Abstract: Understanding catalysis from the molecular scale to the materials scale rely on the combined effort of the experimental characterization and theoretical modelling. Currently, there is a significant development for the in-situ and in particular operando experimental techniques that calls for the simultaneous development of methodologies for theoretical modelling. In fact, several promising methods have been developed and applied in the theoretical modelling of heterogeneous catalysis under the operando conditions. Here we provide a brief overview of these methods addressing their advances as well as the challenges. In particular, the microkintics is required to bridge the microscopic information and the macroscopic properties, which is the most important to the catalyst rational design. However, the accurate and efficient microkinetic method is still lacking. Recently, we propose a method, namely XPK, to extend the phenomenological kinetics for the accurate and efficient microkinetic modeling of heterogeneous catalysis. The advance of such methods will promote the development of the predictive theoretical modelling under operando conditions and will be beneficial to the computation-based rational design of catalysts.

Key words: microkinetics, extended phenomenological kinetics, operando, heterogeneous catalysis, theoretical modelling