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Title: 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 O 2 is to a large extent unexplained, given that unsupported Au cannot generally dissociate O 2, while large ensembles of Ag atoms (>4) are generally necessary to lower the O 2 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 O 2 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. O 2 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:
 [1];  [1];  [1]
  1. 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:
Journal Article: 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. doi:10.1021/acs.jpcc.6b03371.
Montemore, Matthew M., Madix, Robert J., and Kaxiras, Efthimios. Wed . "How Does Nanoporous Gold Dissociate Molecular Oxygen?". United States. doi: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},
issn = {1932-7447},
number = 30,
volume = 120,
place = {United States},
year = {2016},
month = {7}
}

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Cited by: 29 works
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Works referencing / citing this record:

Aerobic Methanol Oxidation over Unsupported Nanoporous Gold: The Influence of an Added Base
journal, May 2019

  • Lackmann, Anastasia; Mahr, Christoph; Rosenauer, Andreas
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Electrocatalytic methanol oxidation with nanoporous gold: microstructure and selectivity
journal, January 2017

  • Graf, Matthias; Haensch, Mareike; Carstens, Jörg
  • Nanoscale, Vol. 9, Issue 45
  • DOI: 10.1039/c7nr05124g

Aerobic Methanol Oxidation over Unsupported Nanoporous Gold: The Influence of an Added Base
journal, May 2019

  • Lackmann, Anastasia; Mahr, Christoph; Rosenauer, Andreas
  • Catalysts, Vol. 9, Issue 5
  • DOI: 10.3390/catal9050416

Oxygen Adsorption and Low-Temperature CO Oxidation on a Nanoporous Au Catalyst: Reaction Mechanism and Foreign Metal Effects
journal, January 2018


Independent control over residual silver content of nanoporous gold by galvanodynamically controlled dealloying
journal, January 2018

  • Lackmann, Anastasia; Bäumer, Marcus; Wittstock, Gunther
  • Nanoscale, Vol. 10, Issue 36
  • DOI: 10.1039/c8nr03699c

Methanol oxidation on the Pt(321) surface: a theoretical approach on the role of surface morphology and surface coverage effects
journal, January 2019

  • Tomaschun, Gabriele; Klüner, Thorsten
  • Physical Chemistry Chemical Physics, Vol. 21, Issue 33
  • DOI: 10.1039/c9cp03291f