DFT-Based Multiscale Modeling of Heterogeneous (Electro)Catalytic Reactions

Abstract

The modeling of heterogeneous thermo- and electrocatalysis explores complex materials, intricate chemical reactions, various interfaces, and spans over multiple time and length scales. This requires tools that are able to capture the behavior of these diverse phenomena and bridge atomistic and macroscopic regimes. Density functional theory (DFT) forms a foundational approach for describing the microscopic properties of catalytic materials and reactions. Extending DFT to constant-potential calculations enables the study of systems at a fixed electrode potential while combining DFT with implicit or explicit solvent models allows for considering solvent effects at solid–liquid interfaces. By exploiting DFT-computed free energies, we can develop kinetic Monte Carlo and microkinetic simulation frameworks to investigate reaction kinetics while accounting for reaction conditions and mass transfer effects. The review and discussion the various levels of multiscale modeling and their connections leads to three key conclusions: (1) the relevant reaction conditions, mechanisms, interactions etc. need to be described at each level, (2) while easy-to-use software and methods for each level are available, they should not be treated as black boxes as the choices and assumptions are easily propagated between the levels, and (3) multiscale models allow one to embrace the complexity of (electro)catalytic reactions.