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Potential-Dependent Adsorption of CO and Its Low-Overpotential Reduction to CH_3CH_2OH on Cu(511) Surface Reconstructed from Cu(pc): Operando Studies by Seriatim STM-EQCN-DEMS

Tsang, Chu F. and Javier, Alnald C. and Kim, Youn-Geun and Baricuatro, Jack H. and Cummins, Kyle D. and Kim, Jutae and Jerkiewicz, Gregory and Hemminger, John C. and Soriaga, Manuel P. (2018) Potential-Dependent Adsorption of CO and Its Low-Overpotential Reduction to CH_3CH_2OH on Cu(511) Surface Reconstructed from Cu(pc): Operando Studies by Seriatim STM-EQCN-DEMS. Journal of the Electrochemical Society, 165 (15). J3350-J3354. ISSN 0013-4651. http://resolver.caltech.edu/CaltechAUTHORS:20181128-160202260

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Abstract

Operando scanning tunneling microscopy first revealed that application of a CO_2-reduction potential to a Cu(pc) electrode in 0.1 M KOH resulted in the reconstruction of the selvedge to an x-layer stack of well-ordered Cu(100) terraces, Cu(pc)-x[Cu(100)]. Subsequent Cu↔Cu_2O oxidation-reduction cycles between −0.90 V and 0.10 V SHE converted the reconstructed region to a stepped Cu(S)-[3(100) × (111)], or Cu(511), surface. Differential electrochemical mass spectrometry showed that reduction of CO produced only CH_3CH_2OH at the lowest overpotential. Later application of STM and surface infrared spectroscopy uncovered a potential, above which no CO adsorption occurs. In this study, electrochemical quartz crystal nanobalance was combined with STM and DEMS as a prelude to the acquisition of CO coverages as continuous functions of concentration and potential; in heterogeneous catalysis, surface coverage are important since the reaction rate are functions of those quantities. Also equally critical is the knowledge of the packing arrangement at the onset of the reaction because, if “CO dimers” were indeed the precursors to C_(2+) products, reduction can only be initiated when the adlayer consists of closely packed CO; otherwise, dimerization will not transpire if the molecules were far apart. The results indicate that the catalysis lags the adsorption, and starts only when CO adsorption is saturated.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1149/2.0451815jesDOIArticle
ORCID:
AuthorORCID
Kim, Youn-Geun0000-0002-5936-6520
Soriaga, Manuel P.0000-0002-0077-6226
Alternate Title:Potential-Dependent Adsorption of CO and Its Low-Overpotential Reduction to CH3CH2OH on Cu(511) Surface Reconstructed from Cu(pc): Operando Studies by Seriatim STM-EQCN-DEMS
Additional Information:© 2018 The Author(s). Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/by/4.0/), which permits unrestricted reuse of the work in any medium, provided the original work is properly cited. Manuscript submitted August 10, 2018. Revised manuscript received October 15, 2018. Published November 15, 2018. This paper is part of the JES Focus Issue on Electrocatalysis — In Honor of Radoslav Adzic. 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
Subject Keywords:Surface Science; Electrochemical quartz crystal nanobalance; Potential-dependence of CO adsorption on Cu(511) in KOH; Seriatim STM-EQCN-DEMS
Record Number:CaltechAUTHORS:20181128-160202260
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20181128-160202260
Official Citation:Chu F. Tsang, Alnald C. Javier, Youn-Geun Kim, Jack H. Baricuatro, Kyle D. Cummins, Jutae Kim, Gregory Jerkiewicz, John C. Hemminger, and Manuel P. Soriaga. Potential-Dependent Adsorption of CO and Its Low-Overpotential Reduction to CH3CH2OH on Cu(511) Surface Reconstructed from Cu(pc): Operando Studies by Seriatim STM-EQCN-DEMS. J. Electrochem. Soc. 2018 165(15): J3350-J3354; doi:10.1149/2.0451815jes
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:91321
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:29 Nov 2018 00:09
Last Modified:29 Nov 2018 00:09

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