Dynamic Structural Evolution of Active Sites and Effect on Heterogeneous Catalysis: Theoretical Insights

The exploration of structure‐activity relationships is one of the key subjects for the rational design of heterogeneous catalysts. Advancements in characterization techniques have unveiled significant geometric and electronic structural changes at active sites under working conditions. This dynamic nature of active sites presents a formidable challenge in determining their structure‐activity relationships. Over the past decade, considerable theoretical studies have concentrated on deciphering the complex catalytic processes that occur at these dynamic active sites under working conditions, with much success in methodology, models, and mechanisms. Herein, we review key factors influencing active site evolution, such as surface adsorbates, temperature, and electrochemical potential. We also provide an overview of recent progress in understanding the effects of active site evolution on their catalytic performance. A better understanding to the dynamic evolution of active sites and corresponding effects on the catalysis under working conditions can help in the rational design of novel heterogeneous catalysts.