Please do not adjust margins
ChemComm
Page 4 of 4
DOI: 10.1039/C7CC05487D
COMMUNICATION
Journal Name
4
C. Z. Li, X. C. Zhao, A. Q. Wang, G. W. Huber and T. Zhang,
Chem. Rev., 2015, 115, 11559.
E. Furimsky, Appl. Catal. A: Gen., 2000, 199, 147.
A. G. Sergeev, J. F. Hartwig, Science, 2011, 332, 439.
Y. L. Ren, M. J. Yan, J. J. Wang, Z. C. Zhang, K. S. Yao, Angew.
Chem. Int. Ed., 2013, 52, 12674.
Having identified the catalyst with the best performance for
the hydrogenolysis of inert aryl C−O bonds, we also tested the
catalytic ability of WxC@CS-3h in hydrogenolysis of various
aromatic ethers under optimal reaction conditions. The
5
6
7
efficient cleavage of aryl C−O bonds is an important process
for the manufacturing of value-added aromatic compounds
such as PhOH and benzene in good yields, particularly because
these are the most abundant linkages in oxygen-rich
8
9
M. Wang, H. Shi, D. M. Camaioni, J. A. Lercher, Angew.
Chem. Int. Ed., 2017, 56, 2110.
P. Alvarez-Bercedo, R. Martin, J. Am. Chem. Soc., 2010, 132,
17352.
performance of WxC@CS-3h for hydrogenolysis of various 10 S. Kusumoto, K. Nozaki, Nat. Commun., 2015, 6, 6296.
lignocellulosic biomass.1,2,36 Table
2 shows the catalytic
11 H. J. Xu, B. Yu, H. Y. Zhang, Y. F. Zhao, Z. Z. Yang, J. L. Xu, B. X.
Han and Z. M. Liu, Chem. Commun., 2015, 51, 12212.
12 J. He, C. Zhao, J. A. Lercher, J. Am. Chem. Soc., 2012, 134,
20768.
13 W. Schutyser, S. V. dan Bosch, J. Dijkmans, S. Turner, M.
Meledina, G. V. Tendeloo, D. P. Debecker, B. F. Sels,
ChemSusChem, 2015, 8, 1805.
aromatic ethers. Diphenyl ether was ultimately converted into
benzene and PhOH through direct hydrogenolysis of the aryl
C−O bond without other side reactions. Almost full conversion
and high selectivity for benzene were achieved when anisole
was used as the substrate. Similarly, the reaction with
phenetole and veratrole as the substrates showed high
conversion and considerable selectivity for benzene as the
final product although a small amount of PhOH was detected
14 W. J. Song, Y. S. Liu, E. Barath, C. Zhao, J. A. Lercher, Green
Chem., 2015, 17, 1204.
owing to the hydrogenolysis of the weaker aliphatic C
−
O
15 H. H. Fang, J. W. Zheng, X. L. Luo, J. M. Du, A. Roldan, S. Leoni
and Y. Z. Yuan, Appl. Catal. A: Gen., 2017, 529, 20.
16 M. Zaheer, R. Kempe, ACS Catal., 2015, 5, 1675.
17 M. Zaheer, J. Hermannsdörfer, W. P. Kretschmer, Günter
Motz, and R. Kempe, ChemCatChem, 2014, 6, 91.
18 Q. F. Gong, Y. Wang, Q. Hu, J. G. Zhou, R. F. Feng, P. N.
Duchesne, P. Zhang, F. J. Chen, N. Han, Y. F. Li, C. H. Jin, Y. G.
Li and S. T. Lee, Nat. Commun., 2016, 7, 13216.
19 R. W. Gosselink, D. R. Stellwagen and J. H. Bitter, Angew.
Chem. Int. Ed., 2013, 52, 5089.
20 S. A. W. Hollak, R. W. Gosselink, D. S. van Es and J. H. Bitter,
ACS Catal., 2013, 3, 2837.
21 A. L. Jongerius, R. W. Gosselink, J. Dijkstra, J. H. Bitter, P. C. A.
Bruijnincx and B. M. Weckhuysen, ChemCatChem, 2013, 5,
2964.
22 C. Z. Li, M. Y. Zheng, A. Q. Wang and T. Zhang, Energy
Environ. Sci., 2012, 5, 6383.
23 R. Ma, K. Cui, L. Yang, X. L. Ma and Y. D. Li, Chem. Commun.,
2015, 51, 10299.
24 C. J. Chen, W. S. Lee and A. Bhan, Appl. Catal. A: Gen., 2016,
510, 42.
25 A. Villa, S. Campisi, C. Giordano, K. Otte and L. Prati, ACS
Catal., 2012, 2, 1377.
26 J. G. Chen, Chem. Rev., 1996, 96, 1477.
27 W. S. Lee, Z. S. Wang, R. J. Wu, A. Bhan, J. Catal., 2014, 319,
44.
28 M. M. Sullivan, C. J. Chen and A. Bhan, Catal. Sci. Technol.,
2016, 6, 602.
29 S. Han, D. H. Youn, M. H. Lee and J. S. Lee, ChemCatChem,
2015, 7, 1483.
30 X. F. Yang, Y. C. Kimmel, J. Fu, B. E. Koel, J. G. Chen, ACS
Catal., 2012,2,765.
31 Y. K. Hong, D. W. Lee, H. J. Eom and K. Y. Lee, Appl. Catal. B:
Environ., 2014, 150–151, 438.
32 S. K. Wu, P. C. Lai, Y. C. Lin, H. P. Wan, H. T. Lee and Y. H.
Chang, ACS Sustain. Chem. Eng., 2013, 1, 349.
33 Y. C. Lin, C. L. Li, H. P. Wan, H. T. Lee, C. F. Liu, Energy &
Fuels, 2011,25,890.
34 J. M. Sun, A. M. Karim, H. Zhang, L. Kovarik, X. H. S. Li, A. J.
Hensley, J. S. McEwen, Y. Wang, J. Catal., 2013, 306, 47.
35 J. R. Kitchin, J. K. Nørskov, M. A. Barteau, J. G. Chen, Catal.
Today, 2005, 105, 66.
36 M. Saidi, F. Samimi, D. Karimipourfard, T. Nimmanwudipong,
B. C. Gates, M. R. Rahimpour, Energy Environ. Sci., 2014, 7,
103.
bonds. The results of the hydrogenolysis of 2,6-
dimethoxyphenol were similar to that of GUA, displaying a
93.3% conversion and 86.3% PhOH selectivity at 350 oC
through the cleavage of two aryl Ar−OMe bonds.
In conclusion, the WxC@CS-t catalysts with identified phase
compositions are successfully synthesized through controlled
carburization of the phenolic polymers prepared by
polycondensation. Unlike other metal catalysts favoring the
saturation of aromatic rings, the optimized WxC@CS-3h
catalyst shows particularly selective cleavage of aryl C–O
bonds even at a high temperature and high H2 pressure. The
WxC@CS-3h efficiently catalyzes the hydrogenolysis of Ar–
OMe bond in GUA to yield PhOH instead of hydrogenolysis the
weaker aliphatic ArO–Me bonds, preventing the formation of
the hydrogenated ring products. This catalyst also exhibits
excellent capability for the hydrogenolysis of various aromatic
ethers, resulting in a high yield of aromatic compounds such as
PhOH and benzene. Therefore, we envision that our findings
into the one-pot prepared WxC@CS-t may serve as a new
approach for the design of active carbide catalysts to
demonstrate the importance of the active phases and the
mode of carbon insertion by carburization for hydrogenolysis
catalysis.
This work was supported by the National Key Research and
Development Program of China (2017YFA0206801), the
Natural Science Foundation of China (21403178, 91545115,
and 21473145), the Program for Innovative Research Team in
Chinese Universities (IRT_14R31), the Fundamental Research
Funds for the Central Universities (20720170024 and
20720170026), and the Natural Science Foundation of Fujian
Province of China (2017J05027).
Notes and references
1
2
3
J. Zakzeski, P. C. A. Bruijinincx, A. L. Jongerius and B. M.
Weckhuysen, Chem. Rev., 2010, 110, 3552.
J. C. Serrano-Ruiz and J. A. Dumesic, Energy Environ. Sci.,
2011, 4, 83.
A. J. Ragauskas, G. T. Beckham, M. J. Biddy, R. Chandra, F.
Chen, M. F. Davis, B. H. Davison, R. A. Dixon, P. Gilna, M.
Keller, P. Langan, A. K. Naskar, J. N. Saddler, T. J. Tschaplinski,
G. A. Tuskan and C. E. Wyman, Science, 2014, 344, 709.
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins