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Title: An in-situ electrochemical IR investigation of solution CO electro-oxidation on a polycrystalline Au surface in an alkaline electrolyte: Identification of active reaction intermediates

Abstract

Here we report an in-situ electrochemical surface enhanced IR reflection absorption spectroscopic (SEIRAS) study of carbon monoxide electro-oxidation reaction (COR) of CO dissolved in alkaline supporting electrolyte (COsol). With judiciously chosen concentration of OH-, we were able to observe for the first time the vibrational band of the weakly adsorbed COw in an alkaline solution and identify it as the active reaction intermediate for the COR of COsol, as in the acidic media. With the help of deuterium labeling, we were also able to confirm spectroscopically, again for the first time, the previously proposed CO-adsorption-promoted-OH-adsorption hypothesis. We proposed a reaction mechanism accordingly that consists of (1) CO-adsorption-promoted OH adsorption, (2) formation of weakly-bound COw from COsol, and (3) the oxidation of COw by a surface-anchored weakly-hydrogen-bound species. We believe that the synergistic actions of these elemental chemical processes are the reasons for the observed unusually high activity of COR of COsol in an alkaline solution.

Authors:
ORCiD logo [1]; ORCiD logo [1]
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  1. Georgetown University, Washington, DC (United States)
Publication Date:
Research Org.:
Georgetown Univ., Washington, DC (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1533978
Alternate Identifier(s):
OSTI ID: 1550515
Grant/Contract Number:  
FG02-07ER15895
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Electroanalytical Chemistry
Additional Journal Information:
Journal Volume: 800; 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; carbon monoxide electro-oxidation reaction; in situ SEIRAS; weakly-bound CO; CO-adsorption-promoted OH adsorption; alkaline solution

Citation Formats

Chen, De-Jun, and Tong, YuYe J. An in-situ electrochemical IR investigation of solution CO electro-oxidation on a polycrystalline Au surface in an alkaline electrolyte: Identification of active reaction intermediates. United States: N. p., 2017. Web. doi:10.1016/j.jelechem.2017.04.045.
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Chen, De-Jun, & Tong, YuYe J. An in-situ electrochemical IR investigation of solution CO electro-oxidation on a polycrystalline Au surface in an alkaline electrolyte: Identification of active reaction intermediates. United States. https://doi.org/10.1016/j.jelechem.2017.04.045
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Chen, De-Jun, and Tong, YuYe J. Wed . "An in-situ electrochemical IR investigation of solution CO electro-oxidation on a polycrystalline Au surface in an alkaline electrolyte: Identification of active reaction intermediates". United States. https://doi.org/10.1016/j.jelechem.2017.04.045. https://www.osti.gov/servlets/purl/1533978.
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@article{osti_1533978,
title = {An in-situ electrochemical IR investigation of solution CO electro-oxidation on a polycrystalline Au surface in an alkaline electrolyte: Identification of active reaction intermediates},
author = {Chen, De-Jun and Tong, YuYe J.},
abstractNote = {Here we report an in-situ electrochemical surface enhanced IR reflection absorption spectroscopic (SEIRAS) study of carbon monoxide electro-oxidation reaction (COR) of CO dissolved in alkaline supporting electrolyte (COsol). With judiciously chosen concentration of OH-, we were able to observe for the first time the vibrational band of the weakly adsorbed COw in an alkaline solution and identify it as the active reaction intermediate for the COR of COsol, as in the acidic media. With the help of deuterium labeling, we were also able to confirm spectroscopically, again for the first time, the previously proposed CO-adsorption-promoted-OH-adsorption hypothesis. We proposed a reaction mechanism accordingly that consists of (1) CO-adsorption-promoted OH adsorption, (2) formation of weakly-bound COw from COsol, and (3) the oxidation of COw by a surface-anchored weakly-hydrogen-bound species. We believe that the synergistic actions of these elemental chemical processes are the reasons for the observed unusually high activity of COR of COsol in an alkaline solution.},
doi = {10.1016/j.jelechem.2017.04.045},
journal = {Journal of Electroanalytical Chemistry},
number = C,
volume = 800,
place = {United States},
year = {Wed Apr 26 00:00:00 EDT 2017},
month = {Wed Apr 26 00:00:00 EDT 2017}
}
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https://doi.org/10.1016/j.jelechem.2017.04.045
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