Electron Transfer in Solids and Activation of Molecules

Comprehensive Summary Electron transfer (ET) plays a fundamental role in heterogeneous catalysis, critically influencing the activation and transformation of molecules. At metal‐support interfaces, spontaneous charge redistribution modulates the electronic structures of both the metal and support, thereby promoting mass transfer, enhancing intrinsic reaction kinetics, and enabling synergistic catalytic behavior. In well‐designed photo‐driven systems, the directed migration of photogenerated carriers promotes the cleavage of highly inert bonds under mild conditions. In intermetallic compounds, internal electron transfer driven by electronegativity differences can generate well‐defined active sites that enhance both catalytic activity and selectivity. In this review, we introduce the mechanisms and effects of electron transfer across three catalytic systems: metal‐support interfaces, photo‐driven catalysis, and intermetallic compounds. We further propose that achieving precise atomic‐level control over these electron‐transfer pathways, along with elucidating the influence of intrinsic electron properties such as spin and orbital configuration, are crucial for developing next‐generation high‐performance catalysts. Key Scientists This timeline highlights a selection of landmark achievements in electron transfer theory and its applications in catalysis, and places the authors' contributions within this historical context: