Gram-Scale Synthesis of an Ultrastable 38-Nuclei Copper(I) Alkynide Nanocluster for Unraveling Bifunctional Photocatalysis

Developing earth-abundant single catalysts capable of simultaneously driving redox reactions is highly desirable, yet it remains elusive due to band gap engineering complexity and rapid charge recombination. Herein, gram-scale synthesis of an ultrastable copper(I) alkynyl nanocluster (Cu38) was realized, and its bifunctionalization was comprehensively studied. Cu38 features a sandwiched structure comprising two Cu10 units and a peanut-like Cu18 unit at the waist. Two types of in-situ reactions involving the oxidization of phenylphosphinic acid and the release of C22– ions from alkynol, occur in this assembly system. The stepwise assembly process of Cu38 was revealed through mass spectrometry. Catalysis studies reveal that Cu38 realizes synchronous photocatalysis disposal in the binary CrVI/dye system due to its appropriate band gap and efficient carrier separation, which are further corroborated by density functional theory (DFT) calculations. This work provides strategic guidance for constructing ultrastable high-nuclearity CuI nanoclusters and new insights into achieving multiple catalytic half-reactions using redox-type nanoclusters.