Abstract
Atomically precise nanoclusters are desirable for understanding the structure-property relationships in the electrocatalytic CO(2) reduction reaction (eCO(2)RR), but suitable related models are lacking, especially those of low- or zerovalent noble metal nanoclusters and their alloyed analogues. We first developed a photochemical method toward silver nanocluster Ag(19)(4- (t) BuPhC≡C)(14)(Dpppe)(3)(SbF(6))(3) (Ag (19) -2e) and then related copper-doped alloyed nanocluster Ag(12)Cu(7)(4- (t) BuPhC≡C)(14)(Dpppe)(3)Cl(3)(SbF(6))(2) (Ag (12) Cu (7) -0e). Herein, we present a larger alloyed nanocluster, Ag(19)Cu(2)(4- (t) BuPhC≡C)(16)(Dpppe)(4)(SbF(6))(3) (Ag (19) Cu (2) -2e) and investigate the relationship between the structures and the eCO(2)RR performance of those related nanoclusters. The UV-vis and mass spectra revealed that Ag (19) Cu (2) -2e forms via light-induced Ag (19) -2e generation followed by Cu-(II) attachment. eCO(2)RR tests showed that Ag (19) -2e is the least efficient, while its dicopper alloyed Ag (19) Cu (2) -2e favors formate, highlighting the important role of copper doping in regulating Ag cluster catalysis. This conclusion is further confirmed by the good catalytic performance of Ag (12) Cu (7) -0e, which demonstrated the best C(1) product selectivity for both CO and formate. Experimental and theoretical calculations indicate that its excellent catalytic performance is attributed to the removal of Cl ligands, exposing active Ag sites for launching the eCO(2)RR process. This work not only demonstrates that copper-doped silver nanoclusters significantly enhance catalytic activity but also reveals that varying copper doping levels enable modulation of product selectivity in eCO(2)RR.