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(CCArF)(14)(PPh3)(4) (CCArF: 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 Ag-6 metal kernel capped by two Ag4Cu1(CCArF)(7)(PPh3)(2) metal-ligand units. Remarkably, it exhibits excellent bifunctional catalytic performance for 4-nitrophenol reduction and the electrochemical CO2 reduction reaction (eCO(2)RR). In 4-nitrophenol reduction, it adopts first-order reaction kinetics with a rate constant of 0.137 min(-1), while in the eCO(2)RR, 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 eCO(2)RR. 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.

Automated summary

We report the synthesis, structure anatomy, and catalytic properties of Ag14Cu2 nanoclusters. Ag14Cu2 has a robust electronic structure and distinctive absorbance feature. It exhibits excellent catalytic performance and stability in 4-nitrophenol reduction and CO2 reduction reaction.