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
Abstract
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.
- Authors:
-
- 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)
- Publication Date:
- Research Org.:
- California Institute of Technology (CalTech), Pasadena, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1801623
- Alternate Identifier(s):
- OSTI ID: 1598366
- Grant/Contract Number:
- SC0004993
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Electroanalytical Chemistry
- Additional Journal Information:
- Journal Volume: 857; Journal Issue: C; Journal ID: ISSN 1572-6657
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 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
Citation Formats
Baricuatro, Jack H., Kim, Youn-Geun, Tsang, Chu F., Javier, Alnald C., Cummins, Kyle D., and Hemminger, John C. 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. United States: N. p., 2019.
Web. doi:10.1016/j.jelechem.2019.113704.
Baricuatro, Jack H., Kim, Youn-Geun, Tsang, Chu F., Javier, Alnald C., Cummins, Kyle D., & Hemminger, John C. 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. United States. https://doi.org/10.1016/j.jelechem.2019.113704
Baricuatro, Jack H., Kim, Youn-Geun, Tsang, Chu F., Javier, Alnald C., Cummins, Kyle D., and Hemminger, John C. Thu .
"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". United States. https://doi.org/10.1016/j.jelechem.2019.113704. https://www.osti.gov/servlets/purl/1801623.
@article{osti_1801623,
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},
author = {Baricuatro, Jack H. and Kim, Youn-Geun and Tsang, Chu F. and Javier, Alnald C. and Cummins, Kyle D. and Hemminger, John C.},
abstractNote = {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.},
doi = {10.1016/j.jelechem.2019.113704},
journal = {Journal of Electroanalytical Chemistry},
number = C,
volume = 857,
place = {United States},
year = {Thu Nov 28 00:00:00 EST 2019},
month = {Thu Nov 28 00:00:00 EST 2019}
}
Web of Science
Works referenced in this record:
Homogeneously Catalyzed Electroreduction of Carbon Dioxide—Methods, Mechanisms, and Catalysts
journal, January 2018
- Francke, Robert; Schille, Benjamin; Roemelt, Michael
- Chemical Reviews, Vol. 118, Issue 9
Selective Formation of C2 Compounds from Electrochemical Reduction of CO 2 at a Series of Copper Single Crystal Electrodes
journal, January 2002
- Hori, Yoshio; Takahashi, Ichiro; Koga, Osamu
- The Journal of Physical Chemistry B, Vol. 106, Issue 1
Seriatim ECSTM-ECPMIRS of the adsorption of carbon monoxide on Cu(100) in alkaline solution at CO2-reduction potentials
journal, June 2018
- Baricuatro, Jack H.; Kim, Youn-Geun; Korzeniewski, Carol L.
- Electrochemistry Communications, Vol. 91
In situ scanning tunneling microscopy in electrolyte solutions
journal, July 1998
- Itaya, Kingo
- Progress in Surface Science, Vol. 58, Issue 3, p. 121-247
Electrochemical CO2 Reduction on Metal Electrodes
book, January 2008
- Hori, Y.; Vayenas, Constantinos G.; White, Ralph E.
- Modern Aspects of Electrochemistry, p. 89-189
Molecular Orbital View of Chemisorbed Carbon Monoxide
journal, October 1964
- Blyholder, George
- The Journal of Physical Chemistry, Vol. 68, Issue 10
Regulating the Product Distribution of CO Reduction by the Atomic-Level Structural Modification of the Cu Electrode Surface
journal, June 2016
- Kim, Youn-Geun; Javier, Alnald; Baricuatro, Jack H.
- Electrocatalysis, Vol. 7, Issue 5
Analysis of the mass response of the electrochemical quartz-crystal nanobalance in horizontal and vertical geometry
journal, September 1999
- Jerkiewicz, Gregory; Vatankhah, Gholam; Zolfaghari, Alireza
- Electrochemistry Communications, Vol. 1, Issue 9
Mixed Copper States in Anodized Cu Electrocatalyst for Stable and Selective Ethylene Production from CO 2 Reduction
journal, June 2018
- Lee, Si Young; Jung, Hyejin; Kim, Nak-Kyoon
- Journal of the American Chemical Society, Vol. 140, Issue 28
Electrocatalytic and homogeneous approaches to conversion of CO 2 to liquid fuels
journal, January 2009
- Benson, Eric E.; Kubiak, Clifford P.; Sathrum, Aaron J.
- Chem. Soc. Rev., Vol. 38, Issue 1
Site‐specific properties and dynamical dipole coupling of CO molecules adsorbed on a vicinal Cu(100) surface
journal, November 1994
- Borguet, Eric; Dai, Hai‐Lung
- The Journal of Chemical Physics, Vol. 101, Issue 10
New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces
journal, January 2012
- Kuhl, Kendra P.; Cave, Etosha R.; Abram, David N.
- Energy & Environmental Science, Vol. 5, Issue 5
Surface Reconstruction of Polycrystalline Cu Electrodes in Aqueous KHCO3 Electrolyte at Potentials in the Early Stages of CO2 Reduction
journal, April 2018
- Kim, Youn-Geun; Baricuatro, Jack H.; Soriaga, Manuel P.
- Electrocatalysis, Vol. 9, Issue 4
Potential-Dependent Adsorption of CO and Its Low-Overpotential Reduction to CH 3 CH 2 OH on Cu(511) Surface Reconstructed from Cu(pc): Operando Studies by Seriatim STM-EQCN-DEMS
journal, January 2018
- Tsang, Chu F.; Javier, Alnald C.; Kim, Youn-Geun
- Journal of The Electrochemical Society, Vol. 165, Issue 15
A Thin-Layer Electrochemical Cell for Infrared Spectroscopic Measurements of the Electrode/Electrolyte Interface
journal, May 1985
- Seki, H.; Kunimatsu, K.; Golden, W. G.
- Applied Spectroscopy, Vol. 39, Issue 3
Electrocatalytic Conversion of Carbon Dioxide to Methane and Methanol on Transition Metal Surfaces
journal, August 2014
- Kuhl, Kendra P.; Hatsukade, Toru; Cave, Etosha R.
- Journal of the American Chemical Society, Vol. 136, Issue 40
LEED and surface potential study of carbon monoxide and Xenon adsorbed on Cu(100)
journal, December 1971
- Chesters, M. A.; Pritchard, J.
- Surface Science, Vol. 28, Issue 2
A DEMS Study of the Reduction of CO2, CO, and HCHO Pre-Adsorbed on Cu Electrodes: Empirical Inferences on the CO2RR Mechanism
journal, January 2015
- Javier, Alnald; Chmielowiec, Brian; Sanabria-Chinchilla, Jean
- Electrocatalysis, Vol. 6, Issue 2
Surface reconstruction of pure-Cu single-crystal electrodes under CO-reduction potentials in alkaline solutions: A study by seriatim ECSTM-DEMS
journal, November 2016
- Kim, Youn-Geun; Javier, Alnald; Baricuatro, Jack H.
- Journal of Electroanalytical Chemistry, Vol. 780
Structure Sensitivity of the Electrochemical Reduction of Carbon Monoxide on Copper Single Crystals
journal, April 2013
- Schouten, Klaas Jan P.; Pérez Gallent, Elena; Koper, Marc T. M.
- ACS Catalysis, Vol. 3, Issue 6
The Evolution of the Polycrystalline Copper Surface, First to Cu(111) and Then to Cu(100), at a Fixed CO 2 RR Potential: A Study by Operando EC-STM
journal, December 2014
- Kim, Youn-Geun; Baricuatro, Jack Hess; Javier, Alnald
- Langmuir, Vol. 30, Issue 50
A mechanistic model for the electrochemical facetting of metals with development of preferred crystallographic orientations
journal, February 1988
- Albano, E. V.; Mártin, H. O.; Arvia, A. J.
- Electrochimica Acta, Vol. 33, Issue 2
Infrared Study of Adsorbed Molecules on Metal Surfaces by Reflection Techniques
journal, January 1966
- Greenler, Robert G.
- The Journal of Chemical Physics, Vol. 44, Issue 1