Toward computational design of chemical reactions with reaction phase diagram

Abstract Density functional theory (DFT) was rapidly developed and achieved a great success in the last decades. As the advancement of general concepts in heterogeneous catalysis, theoretical study of chemical reactions based on DFT calculations has become more and more feasible, which provides a guideline for the rational design of novel catalysts toward higher reaction activity and specific selectivity. Here, we review an innovate scheme, namely reaction phase diagram (RPD), which can offer not only an in‐depth understanding of reaction mechanisms, but also the prediction of catalytic activity and selectivity trend over a collection of catalysts. The RPD analysis was successfully applied to understand the activity variation of CO 2 electroreduction to CO and formic acid, as well as thermochemical hydrogenation and dehydrogenation. Meanwhile, the RPD analysis also exhibits a success of studying the product selectivity in syngas conversion to methane, ethanol, and methanol with complicated reaction pathways. At the end, we review a successful case of catalyst rational design with a target of NO selective electroreduction to ammonia. The foundation of RPD analysis is based on the scaling relation of adsorption energies and the correlation between kinetic barriers and reaction energies at elementary steps. Therefore, microkinetic modeling is complementary to the RPD analysis. A few of limitations and the prospect of the development regarding the RPD analysis are addressed in this review. This article is categorized under: Structure and Mechanism > Reaction Mechanisms and Catalysis