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Title: Electrochemical CO 2 reduction on Au surfaces: mechanistic aspects regarding the formation of major and minor products

Abstract

In the future, industrial CO 2 electroreduction using renewable energy sources could be a sustainable means to convert CO 2 and water into commodity chemicals at room temperature and atmospheric pressure. This study focuses on the electrocatalytic reduction of CO 2 on polycrystalline Au surfaces, which have high activity and selectivity for CO evolution. Here, we explore the catalytic behavior of polycrystalline Au surfaces by coupling potentiostatic CO 2 electrolysis experiments in an aqueous bicarbonate solution with high sensitivity product detection methods. We observed the production of methanol, in addition to detecting the known products of CO 2 electroreduction on Au: CO, H 2 and formate. We suggest a mechanism that explains Au's evolution of methanol. Specifically, the Au surface does not favor C-O scission, and thus is more selective towards methanol than methane. These insights could aid in the design of electrocatalysts that are selective for CO 2 electroreduction to oxygenates over hydrocarbons.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [2];  [2]; ORCiD logo [2]
  1. Stanford Univ., CA (United States). Dept. of Chemical Engineering
  2. Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis, Dept. of Chemical Engineering; SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE; National Science Foundation (NSF)
OSTI Identifier:
1369311
Grant/Contract Number:
AC02-76SF00515; 1066515; FA9550-10-1-0572
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 19; Journal Issue: 24; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Cave, Etosha R., Montoya, Joseph H., Kuhl, Kendra P., Abram, David N., Hatsukade, Toru, Shi, Chuan, Hahn, Christopher, Nørskov, Jens K., and Jaramillo, Thomas F. Electrochemical CO2 reduction on Au surfaces: mechanistic aspects regarding the formation of major and minor products. United States: N. p., 2017. Web. doi:10.1039/c7cp02855e.
Cave, Etosha R., Montoya, Joseph H., Kuhl, Kendra P., Abram, David N., Hatsukade, Toru, Shi, Chuan, Hahn, Christopher, Nørskov, Jens K., & Jaramillo, Thomas F. Electrochemical CO2 reduction on Au surfaces: mechanistic aspects regarding the formation of major and minor products. United States. doi:10.1039/c7cp02855e.
Cave, Etosha R., Montoya, Joseph H., Kuhl, Kendra P., Abram, David N., Hatsukade, Toru, Shi, Chuan, Hahn, Christopher, Nørskov, Jens K., and Jaramillo, Thomas F. Fri . "Electrochemical CO2 reduction on Au surfaces: mechanistic aspects regarding the formation of major and minor products". United States. doi:10.1039/c7cp02855e. https://www.osti.gov/servlets/purl/1369311.
@article{osti_1369311,
title = {Electrochemical CO2 reduction on Au surfaces: mechanistic aspects regarding the formation of major and minor products},
author = {Cave, Etosha R. and Montoya, Joseph H. and Kuhl, Kendra P. and Abram, David N. and Hatsukade, Toru and Shi, Chuan and Hahn, Christopher and Nørskov, Jens K. and Jaramillo, Thomas F.},
abstractNote = {In the future, industrial CO2 electroreduction using renewable energy sources could be a sustainable means to convert CO2 and water into commodity chemicals at room temperature and atmospheric pressure. This study focuses on the electrocatalytic reduction of CO2 on polycrystalline Au surfaces, which have high activity and selectivity for CO evolution. Here, we explore the catalytic behavior of polycrystalline Au surfaces by coupling potentiostatic CO2 electrolysis experiments in an aqueous bicarbonate solution with high sensitivity product detection methods. We observed the production of methanol, in addition to detecting the known products of CO2 electroreduction on Au: CO, H2 and formate. We suggest a mechanism that explains Au's evolution of methanol. Specifically, the Au surface does not favor C-O scission, and thus is more selective towards methanol than methane. These insights could aid in the design of electrocatalysts that are selective for CO2 electroreduction to oxygenates over hydrocarbons.},
doi = {10.1039/c7cp02855e},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 24,
volume = 19,
place = {United States},
year = {Fri Jan 06 00:00:00 EST 2017},
month = {Fri Jan 06 00:00:00 EST 2017}
}

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Cited by: 4works
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  • Electroreduction of [Ru(bpy){sub 2}(CO){sub 2}]{sup 2+} in CH{sub 3}CN induces deposition of a [Ru{sup 0}(bpy)(CO){sub 2}{sub n}] film on the electrode. The authors used cyclic voltammetry to study the electrocatalytic effects of this film in the reduction of CO{sub 2}.
  • Electrochemical reduction of CO 2 using renewable sources of electrical energy holds promise for converting CO 2 to fuels and chemicals. Since this process is complex and involves a large number of species and physical phenomena, a comprehensive understanding of the factors controlling product distribution is required. While the most plausible reaction pathway is usually identified from quantum-chemical calculation of the lowest free-energy pathway, this approach can be misleading when coverages of adsorbed species determined for alternative mechanism differ significantly, since elementary reaction rates depend on the product of the rate coefficient and the coverage of species involved in themore » reaction. Moreover, cathode polarization can influence the kinetics of CO 2 reduction. Here in this work, we present a multiscale framework for ab initio simulation of the electrochemical reduction of CO 2 over an Ag(110) surface. A continuum model for species transport is combined with a microkinetic model for the cathode reaction dynamics. Free energies of activation for all elementary reactions are determined from density functional theory calculations. Using this approach, three alternative mechanisms for CO 2 reduction were examined. The rate-limiting step in each mechanism is **COOH formation at higher negative potentials. However, only via the multiscale simulation was it possible to identify the mechanism that leads to a dependence of the rate of CO formation on the partial pressure of CO 2 that is consistent with experiments. Additionally, simulations based on this mechanism also describe the dependence of the H 2 and CO current densities on cathode voltage that are in strikingly good agreement with experimental observation.« less
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