Page 7 of 8
Journal Name
Green Chemistry
DOI: 10.1039/C5GC00326A
laboratory17. The distillate was then washed with KHCO3,
extracted with
Collaborative Innovation Center of Chemistry for Energy Materials,
a
n
ꢀhexane and concertrated. The resulted mixture CAS Key Laboratory of Urban Pollutant Conversion, Anhui Province
was analyzed by GCꢀMS and GC. Phenols took about 72 wt % Key Laboratory of Biomass Clean Energy, Department of Chemistry,
of the result mixture, while the other 28 wt% of the mixture University of Science and Technology of China, Hefei 230026 (China)
cannot be identified (Figure S4 and Table S2). Hydrogenolysis b College of Chemical Engineering, Nanjing Forestry University, Nanjing
of these primitive phenols over RuꢀWOx/SiAl catalyst formed a 210037 (china)
mixture of arenes and saturated alkanes, together with some
†
Footnotes should appear here. These might include comments
unreacted phenols. Quantitative analysis of the resulted mixture relevant to but not central to the matter under discussion, limited
by GC revealed that a yield of 36 wt% of the final products experimental and spectral data, and crystallographic data.
could be detected. Among these products, arenes took about 75 Electronic Supplementary Information (ESI) available: [details of any
wt%, alkanes 10 wt% and the remained phenols and other by supplementary information available should be included here]. See
products 15 wt% (Table 3 and Table S3). Overall, these results DOI: 10.1039/c000000x/
further demonstrated that the RuꢀW type catalysts were
promising candidates for the selective cleavage of phenols (1) J. Zakzeski, P. C. A. Bruijnincx, A. L. Jongerius, B. M. Weckhuysen,
derived from lignin to yield arenes.
Chem. Rev. 2010, 110, 3552.
(2) (a) A. oledano, L. Serrano, A. M. Balu, R. Luque, A. Pineda, J. Labidi,
ChemSusChem 2013, 6, 529. (b) Q. Song, F. Wang, J. Cai, Y. Wang, J.
Zhang, W. Yu, J. Xu, Energy Environ. Sci., 2013, 6, 994.
(3) E. Furimsky, Appl. Catal., 2000, 199, 147.
Table 3 Hyrogenolysis of the Primitive phenols extracted from
pyrolysis lignin.
Primitive phenol 100.0 mg
Identified phenols
72 wt%
Unknow mixture
28 wt%
(4) (a) A. G. Sergeev, J. F. Hartwig, Science 2011, 332, 439. (b) J. He, C.
Zhao, J. A. Lercher, J. Am. Chem. Soc. 2012, 134, 20768. (c) A. G. Sergeev,
J. D. Webb, J. F. Hartwig, J. Am. Chem. Soc. 2012, 134, 20226. (d) V.
Molinari, C. Giordano, M. Antonietti, D. Esposito, J. Am. Chem. Soc. 2014,
136, 1758.
Detected products after reaction 36.2 (mg)
Benzene
Toluene
6.1
cyclohexane
1.0
0.9
1.1
0.7
7.0
10.2
4.0
Methylcyclohexane
Ethylcyclohexane
Propylcyclohexane
Total alkanes
Ethylbenzene
Propylbenzene
Total arenes
75 wt%
10 wt%
(5) Y. Ren, M. Yan, J. Wang, Z. C. Zhang, K. Yao, Angew. Chem. Int. Ed.
2013, 52, 12674.
Unknow products and remained phenols 15 wt%
(6) J. M. Nichols, L. M. Bishop, R. G. Bergman, J. A. Ellman, J. Am. Chem.
Soc. 2010, 132, 12554.
4 Conclusions
(7) (a) T. H. Parsell, B. C. Owen, I. Klein, T. M. Jarrell, C. L. Marcum, L. J.
Haupert, L. M. Amundson, H. I. Kenttämaa, F. Ribeiro, J. T. Miller, M. M.
AbuꢀOmar, Chem. Sci. 2013, 4, 806. (b) M. V. Galkin, J. S. M. Samec,
ChemSusChem, 2014, 7, 2154.
In conclusion, we have demonstrated a highly active catalytic
system based on bimetallic RuꢀW catalysts for the selective
cleavage of CArꢀO bonds in phenols. The ꢀhydroxyl and ꢀ
methoxyl groups on the aromatic ring could be easily removed
to yield the corresponding arenes with high selectivity under
hydrogen atmosphere. Researches on the catalysts revealed that
synergism between the Ru particles and W particles was the
key to the hydrogenolysis reactions. Besides, the catalyst also
showed excellent activities in the hydrogenolysis of various
phenolic compounds with different functionalities and three
dimeric lignin model compounds with αꢀOꢀ4, βꢀOꢀ4 and 4ꢀOꢀ5
ether linkages. Finally, the RuꢀW catalyst was applied to the
hydrogenolysis of the phenols separated from the real bioꢀoil,
yielding arenes in high selectivities. These promising results
open a new route for the valorization of phenols derived lignin
which would greatly extend the application areas of lignin.
Detailed studies of the reaction mechanism are still underway.
(8) (a) J. D. Nguyen, B. S. Matsuura, C. R. J. Stephenson, J. Am. Chem. Soc.
2014, 136, 1218. (b) M. C. Haibach, N. Lease, A. S. Goldman, Angew. Chem.
Int. Ed., 2014, 53, 10160.
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Am. Chem. Soc. 2013, 135, 6415. (c) M. Chatterjee, T. Ishizaka, A. Suzuki, H.
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Tomishige, Green Chem. 2014, 16, 2197.
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Acknowledgements
(13) Y. Wang, R. Rinaldi, Angew. Chem. Int. Ed. 2013, 52, 11499.
(14) (a) P. ÁlvarezꢀBercedo, R. Martin, J. Am. Chem. Soc. 2010, 132, 17352.
(b) M. Tobisu, K. Yamakawa, T. Shimasaki, N. Chatani, Chem. Commun.,
2011, 47, 2946.
This work was supported by the 973 Program (2012CB215306),
NSFC (21325208, 21172209, 21272050), CAS (KJCX2ꢀEWꢀ
J02), SRFDP (20123402130008), FRFCU and PCSIRT.
(15) (a) M. Chia, Y. J. PaganꢀTorres, D. Hibbitts, Q. Tan, H. N. Pham, A. K.
Datye, M. Neurock, R. J. Davis, J. A. Dumesic, J. Am. Chem.
Soc. 2011, 133, 12675. (b) A. C. Atesin, N. A. Ray, P. C. Stair, T. J. Marks, J.
Am. Chem. Soc. 2012, 134, 14682.
Notes and references
This journal is © The Royal Society of Chemistry 2012
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