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Carbon Monoxide as a Promoter of Atomically Dispersed Platinum Catalyst in Electrochemical Hydrogen Evolution Reaction Han Chang Kwon, Minho Kim, Jan Phillip Grote, Sung June Cho, Min Wook Chung, Haesol Kim, Da Hye Won, Aleksandar R. Zeradjanin, Karl J. J. Mayrhofer, Minkee Choi, Hyungjun Kim, and Chang Hyuck Choi J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b09211 • Publication Date (Web): 01 Nov 2018 Downloaded from http://pubs.acs.org on November 1, 2018
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Journal of the American Chemical Society
Carbon Monoxide as a Promoter of Atomically Dispersed Platinum Catalyst in Electrochemical Hydrogen Evolution Reaction Han Chang Kwon,†,§ Minho Kim,‡,§ Jan-Philipp Grote,║ Sung June Cho,О Min Wook Chung,┴ Haesol Kim,┴ Da Hye Won,□ Aleksandar R. Zeradjanin,║,∆ Karl J. J. Mayrhofer,║,∆,# Minkee Choi,† Hyungjun Kim,*,‡ and Chang Hyuck Choi*,┴ Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology, Daejeon 34141, Republic of Korea ‡ Department of Chemistry, Korea Advanced Institute of Science and Technology, Daejeon 34141, Republic of Korea ║ Max-Planck-Institut für Eisenforschung GmbH, Max-Planck-Strasse 1, 40237 Düsseldorf, Germany О Department of Applied Chemical Engineering, Chonnam National University, Gwangju 61186, Republic of Korea ┴ School of Materials Science and Engineering, Gwangju Institute of Science and Technology, Gwangju 61005, Republic of Korea □ Clean Energy Research Center, Korea Institute of Science and Technology, Seoul 02792, Republic of Korea ∆ Helmholtz-Institute Erlangen-Nürnberg for Renewable Energy, Forschungszentrum Jülich, Egerlandstrasse 3, 91058 Erlangen, Germany # Department of Chemical and Biological Engineering, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstrasse 3, 91058 Erlangen, Germany KEYWORDS. carbon monoxide, electrochemistry, hydrogen evolution reaction, platinum, single-atom catalyst †
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 towards 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.
INTRODUCTION In electrocatalysis, carbon monoxide is widely known as a strong poisoning agent of platinum.1 Carbon monoxide is irreversibly adsorbed on a Pt surface, inducing changes in electronic properties (i.e. electronic effects) or site-access blockage (i.e. geometric effects) of active Pt sites.2 In general, the COadsorption exacerbates either catalytic activity or selectivity of Pt even at very low concentrations of
