Electric Field Effects in Electrochemical CO2 Reduction

Leanne D. Chen, Makoto Urushihara, Karen Chan, Jens K. Nørskov*

*Corresponding author for this work

Research output: Contribution to journalJournal articleResearchpeer-review

Abstract

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. The computed polarization curves show reasonable agreement with experiment without fitting any parameters.

Original languageEnglish
JournalACS Catalysis
Volume6
Issue number10
Pages (from-to)7133-7139
ISSN2155-5435
DOIs
Publication statusPublished - 2016
Externally publishedYes

Keywords

  • CO reduction
  • Density functional theory
  • Field effects

Cite this

Chen, Leanne D. ; Urushihara, Makoto ; Chan, Karen ; Nørskov, Jens K. / Electric Field Effects in Electrochemical CO2 Reduction. In: ACS Catalysis. 2016 ; Vol. 6, No. 10. pp. 7133-7139.
@article{d882d75e24c8423ab5bee038eef3e5ce,
title = "Electric Field Effects in Electrochemical CO2 Reduction",
abstract = "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. The computed polarization curves show reasonable agreement with experiment without fitting any parameters.",
keywords = "CO reduction, Density functional theory, Field effects",
author = "Chen, {Leanne D.} and Makoto Urushihara and Karen Chan and N{\o}rskov, {Jens K.}",
year = "2016",
doi = "10.1021/acscatal.6b02299",
language = "English",
volume = "6",
pages = "7133--7139",
journal = "A C S Catalysis",
issn = "2155-5435",
publisher = "American Chemical Society",
number = "10",

}

Electric Field Effects in Electrochemical CO2 Reduction. / Chen, Leanne D.; Urushihara, Makoto; Chan, Karen; Nørskov, Jens K.

In: ACS Catalysis, Vol. 6, No. 10, 2016, p. 7133-7139.

Research output: Contribution to journalJournal articleResearchpeer-review

TY - JOUR

T1 - Electric Field Effects in Electrochemical CO2 Reduction

AU - Chen, Leanne D.

AU - Urushihara, Makoto

AU - Chan, Karen

AU - Nørskov, Jens K.

PY - 2016

Y1 - 2016

N2 - 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. The computed polarization curves show reasonable agreement with experiment without fitting any parameters.

AB - 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. The computed polarization curves show reasonable agreement with experiment without fitting any parameters.

KW - CO reduction

KW - Density functional theory

KW - Field effects

U2 - 10.1021/acscatal.6b02299

DO - 10.1021/acscatal.6b02299

M3 - Journal article

VL - 6

SP - 7133

EP - 7139

JO - A C S Catalysis

JF - A C S Catalysis

SN - 2155-5435

IS - 10

ER -