Theory and applications of surface micro‐kinetics in the rational design of catalysts using density functional theory calculations

Rational design of catalysts has long been an important and challenging goal in heterogeneous catalysis. To achieve this target, density functional theory ( DFT ) calculations and micro‐kinetics are two of the cornerstones. The DFT calculations make it possible to obtain microscopic properties of catalytic systems by computational simulations, and the micro‐kinetic modeling of surface reactions provides a tool to link quantum‐chemical data with macroscopic behaviors of the systems. In this review, we focus on the basic concepts and latest theoretical progresses of strategies for the catalysts design, including Brønsted−Evans−Polanyi relation, the volcano curve, and the activity window. Among the progresses, the theory of chemical potential kinetics in heterogeneous catalysis and its implications on catalysts design, which was developed by our group, are described in detail with extensive derivations. Furthermore, the applications of this method on screening low‐cost counter electrodes for dye‐sensitized solar cells are presented with experimental evidences. WIREs Comput Mol Sci 2017, 7:e1321. doi: 10.1002/wcms.1321 This article is categorized under: Structure and Mechanism > Reaction Mechanisms and Catalysis Theoretical and Physical Chemistry > Reaction Dynamics and Kinetics