Understanding Trends in the Electrocatalytic Activity of Metals and Enzymes for CO 2 Reduction to CO

作者：Heine Anton Hansen, Joel B. Varley, Andrew A. Peterson, Jens K. Nørskov · 发表于：The Journal of Physical Chemistry Letters · 年份：2013 · DOI：10.1021/jz3021155 · 被引用次数：746 · 研究领域：CO2 Reduction Techniques and Catalysts、Ionic liquids properties and applications、Advanced Thermoelectric Materials and Devices

We develop a model based on density functional theory calculations to describe trends in catalytic activity for CO2 electroreduction to CO in terms of the adsorption energy of the reaction intermediates, CO and COOH. The model is applied to metal surfaces as well as the active site in the CODH enzymes and shows that the strong scaling between adsorbed CO and adsorbed COOH on metal surfaces is responsible for the persistent overpotential. The active site of the CODH enzyme is not subject to these scaling relations and optimizes the relative binding energies of these adsorbates, allowing for an essentially reversible process with a low overpotential.