Advances and Challenges in Speciation Measurement and Microkinetic Modeling for Gas–Solid Heterogeneous Catalysis
Wenhao Yuan, Zaili Xiong, Meirong Zeng, Zhongyue Zhou, Zhandong Wang, Jiuzhong Yang, Long Zhao, Yang Pan, Fei Qi
Abstract
Microkinetic modeling of heterogeneous catalysis serves as an efficient tool bridging atom-scale first-principles calculations and macroscale industrial reactor simulations. Fundamental understanding of the microkinetic mechanism relies on a combination of experimental and theoretical studies. This Perspective presents an overview of the latest progress of experimental and microkinetic modeling approaches applied to gas–solid catalytic kinetics. Then, opportunities and challenges are presented based on recent research progress in gas–solid catalysis and combustion chemistry. For experimental approaches, the importance of ideal catalytic reactors, structured catalysts, and precise elementary rate measurements is emphasized. Additionally, integrating spatiotemporally resolved operando gas-phase diagnostics with surface-adsorbed species characterization methods offers new opportunities for gaining deeper insights into gas–surface reactions. In microkinetic modeling, a hybrid rate parameter evaluation approach that combines first-principles calculations with semiempirical methods, followed by automated mechanism generation and data-driven optimization, opens new avenues for efficiently constructing surface mechanisms. Furthermore, extending microkinetic modeling beyond mean-field approximations allows simulations under realistic catalyst operating conditions. Finally, the critical role of gas-phase mechanisms and comprehensive microkinetic modeling analyses in advancing our fundamental understanding of gas–solid catalytic processes is highlighted.