Copper Doping Boosts Electrocatalytic CO 2 Reduction of Atomically Precise Gold Nanoclusters

Unraveling the atomistic synergistic effects of nanoalloys on the electrocatalytic CO 2 reduction reaction (eCO 2 RR), especially in the presence of copper, is of paramount importance. However, this endeavor encounters significant challenges due to the lack of the crystallographically determined atomic-level structure of appropriate monometallic and bimetallic analogues. Herein, we report a one-pot synthesis and structure characterization of a AuCu nanoalloy cluster catalyst, [Au 15 Cu 4 (DPPM) 6 Cl 4 (C≡CR) 1 ] 2+ (denoted as Au 15 Cu 4 ). Single-crystal X-ray diffraction analysis reveals that Au 15 Cu 4 comprises two interpenetrating incomplete, centered icosahedra (Au 9 Cu 2 and Au 8 Cu 3 ) and is protected by six DPPM, four halide, and one alkynyl ligand. The Au 15 Cu 4 cluster and its closest monometal structural analogue, [Au 18 (DPPM) 6 Br 4 ] 2+ (denoted as Au 18 ), as model syst…