Journal of the American Chemical Society
Page 4 of 15
ment on the selectivity to methanol observed experimentally
(Figure 2).
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Porosoff, M. D.; Yang, X.; Boscoboinik,
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In summary, the reduction of CO2 by hydrogen was studied
over Au/TiO and Au/CeO /TiO surfaces. It was found that the
presence of small coverages of CeOx (~0.1 ML) stabilizes the
formation of small Au nanoparticles, significantly promoting their
activity in both CO and methanol production and improving their
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Rodemerck, U.; Holeňa, M.; Wagner, E.;
2
x
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(
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selectivity towards methanol The existence of carboxylate species
.
is supported by APꢀXPS under in-situ reaction conditions. In the
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1996, 38, 175.
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Au/CeO /TiO surface an electronic metalꢀsupport interaction
x
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0
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0
promotes both CO adsorption and activation. The DFT calculaꢀ
2
tions further reveal that Au nanoparticles supported on the Ceꢀ
O /TiO mixed oxide support decreases the reaction barriers for
x
2
Catal., A 2000, 204, 143.
CO and methanol production. The interaction of CeO with Au
x
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Staudt, T.; Lykhach, Y.; Tsud, N.; Skála,
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2
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unprecedented low pressures of hydrogen.
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ASSOCIATED CONTENT
Supporting Information
Stacchiola, D.; Ma, S.; Liu, P.; Nambu, A.; Sanz, J. F.;
Hrbek, J.; Rodriguez, J. A. Proc. Natl. Acad. Sci 2009, 106,
4975.
Experimental details including surface preparation and characteriꢀ
zation in UHV, kinetic study by TPR under ambient pressures and
more detailed analysis of the APꢀXPS data and DFT results. This
material is available free of charge via the Internet at
http://pubs.acs.org.
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Mater. 2007, 19, 1215.
14) Park, J. B.; Graciani, J.; Evans, J.;
Zhou, K.; Yang, Z.; Yang, S. Chem.
(
Stacchiola, D.; Senanayake, S. D.; Barrio, L.; Liu, P.; Sanz,
J. F.; Hrbek, J.; Rodriguez, J. A. J. Am. Chem. Soc. 2010,
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AUTHOR INFORMATION
Corresponding Author
1
(
15)
P.; Rodriguez, J. A. J. Chem. Phys. 2010, 131, 104703.
16) Haruta, M.; Yamada, N.; Kobayashi, T.;
Iijima, S. J. Catal. 1989, 115, 301.
Graciani, J.; Plata, J. J.; Sanz, J. F.; Liu,
Dr. Dario Stacchiola Eꢀmail: djs@bnl.gov
Prof. Jingguang G. Chen Eꢀmail: jgchen@columbia.edu
(
Present Addresses
Chemistry Department, Brookhaven National Laboratory (BNL)
Upton, NY 11973 (USA)
(17)
Haruta, M.; Tsubota, S.; Kobayashi, T.;
Kageyama, H.; Genet, M. J.; Delmon, B. J. Catal. 1993,
144, 175.
Department of Chemical Engineering, Columbia University
5
00 W. 120th St., New York, NY 10027 (USA)
(18)
Sakurai, H.; Tsubota, S.; Haruta, M.
Appl. Catal., A 1993, 102, 125.
Notes
(
19)
996, 29, 361.
20)
Sakurai, H.; Haruta, M. Catal. Today
The authors declare no competing financial interests.
1
(
Remediakis, I. N.; Lopez, N.; Nørskov, J.
ACKNOWLEDGMENT
K. Appl. Catal., A 2005, 291, 13.
The work was sponsored under Contract No. DEꢀAC02ꢀ
(21)
Lopez, N.; Nørskov, J. K. J. Am. Chem.
9
8CH10886 with the U.S. Department of Energy, Office of
Soc. 2002, 124, 11262.
Science. This research used resources of the Center for Functionꢀ
al Nanomaterials and National Synchrotron Light Source, which
are U.S. DOE Office of Science User Facilities at Brookhaven
National Laboratory under Contract No. DEꢀSC0012704 and the
National Energy Research Scientific Computing Center (NERSC)
supported by the Office of Science of the US Department of
Energy under Contract No. DEꢀAC02ꢀ05CH11231.
(
22)
Graciani, J.; Mudiyanselage, K.; Xu, F.;
Baber, A. E.; Evans, J.; Senanayake, S. D.; Stacchiola, D.
J.; Liu, P.; Hrbek, J.; Sanz, J. F.; Rodriguez, J. A. Science
2
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D. R. Surf. Sci. 1998, 409, 307.
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(
Mullins, D. R.; Overbury, S. H.; Huntley,
(
Y.; Lin, S. D.; Cheng, H.; Chen, J.ꢀM.; Lee, J.ꢀF.; Lin, T.ꢀ
S. J. Am. Chem. Soc. 2012, 134, 10251.
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