Methodology for kinetic studies of heterogeneous catalytic reactions

Kinetics of heterogeneous catalytic reactions, which bridges the gap between macroscopic performance and microscopic mechanisms, is of central importance to the rational design of catalysts. This review provides a systematic overview of the methodologies in this field. It begins with fundamental concepts, including catalytic cycles and rate-determining steps, and proceeds to elucidate classic surface reaction mechanisms such as the Langmuir-Hinshelwood and Eley-Rideal models. The discussion also covers theoretical approaches, including the steady-state approximation and quasi-equilibrium assumption, and introduces key experimental techniques like the kinetic isotope effect. Using typical catalytic systems—including ammonia synthesis, biomass conversion, and the selective oxidation of methane—as case studies, this review details how kinetic analysis is employed to construct rate equations, identify key intermediates, and determine dominant reaction pathways. This process reveals the fundamental relationship between the structure and performance of a catalyst. Finally, this review concludes that the synergistic integration of kinetic studies with in-situ characterization techniques and theoretical computations offers a critical pathway toward a deeper understanding of the nature of catalysis and facilitates the targeted development of high-performance catalysts.