Inhibited proton transfer enhances Au-catalyzed CO[subscript 2]-to-fuels selectivity
CO[subscript 2] reduction in aqueous electrolytes suffers efficiency losses because of the simultaneous reduction of water to H[subscript 2]. We combine in situ surface-enhanced IR absorption spectroscopy (SEIRAS) and electrochemical kinetic studies to probe the mechanistic basis for kinetic bifurca...
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ftmit:oai:dspace.mit.edu:1721.1/107143 2023-06-11T04:10:55+02:00 Inhibited proton transfer enhances Au-catalyzed CO[subscript 2]-to-fuels selectivity Inhibited proton transfer enhances Au-catalyzed CO2-to-fuels selectivity Wuttig, Anna Yaguchi, Momo Motobayashi, Kenta Osawa, Masatoshi Surendranath, Yogesh Massachusetts Institute of Technology. Department of Chemistry Wuttig, Anna Surendranath, Yogesh 2016-02 application/pdf http://hdl.handle.net/1721.1/107143 en_US eng National Academy of Sciences (U.S.) http://dx.doi.org/10.1073/pnas.1602984113 Proceedings of the National Academy of Sciences 0027-8424 1091-6490 http://hdl.handle.net/1721.1/107143 Wuttig, Anna et al. “Inhibited Proton Transfer Enhances Au-Catalyzed CO 2 -to-Fuels Selectivity.” Proceedings of the National Academy of Sciences 113.32 (2016): E4585–E4593. © 2016 National Academy of Sciences orcid:0000-0001-9519-7907 orcid:0000-0003-1016-3420 Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. PNAS Article http://purl.org/eprint/type/JournalArticle 2016 ftmit https://doi.org/10.1073/pnas.1602984113 2023-05-29T08:47:42Z CO[subscript 2] reduction in aqueous electrolytes suffers efficiency losses because of the simultaneous reduction of water to H[subscript 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[subscript 2] and CO production on polycrystalline Au electrodes. Under the conditions of CO[subscript 2] reduction catalysis, electrogenerated CO species are irreversibly bound to Au in a bridging mode at a surface coverage of ∼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 CO[subscript 2] 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[subscript 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[subscript 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. MIT International Science and Technology Initiatives MISTI (Hayashi Seed Fund) United States. Air Force Office of Scientific Research (Award FA9550-15-1-0135) Massachusetts Institute of Technology. Department of Chemistry National Science Foundation (U.S.). Graduate Research Fellowship Program Article in Journal/Newspaper Carbonic acid DSpace@MIT (Massachusetts Institute of Technology) Proceedings of the National Academy of Sciences 113 32 E4585 E4593 |
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English |
description |
CO[subscript 2] reduction in aqueous electrolytes suffers efficiency losses because of the simultaneous reduction of water to H[subscript 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[subscript 2] and CO production on polycrystalline Au electrodes. Under the conditions of CO[subscript 2] reduction catalysis, electrogenerated CO species are irreversibly bound to Au in a bridging mode at a surface coverage of ∼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 CO[subscript 2] 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[subscript 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[subscript 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. MIT International Science and Technology Initiatives MISTI (Hayashi Seed Fund) United States. Air Force Office of Scientific Research (Award FA9550-15-1-0135) Massachusetts Institute of Technology. Department of Chemistry National Science Foundation (U.S.). Graduate Research Fellowship Program |
author2 |
Massachusetts Institute of Technology. Department of Chemistry Wuttig, Anna Surendranath, Yogesh |
format |
Article in Journal/Newspaper |
author |
Wuttig, Anna Yaguchi, Momo Motobayashi, Kenta Osawa, Masatoshi Surendranath, Yogesh |
spellingShingle |
Wuttig, Anna Yaguchi, Momo Motobayashi, Kenta Osawa, Masatoshi Surendranath, Yogesh Inhibited proton transfer enhances Au-catalyzed CO[subscript 2]-to-fuels selectivity |
author_facet |
Wuttig, Anna Yaguchi, Momo Motobayashi, Kenta Osawa, Masatoshi Surendranath, Yogesh |
author_sort |
Wuttig, Anna |
title |
Inhibited proton transfer enhances Au-catalyzed CO[subscript 2]-to-fuels selectivity |
title_short |
Inhibited proton transfer enhances Au-catalyzed CO[subscript 2]-to-fuels selectivity |
title_full |
Inhibited proton transfer enhances Au-catalyzed CO[subscript 2]-to-fuels selectivity |
title_fullStr |
Inhibited proton transfer enhances Au-catalyzed CO[subscript 2]-to-fuels selectivity |
title_full_unstemmed |
Inhibited proton transfer enhances Au-catalyzed CO[subscript 2]-to-fuels selectivity |
title_sort |
inhibited proton transfer enhances au-catalyzed co[subscript 2]-to-fuels selectivity |
publisher |
National Academy of Sciences (U.S.) |
publishDate |
2016 |
url |
http://hdl.handle.net/1721.1/107143 |
genre |
Carbonic acid |
genre_facet |
Carbonic acid |
op_source |
PNAS |
op_relation |
http://dx.doi.org/10.1073/pnas.1602984113 Proceedings of the National Academy of Sciences 0027-8424 1091-6490 http://hdl.handle.net/1721.1/107143 Wuttig, Anna et al. “Inhibited Proton Transfer Enhances Au-Catalyzed CO 2 -to-Fuels Selectivity.” Proceedings of the National Academy of Sciences 113.32 (2016): E4585–E4593. © 2016 National Academy of Sciences orcid:0000-0001-9519-7907 orcid:0000-0003-1016-3420 |
op_rights |
Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. |
op_doi |
https://doi.org/10.1073/pnas.1602984113 |
container_title |
Proceedings of the National Academy of Sciences |
container_volume |
113 |
container_issue |
32 |
container_start_page |
E4585 |
op_container_end_page |
E4593 |
_version_ |
1768385670350372864 |