期刊
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
卷 113, 期 32, 页码 E4585-E4593出版社
NATL ACAD SCIENCES
DOI: 10.1073/pnas.1602984113
关键词
carbon dioxide reduction; catalyst selectivity; in situ spectroscopy; proton-coupled electron transfer
资金
- Air Force Office of Scientific Research under AFOSR [FA9550-15-1-0135]
- MIT Department of Chemistry
- New Energy and Industrial Technology Development Organization
- National Science Foundation
- Massachusetts Institute of Technology (MIT) International Science and Technology Initiatives
- Hayashi Seed Grant for Travel Funds
- Grants-in-Aid for Scientific Research [25810044] Funding Source: KAKEN
CO2 reduction in aqueous electrolytes suffers efficiency losses because of the simultaneous reduction of water to H-2. We combine in situ surface-enhanced IR absorption spectroscopy (SEIRAS) and electrochemical kinetic studies to probe the mechanistic basis for kinetic bifurcation between H-2 and CO production on polycrystalline Au electrodes. Under the conditions of CO2 reduction catalysis, electrogenerated CO species are irreversibly bound to Au in a bridging mode at a surface coverage of similar to 0.2 and act as kinetically inert spectators. Electrokinetic data are consistent with a mechanism of CO production involving rate-limiting, single-electron transfer to CO2 with concomitant adsorption to surface active sites followed by rapid one-electron, two-proton transfer and CO liberation from the surface. In contrast, the data suggest an H-2 evolution mechanism involving rate-limiting, single-electron transfer coupled with proton transfer from bicarbonate, hydronium, and/or carbonic acid to form adsorbed H species followed by rapid one-electron, one-proton, or H recombination reactions. The disparate proton coupling requirements for CO and H-2 production establish a mechanistic basis for reaction selectivity in electrocatalytic fuel formation, and the high population of spectator CO species highlights the complex heterogeneity of electrode surfaces under conditions of fuel-forming electrocatalysis.
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