Graphene-supported Au-Pd bimetallic nanoparticles with excellent catalytic performance in selective oxidation of methanol to methyl formate

Article abstract of DOI:10.1039/c3cc43948h

Graphene supported Au-Pd bimetallic nanoparticles exhibit high catalytic activity in methanol selective oxidation, with a methanol conversion of 90.2% and selectivity of 100%, to methyl formate at 70 °C, owing to the synergism of Au and Pd particles as well as the strong interaction between graphene and Au-Pd nanoparticles.

Full text of DOI:10.1039/c3cc43948h

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DOI: 10.1039/C3CC43948H
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ARTICLE TYPE
Graphene-supported Au-Pd bimetallic nanoparticles with excellent
catalytic performance in selective oxidation of methanol to methyl
formate†
a,c
a
b
a
a
a
Ruiyi Wang, Zhiwei Wu, Chengmeng Chen, Zhangfeng Qin,* Huaqing Zhu, Guofu Wang, Hao
a
a,c
a,c
a
a
5
Wang, Chengming Wu, Weiwen Dong, Weibin Fan and Jianguo Wang*
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
DOI: 10.1039/b000000x
1
1,12
Graphene supported Au-Pd bimetallic nanoparticles exhibit
high catalytic activity in methanol selective oxidation, with a
methanol conversion of 90.2% and selectivity of 100% to
methyl formate at 70 °C, owing to the synergism of Au and
Pd particles as well as the strong interaction between
graphene and Au-Pd nanoparticles.
Ru and AuꢀPt have been dispersed on graphene,
impressive catalytic behaviors in various reactions.
showing
1
0
50
In this work, AuꢀPd bimetallic nanoparticles were dispersed
uniformly on graphene through the depositionꢀprecipitation
method (ESI†); the resultant materials are denoted as Aumꢀ
Pd /Graphene, where m and n are the weight percentage
loadings of Au and Pd, respectively. With Au ꢀPd /Graphene
n
m
n
In recent years, with the flourishing of methanol economy, 55 as the catalyst in methanol oxidation, high conversion of
1
2
2
3
3
4
4
5
0
5
0
5
0
5
methanol has become an important platform feedstock for the
synthesis of various fuels and chemicals. Among the diverse
routes for methanol conversion and utilization, the selective
oxidation of methanol to methyl formate (MF) is attractive as
a simple and environmentally benign process to get valuable
methanolꢀdownꢀstream products. A wide array of catalysts are
used in methanol oxidation, including nonꢀnoble metal oxides
methanol and selectivity to MF was achieved under mild
conditions, which has been scarcely reported in open literature.
The graphene support is obtained by vacuum promoted
thermal expansion of graphene oxide (GO); it owns a high
surface area and high density of surface oxygenꢀcontaining
6
6
7
0
5
0
13
functionalities, which is beneficial to get highly dispersed
metal particles, as proved by the N sorption isotherms and
XRD patterns of Au ꢀPd /Graphene (Figs. S2 and S3, ESI†).
2
(
SnO ꢀMo O , V O ꢀTiO and Fe O /SiO ) and heteropoly
m
n
2
2
3
2
5
2
2
3
2
1
The SEM image of Au2.0ꢀPd1.0/Graphene (Fig. 1a) reveals
that the AuꢀPd nanoparticles are uniformly dispersed on the
graphene support in spherical shape. The TEM image (Fig. 1b)
indicates that the nanoparticles tend to take a twinned
structure. The particle size estimated from randomly selecting
300 typical particles is in the range of 2–15 nm with an
average of 7.5 nm (Fig. 1c). In the HRTEM image (Fig. 1d),
Au (111) planes with dꢀspacing of 0.233 nm and Pd planes
acids; however, their performances (in terms of methanol
conversion and selectivity to MF at low temperature) are still
somewhat insufficient for practical application. Recently,
Wittstock et al. reported that nanoporous AuꢀAg catalyst by
dealloying of AuꢀAg alloys shows superior activity for
2
methanol oxidation to MF at room temperature; since then,
methanol oxidation over bimetallic catalysts under mild
conditions has attracted extensive attentions.
(
111) with dꢀspacing of 0.221 nm are further identified;
Ever since Haruta’s pioneer work in preparing gold
3
nanoparticles for CO oxidation, gold catalysts and goldꢀM
moreover, Pd and Au tend to be staggered together. Kesavan
et al. also found that AuꢀPd bimetallic nanoparticles form
bimetallic catalysts are in the spotlight because of their
4
,5
excellent catalytic behavior at low temperature. Especially, 75 twinned particles with (111) planes on active carbon, which is
9
active in toluene oxidation. The oxidation of methanol in this
work may also take place at the junction of the goldꢀpalladium
twined particles, where Au and Pd nanoparticles have
complementary effect on electron exchange, just as that
the bimetallic goldꢀpalladium catalysts are becoming the most
important and exciting ones, which were widely used in the
6
7
8
oxidation of CO, alcohols, methane to methanol, and
9
toluene. In our previous work, we also found that AuꢀPd/SiO2
catalyst is active for methanol oxidation to MF, with a 80 observed in CO oxidation over AuꢀPd/SiO
and in formic acid,
2
6
,14
methanol conversion of 25.3% and selectivity of 100% to MF
glyoxal and glucose oxidation over AuꢀPd/C.
10
Fig. 2 shows the XPS spectra of various catalysts. For
at 100 °C; moreover, the nature of supports has a great
impact on the performance of AuꢀPd bimetallic catalysts.
Graphene, a single layer of carbon atoms densely packed
Au2.0/Graphene in Au 4f region, the peaks around the binding
0
energies (BEs) of 84.1 and 87.7 eV are attributed to Au 4f
7/2
into a hexagonal honeycomb network, is a promising catalyst 85 and 4f5/2, respectively, while the peaks at 85.4 and 89.4 eV are
δ+ 15
support owing to its large surface area, special structure and
assigned to cationic gold species Au . Compared with that
1
1
0
unique conductive properties.
Many monometallic and
of Au2.0/Graphene, the Au 4f7/2 peaks of Au2.0ꢀPd1.0/Graphite,
Au2.0ꢀPd1.0/CNTs and Au2.0ꢀPd1.0/Graphene shift to lower BEs,
bimetallic nanoparticles, such as Pd, Au, Pt, Ag, AuꢀPd, Pdꢀ
This journal is © The Royal Society of Chemistry [year]
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DOI: 10.1039/C3CC43948H
5
i.e. from 84.1 eV to 83.9, 83.7 and 83.6 eV, respectively. For
–0.1 eV shift for Pd 3d peak in AuꢀPd/SiO2 and Hsu et al.
Pd1.0/Graphene in the Pd 3d region, the peaks at 342.6 and
observed a –0.5 eV shift for Pd 3d peak in Au@Pd coreꢀ
shell nanoparticle. In current work, a maximum shift of –0.5
5/2
2
+
0
17
3
37.2 eV are attributed to Pd species; Pd species is not
identified, as no reducing agent is used during the catalyst 25 eV for Au 4f7/2 and –0.6 eV for Pd 3d peak in Au2.0
preparation. Compared with Pd1.0/Graphene, the peaks for Pd1.0/Graphene is observed, much larger than those for other
ꢀ
5
2
+
Pd
in Au2.0ꢀPd1.0/Graphite, Au2.0ꢀPd1.0/CNTs and Au2.0
ꢀ
AuꢀPd catalysts, which means a especially strong synergism
between Au and Pd in the AuꢀPd/Graphene catalysts.
Moreover, as graphene support is rich in π electrons and Au
Pd1.0/Graphene also moves to lower BEs, i.e. from 342.6 eV
to 342.4, 342.2 and 342.0 eV, respectively.
18
30
species may act as an electronic promoter for Pd, the transfer
of these electrons to the electronꢀdeficient Pd sites and
thereon the reduction of PdO is then promoted, resulting in
0
abundant Pd species in Au2.0ꢀPd1.0/Graphene (Fig. 2).
The Au L3 edge EXAFS results (Fig. S5, ESI†) indicate
that the bond length RAuꢀAu of Au2.0ꢀPd1.0/Graphene are greatly
decreased, compared with that of Au foil, which should be
attributed to the partial alloying of AuꢀPd besides to the lattice
contraction from surface tension; part of Pd atoms has entered
35
19
the Au lattice, as RPdꢀPd is much shorter than RAuꢀAu
.
40
Table 1 Catalytic performance of various AuꢀPd catalysts in methanol
oxidation to MF
a
b
b
c
Entry Support Loading (wt.%) Temp. xMeOH
s
MF
i
(%)
CO
TOF
ꢀ1
Au
2.0
2.0
2.0
2.0
ꢀꢀ
Pd
1.0
1.0
1.0
1.0
ꢀꢀ
(°C) (%)
2
(s )
1
2
3
4
5
6
7
8
9
Al
TiO
CNTs
Graphite
Graphene
Graphene
Graphene
Graphene
Graphene
2
O
2
3
70
40
75
75
ꢀꢀ
74.9 41.2 58.8 0.011
33.8 19.7 80.3 0.002
17.1 100.0 0.0 0.072
22.1 100.0 0.0 0.092
ꢀꢀ
ꢀꢀ
ꢀꢀ
0
10
Fig. 1 SEM image (a), TEM image (b), particle size distribution (c), and
2.0
ꢀꢀ
ꢀꢀ
80
70
80
75
80
40
70
5.0 100.0 0.0 0.040
9.9 100.0 0.0 0.088
18.4 100.0 0.0 0.154
24.3 100.0 0.0 0.138
33.7 100.0 0.0 0.117
24.7 100.0 0.0 0.103
90.2 100.0 0.0 0.377
HRTEM image (d) of the Au2.0ꢀPd1.0/Graphene catalyst.
1.0
0.5
1.0
2.0
1.0
1.0
1.0
2.0
1.0
1.0
1.0
2.0
2.0
2.0
4.0
a)
0
Au 4f
87.7
89.4
84.1 Au
10 Graphene
11 Graphene
12 Graphene
δ+
Au
85.4
(5)
1
3
Graphene
85 100.0 87.9 12.1 0.368
70 75.5 16.3 83.7 0.026
(
4)
3)
14 Graphene
(
(a) Reaction conditions (ESI†): the flow rate of feed stream (6.4 vol.%
CH OH + 70.2 vol.% O + balanced Ar) is 42.8 ml/min; 60 mg catalyst is
used for those with carbonaceous support (equivalent to a gas hourly
3
2
(1)
ꢀ1
ꢀ1
45
space velocity (GHSV) of 42,800 mlꢁg ꢁh ) and 700 mg catalyst is used
ꢀ1 ꢀ1
92
90
88
86
84
82
for AuꢀPd/Al
2
O
3
and AuꢀPd/TiO
2
(a GHSV of 3,669 mlꢁg ꢁh ).
. Methanol conversion is
Binding energy (eV)
(b) The effluents consist of CH
3
OH, MF and CO
2
b) Pd 3d
340.2
334.8
determined by xMeOH = (nMeOH,feed–nMeOH,outlet)/nMeOH,feed×100% and the
i i,outlet
selectivity to each product by s = (n ×k )/(nMeOH,feed–nMeOH,outlet)×100%,
0
Pd
342.6
337.2
i
2
Pd
+
(5)
(4)
(3)
50 where k
i
is the carbon number in one molecule of product i (ESI†).
(c) Turnover frequency (TOF), the number of methanol molecules
converted to MF per active site and second, is estimated on the basis of
surface Au and Pd atoms (ESI†).
Table 1 shows the performance of the AuꢀPd catalysts with
55 different supports and Au and Pd loadings. AuꢀPd/Al O and
(2)
2
3
AuꢀPd/TiO display very low activity in methanol oxidation
2
348
344
340
336
332
Binding energy (eV)
and poor selectivity to MF (Entries 1 and 2); however, the
catalysts of AuꢀPd supported on carbonaceous supports,
especially on graphene (Entries 8–14 and Fig. S6, ESI†),
exhibit much higher activity and better selectivity to MF. Pure
graphene is nonꢀactive for methanol oxidation (Entry 5) and
the single metal Pd or Au supported on graphene also shows
very low activity (Entries 6 and 7) under current conditions.
Comparatively, bimetallic AuꢀPd catalysts supported on
graphene exhibit much higher activity (Entries 8–14). These
suggest that a synergism effect is present between Au and Pd
and graphene as a support is superior to Al O , TiO , graphite
Fig. 2 Au 4f (a) and Pd 3d (b) XPS spectra of the Au2.0/Graphene (1),
Pd1.0/Graphene (2), Pd1.0/Graphite (3), Au2.0ꢀPd1.0/CNTs (4), and Au2.0
Pd1.0/Graphene (5) catalysts.
ꢀ
6
0
1
5
The much lower BEs of both Au and Pd in Au2.0
ꢀ
Pd1.0/Graphene should be attributed to the electron exchange
between Au and Pd, i.e. a synergism between Au and Pd
The span of the BE shifts in the XPS spectra
reflects the extent of this synergism between AuꢀPd bimetallic
6
,16
nanoparticles.
65
20
nanoparticles; Xu et al. reported a –0.4 eV shift for Au 4f and
2
3
2
2
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DOI: 10.1039/C3CC43948H
c
and carbon nanotubes (CNTs) to embody this synergism effect.
Graphene used here as a support is able to anchor the AuꢀPd
nanoparticles with a uniform dispersion during the reaction.
University of Chinese Academy of Sciences, Beijing 100049, PR China
† Electronic Supplementary Information (ESI) available: More
Experimental Details and Results of Catalyst Characterization and
Reaction Tests. See DOI: 10.1039/b000000x/
60
20
The catalytic performance of AuꢀPd/Graphene is also
related to the loadings of Au and Pd and reaction temperature
1
(a) A. Mamoru, J. Catal. 1982, 77, 279; (b) A.S. Elmi, E. Tronconi,
C. Cristiani, J.P. Gomez, P. Forzatti, G. Busca, Ind. Eng. Chem. Res.,
1989, 28, 387; (c) C. Wang, R.J. Willey, J. Catal., 2001, 202, 211; (d)
H.C. Liu, E. Iglesia, J. Catal., 2004, 223, 161.
5
(
Table 1 and Fig. S7, ESI†). Au2.0ꢀPd1.0/Graphene performs
best in methanol oxidation to MF, with a methanol conversion
of 90.2% and selectivity of 100% to MF at 70 °C (Entry 12);
2
3
4
A. Wittstock, V. Zielasek, J. Biener, C.M. Friend, M. Bäumer,
Science, 2010, 327, 319.
M. Haruta, N. Yamada, T. Kobayashi, S. Lijima, J. Catal., 1989, 115,
301.
(a) G.J. Huctchings, Chem. Commun., 2008, 10, 1148; (b) H. Wang,
H.Q. Zhu, Z.F. Qin, F.X. Liang, G.F. Wang, J.G. Wang, J. Catal.,
–
1
it gives a turnover frequency (TOF) of 0.377 s at 70 °C,
–
1
1
1
2
2
3
3
4
4
5
0
5
0
5
0
5
0
5
0
much higher than the AuꢀAg catalyst with a TOF of 0.11 s
for methanol oxidation at 80 °C reported by Wittstock et al.,
2
suggesting that the AuꢀPd/Graphene catalyst here with much
lower fraction of noble metals is yet more effective for
methanol oxidation to MF than the pure AuꢀAg catalyst.
2
009, 264, 154.
5
6
7
B. Xu, X. Liu, J. Haubrich, R.J. Madix, C.M. Friend, Angew. Chem.
Int. Ed., 2009, 48, 4206.
J. Xu, T. White, P. Li, C.H. He, J.G. Yu, W.K. Yuan, Y.F. Han, J.
Am. Chem. Soc., 2010, 132, 10398.
(a) D.I. Enache, J.K. Edwards, P. Landon, B. Solsona, A.F. Carley,
A.A. Herzing, M. Watanabe, C.J. Kiely, D.W. Knight, G.J.
Hutchings, Science, 2006, 311, 362; (b) D. Wang, A. Villa, F. Porta,
D. Su, L. Prati, Chem. Commun., 2006, 18, 1956.
A long term test of 48 h was conducted over the Au2.0
ꢀ
Pd1.0/Graphene catalyst at 70 °C (Fig. S8, ESI†). It exhibits a
good stability throughout the test; the conversion of methanol
remains above 85% and the selectivity to MF is fixed at 100%.
During the test, only MF and methanol are detected in the
effluents; by comparing the mass of methanol consumed with
that of the products formed, a well carbon mass balance is
obtained; the fraction of unclaimed carbonꢀcontaining
products is less than 4%, suggesting that the formation of any
other byproducts is negligible (Table S2, ESI†).
A comparison of the TEM image of the spent catalyst with
that of the fresh one indicates that the particle size is only
increased slightly from 7.4 to 7.9 nm and the Au L3 edge
EXAFS results also suggest that the local structural
environment of Au is almost unchanged after the reaction
(Figs. S5 and S9, ESI†), suggesting that the AuꢀPd bimetallic
nanoparticles and twined AuꢀPd alloy structure are stable
during the methanol oxidation under current conditions.
8
9
M.H.A. Rahim, M.M Forde, R.L. Jenkins, C. Hammond, Q. He, N.
Dimitratos, J.A. LopezꢀSanchez, A.F. Carley, S.H. Taylor, D.J.
Willock, D.M. Murphy, C.J. Kiely, G.J. Hutchings, Angew.Chem. Int.
Ed., 2012, 51, 1.
L. Kesavan, R. Tiruvalam, M.H.A. Rahim, M.I.B. Saiman, D.I.
Enache, R.L. Jenkins, N. Dimitratos, J.A.L. Sanchez, S.H. Taylor,
D.W. Knight, C.J. Kiely, G.J. Hutching, Science, 2011, 331, 195.
R.P. Shi, H. Wang, H.Q. Zhu, Z.W. Wu, Z.F. Qin, W.B. Fan, J.G.
Wang, J. Fuel. Chem. Tech., 2012, 40, 985.
1
1
0
1
H. Chen, Y. Li, F.B. Zhang, G.L. Zhang, X.B. Fan, J. Mater. Chem.,
2
011, 21, 17658.
12 (a) X.M. Chen, G.H. Wu, J.M. Chen, X. Chen, Z.X. Xie, X.R. Wang,
J. Am. Chem. Soc., 2011, 133, 3693; (b) R. Muszynski, B. Seger,
P.V. Kamat, J. Phys. Chem. C, 2008, 112, 5263; (c) P. Kundu, C.
Nethravathi, P.A. Deshpande, M. Rajamathi, G. Madras, N.
Ravishankar, Chem. Mater., 2011, 23, 2772; (d) S. Liu, J.Q. Tian, L.
Wang, H.L. Li, Y.W. Zhang, X.P. Sun, Macromolecules, 2010, 43,
10078; (e) R. Awasthi, R.N. Singh, Carbon, 2013, 51, 282; (f) S.
Zhang, Y. Shao, H.G. Liao, J. Liu, I.A. Aksay, G. Yin, Y. Lin, Chem.
Mater., 2011, 23, 1079.
Au2.0ꢀPd1.0/Graphene catalyst performs excellently in the
selective oxidation of methanol to MF by molecular oxygen,
which may be attributed to the following factors: Firstly, the
graphene has a large surface area allowing a fine and uniform
dispersion of the AuꢀPd bimetallic nanoparticles, which may
provide abundant active sites. Secondly, the AuꢀPd
nanoparticles tend to form a twinꢀparticles structure with
Au&Pd (111) planes, which will be of benefit to the catalytic
reaction. Thirdly, a synergism is present between the Au and
Pd particles with electronic exchange. Lastly, the conductive
characteristic of graphene may promote the electronic
exchange between Au and Pd and even supply π electrons to
1
3
(a) C.M. Chen, Q. Zhang, M.G. Yang, C.H. Huang, Y.G. Yang, M.Z.
Wang, Carbon, 2012, 50, 3572; (b) C. Xu, X. Wang, J. Zhu, J. Phys.
Chem. C, 2008, 112, 19841.
14 (a) S. Hermans, A. Deffernez, M. Devillers, Appl. Catal. A, 2011,
95, 19; (b) G. Zhang, Y. Wang, X. Wang, Y. Chen, Y. Zhou, Y.
3
Tang, L. Lu, J. Bao, T. Lu, Appl. Catal. B, 2011, 102, 614.
D.A. Bulushev, I. Yuranov, E.I. Suvorova, P.A. Buffat, L. Kiwiꢀ
Minsker, J. Catal. 2004, 224, 8.
1
5
16 Y.S. Lee, Y.S. Jeon, Y.D. Chung, K.Y. Lim, C.M. Whang, S.J. Oh, J.
Korea Phys. Soc., 2000, 37, 451.
17 C. Hsu, C. Huang, Y. Hao, F. Liu, Electrochem. Comm., 2012, 23,
2
1
AuꢀPd nanoparticles,
which can then strengthen the
1
33.
synergism of AuꢀPd and enhance the catalytic performance.
The authors thank Dr. S. Zhang and Prof. Y. Huang et al. in
Shanghai Synchrotron Radiation Facility for the help in
EXAFS measurements as well as the financial supports of
National Basic Research Program of China (2011CB201400),
Natural Science Foundation of China (21227002, 21203231)
and Shanxi Province of China (2011011006ꢀ3, 2012021005ꢀ3).
1
8
(a) M. Sankar, N. Dimitratos, P.J. Miedziak, P.P. Wells, C.J. Kiely,
G.J. Hutchings, Chem. Soc. Rev., 2012, 41, 8099; (b) P.
Kittisakmontree, B. Pongthawornsakun, H. Yoshida, S. Fujita, M.
Arai, J. Panpranot, J. Catal., 2013, 297, 155.
1
2
2
9
0
1
X.W. Teng, Q. Wang, P. Liu, W.Q. Han, A. Frenkel, W. Wen, N.
Marinkovic, J.C. Hanson, J.A. Rodriguez, J. Am. Chem. Soc., 2008,
1
30, 1093.
C.M. Chen, Q. Zhang, J.Q. Huang, W. Zhang, X.C. Zhao, C.H.
Huang, F. Wei, Y.G. Yang, M.Z. Wang, D.S. Su, J. Mater. Chem.,
2
012, 22, 13947.
Notes and references
K.S. Subrahmanyam, A.K. Manna, S.K. Pati, C.N.R. Rao, Chem.
Phys. Lett., 2010, 497, 70.
a
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry,
5
5
Chinese Academy of Sciences, P.O. Box 165, Taiyuan, Shanxi 030001, PR
China. E-mail: qzhf@sxicc.ac.cn (Z. Qin); iccjgw@sxicc.ac.cn (J. Wang)
Key Laboratory of Carbon Materials, Institute of Coal Chemistry, the
b
Chinese Academy of Sciences, P.O. Box 165, Taiyuan 030001, PR China
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Graphic Abstract
Graphene-supported Au-Pd bimetallic nanoparticles with excellent
catalytic performance in selective oxidation of methanol to methyl
formate
a,c
a
b
a,*
a
Ruiyi Wang , Zhiwei Wu , Chengmeng Chen , Zhangfeng Qin , Huaqing Zhu , Guofu
a
a
a,c
a,c
a
a,*
Wang , Hao Wang , Chengming Wu , Weiwen Dong , Weibin Fan , Jianguo Wang
a
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of
Sciences, P.O. Box 165, Taiyuan, Shanxi 030001, PR China
b
Key Laboratory of Carbon Materials, Institute of Coal Chemistry, the Chinese Academy of
Sciences, P.O. Box 165, Taiyuan 030001, PR China
c
University of Chinese Academy of Sciences, Beijing 100049, PR China
2
CH
3
OH
Auδ+
Au0
Pd0
1
/2O
2
Pd2+
2
MF+H O
Graphene support improves the electrons
exchange between Au and Pd and even
transfers electrons with the AuꢀPd system
Graphene supported Au-Pd bimetallic nanoparticles exhibit excellent catalytic performance
in selective oxidation of methanol to methyl formate at low temperature.
*
Corresponding authors. Tel.: +86-351-4046092; Fax: +86-351-4041153.
E-mail address: qzhf@sxicc.ac.cn (Z. Qin); iccjgw@sxicc.ac.cn (J. Wang)
Postal Address: Prof. Jianguo WANG; Prof. Zhangfeng QIN
State Key Laboratory of Coal Conversion
Institute of Coal Chemistry, Chinese Academy of Sciences
P. O. Box 165
Taiyuan, Shanxi 030001
PR China