Toward Computational Design of Catalysts for CO₂ Selective Reduction via Reaction Phase Diagram Analysis

Abstract

Abstract Chemical conversion of carbon dioxide (CO 2 ) into value‐added chemicals, for example, ethanol, has been recognized to be one of the most effective ways of carbon sources cycling. However, the selectivity controlling of CO 2 reduction is still a challenging problem due to the formation of a variety of products, such as methanol, methane, formic acid, and carbon monoxide, associating with complicated reaction mechanisms. Herein, a simple and effective theoretical analysis of “reaction phases diagram” to understand the selectivity of CO 2 reduction, based on the principle of reaction free energies with sequential priority is proposed. Using this principle, the fundamental understanding of the formation of different products in CO 2 reduction is rationalized. On the basis of reaction free energies’ analysis, the selectivity trends of CO 2 reduction to methane, methanol, and ethanol from a number of experiments are discussed. At the end, the selectivity trends with a computer algorithm of searching full reaction pathways, explaining well the effects from catalyst sizes, substrate observed in experiments, are confirmed.