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J Am Chem Soc. 2018 Nov 28;140(47):16198-16205. doi: 10.1021/jacs.8b09211. Epub 2018 Nov 12.

Carbon Monoxide as a Promoter of Atomically Dispersed Platinum Catalyst in Electrochemical Hydrogen Evolution Reaction.

Author information

1
Department of Chemical and Biomolecular Engineering , Korea Advanced Institute of Science and Technology , Daejeon 34141 , Republic of Korea.
2
Department of Chemistry , Korea Advanced Institute of Science and Technology , Daejeon 34141 , Republic of Korea.
3
Max-Planck-Institut für Eisenforschung GmbH , Max-Planck-Strasse 1 , 40237 Düsseldorf , Germany.
4
Department of Applied Chemical Engineering , Chonnam National University , Gwangju 61186 , Republic of Korea.
5
School of Materials Science and Engineering , Gwangju Institute of Science and Technology , Gwangju 61005 , Republic of Korea.
6
Clean Energy Research Center , Korea Institute of Science and Technology , Seoul 02792 , Republic of Korea.
7
Helmholtz-Institute Erlangen-Nürnberg for Renewable Energy , Forschungszentrum Jülich , Egerlandstrasse 3 , 91058 Erlangen , Germany.
8
Department of Chemical and Biological Engineering , Friedrich-Alexander-Universität Erlangen-Nürnberg , Egerlandstrasse 3 , 91058 Erlangen , Germany.

Abstract

Carbon monoxide is widely known to poison Pt during heterogeneous catalysis owing to its strong donor-acceptor binding ability. Herein, we report a counterintuitive phenomenon of this general paradigm when the size of Pt decreases to an atomic level, namely, the CO-promoting Pt electrocatalysis toward hydrogen evolution reactions (HER). Compared to pristine atomic Pt catalyst, reduction current on a CO-modified catalyst increases significantly. Operando mass spectroscopy and electrochemical analyses demonstrate that the increased current arises due to enhanced H2 evolution, not additional CO reduction. Through structural identification of catalytic sites and computational analysis, we conclude that CO-ligation on the atomic Pt facilitates Hads formation via water dissociation. This counterintuitive effect exemplifies the fully distinct characteristics of atomic Pt catalysts from those of bulk Pt, and offers new insights for tuning the activity of similar classes of catalysts.

PMID:
30383962
DOI:
10.1021/jacs.8b09211

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