How Heterogeneity Affects Cooperative Communications within Single Nanocatalysts

Abstract

Catalysis remains one of the most essential methods in chemical research and industry. Recent experiments have discovered an unusual phenomenon of catalytic cooperativity, when a reaction at one active site can stimulate reactions at neighboring sites within single nanoparticles. While theoretical analysis established that the transport of charged holes is responsible for this phenomenon, it does not account for inhomogeneity in the structural and dynamic properties of single nanocatalysts. Here, we investigate the effect of heterogeneity on catalytic communications by extending a discrete-state stochastic framework to random distributions of the transition rates. Our explicit calculations of spatial and temporal properties of heterogeneous systems in comparison with homogeneous systems predict that the strength of cooperativity increases, while the communication lifetimes and distances decrease. Monte Carlo computer simulations support theoretical calculations, and microscopic arguments to explain these observations are also presented. Our theoretical analysis clarifies some important aspects of molecular mechanisms of catalytic processes.