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Selective conversion of CO into ethanol on Cu(511) surface reconstructed from Cu(pc): Operando studies by electrochemical scanning tunneling microscopy, mass spectrometry, quartz crystal nanobalance, and infrared spectroscopy

Journal Article · · Journal of Electroanalytical Chemistry
 [1];  [2];  [3];  [2];  [2];  [4]
  1. California Institute of Technology (CalTech), Pasadena, CA (United States); OSTI
  2. California Institute of Technology (CalTech), Pasadena, CA (United States)
  3. California Institute of Technology (CalTech), Pasadena, CA (United States); Univ. of California, Irvine, CA (United States)
  4. Univ. of California, Irvine, CA (United States)
+ Show Author Affiliations
A polycrystalline copper, surface-terminated by a well-defined (511)-oriented facet, was electrochemically generated by a series of step-wise surface reconstruction and iterations of mild oxidative-reductive processes in 0.1 M KOH. The electrochemical reduction of CO on the resultant stepped surface was investigated by four surface-sensitive operando methodologies: electrochemical scanning tunneling microscopy (STM), electrochemical quartz crystal nanobalance (EQCN), differential electrochemical mass spectrometry (DEMS), and polarization-modulation infrared spectroscopy (PMIRS). The stepped surface catalyzed the facile conversion of CO into ethanol, the exclusive alcohol product at a low overpotential of -1.06 V (SHE) or -0.3 V (RHE). The chemisorption of CO was found to be a necessary prelude to ethanol production; i.e. the surface coverages, rather than solution concentrations, of CO and its surface-bound intermediates primarily dictate the reaction rates (current densities). Contrary to the expected predominance of undercoordinated step-site reactivity over the coordination chemistry of vicinal surfaces, vibrational spectroscopic evidence reveals the involvement of terrace-bound CO adsorbates during the multi-atomic transformations associated with the production of ethanol.
Research Organization:
California Institute of Technology (CalTech), Pasadena, CA (United States)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC)
Grant/Contract Number:
SC0004993
OSTI ID:
1801623
Alternate ID(s):
OSTI ID: 1598366
Journal Information:
Journal of Electroanalytical Chemistry, Journal Name: Journal of Electroanalytical Chemistry Journal Issue: C Vol. 857; ISSN 1572-6657
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (1)

Electrochemical CO 2 reduction on nanostructured metal electrodes: fact or defect? journal January 2020

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Operando electrode-surface microscopy
Operando molecular vibrational spectroscopy
CO adsorption on Cu vicinal surface
chemistry
electrochemically generated Cu(511) surface
electrochemistry
selective reduction of CO into ethanol