塔菲尔方程
析氧
热力学
过渡状态
催化作用
电催化剂
化学动力学
吉布斯自由能
从头算
化学
计算化学
物理化学
电化学
动力学
物理
电极
有机化学
量子力学
作者
Kai S. Exner,Iman Sohrabnejad‐Eskan,Herbert Over
标识
DOI:10.1021/acscatal.7b03142
摘要
Extended Tafel plots at various temperatures for an electrocatalyzed reaction and (possibly) its reversed reaction on single-crystalline model electrodes allow for constructing the (essential part of the) free energy surface, in particular the free energies of the transition states (TS). Free energies of the reaction intermediates (RIs) including the chemical nature of active surface sites (S) are hardly accessible to experiment and need therefore to be taken from constrained ab initio thermodynamics calculations. The compact compilation of experimental kinetic data in the form of a free energy diagram enables a critical assessment and validation of theoretical free energy landscapes based on first-principles kinetics. For three prototypical electrocatalyzed reactions, namely the chlorine evolution reaction (CER) and oxygen evolution reaction (OER) over RuO2(110) as well as hydrogen evolution reaction (HER) on Pt(111), we exemplify this universal approach and discuss potential benefits for theoretical modeling of electrocatalyzed reaction.
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