How Does Nanoporous Gold Dissociate Molecular Oxygen?

Montemore, Matthew M.; Madix, Robert J.; Kaxiras, Efthimios

doi:10.1021/acs.jpcc.6b03371

Title: How Does Nanoporous Gold Dissociate Molecular Oxygen?

Journal Article · Wed Jul 13 00:00:00 EDT 2016 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.6b03371· OSTI ID:1387899

Montemore, Matthew M. ^[1]; Madix, Robert J. ^[1]; Kaxiras, Efthimios ^[1]

Harvard Univ., Cambridge, MA (United States)

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.

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Research Organization:: 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 Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012573; AC02-05CH11231

OSTI ID:: 1387899

Journal Information:: Journal of Physical Chemistry. C, Vol. 120, 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; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 36 works

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Methanol oxidation on the Pt(321) surface: a theoretical approach on the role of surface morphology and surface coverage effects Tomaschun, Gabriele; Klüner, Thorsten Physical Chemistry Chemical Physics, Vol. 21, Issue 33 https://doi.org/10.1039/c9cp03291f	journal	January 2019
Oxygen Adsorption and Low-Temperature CO Oxidation on a Nanoporous Au Catalyst: Reaction Mechanism and Foreign Metal Effects Wang, L. C.; Zhong, Y.; Widmann, D. Topics in Catalysis, Vol. 61, Issue 5-6 https://doi.org/10.1007/s11244-017-0881-2	journal	January 2018
Aerobic Methanol Oxidation over Unsupported Nanoporous Gold: The Influence of an Added Base Lackmann, Anastasia; Mahr, Christoph; Rosenauer, Andreas Catalysts, Vol. 9, Issue 5 https://doi.org/10.3390/catal9050416	journal	May 2019
Independent control over residual silver content of nanoporous gold by galvanodynamically controlled dealloying Lackmann, Anastasia; Bäumer, Marcus; Wittstock, Gunther Nanoscale, Vol. 10, Issue 36 https://doi.org/10.1039/c8nr03699c	journal	January 2018
Electrocatalytic methanol oxidation with nanoporous gold: microstructure and selectivity Graf, Matthias; Haensch, Mareike; Carstens, Jörg Royal Society of Chemistry (RSC) https://doi.org/10.15480/882.2007	text	January 2017

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