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

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 (Cu₁) 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 Cu₁ and Cu nanocluster (Cu_n) ensemble sites with a dynamic active configuration, which is unavailable by conventional thermal reduction methodology, for adaptive multisubstrate H₂ 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.