Catalysis Science & Technology
Page 7 of 9Journal Name
DOI: 10.1039/C4CY01285B
Cite this: DOI: 10.1039/c0xx00000x
ARTICLE TYPE
35 a State Key Laboratory of Chemical Engineering, East China University
of Science and Technology, Shanghai, 200237, P. R. China. E-mail:
metallic Ir attacks the CꢀO bond of the adsorbed glycerol to
generate unsaturated intermediates.4f,27 Subsequent hydrogenation
of these unsaturated intermediates leads to the formation of the
observed hydrogenolysis products, while further deoxygenation
b Department of Chemical Engineering, University of California, Santa
Barbara, CA 93106-9510, USA. E-mail: sscott@engineering.ucsb.edu
5
of these unsaturated intermediates results in the formation of 40 † Electronic Supplementary Information (ESI) available: [N2ꢀadsorption
of KITꢀ6, Table of currently developed catalytic system for glycerol
hydrogenolysis, XRD and NH3ꢀTPD is available in supporting
information]. See DOI: 10.1039/b000000x/
overꢀhydrogenolysis products (1ꢀPO/2ꢀPO).
1
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Scheme 2 Possible reaction pathway for glycerol hydrogenolysis over
alloyed IrꢀRe/KITꢀ6ꢀR.
Representative reports on glycerol hydrogenolysis to 1,3ꢀpropanediol:
a) Y. Nakagawa, Y. Shinmi, S. Koso and K. Tomishige, J. Catal.,
2010, 272, 191; b) O. M. Daniel, A. Delariva, E. L. Kunkes, A. K.
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Tomishige, Appl. Catal. B, 2011, 105, 117; g) J. Ten Dam, K.
Djanashvili, F. Kapteijn and U. Hanefeld, ChemCatChem, 2013, 5,
497; h) R. Arundhathi, T. Mizugaki, T. Mitsudome, K. Jitsukawa
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10 4. Conclusions
In summary, the correlation between bimetallic IrꢀRe structure
and thermal treatment is investigated, and the resulting different
structured bimetallic IrꢀRe catalysts are applied in glycerol
hydrogenolysis to examine the relationship between bimetallic Irꢀ
15 Re structure and catalytic performance. It is revealed that, direct
reduction of the impregnated sample without prior calcination
renders Re species fully reducible, favoring the formation of Irꢀ
Re alloy. In contrast, when calcination treatment is employed,
reduction of Re species is inhibited, resulting in the formation of
20 IrꢀReOx after the subsequent reduction of the bimetallic catalyst.
Compared with the catalyst with IrꢀReOx structure, the IrꢀRe
alloy catalyst shows remarkably improved activity in glycerol
hydrogenolysis and doubled 1,3ꢀpropanediol formation rate,
which results from the higher density of active center. Besides,
25 the IrꢀRe alloy catalyst also exhibits enhanced resistance against
particle sintering. This readilyꢀprepared alloyed IrꢀRe catalyst
may be useful in other CꢀO bond hydrogenolysis reactions, such
as the disassembly of lignin.
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Y. Amada, H. Watanabe, M. Tamura, Y. Nakagawa, K. Okumura and
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Acknowledgements
Z. Wang, S. Skiles, F. Yang and D. W. Goodman, Catal. Today,
2012, 181, 75.
30 This work was supported by the National Natural Science
Foundation of China (21106047). S.L.S. thanks the Center for
Enabling New Technologies through Catalysis (CENTC) for
financial support.
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Notes and references
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