dc.contributor.author | Wuttig, Anna | |
dc.contributor.author | Yaguchi, Momo | |
dc.contributor.author | Motobayashi, Kenta | |
dc.contributor.author | Osawa, Masatoshi | |
dc.contributor.author | Surendranath, Yogesh | |
dc.date.accessioned | 2017-02-23T21:14:15Z | |
dc.date.available | 2017-02-23T21:14:15Z | |
dc.date.issued | 2016-07 | |
dc.date.submitted | 2016-02 | |
dc.identifier.issn | 0027-8424 | |
dc.identifier.issn | 1091-6490 | |
dc.identifier.uri | http://hdl.handle.net/1721.1/107143 | |
dc.description.abstract | 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. | en_US |
dc.description.sponsorship | MIT International Science and Technology Initiatives | en_US |
dc.description.sponsorship | MISTI (Hayashi Seed Fund) | en_US |
dc.description.sponsorship | United States. Air Force Office of Scientific Research (Award FA9550-15-1-0135) | en_US |
dc.description.sponsorship | Massachusetts Institute of Technology. Department of Chemistry | en_US |
dc.description.sponsorship | National Science Foundation (U.S.). Graduate Research Fellowship Program | en_US |
dc.language.iso | en_US | |
dc.publisher | National Academy of Sciences (U.S.) | en_US |
dc.relation.isversionof | http://dx.doi.org/10.1073/pnas.1602984113 | en_US |
dc.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. | en_US |
dc.source | PNAS | en_US |
dc.title | Inhibited proton transfer enhances Au-catalyzed CO[subscript 2]-to-fuels selectivity | en_US |
dc.title.alternative | Inhibited proton transfer enhances Au-catalyzed CO2-to-fuels selectivity | en_US |
dc.type | Article | en_US |
dc.identifier.citation | 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 | en_US |
dc.contributor.department | Massachusetts Institute of Technology. Department of Chemistry | en_US |
dc.contributor.mitauthor | Wuttig, Anna | |
dc.contributor.mitauthor | Surendranath, Yogesh | |
dc.relation.journal | Proceedings of the National Academy of Sciences | en_US |
dc.eprint.version | Final published version | en_US |
dc.type.uri | http://purl.org/eprint/type/JournalArticle | en_US |
eprint.status | http://purl.org/eprint/status/PeerReviewed | en_US |
dspace.orderedauthors | Wuttig, Anna; Yaguchi, Momo; Motobayashi, Kenta; Osawa, Masatoshi; Surendranath, Yogesh | en_US |
dspace.embargo.terms | N | en_US |
dc.identifier.orcid | https://orcid.org/0000-0001-9519-7907 | |
dc.identifier.orcid | https://orcid.org/0000-0003-1016-3420 | |
mit.license | PUBLISHER_POLICY | en_US |
mit.metadata.status | Complete | |