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

Baricuatro, Jack H.; Kim, Youn-Geun; Tsang, Chu F.; Javier, Alnald C.; Cummins, Kyle D.; Hemminger, John C.

doi:10.1016/j.jelechem.2019.113704

Title: 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 · Thu Nov 28 00:00:00 EST 2019 · Journal of Electroanalytical Chemistry

DOI:https://doi.org/10.1016/j.jelechem.2019.113704· OSTI ID:1801623

Baricuatro, Jack H. ^[1];

^[1]; Tsang, Chu F. ^[2]; Javier, Alnald C. ^[1]; Cummins, Kyle D. ^[1]; Hemminger, John C. ^[3]

California Institute of Technology (CalTech), Pasadena, CA (United States)
California Institute of Technology (CalTech), Pasadena, CA (United States); Univ. of California, Irvine, CA (United States)
Univ. of California, Irvine, CA (United States)

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.

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Research Organization:: California Institute of Technology (CalTech), Pasadena, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: SC0004993

OSTI ID:: 1801623

Alternate ID(s):: OSTI ID: 1598366

Journal Information:: Journal of Electroanalytical Chemistry, Vol. 857, Issue C; ISSN 1572-6657

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 6 works

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Related Subjects

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

Title: 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

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