Dopant Engineering of Isostructural Metal Nanoclusters for Modulating CO 2 Electroreduction

ABSTRACT Achieving atomic‐level insight into how dopants regulate the electrocatalytic CO 2 reduction reaction (eCO 2 RR) of metal nanoparticles is challenging due to the lack of well‐defined, compositionally tunable, and structurally identical model systems. Herein, we report two isostructural nanoclusters: [Au 10 Ag 4 (DPPP) 5 Cl 4 ] 2+ ( Au 10 Ag 4 ) and [Au 9 Ag 2 Cu 3 (DPPP) 5 Cl 4 ] 2+ ( Au 9 Ag 2 Cu 3 ), which differ only in metal composition (Au─Ag vs. Au─Ag─Cu). Together with the isostructural monometallic [Au 14 (DPPP) 5 Br 4 ] 2+ ( Au 14 ), they serve as ideal platforms to elucidate dopant effects on eCO 2 RR. Electrochemical studies reveal that Ag doping ( Au 10 Ag 4 ) suppresses both CO selectivity and activity of Au 14 , whereas further Cu incorporation ( Au 9 Ag 2 Cu 3 ) not only enhances these metrics relative to Au 10 Ag 4 but also surpasses Au 14 . Specifically, Au 9 Ag…