Unraveling the Complexity of Catalytic Reactions via Kinetic Monte Carlo Simulation: Current Status and Frontiers

Over the past two decades, the necessity for predictive models of chemical kinetics on catalytic surfaces has motivated the development of ab initio kinetic Monte Carlo (KMC) simulation frameworks. These frameworks have been successfully used to investigate chemistries of academic interest and industrial importance, such as CO oxidation, NO oxidation and reduction, ethylene hydrogenation, CO hydrogenation to ethanol, and water-gas shift. These studies have shed light on the effect of catalyst composition, surface structure, lateral interactions, and operating conditions on the apparent turnover frequency of the chemistries of interest. Yet, extending the existing KMC approaches to study large chemistries on complex catalytic structures poses several challenges. In this review, we discuss the recent milestones in the area of KMC simulation of chemical kinetics on catalytic surfaces and review a number of studies that have furthered our fundamental understanding of specific chemistries. In addition, we provide directions for future research aiming toward incorporating detailed physics and chemistry, as well as assessing and improving the accuracy of KMC methods, toward developing quantitative models of surface kinetics.