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Surface reconstruction of pure-Cu single-crystal electrodes under Co-reduction potentials in alkaline solutions: A study by seriatim ECSTM-DEMS

Kim, Youn-Geun and Javier, Alnald and Baricuatro, Jack H. and Torelli, Daniel and Cummins, Kyle D. and Tsang, Chu F. and Hemminger, John C. and Soriaga, Manuel P. (2016) Surface reconstruction of pure-Cu single-crystal electrodes under Co-reduction potentials in alkaline solutions: A study by seriatim ECSTM-DEMS. Journal of Electroanalytical Chemistry, 780 . pp. 290-295. ISSN 1572-6657. doi:10.1016/j.jelechem.2016.09.029.

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Quasi-operando electrochemical scanning tunneling microscopy (ECSTM) recently showed that a polycrystalline Cu electrode kept in 0.1 M KOH at − 0.9 V (SHE), a potential very close to that for electrochemical CO reduction, underwent a two-step surface reconstruction, initially to Cu(111), or Cu(pc)-[Cu(111)], and terminally to Cu(100), or Cu(pc)-[Cu(100)]. When subjected to monolayer-limited Cu_((s)) ↔ Cu_2O_((s)) oxidation-reduction cycles (ORC), the Cu(pc)-[Cu(100)] surface was further transformed to Cu(pc)-[Cu(511)] that produced C_2H_5OH exclusively, as detected by differential electrochemical mass spectrometry, at an overvoltage lower by 645 mV relative to that for the formation of hydrocarbons. In this paper, results are presented from studies with the native monocrystalline surfaces Cu(111), Cu(100) and Cu(110). Whereas the intermediate Cu(pc)-[Cu(111)] layer was eventually converted to Cu(pc)-[Cu(100)], the surface of a pristine Cu(111) single crystal itself showed no such conversion. The surface of an original Cu(100) electrode likewise proved impervious to potential perturbations. In contrast, the outer plane of a Cu(110) crystal underwent three transformations: first to disordered Cu(110)-d[Cu(110)], then to disordered Cu(110)-d[Cu(111)], and finally to an ordered Cu(110)-[Cu(100)] plane. After multiple ORC, the converted [Cu(100)] lattice atop the Cu(110) crystal did not generate ethanol, in contrast to the [Cu(100)] phase above the Cu(pc) bulk. Quasi-operando ECSTM captured the disparity: Post-ORC, Cu(110)-[Cu(100)] was converted, not to Cu(110)-[Cu(511)], but to an ordered but catalytically inactive Cu(110)-[Cu(111)]; hence, no C2H5OH production upon reduction of CO, as would have been the case for a stepped Cu(511) surface.

Item Type:Article
Related URLs:
URLURL TypeDescription
Kim, Youn-Geun0000-0002-5936-6520
Javier, Alnald0000-0002-0306-5462
Torelli, Daniel0000-0002-6222-817X
Hemminger, John C.0000-0003-2467-6630
Soriaga, Manuel P.0000-0002-0077-6226
Additional Information:© 2016 Elsevier. Received 31 July 2016; revised 17 September 2016; accepted 20 September 2016; available online 21 September 2016. 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.
Errata:A publisher's error resulted in this article appearing in the wrong issue. The article is reprinted here for the reader's convenience and for the continuity of the special issue. For citation purposes, please use the original publication details; Journal of Electroanalytical Chemistry Volume 780, 1 November 2016, Pages 290–295
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0004993
Subject Keywords:Surface reconstruction of Cu electrodes under CO-reduction potentials; Quasi-operando electrochemical scanning tunneling microscopy; Differential electrochemical mass spectrometry; Seriatim ECSTM-DEMS
Record Number:CaltechAUTHORS:20161010-151601789
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Official Citation:Youn-Geun Kim, Alnald Javier, Jack H. Baricuatro, Daniel Torelli, Kyle D. Cummins, Chu F. Tsang, John C. Hemminger, Manuel P. Soriaga, Surface reconstruction of pure-Cu single-crystal electrodes under CO-reduction potentials in alkaline solutions: A study by seriatim ECSTM-DEMS, Journal of Electroanalytical Chemistry, Volume 780, 1 November 2016, Pages 290-295, ISSN 1572-6657, (
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:70973
Deposited By: Melissa Ray
Deposited On:12 Oct 2016 19:24
Last Modified:11 Nov 2021 04:38

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