Electronic Effects Determine the Selectivity of Planar Au–Cu Bimetallic Thin Films for Electrochemical CO(2) Reduction
[Image: see text] Au–Cu bimetallic thin films with controlled composition were fabricated by magnetron sputtering co-deposition, and their performance for the electrocatalytic reduction of CO(2) was investigated. The uniform planar morphology served as a platform to evaluate the electronic effect is...
Autores principales: | , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American
Chemical Society
2019
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6509640/ https://www.ncbi.nlm.nih.gov/pubmed/30969748 http://dx.doi.org/10.1021/acsami.9b01553 |
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author | Liu, Kai Ma, Ming Wu, Longfei Valenti, Marco Cardenas-Morcoso, Drialys Hofmann, Jan P. Bisquert, Juan Gimenez, Sixto Smith, Wilson A. |
author_facet | Liu, Kai Ma, Ming Wu, Longfei Valenti, Marco Cardenas-Morcoso, Drialys Hofmann, Jan P. Bisquert, Juan Gimenez, Sixto Smith, Wilson A. |
author_sort | Liu, Kai |
collection | PubMed |
description | [Image: see text] Au–Cu bimetallic thin films with controlled composition were fabricated by magnetron sputtering co-deposition, and their performance for the electrocatalytic reduction of CO(2) was investigated. The uniform planar morphology served as a platform to evaluate the electronic effect isolated from morphological effects while minimizing geometric contributions. The catalytic selectivity and activity of Au–Cu alloys was found to be correlated with the variation of electronic structure that was varied with tunable composition. Notably, the d-band center gradually shifted away from the Fermi level with increasing Au atomic ratio, leading to a weakened binding energy of *CO, which is consistent with low CO coverage observed in CO stripping experiments. The decrease in the *CO binding strength results in the enhanced catalytic activity for CO formation with the increase in Au content. In addition, it was observed that copper oxide/hydroxide species are less stable on Au–Cu surfaces compared to those on the pure Cu surface, where the surface oxophilicity could be critical to tuning the binding strength of *OCHO. These results imply that the altered electronic structure could explain the decreased formation of HCOO(–) on the Au–Cu alloys. In general, the formation of CO and HCOO(–) as main CO(2) reduction products on planar Au–Cu alloys followed the shift of the d-band center, which indicates that the electronic effect is the major governing factor for the electrocatalytic activity of CO(2) reduction on Au–Cu bimetallic thin films. |
format | Online Article Text |
id | pubmed-6509640 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | American
Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-65096402019-05-13 Electronic Effects Determine the Selectivity of Planar Au–Cu Bimetallic Thin Films for Electrochemical CO(2) Reduction Liu, Kai Ma, Ming Wu, Longfei Valenti, Marco Cardenas-Morcoso, Drialys Hofmann, Jan P. Bisquert, Juan Gimenez, Sixto Smith, Wilson A. ACS Appl Mater Interfaces [Image: see text] Au–Cu bimetallic thin films with controlled composition were fabricated by magnetron sputtering co-deposition, and their performance for the electrocatalytic reduction of CO(2) was investigated. The uniform planar morphology served as a platform to evaluate the electronic effect isolated from morphological effects while minimizing geometric contributions. The catalytic selectivity and activity of Au–Cu alloys was found to be correlated with the variation of electronic structure that was varied with tunable composition. Notably, the d-band center gradually shifted away from the Fermi level with increasing Au atomic ratio, leading to a weakened binding energy of *CO, which is consistent with low CO coverage observed in CO stripping experiments. The decrease in the *CO binding strength results in the enhanced catalytic activity for CO formation with the increase in Au content. In addition, it was observed that copper oxide/hydroxide species are less stable on Au–Cu surfaces compared to those on the pure Cu surface, where the surface oxophilicity could be critical to tuning the binding strength of *OCHO. These results imply that the altered electronic structure could explain the decreased formation of HCOO(–) on the Au–Cu alloys. In general, the formation of CO and HCOO(–) as main CO(2) reduction products on planar Au–Cu alloys followed the shift of the d-band center, which indicates that the electronic effect is the major governing factor for the electrocatalytic activity of CO(2) reduction on Au–Cu bimetallic thin films. American Chemical Society 2019-04-10 2019-05-08 /pmc/articles/PMC6509640/ /pubmed/30969748 http://dx.doi.org/10.1021/acsami.9b01553 Text en Copyright © 2019 American Chemical Society This is an open access article published under a Creative Commons Non-Commercial No Derivative Works (CC-BY-NC-ND) Attribution License (http://pubs.acs.org/page/policy/authorchoice_ccbyncnd_termsofuse.html) , which permits copying and redistribution of the article, and creation of adaptations, all for non-commercial purposes. |
spellingShingle | Liu, Kai Ma, Ming Wu, Longfei Valenti, Marco Cardenas-Morcoso, Drialys Hofmann, Jan P. Bisquert, Juan Gimenez, Sixto Smith, Wilson A. Electronic Effects Determine the Selectivity of Planar Au–Cu Bimetallic Thin Films for Electrochemical CO(2) Reduction |
title | Electronic
Effects Determine the Selectivity of Planar
Au–Cu Bimetallic Thin Films for Electrochemical CO(2) Reduction |
title_full | Electronic
Effects Determine the Selectivity of Planar
Au–Cu Bimetallic Thin Films for Electrochemical CO(2) Reduction |
title_fullStr | Electronic
Effects Determine the Selectivity of Planar
Au–Cu Bimetallic Thin Films for Electrochemical CO(2) Reduction |
title_full_unstemmed | Electronic
Effects Determine the Selectivity of Planar
Au–Cu Bimetallic Thin Films for Electrochemical CO(2) Reduction |
title_short | Electronic
Effects Determine the Selectivity of Planar
Au–Cu Bimetallic Thin Films for Electrochemical CO(2) Reduction |
title_sort | electronic
effects determine the selectivity of planar
au–cu bimetallic thin films for electrochemical co(2) reduction |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6509640/ https://www.ncbi.nlm.nih.gov/pubmed/30969748 http://dx.doi.org/10.1021/acsami.9b01553 |
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