Synthesis, structure anatomy, and catalytic properties of Ag14Cu2 nanoclusters co-protected by alkynyl and phosphine ligands

We report the synthesis, structure anatomy, and catalytic properties of Ag14Cu2(CCArF)14(PPh3)4 (CCArF: 3,5-bis(trifluoromethyl)phenylacetylene) nanoclusters, denoted as Ag14Cu2. Ag14Cu2 has a robust electronic structure with two free valence electrons, and it has a distinctive absorbance feature. Single-crystal X-ray diffraction (SC-XRD) disclosed that Ag14Cu2 possesses an octahedral Ag6 metal kernel capped by two Ag4Cu1(CCArF)7(PPh3)2 metal-ligand units. Remarkably, it exhibits excellent bifunctional catalytic performance for 4-nitrophenol reduction and the electrochemical CO2 reduction reaction (eCO2RR). In 4-nitrophenol reduction, it adopts first-order reaction kinetics with a rate constant of 0.137 min-1, while in the eCO2RR, it shows a CO faradaic efficiency (FECO) of 83.71% and a high current density of 92.65 mA cm-2 at -1.6 V vs. RHE. Moreover, Ag14Cu2 showed robust long-term stability with no significant decay in current density and FECO over 10 h of continuous operation in the eCO2RR. This study not only enriches the potpourri of alkynyl-protected bimetallic AgCu nanoclusters, but also demonstrates the great potential of employing metal nanoclusters for bifunctional catalytic applications.