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
Abstract
Operando scanning tunneling microscopy first revealed that application of a CO2-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↔Cu2O 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 CH3CH2OH 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 C2+ 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 startsmore »
- Publication Date:
- Research Org.:
- California Institute of Technology (CalTech), Pasadena, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1482406
- Alternate Identifier(s):
- OSTI ID: 1610793
- Grant/Contract Number:
- SC0004993
- Resource Type:
- Published Article
- Journal Name:
- Journal of the Electrochemical Society
- Additional Journal Information:
- Journal Name: Journal of the Electrochemical Society Journal Volume: 165 Journal Issue: 15; Journal ID: ISSN 0013-4651
- Publisher:
- IOP Publishing - The Electrochemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; Electrochemistry; Materials Science
Citation Formats
Tsang, Chu F., Javier, Alnald C., Kim, Youn-Geun, Baricuatro, Jack H., Cummins, Kyle D., Kim, Jutae, Jerkiewicz, Gregory, Hemminger, John C., and Soriaga, Manuel P.. 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. United States: N. p., 2018.
Web. doi:10.1149/2.0451815jes.
Tsang, Chu F., Javier, Alnald C., Kim, Youn-Geun, Baricuatro, Jack H., Cummins, Kyle D., Kim, Jutae, Jerkiewicz, Gregory, Hemminger, John C., & Soriaga, Manuel P.. 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. United States. https://doi.org/10.1149/2.0451815jes
Tsang, Chu F., Javier, Alnald C., Kim, Youn-Geun, Baricuatro, Jack H., Cummins, Kyle D., Kim, Jutae, Jerkiewicz, Gregory, Hemminger, John C., and Soriaga, Manuel P.. Thu .
"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". United States. https://doi.org/10.1149/2.0451815jes.
@article{osti_1482406,
title = {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},
author = {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.},
abstractNote = {Operando scanning tunneling microscopy first revealed that application of a CO2-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↔Cu2O 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 CH3CH2OH 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 C2+ 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.},
doi = {10.1149/2.0451815jes},
journal = {Journal of the Electrochemical Society},
number = 15,
volume = 165,
place = {United States},
year = {2018},
month = {11}
}
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