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Capacitive electronic metal-support interactions: outer surface charging of supported catalyst particles

Capacitive electronic metal-support interactions: outer surface charging of supported catalyst particles
Capacitive electronic metal-support interactions: outer surface charging of supported catalyst particles
Electronic metal–support interactions (EMSI) in catalysis are commonly rationalized in terms of an electron transfer between support material and supported metal catalyst particles. This general perspective, however, cannot fully explain experimentally observed EMSI for metallic nanoparticu- late catalysts, because the strong charge screening of metals should locally confine effects of direct electronic interaction with the support to the catalyst–support interface (CSI), which, apart from the perimeter, is largely inaccessible for catalysis reactants. The concept of capacitive EMSI is proposed here for catalyst particles at the nanometer scale, where electronic equilibration results in a long-range charging of the catalytically active outer surface (CAOS) bypassing the expected strong metallic charge screening, which is confirmed and quantified by electrostatic and density functional theory simulations revealing a strong dependence on the coverage of the support surface with catalyst particles. This long-range charge transfer leads to a shift of the local work function at the CAOS. In order to describe the catalytic consequences, an amendment of d-band theory in terms of ‘d-band + work function’ is proposed. Furthermore, the charging of remote catalytic sites at the CAOS scales with the relative dielectric constant of the surrounding medium and it is concluded that EMSI can have surprisingly strong influence especially in the presence of a strongly polarisable dielectric.
1550-235X
Binninger, Tobias
b5224279-1d2f-4806-97ea-e7bbb16e5d71
Schmidt, Thomas J.
27eaeede-d918-4d17-b54f-e75006475455
Kramer, Denis
1faae37a-fab7-4edd-99ee-ae4c30d3cde4
Binninger, Tobias
b5224279-1d2f-4806-97ea-e7bbb16e5d71
Schmidt, Thomas J.
27eaeede-d918-4d17-b54f-e75006475455
Kramer, Denis
1faae37a-fab7-4edd-99ee-ae4c30d3cde4

Binninger, Tobias, Schmidt, Thomas J. and Kramer, Denis (2017) Capacitive electronic metal-support interactions: outer surface charging of supported catalyst particles. Physical Review B, 96 (16). (doi:10.1103/PhysRevB.96.165405).

Record type: Article

Abstract

Electronic metal–support interactions (EMSI) in catalysis are commonly rationalized in terms of an electron transfer between support material and supported metal catalyst particles. This general perspective, however, cannot fully explain experimentally observed EMSI for metallic nanoparticu- late catalysts, because the strong charge screening of metals should locally confine effects of direct electronic interaction with the support to the catalyst–support interface (CSI), which, apart from the perimeter, is largely inaccessible for catalysis reactants. The concept of capacitive EMSI is proposed here for catalyst particles at the nanometer scale, where electronic equilibration results in a long-range charging of the catalytically active outer surface (CAOS) bypassing the expected strong metallic charge screening, which is confirmed and quantified by electrostatic and density functional theory simulations revealing a strong dependence on the coverage of the support surface with catalyst particles. This long-range charge transfer leads to a shift of the local work function at the CAOS. In order to describe the catalytic consequences, an amendment of d-band theory in terms of ‘d-band + work function’ is proposed. Furthermore, the charging of remote catalytic sites at the CAOS scales with the relative dielectric constant of the surrounding medium and it is concluded that EMSI can have surprisingly strong influence especially in the presence of a strongly polarisable dielectric.

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Capacitive Electronic Metal-Support Interactions: Outer Surface Charging of Supported Catalyst Particles - Accepted Manuscript
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Accepted/In Press date: 7 September 2017
e-pub ahead of print date: 4 October 2017

Identifiers

Local EPrints ID: 414167
URI: https://eprints.soton.ac.uk/id/eprint/414167
ISSN: 1550-235X
PURE UUID: 808154c5-4d12-49a0-945c-78324811d865

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Date deposited: 15 Sep 2017 16:30
Last modified: 20 Jul 2019 04:51

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