Chemical kinetics of heterogeneous catalysis: experimental research methodologies and case studies of site-isolated materials

Heterogeneous catalysts mediate chemical reactions at fluid–solid interfaces and contain active sites of diverse structure and function. Chemical kinetic processes at surfaces connect to macroscopic measurements through transport processes; thus, intrinsic kinetic measurements require rendering irrelevant, or accurately modeling the influences of, gradients in thermodynamic activity and temperature between active sites and bulk fluid phases. Quantifying turnover rates further requires methods to quantify the density of putative active sites on catalyst surfaces. This review discusses experimental research methodologies to perform quantitative kinetic studies of heterogeneous catalysis, highlighting examples from contemporary research reports with a focus on site-isolated materials.