Substrate‐Adapted Active Site Self‐Evolving Reconfiguration Boosting Catalytic Effect on Acetylene Semihydrogenation

Abstract The facile synthesis of highly substrate‐adapted catalysts with dynamic active site adaptability remains a persistent challenge in heterogeneous catalysis. Herein, breaking through conventional catalyst preparation route of design–synthesis–evaluation iteration, we demonstrate an active site self‐evolving reconfiguration strategy for spontaneous construction of an adaptive multimolecular activation catalyst, such as for acetylene semihydrogenation. Specifically, a metastable Cu single atom (Cu 1 ) precursor as structural seed reconstructs to an exceptional acetylene semihydrogenation catalyst under moderate operational conditions, which undergoes a copper active site reconfiguration employing reactants themselves as inducing medium. This self‐evolving reconfiguration creates cooperative Cu 1 and Cu nanocluster (Cu n ) ensemble sites with a dynamic active configuration, which is unavailable by conventional thermal reduction methodology, for adaptive multisubstrate H 2 and acetylene activation. Hence, the resulting catalyst achieves full acetylene conversion with 96% ethylene selectivity and robust durability (>30 h) at a record‐low temperature of 120 °C, superior to reported copper‐based analogues. Such spontaneous active site self‐evolving reconfiguration offers a new possibility for intelligent catalyst engineering.