Intrinsic Relation between Hot Electron Flux and Catalytic Selectivity during Methanol Oxidation

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Catalytic selectivity, or the production of only one desired molecule that may be used as a fuel or chemical out of several thermodynamically possible molecules, is the foundation of surface chemistry. During catalytic reactions, electronic excitation taking place on the surface creates energetic electrons called "hot electrons" that have a significant impact on catalytic reactions. Despite its importance in fundamentally understanding electronic excitation on the surface, no reports show the relation between hot electron flow and catalytic selectivity. Here, using a Pt/n-type TiO2 Schottky nanodiode, we show the intrinsic relation between hot electron flow and catalytic selectivity. On the Pt thin film, hot electron flow was generated by methanol oxidation exhibiting a two-path reaction of either full oxidation to CO2 or partial oxidation to methyl formate; a steady-state chemicurrent was detected. We show that the activation energy of the chemicurrent is quite close to that of the turnover frequency, indicating that the chemicurrent originated from the catalytic reaction on the Pt thin film. The dependence of the chemicurrent on methanol partial pressure was investigated by varying the partial pressure of methanol (1-4 Torr). We show that hot electron generation is more effective in the reaction pathway that produces methyl formate. On the basis of these results, we conclude that the selectivity for methyl formate production correlates well with hot electron generation because of the higher exothermicity of generating the intermediate, as was confirmed using theoretical calculations based on the density functional theory.
Publisher
AMER CHEMICAL SOC
Issue Date
2019-09
Language
English
Article Type
Article
Citation

ACS CATALYSIS, v.9, no.9, pp.8424 - 8432

ISSN
2155-5435
DOI
10.1021/acscatal.9b02402
URI
http://hdl.handle.net/10203/267736
Appears in Collection
EEW-Journal Papers(저널논문)
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