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The Role of Surface-Bound Dihydropyridine Analogues in Pyridine-Catalyzed CO(2) Reduction over Semiconductor Photoelectrodes
[Image: see text] We propose a general reaction mechanism for the pyridine (Py)-catalyzed reduction of CO(2) over GaP(111), CdTe(111), and CuInS(2)(112) photoelectrode surfaces. This mechanism proceeds via formation of a surface-bound dihydropyridine (DHP) analogue, which is a newly postulated inter...
Autores principales: | , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2017
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5620980/ https://www.ncbi.nlm.nih.gov/pubmed/28979938 http://dx.doi.org/10.1021/acscentsci.7b00233 |
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author | Senftle, Thomas P. Lessio, Martina Carter, Emily A. |
author_facet | Senftle, Thomas P. Lessio, Martina Carter, Emily A. |
author_sort | Senftle, Thomas P. |
collection | PubMed |
description | [Image: see text] We propose a general reaction mechanism for the pyridine (Py)-catalyzed reduction of CO(2) over GaP(111), CdTe(111), and CuInS(2)(112) photoelectrode surfaces. This mechanism proceeds via formation of a surface-bound dihydropyridine (DHP) analogue, which is a newly postulated intermediate in the Py-catalyzed mechanism. Using density functional theory, we calculate the standard reduction potential related to the formation of the DHP analogue, which demonstrates that it is thermodynamically feasible to form this intermediate on all three investigated electrode surfaces under photoelectrochemical conditions. Hydride transfer barriers from the intermediate to CO(2) demonstrate that the surface-bound DHP analogue is as effective at reducing CO(2) to HCOO(–) as the DHP((aq)) molecule in solution. This intermediate is predicted to be both stable and active on many varying electrodes, therefore pointing to a mechanism that can be generalized across a variety of semiconductor surfaces, and explains the observed electrode dependence of the photocatalysis. Design principles that emerge are also outlined. |
format | Online Article Text |
id | pubmed-5620980 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2017 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-56209802017-10-04 The Role of Surface-Bound Dihydropyridine Analogues in Pyridine-Catalyzed CO(2) Reduction over Semiconductor Photoelectrodes Senftle, Thomas P. Lessio, Martina Carter, Emily A. ACS Cent Sci [Image: see text] We propose a general reaction mechanism for the pyridine (Py)-catalyzed reduction of CO(2) over GaP(111), CdTe(111), and CuInS(2)(112) photoelectrode surfaces. This mechanism proceeds via formation of a surface-bound dihydropyridine (DHP) analogue, which is a newly postulated intermediate in the Py-catalyzed mechanism. Using density functional theory, we calculate the standard reduction potential related to the formation of the DHP analogue, which demonstrates that it is thermodynamically feasible to form this intermediate on all three investigated electrode surfaces under photoelectrochemical conditions. Hydride transfer barriers from the intermediate to CO(2) demonstrate that the surface-bound DHP analogue is as effective at reducing CO(2) to HCOO(–) as the DHP((aq)) molecule in solution. This intermediate is predicted to be both stable and active on many varying electrodes, therefore pointing to a mechanism that can be generalized across a variety of semiconductor surfaces, and explains the observed electrode dependence of the photocatalysis. Design principles that emerge are also outlined. American Chemical Society 2017-08-25 2017-09-27 /pmc/articles/PMC5620980/ /pubmed/28979938 http://dx.doi.org/10.1021/acscentsci.7b00233 Text en Copyright © 2017 American Chemical Society This is an open access article published under a Creative Commons Attribution (CC-BY) License (http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html) , which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited. |
spellingShingle | Senftle, Thomas P. Lessio, Martina Carter, Emily A. The Role of Surface-Bound Dihydropyridine Analogues in Pyridine-Catalyzed CO(2) Reduction over Semiconductor Photoelectrodes |
title | The Role of Surface-Bound Dihydropyridine Analogues
in Pyridine-Catalyzed CO(2) Reduction over Semiconductor
Photoelectrodes |
title_full | The Role of Surface-Bound Dihydropyridine Analogues
in Pyridine-Catalyzed CO(2) Reduction over Semiconductor
Photoelectrodes |
title_fullStr | The Role of Surface-Bound Dihydropyridine Analogues
in Pyridine-Catalyzed CO(2) Reduction over Semiconductor
Photoelectrodes |
title_full_unstemmed | The Role of Surface-Bound Dihydropyridine Analogues
in Pyridine-Catalyzed CO(2) Reduction over Semiconductor
Photoelectrodes |
title_short | The Role of Surface-Bound Dihydropyridine Analogues
in Pyridine-Catalyzed CO(2) Reduction over Semiconductor
Photoelectrodes |
title_sort | role of surface-bound dihydropyridine analogues
in pyridine-catalyzed co(2) reduction over semiconductor
photoelectrodes |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5620980/ https://www.ncbi.nlm.nih.gov/pubmed/28979938 http://dx.doi.org/10.1021/acscentsci.7b00233 |
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