Understanding the Dynamic Evolution of Active Sites among Single Atoms, Clusters, and Nanoparticles

Abstract Catalysis remains a cornerstone of chemical research, with the active sites of catalysts being crucial for their functionality. Identifying active sites, particularly during the reaction process, is crucial for elucidating the relationship between a catalyst's structure and its catalytic property. However, the dynamic evolution of active sites within heterogeneous metal catalysts presents a substantial challenge for accurately pinpointing the real active sites. The advent of in situ and operando characterization techniques has illuminated the path toward understanding the dynamic changes of active sites, offering robust scientific evidence to support the rational design of catalysts. There is a pressing need for a comprehensive review that systematically explores the dynamic evolution among single atoms, clusters, and nanoparticles as active sites during the reaction process, utilizing in situ and operando characterization techniques. This review aims to delineate the effects of various reaction factors on dynamic evolution of active sites among single atoms, clusters, and nanoparticles. Moreover, several in situ and operando techniques are elaborated with emphases on tracking the dynamic evolution of active sites, linking them to catalytic properties. Finally, it discusses challenges and future perspectives in identifying active sites during the reaction process and advancing in situ and operando characterization techniques.