密度泛函理论
电化学
从头算
化学
极化(电化学)
催化作用
电场
化学物理
从头算量子化学方法
金属
计算化学
电极
分子
物理化学
有机化学
物理
量子力学
作者
Leanne D. Chen,Makoto Urushihara,Karen Chan,Jens K. Nørskov
标识
DOI:10.1021/acscatal.6b02299
摘要
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.
科研通智能强力驱动
Strongly Powered by AbleSci AI