Application of Spatially Resolved Kinetic Monte Carlo Simulations in Microkinetic Modelling of Heterogeneous Catalytic Reactions

Microkinetic modelling occupies a central role in heterogeneous catalysis research by enabling a detailed mechanistic and kinetic understanding of catalytic reactions. While successful in elucidating multiple catalytic systems, microkinetic models are commonly constructed by assuming that all active sites are homogeneous and equivalent in reactivity. For systems where this assumption break down, spatially resolved kinetic Monte Carlo (kMC) methods can provide a robust protrayal of reaction kinetics.

In this dissertation, I will describe the application of spatially resolved kMC methods in three distinct reaction systems. The first system pertains to reactions on catalytic surfaces, where interactions between proximal adsorbed reaction intermediates can affect potential energy landscapes (and ultimately kinetics) of elementary steps in which they participate. The second system relates to NOx Selective Catalytic Reduction (SCR) on Cu-exchanged Chabazite zeolites, where SCR-active, mobile and cationic Cu complexes are electrostatically tethered to anionic Al centres, influencing their ability to participate in the catalysis. The third system relates to non-steady microkinetic modelling of temperature programmed evolution of NH3 from plasma induced N, where temperature dependent surface hopping of reaction intermediates and reaction rate constants of surface reactions are explicitly incorporated through stochastic lattice-kMC methods.