under oxygen atmosphere.
produce glycolaldehyde as well as its (hemi)acetalization
products 2,2-dimethoxyethanol and 1,1,2-trimethoxyethane, and
(
3) conversion of glycolaldehyde as well as its (hemi)acetols in
to form MG. Among the three steps, the first step to form
glucose is the slowest step; upon its formation, the subsequent
C-C cleavage proceeds rapidly under the catalysis of WO
O
2
x
This article is protected by copyright. All rights reserved.

ChemSusChem
10.1002/cssc.201601714
COMMUNICATION
because it is kinetically favored at elevated temperatures.[16]
Immediately after the C-C cleavage, the further transformation of
glycolaldehyde to MG occurs rapidly with the promotion of both
poorly crystallized WO
and WO
surface,[19] or through a
3
x
homogenous mechanism by forming dissolved WO
hydrate,[11] or both. The homogeneous mechanism could be
approved by the reusability test of W C/CMK-3 catalyst. As
x
or its
acidic WO
x
and O
2
atmosphere.
2
shown in Fig. S9, the catalyst could be reused for at least 6
times without appreciable deactivation; in the 7th and 8th runs the
MG yield declined gradually. Concomitantly, significant leaching
of W component occurred (W content dropped from 34.4 wt% to
a
1
7.3 wt%) and the
crystallized WO phase after the consecutive 8 runs (Fig. 2a).
These results suggest that upon the poorly crystallized WO or
WO becomes highly crystallized in supercritical methanol
2
W C phase transformed into highly
W2C/CMK-3 fresh
3
W
2
C/CMK-3 used in N
2
3
x
W
W
W
2C (JCPDS 00-035-0776)
solvent during the reaction, they are robust against leaching
meanwhile the number of coordinately unsaturated sites is
reduced greatly, both of which lead to activity loss. Fortunately,
the dissolved W species could be recovered by distillation of the
products.
One issue associated with the practical application is the
catalyst adaptability to raw biomass feedstock. To our delight,
when raw cellulosic biomass materials, such as birch, cornstalk,
and miscanthus were simply pretreated with hot water and then
used as the feedstock, satisfactory MG yields (birch gave MG
yield as high as 49.1 C%, cornstalk gave 33.3 C% and
miscanthus gave 46.2 C%) were obtained (Table S3).
Compared with the conversion of pure microcellulose, the lignin
component in the biomass did not much negatively affect the
conversion of cellulose; instead, it was also converted into
phenolic compounds (Fig. S10) in accordance with the previous
report.[20]
2
C/CMK-3 used in O
2
2
1st
8th
2C/CMK-3 used in O
WO
used in O2
WO3 (JCPDS 01-085-2460)
X fresh
WOX
10
20
30
40
50
60
70
80
2
Theta (degree)
b
1
00
100
80
60
40
20
0
8
6
4
2
0
0
0
0
0
Conversion
Ethylene glycol
Ethanol
2
-Butanol
n-Propanol
1
80
200
220
240
260
280
C)
300
320
340
Figure 2. XRD patterns of W
2
C/CMK-3 and WOx catalysts before and after
Temperature (
o
the reaction in different atmosphere (a) and SEM images of the W
d) and WOx (c, e) before (b, c) and after the reaction (d, e).
2
C/CMK-3 (b,
d
1
00
100
80
60
40
20
0
Conversion
Ethanol
8
6
4
2
0
0
0
0
0
2-Butanol
n-Propanol
The nature of the catalytically active sites was probed by
characterizations of the most efficient catalysts W C/CMK-3 and
WO before and after the reaction. Both XRD and electron
microscopy (SEM and TEM) revealed that W C nanoparticles on
the CMK-3 support were transformed into needle-like WO
phase after the reaction in O (Fig.2 and Fig. S8). Concurrent
with this phase transformation was a great enhancement in both
activity and selectivity to MG. Akin to the WO derived from W C,
the highly active WO (x = 2.8) catalyst used here was also
2
x
2
0
2
4
6
8
10 12 14 16 18 20 22 24
Time (h)
3
2
Figure 3. Hydrogenation of MG into EG and EtOH. (a) TEM micrograph of
Cu/SiO
2
catalyst; (b) temperature dependence of the product distribution; (c)
3
2
o
time course of MG conversion and product distribution at 200 C; (d) Time
course of MG conversion and product distribution at 280 oC. Reaction
conditions: 10% MG in THF solution was continuously fed into a fixed bed
x
poorly crystallized, with a needle-like morphology and a large
2
reactor packed with
2
mL catalyst. The liquid flow rate was
2
ml/h
gas flow rate was 33.3 ml/min
2
/MG = 46.
surface area (126 m /g). Both of them are quite different from
-
1
corresponding to a LHSV of 1 h and the H
2
the commercial WO
area (17 m /g), and poorly active in reaction. All these results
3
which is highly crystallized, low-surface-
-1
corresponding to a GHSV 1000 h , H
2
3 x
point to the poorly crystallized, large-surface-area WO and WO
as the active phase in the reaction. They catalyze the reaction
either via the low-coordination sites which are abundant on the
The MG obtained from renewable biomass was further
tested for hydrogenation over Cu/SiO catalyst with a fixed bed
2
This article is protected by copyright. All rights reserved.

ChemSusChem
10.1002/cssc.201601714
COMMUNICATION
o
reactor under the reaction condition of 3 MPa H
The Cu/SiO
2
, 180 ~ 340 C.
807; c) N. Wei, J. Quarterman, S. R. Kim, J. H. D. Cate, Y. S. Jin, Nat.
Commun. 2013, 4, 2580.
2
catalyst was prepared with ammonia evaporation
hydrothermal method[13c] and the resultant Cu nanoparticles with
[3]
a) Y. Wang, et al., Nat. Commun. 2013, 4, 2141; b) Q. N. Xia, Q. Cuan,
X. H. Liu, X. Q. Gong, G. Z. Lu, Y. Q. Wang, Angew. Chem. Int. Ed.
an average size of 2-3 nm are highly dispersed on the SiO
support (Fig.3a). Over this catalyst, MG was almost
2
2014, 53, 9755-9760.
[
4] a) T. L. Lohr, T. J. Marks, Nat. Chem. 2015, 7, 477-482; b) V. Froidevaux,
o
o
quantitatively converted to EG at 200 C, and to EtOH at 280 C
with a selectivity of 50% (Fig. 3b). The catalyst was stable during
C. Negrell, S. Caillol, J. P. Pascault, B. Boutevin, Chem. Rev. 2016,
DOI: 10.1021/acs.chemrev.6b00486.
2
4 h-run, steadily producing EG and EtOH at their respective
[5]
a) L. Bui, H. Luo, W. R. Gunther, Y. Román-Leshkov, Angew. Chem. Int.
Ed. 2013, 52, 8022-8025; b) X. D. Li, P. Jia, T. F. Wang, ACS Catal.
optimum temperatures (Fig. 3c-d). Thus, MG serves as a
platform molecule for the production of EG and EtOH from
renewable cellulosic biomass. In comparison with the one-pot
production of EG from cellulose we developed earlier,[10,11] the
current cellulose-MG-EG two-step route has the advantage of
saving separation cost (boiling points of the main and side
products are listed in Table S4), and is more flexible by the facile
switching between valuable fine chemical MG and bulk chemical
EG depending on the market. More importantly, the two-step
2
016, 6, 7621-7640.
a) M. Shiramizu, F. D. Toste, Angew. Chem. Int. Ed. 2013, 52, 12905-
2909; b) G. S. Zhang, M. M. Zhu, Q. Zhang, Y. M. Liu, H. Y. He, Y.
[
6]
7]
1
Cao, Green Chem. 2016, 18, 2155-2164.
[
a) C. Luo, S. Wang, H. Liu, Angew. Chem. Int. Ed. 2007, 46, 7636-7639;
b) N. Villandier, A. Corma, Chem. Commun. 2010, 46, 4408-4410.
a) Y. P. Huo, H. Q. Zeng, Y. G. Zhang, ChemSusChem 2016, 9, 1078-
1080; b) F. Jérôme, G. Chatel, K. D. O. Vigier, Green Chem. 2016, 18,
3903-3913.
[8]
[
9] a) H. Kobayashi, H. Kaiki, A. Shrotri, K. Techikawara, A. Fukuoka, Chem.
Sci. 2016, 7, 692-696; b) A. Fukuoka, P. L. Dhepe, Angew. Chem. Int.
Ed. 2006, 45, 5161-5163.
cellulose-MG-EtOH approach provides
a non-fermentation
pathway to the renewable cellulosic ethanol which are currently
the only established biofuel as an additive up to 10% in
gasoline.[21]
[10] N. Ji, T. Zhang, M. Y. Zheng, A. Q. Wang, H. Wang, X. D. Wang, J. G.
Chen, Angew. Chem. Int. Ed. 2008, 47, 8510-8513.
In summary, we have developed a new chemocatalytic
approach for production of MG, EG, and EtOH from renewable
lignocellulose. In the first step, MG was produced up to a yield of
[
11] a) Z. J. Tai, J. Y. Zhang, A. Q. Wang, M. Y. Zheng, T. Zhang, Chem.
Commun. 2012, 48, 7052-7054; b) A. Q. Wang, T. Zhang, Acc. Chem.
Res., 2013, 46, 1377-1386; c) R. Y. Sun, T. T. Wang, M. Y. Zheng, W.
Q. Deng, J. F. Pang, A. Q. Wang, X. D. Wang, T. Zhang, ACS Catal.
57.7 C% from the one-pot transformation of cellulose in
2015, 5, 874-883; d) Y. Liu, C. Luo, H. Liu, Angew. Chem. Int. Ed. 2012,
methanol with the catalysis of WOx and the assistence of
oxygen. Then, both EG and EtOH were produced with a high
selectivity in the second step via hydrogenation/hydrogenolysis
of MG. This approach will pave a new way for the biomass
conversion since MG can serve as a new biomass platform
molecule for production of a variety of bulk and fine chemicals.
51, 3249-3253.
[
12] a) T. Hayashi, T. Inagaki, N. Itayama, H. Baba, Catal. Today 2006, 117,
10-213; b) L. L. Zhang, et al., Green Chem. 2013, 15, 2680-2684.
13] a) Y. Sun, H. Wang, J. H. Shen, H. C. Liu, Z. M. Liu, Catal. Commun.
009, 10, 678-681; b) J. W. Zheng, H. Q. Lin, Y. N. Wang, X. L. Zheng,
2
[
2
X. P. Duan, Y. Z. Yuan, J. Catal. 2013, 297, 110-118; c) J. L. Gong, H.
R. Yue, Y. J. Zhao, S. Zhao, L. Zhao, J. Lv, S. P. Wang, X. B. Ma, J.
Am. Chem. Soc., 2012, 134, 13922-13925.
[
14]
a) D. Q. Ding, J. X. Xi, J. J. Wang, X. H. Liu, G. Z. Lu, Y. Q. Wang,
Green Chem. 2015, 17, 4037-4044; b) W. P. Deng, M. Liu, Q. H. Zhang,
X. S. Tan, Y. Wang, Chem. Commun. 2010, 46, 2668-2670; c) M. S.
Holm, S. Saravanamurugan, E. Taarning, Science 2010, 328, 602-605;
d) F. de Clippel, et al., J. Am. Chem. Soc. 2012, 134, 10089-10101; e)
M. Dusselier, R. D. Clercq, R. Cornelis, B. F. Sels, Catal. Today 2017,
Acknowledgements
This work was financially supported by the National Natural
Science Foundation of China (21373206, 21376045, 21306191,
2
1673228, 21690084, and U1662130) and the Strategic Priority
Research Program of the Chinese Academy of Sciences
XDB17020100).
279, 339-344.
[
15]
16]
a) J. Z. Zhang, X. Liu, M. Sun, X. H. Ma, Y. Han, ACS Catal. 2012, 2,
(
1
698-1702; b) P. Y. Dapsens, C. Mondelli, B. T. Kusema, R. Verel, J.
Pérez-Ramírez, Green Chem. 2014, 16, 1176-1186; c) M. Dusselier, P.
V. Wouwe, S. D. Smet, R. D. Clercq, L. Verbelen, P. V. Puyvelde, F. E.
D. Prez, B. F. Sels, ACS Catal. 2013, 3, 1786-1800.
Keywords: Methyl glycolate • Ethylene glycol • Ethanol •
supported catalysts • biomass
[
a) J. Y. Zhang, B. L. Hou, A. Q. Wang, Z. L. Li, H. Wang, T. Zhang,
AIChE J. 2014, 60, 3804-3813; b) J. Y. Zhang, B. L. Hou, A. Q. Wang,
Z. L. Li, H. Wang, T. Zhang, AIChE J. 2015, 61, 224-238; c) G. H. Zhao,
M. Y. Zheng, J. Y. Zhang, A. Q. Wang, T. Zhang, Ind. Eng. Chem. Res.
[
1]
a) C. O. Tuck, E. Pérez, I. T. Horváth, R. A. Sheldon, M. Poliakoff,
Science 2012, 337, 695-699; b) J. S. Luterbacher, J. M. Rand, D. M.
Alonso, J. Han, J. T. Youngquist, C. T. Maravelias, B. F. Pfleger, J. A.
Dumesic, Science 2014, 343, 277-280; c) H. G. Cha, K. S. Choi, Nat.
Chem. 2015, 7, 328-333; d) C. Li, X. Zhao, A. Wang, G. W. Huber, T.
Zhang, Chem. Rev. 2015, 115, 11559-11624; e) P. A. Jacobs, M.
Dusselier, B. F. Sels, Angew. Chem. Int. Ed. 2014, 53, 8621-8626; f) J.
P. Lange, Angew. Chem. Int. Ed. 2015, 54, 13186-13197; g) R. Rinaldi,
R. Jastrzebski, M. T. Clough, J. Ralph, M. Kennema, P. C. A. Bruijnincx,
B. M. Weckhuysen, Angew. Chem. Int. Ed. 2016, 55, 8164-8215; h) W.
Liu, W. Mu, Y. L. Deng, Angew. Chem. Int. Ed. 2014, 53, 13558-13562.
a) K. Hirajima, M. Taguchi, T. Funazukuri, Ind. Eng. Chem. Res. 2015,
2
013, 52, 9566-9572; d) Y. Liu, C. Luo, H. C. Liu, Angew. Chem. Int. Ed.
012, 51, 3249-3253.
2
[
[
[
[
17]
18]
19]
Y. Zhai, Y. Wan, Y. Cheng, Y. Shi, F. Zhang, B. Tu, D. Zhao, J. Porous
Mater. 2008, 15, 601-611.
L. Q. Xue, K. Cheng, H. X. Zhang, W. P. Deng, Q. H. Zhang, Y. Wang,
Catal. Today 2016, 274, 60-66.
J. Wang, X. C. Zhao, N. Lei, L. Li, L. L. Zhang, S. T. Xu, S. Miao, X. L.
Pan, A. Q. Wang, T. Zhang, ChemSusChem 2016, 9, 784-790.
20] a) Q. Song, F. Wang, J. Y. Cai, Y. H. Wang, J. J. Zhang, W. Q. Yu, J.
Xu, Energy Environ. Sci. 2013, 6, 994-1007; b) R. Ma, W. Y. Hao, X. L.
Ma, Y. Tian, Y. D. Li, Angew. Chem. Int. Ed. 2014, 53, 7310-7315.
21] R. F. Service, Science 2010, 329, 784-785.
[
2]
54, 6052-6059; b) M. E. Himmel, S. Y. Ding, D. K. Johnson, W. S.
Adney, M. R. Nimlos, J. W. Brady, T. D. Foust, Science 2007, 343, 804-
[
This article is protected by copyright. All rights reserved.

ChemSusChem
10.1002/cssc.201601714
COMMUNICATION
Entry for the Table of Contents (Please choose one layout)
Layout 1:
COMMUNICATION
[
a,b]
[a]
A new chemocatalytic conversion
route from cellulosic biomass to
methyl glycolate, ethylene glycol and
ethanol has been developed. In the
first step methyl glycolate is produced
up to a yield of 57.7 C% from the one-
pot transformation of cellulose in
methanol with the catalysis of WOx
and the assistence of oxygen, then
methyl glycolate is further
Gang Xu,
Aiqin Wang,* Jifeng
Pang,[ Xiaochen Zhao, Jinming Xu,
Nian Lei,[ Jia Wang,[a] Mingyuan
Zheng,[a] Jianzhong Yin[b] and Tao
Zhang*[a]
a]
[a]
[a]
a]
Page No. – Page No.
Chemocatalytic Conversion of
Cellulosic Biomass to Methyl
Glycolate, Ethylene Glycol and
Ethanol
hydrogenated in the second step to
ethylene glycol and ethanol over a
2
Cu/SiO catalyst.
This article is protected by copyright. All rights reserved.