Electronic effects determine the selectivity of planar Au-Cu bimetallic thin films for electrochemical CO2 reduction

Kai Liu, Ming Ma, Longfei Wu, Marco Valenti, Drialys Cardenas-Morcoso, Jan P. Hofmann, Juan Bisquert, Sixto Gimenez, Wilson A. Smith (Corresponding author)

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Uittreksel

Au-Cu bimetallic thin films with controlled composition were fabricated by magnetron sputtering co-deposition, and their performance for the electrocatalytic reduction of CO2 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 the 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 of the *CO binding strength results in the enhanced catalytic activity for CO formation with the increase of Au content. In addition, it was observed that copper oxide/hydroxide species are less stable on Au-Cu surfaces compared to those on 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 these alloys. In general, the formation of CO and HCOO─ as main CO2 reduction products on planar Au-Cu alloys followed the shift of d-band center, which indicates the electronic effect is the major governing factor for the electrocatalytic activity of CO2 reduction on Au-Cu bimetallic thin films.
Originele taal-2Engels
Pagina's (van-tot)16546-16555
Aantal pagina's10
TijdschriftACS Applied Materials & Interfaces
Volume11
Nummer van het tijdschrift18
DOI's
StatusGepubliceerd - 8 mei 2019

Vingerafdruk

Carbon Monoxide
Thin films
Electronic structure
Copper oxides
Fermi level
Binding energy
Chemical analysis
Magnetron sputtering
Catalyst activity
Tuning
Experiments

Citeer dit

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 CO2 reduction. In: ACS Applied Materials & Interfaces. 2019 ; Vol. 11, Nr. 18. blz. 16546-16555.
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title = "Electronic effects determine the selectivity of planar Au-Cu bimetallic thin films for electrochemical CO2 reduction",
abstract = "Au-Cu bimetallic thin films with controlled composition were fabricated by magnetron sputtering co-deposition, and their performance for the electrocatalytic reduction of CO2 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 the 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 of the *CO binding strength results in the enhanced catalytic activity for CO formation with the increase of Au content. In addition, it was observed that copper oxide/hydroxide species are less stable on Au-Cu surfaces compared to those on 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 these alloys. In general, the formation of CO and HCOO─ as main CO2 reduction products on planar Au-Cu alloys followed the shift of d-band center, which indicates the electronic effect is the major governing factor for the electrocatalytic activity of CO2 reduction on Au-Cu bimetallic thin films.",
keywords = "Au-Cu alloy, bimetallic catalyst, d-band center, electrochemical carbon dioxide reduction, electronic effect, thin film",
author = "Kai Liu and Ming Ma and Longfei Wu and Marco Valenti and Drialys Cardenas-Morcoso and Hofmann, {Jan P.} and Juan Bisquert and Sixto Gimenez and Smith, {Wilson A.}",
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Liu, K, Ma, M, Wu, L, Valenti, M, Cardenas-Morcoso, D, Hofmann, JP, Bisquert, J, Gimenez, S & Smith, WA 2019, 'Electronic effects determine the selectivity of planar Au-Cu bimetallic thin films for electrochemical CO2 reduction', ACS Applied Materials & Interfaces, vol. 11, nr. 18, blz. 16546-16555. https://doi.org/10.1021/acsami.9b01553

Electronic effects determine the selectivity of planar Au-Cu bimetallic thin films for electrochemical CO2 reduction. / Liu, Kai; Ma, Ming; Wu, Longfei; Valenti, Marco; Cardenas-Morcoso, Drialys; Hofmann, Jan P.; Bisquert, Juan; Gimenez, Sixto; Smith, Wilson A. (Corresponding author).

In: ACS Applied Materials & Interfaces, Vol. 11, Nr. 18, 08.05.2019, blz. 16546-16555.

Onderzoeksoutput: Bijdrage aan tijdschriftTijdschriftartikelAcademicpeer review

TY - JOUR

T1 - Electronic effects determine the selectivity of planar Au-Cu bimetallic thin films for electrochemical CO2 reduction

AU - Liu, Kai

AU - Ma, Ming

AU - Wu, Longfei

AU - Valenti, Marco

AU - Cardenas-Morcoso, Drialys

AU - Hofmann, Jan P.

AU - Bisquert, Juan

AU - Gimenez, Sixto

AU - Smith, Wilson A.

PY - 2019/5/8

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N2 - Au-Cu bimetallic thin films with controlled composition were fabricated by magnetron sputtering co-deposition, and their performance for the electrocatalytic reduction of CO2 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 the 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 of the *CO binding strength results in the enhanced catalytic activity for CO formation with the increase of Au content. In addition, it was observed that copper oxide/hydroxide species are less stable on Au-Cu surfaces compared to those on 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 these alloys. In general, the formation of CO and HCOO─ as main CO2 reduction products on planar Au-Cu alloys followed the shift of d-band center, which indicates the electronic effect is the major governing factor for the electrocatalytic activity of CO2 reduction on Au-Cu bimetallic thin films.

AB - Au-Cu bimetallic thin films with controlled composition were fabricated by magnetron sputtering co-deposition, and their performance for the electrocatalytic reduction of CO2 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 the 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 of the *CO binding strength results in the enhanced catalytic activity for CO formation with the increase of Au content. In addition, it was observed that copper oxide/hydroxide species are less stable on Au-Cu surfaces compared to those on 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 these alloys. In general, the formation of CO and HCOO─ as main CO2 reduction products on planar Au-Cu alloys followed the shift of d-band center, which indicates the electronic effect is the major governing factor for the electrocatalytic activity of CO2 reduction on Au-Cu bimetallic thin films.

KW - Au-Cu alloy

KW - bimetallic catalyst

KW - d-band center

KW - electrochemical carbon dioxide reduction

KW - electronic effect

KW - thin film

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