Density Functional Theory Investigation of Oxidation Intermediates on Gold and Gold–Silver Surfaces

Sensoy, Mehmet Gokhan; Montemore, Matthew M.

doi:10.1021/acs.jpcc.0c01386

Density Functional Theory Investigation of Oxidation Intermediates on Gold and Gold–Silver Surfaces

Journal Article · Wed Apr 01 00:00:00 EDT 2020 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.0c01386· OSTI ID:1843926

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Recep Tayyip Erdogan Univ., Rize (Turkey); Harvard
Harvard Univ., Cambridge, MA (United States); Tulane Univ., New Orleans, LA (United States)

Gold and gold-silver alloys can be active and selective oxidation catalysts. Previous work has suggested that O₂ dissociation occurs at bimetallic step sites on gold-silver alloys, but the site responsible for the rest of the reaction steps has not been studied. As a first step in gaining insight into this issue, in this work we investigated the adsorption of oxygen and other oxidation intermediates on the (111) and (211) facets of gold-silver alloys using density functional theory. Oxygen and silver coverage effects were analyzed, and different model structures were compared. We also examined the energy barriers for the diffusion of atomic oxygen to gain insight into O migration and spillover. On (111) surfaces, O adsorption is much stronger at low O coverage (less than 0.22 ML), while on (211) surfaces O is strongly bound at both high and low O coverage. O diffusion across the step is faster than diffusion along the step. Ag stabilizes O, both when directly bound to it and when in an adjacent site. Ag also reduces repulsive O-O interactions at low O coverage. Our calculated reaction barriers for O-assisted CH₃O dehydrogenation suggest that reaction is faster on steps than on terraces. Overall, our findings suggest that spillover of O from Ag-rich steps to Au-rich terraces does not occur, and that oxidation reactions on gold-silver alloys occurs on step sites. More specifically, oxidation likely occurs either on Ag-rich step sites or on Au-rich step sites that are adjacent to Ag-rich step sites.

View Accepted Manuscript (DOE)

Research Organization:: Harvard Univ., Cambridge, MA (United States)

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

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

OSTI ID:: 1843926

Alternate ID(s):: OSTI ID: 1802397

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 16 Vol. 124; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Density Functional Theory Investigation of Oxidation Intermediates on Gold and Gold–Silver Surfaces

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