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...

Descripción completa

Detalles Bibliográficos
Autores principales: Liu, Kai, Ma, Ming, Wu, Longfei, Valenti, Marco, Cardenas-Morcoso, Drialys, Hofmann, Jan P., Bisquert, Juan, Gimenez, Sixto, Smith, Wilson A.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2019
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
_version_ 1783417285227053056
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
work_keys_str_mv AT liukai electroniceffectsdeterminetheselectivityofplanaraucubimetallicthinfilmsforelectrochemicalco2reduction
AT maming electroniceffectsdeterminetheselectivityofplanaraucubimetallicthinfilmsforelectrochemicalco2reduction
AT wulongfei electroniceffectsdeterminetheselectivityofplanaraucubimetallicthinfilmsforelectrochemicalco2reduction
AT valentimarco electroniceffectsdeterminetheselectivityofplanaraucubimetallicthinfilmsforelectrochemicalco2reduction
AT cardenasmorcosodrialys electroniceffectsdeterminetheselectivityofplanaraucubimetallicthinfilmsforelectrochemicalco2reduction
AT hofmannjanp electroniceffectsdeterminetheselectivityofplanaraucubimetallicthinfilmsforelectrochemicalco2reduction
AT bisquertjuan electroniceffectsdeterminetheselectivityofplanaraucubimetallicthinfilmsforelectrochemicalco2reduction
AT gimenezsixto electroniceffectsdeterminetheselectivityofplanaraucubimetallicthinfilmsforelectrochemicalco2reduction
AT smithwilsona electroniceffectsdeterminetheselectivityofplanaraucubimetallicthinfilmsforelectrochemicalco2reduction