ACS Catalysis
Research Article
(5) (a) Chheda, J. N.; Roman
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-Leshkov, Y.; Dumesic, J. A. Green
This study has shown that suitable solid DODH catalysts can
be generated from ReOx supported on either titania or
activated carbon. The productivity of titania-based catalysts
could be improved by employing high-surface-area titania
materials. For activated carbon based catalysts, long-term
stability needs to be enhanced by adjusting the interaction
between metal oxide and support.
In summary, we investigated the activity and stability of novel
solid DODH catalysts. Titania has proven to be essential for
high catalytic stability of supported ReOx catalysts. ReOx/TiO2
could be recycled six times without significant loss of activity.
XAFS investigations reveal that these catalytically active
materials contain a mixture of Re(VII), Re(IV), and Re(0)
species with a slight increase of ca. 10% of Re(VII) species after
catalysis. The fact that the rhenium composition does not
change much during multiple uses is an indication of the
catalyst’s stability.
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ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
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S
(12) Denning, A. L.; Dang, H.; Liu, Z.; Nicholas, K. M.; Jentoft, F. C.
ChemCatChem 2013, 5, 3567−3570.
Experimental details, nitrogen physisorption, temper-
ature-programmed reduction, elemental analysis, hex-
anediol deoxydehydration, recycling experiments, hot
filtration tests, mass transfer considerations, reproduci-
bility, substrate variation, X-ray absorption spectroscopy,
and transmission electron microscopy (PDF)
(13) Canale, V.; Tonucci, L.; Bressan, M.; d’Alessandro, N. Catal. Sci.
Technol. 2014, 4, 3697−3704.
(14) Yi, J.; Miller, J. T.; Zemlyanov, D. Y.; Zhang, R.; Dietrich, P. J.;
Ribeiro, F. H.; Suslov, S.; Abu-Omar, M. M. Angew. Chem. 2014, 126,
852−855.
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19, 3827−3832. (b) Liu, S.; Senocak, A.; Smeltz, J. L.; Yang, L.;
Wegenhart, B.; Yi, J.; Kenttamaa, H. I.; Ison, E. A.; Abu-Omar, M. M.
̈
AUTHOR INFORMATION
Corresponding Author
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Organometallics 2013, 32, 3210−3219. (c) Li, X.; Wu, D.; Lu, T.; Yi,
G.; Su, H.; Zhang, Y. Angew. Chem. 2014, 126, 4284−4288.
(16) Druce, J. G. F. Rhenium; Cambridge University Press:
Cambridge, U.K., 2013.
Notes
(17) (a) Korstanje, T. J.; Jastrzebski, J. T. B. H.; Klein Gebbink, R. J.
M. ChemSusChem 2010, 3, 695−697. (b) Korstanje, T. J.; de Waard, E.
F.; Jastrzebski, J. T. B. H.; Klein Gebbink, R. J. M. ACS Catal. 2012, 2,
2173−2181.
(18) Also confirmed by elemental analysis not showing any
significant change of the Re content.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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This work was performed as part of the Cluster of Excellence
“Tailor-Made Fuels from Biomass” funded by the Excellence
Initiative by the German federal and state governments to
promote science and research at German universities. H.-U.I.
and A.M.B. also thank the EPSRC for funding. We acknowl-
edge the Diamond Light Source (project SP10306) and ESRF
(CH4194) for provision of beamtime on the beamlines B18
and BM01B, respectively. In particular, we thank Dr. Peter P.
Wells for assistance in performing the XAFS measurements.
(19) (a) Beale, A. M.; Weckhuysen, B. M. Phys. Chem. Chem. Phys.
2010, 12, 5562−5574. (b) Frenkel, A. I.; Yevick, A.; Cooper, C.; Vasic,
R. Annu. Rev. Anal. Chem. 2011, 4, 23−39.
(20) Cimino, A.; De Angelis, B. A.; Gazzoli, D.; Valigi, M. Z. Anorg.
Allg. Chem. 1980, 460, 86−98.
(21) Reduction of unsupported APR at 300 °C led mainly to metallic
rhenium.
ABBREVIATIONS
DODH, deoxydehydration; APR, ammonium perrhenate
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