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Title: Electric field effects in electrochemical CO 2 reduction

Abstract

Electrochemical reduction of CO 2 has the potential to reduce greenhouse gas emissions while providing energy storage and producing chemical feedstocks. A mechanistic understanding of the process is crucial to the discovery of efficient catalysts, and an atomistic description of the electrochemical interface is a major challenge due to its complexity. Here, we examine the CO 2 → CO electrocatalytic pathway on Ag(111) using density functional theory (DFT) calculations and an explicit model of the electrochemical interface. We show that the electric field from solvated cations in the double layer and their corresponding image charges on the metal surface significantly stabilizes key intermediates—*CO 2 and *COOH. At the field-stabilized sites, the formation of *CO is rate-determining. We present a microkinetic model that incorporates field effects and electrochemical barriers from ab initio calculations. As a result, the computed polarization curves show reasonable agreement with experiment without fitting any parameters.

Authors:
 [1];  [2];  [1];  [1]
  1. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  2. Stanford Univ., Stanford, CA (United States); Mitsubishi Materials Corp., Ibaraki (Japan)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1348228
Grant/Contract Number:
SC0004993; AC02-76SF00515
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 6; Journal Issue: 10; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
54 ENVIRONMENTAL SCIENCES; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; CO2 reduction; density functional theory; field effects

Citation Formats

Chen, Leanne D., Urushihara, Makoto, Chan, Karen, and Nørskov, Jens K. Electric field effects in electrochemical CO2 reduction. United States: N. p., 2016. Web. doi:10.1021/acscatal.6b02299.
Chen, Leanne D., Urushihara, Makoto, Chan, Karen, & Nørskov, Jens K. Electric field effects in electrochemical CO2 reduction. United States. doi:10.1021/acscatal.6b02299.
Chen, Leanne D., Urushihara, Makoto, Chan, Karen, and Nørskov, Jens K. 2016. "Electric field effects in electrochemical CO2 reduction". United States. doi:10.1021/acscatal.6b02299. https://www.osti.gov/servlets/purl/1348228.
@article{osti_1348228,
title = {Electric field effects in electrochemical CO2 reduction},
author = {Chen, Leanne D. and Urushihara, Makoto and Chan, Karen and Nørskov, Jens K.},
abstractNote = {Electrochemical reduction of CO2 has the potential to reduce greenhouse gas emissions while providing energy storage and producing chemical feedstocks. A mechanistic understanding of the process is crucial to the discovery of efficient catalysts, and an atomistic description of the electrochemical interface is a major challenge due to its complexity. Here, we examine the CO2 → CO electrocatalytic pathway on Ag(111) using density functional theory (DFT) calculations and an explicit model of the electrochemical interface. We show that the electric field from solvated cations in the double layer and their corresponding image charges on the metal surface significantly stabilizes key intermediates—*CO2 and *COOH. At the field-stabilized sites, the formation of *CO is rate-determining. We present a microkinetic model that incorporates field effects and electrochemical barriers from ab initio calculations. As a result, the computed polarization curves show reasonable agreement with experiment without fitting any parameters.},
doi = {10.1021/acscatal.6b02299},
journal = {ACS Catalysis},
number = 10,
volume = 6,
place = {United States},
year = 2016,
month = 9
}

Journal Article:
Free Publicly Available Full Text
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Cited by: 3works
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