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

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