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Electrocatalytic Reduction of CO_2 on Cu and Au/W Electrode Surfaces: Empirical (DEMS) Confirmation of Computational (DFT) Predictions

Javier, A. and Baricuatro, J. H. and Kim, Y.-G. and Soriaga, M. P. (2017) Electrocatalytic Reduction of CO_2 on Cu and Au/W Electrode Surfaces: Empirical (DEMS) Confirmation of Computational (DFT) Predictions. ECS Transactions, 75 (48). pp. 1-17. ISSN 1938-6737. https://resolver.caltech.edu/CaltechAUTHORS:20180914-100811125

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Abstract

This work describes the employment of differential electrochemical mass spectrometry (DEMS) as a supplementary experimental approach to theory in the study of the reaction mechanism of the Cu-catalyzed electrochemical reduction of CO_2 by investigating the reduction of reactants and (postulated) intermediates. The empirical inferences: (i) CO is one of the first products of CO_2 reduction, as well as the first intermediate in the formation of more reduced products. (ii) Formaldehyde is not a precursor for C=C bond formation but is an intermediate for the production of methane and ethanol. (iii) Both methane and ethanol can be generated from CO_2 through the protonation of CO and through the HCHO intermediate. (iv) The generation of CH_4 and CH_3CH_2OH from CO and CO_2 has a much higher activation barrier than from HCHO; not unexpected since the formaldehyde intermediate is formed after the (computationally determined) rate-limiting CO-protonation step. In this work, DEMS was also used to test the theoretical prediction suggesting the viability of a bimetallic near-surface alloy (NSA) consisting of Au and W as a CO_2-reduction electrocatalyst selective towards the formation of methanol as a product, as opposed to methane, ethylene or ethanol. At an overlayer NSA that consisted of n monolayers (ML) of Au on a polycrystalline W electrode, W(pc)-n[(1×1)-Au], no methane, methanol, ethylene or ethanol was detected when the coverage of Au was at submonolayer (n = 0.5) or multilayer (n ≥ 2) coverages. However, when the NSA contained only 1 ML of Au, methanol was generated exclusively.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1149/07548.0001ecstDOIArticle
ORCID:
AuthorORCID
Javier, A.0000-0002-0306-5462
Kim, Y.-G.0000-0002-5936-6520
Soriaga, M. P.0000-0002-0077-6226
Alternate Title:Electrocatalytic Reduction of CO2 on Cu and Au/W Electrode Surfaces: Empirical (DEMS) Confirmation of Computational (DFT) Predictions
Additional Information:© 2017 ECS - The Electrochemical Society. This material is based upon work performed by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award No. DE-SC0004993.
Group:JCAP
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0004993
Issue or Number:48
Record Number:CaltechAUTHORS:20180914-100811125
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180914-100811125
Official Citation:Alnald Javier, Jack Hess Baricuatro, Youn-Geun Kim, and Manuel P Soriaga Electrocatalytic Reduction of CO2 on Cu and Au/W Electrode Surfaces: Empirical (DEMS) Confirmation of Computational (DFT) Predictions ECS Trans. 2017 75(48): 1-17; doi:10.1149/07548.0001ecst
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:89636
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:14 Sep 2018 21:50
Last Modified:03 Oct 2019 20:17

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