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.