How Does Nanoporous Gold Dissociate Molecular Oxygen?
Abstract
Nanoporous Au and other dilute AgAu alloys are highly active and selective oxidation catalysts. Their ability to dissociate O2 is to a large extent unexplained, given that unsupported Au cannot generally dissociate O2, while large ensembles of Ag atoms (>4) are generally necessary to lower the O2 dissociation barrier significantly. In this work, we identify a site on the surface of dilute AgAu alloys that is stable under reaction conditions and has a low O2 dissociation barrier, in agreement with experimental measurements. Although Ag generally prefers to disperse throughout Au, the presence of adsorbed O near surface steps creates sites of high local Ag concentration, where the Ag atoms sit in the rows next to the step Au atoms. O2 adsorbs on the Au step atoms, but the transition state involves significant Ag–O interaction, resulting in a barrier lower than expected from the adsorption energies of either the initial or final state.
- Authors:
-
- Harvard Univ., Cambridge, MA (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Energy Frontier Research Centers (EFRC) (United States). Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1387899
- Grant/Contract Number:
- SC0012573; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 120; Journal Issue: 30; Related Information: IMASC partners with Harvard University (lead); Fritz Haber Institute; Lawrence Berkeley National Laboratory; Lawrence Livermore National Laboratory; University of Kansas; Tufts University; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (heterogeneous); mesostructured materials; materials and chemistry by design; synthesis (novel materials)
Citation Formats
Montemore, Matthew M., Madix, Robert J., and Kaxiras, Efthimios. How Does Nanoporous Gold Dissociate Molecular Oxygen?. United States: N. p., 2016.
Web. doi:10.1021/acs.jpcc.6b03371.
Montemore, Matthew M., Madix, Robert J., & Kaxiras, Efthimios. How Does Nanoporous Gold Dissociate Molecular Oxygen?. United States. https://doi.org/10.1021/acs.jpcc.6b03371
Montemore, Matthew M., Madix, Robert J., and Kaxiras, Efthimios. Wed .
"How Does Nanoporous Gold Dissociate Molecular Oxygen?". United States. https://doi.org/10.1021/acs.jpcc.6b03371. https://www.osti.gov/servlets/purl/1387899.
@article{osti_1387899,
title = {How Does Nanoporous Gold Dissociate Molecular Oxygen?},
author = {Montemore, Matthew M. and Madix, Robert J. and Kaxiras, Efthimios},
abstractNote = {Nanoporous Au and other dilute AgAu alloys are highly active and selective oxidation catalysts. Their ability to dissociate O2 is to a large extent unexplained, given that unsupported Au cannot generally dissociate O2, while large ensembles of Ag atoms (>4) are generally necessary to lower the O2 dissociation barrier significantly. In this work, we identify a site on the surface of dilute AgAu alloys that is stable under reaction conditions and has a low O2 dissociation barrier, in agreement with experimental measurements. Although Ag generally prefers to disperse throughout Au, the presence of adsorbed O near surface steps creates sites of high local Ag concentration, where the Ag atoms sit in the rows next to the step Au atoms. O2 adsorbs on the Au step atoms, but the transition state involves significant Ag–O interaction, resulting in a barrier lower than expected from the adsorption energies of either the initial or final state.},
doi = {10.1021/acs.jpcc.6b03371},
journal = {Journal of Physical Chemistry. C},
number = 30,
volume = 120,
place = {United States},
year = {Wed Jul 13 00:00:00 EDT 2016},
month = {Wed Jul 13 00:00:00 EDT 2016}
}
Web of Science
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