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

Quanli Shen; Xuzi Cong; Leyi Chen; Lei Wang; Yonggang Liu; Likai Wang; Zhenghua Tang

doi:10.1039/d3dt02838k

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

Dalton Trans. 2023 Nov 21;52(45):16812-16818. doi: 10.1039/d3dt02838k.

Authors

Quanli Shen¹, Xuzi Cong², Leyi Chen¹, Lei Wang¹, Yonggang Liu¹, Likai Wang², Zhenghua Tang¹

Affiliations

¹ New Energy Research Institute, School of Environment and Energy, South China University of Technology, Guangzhou Higher Education Mega Centre, Guangzhou, 510006, China. zhht@scut.edu.cn.
² School of Chemistry and Chemical Engineering, Shandong University of Technology, Zibo, 255049, China. lkwangchem@sdut.edu.cn.

PMID: 37905669
DOI: 10.1039/d3dt02838k

Abstract

We report the synthesis, structure anatomy, and catalytic properties of Ag₁₄Cu₂(CCAr^F)₁₄(PPh₃)₄ (CCAr^F: 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CAr^F)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 (FE_CO) 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 FE_CO 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.