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Research Article

Homoleptic alkynyl-protected Ag32 nanocluster with atomic precision: Probing the ligand effect toward CO2 electroreduction and 4-nitrophenol reduction

Leyi Chen1,§, Fang Sun2,§, Quanli Shen1, Lubing Qin1, Yonggang Liu1, Liang Qiao3, Qing Tang2(), Likai Wang4(), Zhenghua Tang1,5 ()
New Energy Research Institute, School of Environment and Energy, South China University of Technology, Guangzhou Higher Education Mega Centre, Guangzhou 510006, China
School of Chemistry and Chemical Engineering, Chongqing Key Laboratory of Theoretical and Computational Chemistry, Chongqing University, Chongqing 401331, China
China Petrochemical Research Institute, PetroChina Company Limited, Beijing 102206, China
School of Chemistry and Chemical Engineering, Shandong University of Technology, Zibo 255049, China
Guangdong Provincial Key Laboratory of Functional Supramolecular Coordination Materials and Applications, Jinan University, Guangzhou 510632, China

§ Leyi Chen and Fang Sun contributed equally to this work.

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A novel homoleptic alkynyl-protected Ag32 nanocluster was first-time synthesized, and it exhibited superior catalytic performance toward both CO2 electroreduction and 4-nitrophenol reduction than the thiolate and phosphine ligands co-protected Ag32 counterpart. Density functional theory (DFT) calculations revealed that, one ligand stripping off exposed undercoordinated metal atom is the active site for both clusters, and alkynyl-protected Ag32 nanocluster favors the formation of the key *COOH intermediate and the adsorption of 4-nitrophenol.

Abstract

We report a superatomic homoleptic alkynyl-protected Ag32L24 (L = 3,5-bis(trifluoromethylbenzene) acetylide, Ag32 for short) nanocluster with atomic precision, which possesses eight free electrons. Ag32 is formed by an Ag17 core with C3 symmetry and the remaining 15 Ag atoms bond to each other and coordinate with the 24 surface ligands. When applied as electrocatalyst for CO2 reduction reaction (CO2RR), Ag32 exhibited the highest Faradaic efficiency (FE) of CO up to 96.44% at −0.8 V with hydrogen evolution being significantly suppressed in a wide potential range, meanwhile it has a reaction rate constant of 0.242 min−1 at room temperature and an activation energy of 45.21 kJ·mol−1 in catalyzing the reduction of 4-nitrophenol, both markedly superior than the thiolate and phosphine ligand co-protected Ag32 nanocluster. Such strong ligand effect was further understood by density functional theory (DFT) calculations, as it revealed that, one single ligand stripping off from the intact cluster can create the undercoordinated Ag atom as the catalytically active site for both clusters, but alkynyl-protected Ag32 nanocluster possesses a smaller energy barrier for forming the key *COOH intermediate in CO2RR, and favors the adsorption of 4-nitrophenol. This study not only discovers a new member of homoleptic alkynyl-protected Ag nanocluster, but also highlights the great potentials of employing alkynyl-protected Ag nanoclusters as bifunctional catalysts toward various reactions.

Keywords

Ag32 nanoclusteralkynyl ligandligand effectCO2 electroreduction4-nitrophenol reduction

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Nano Research
Volume 15 Issue 10,
October 2022
Pages 8908-8913
DOI: 10.1007/s12274-022-4812-6
Cite this article:
Chen L, Sun F, Shen Q, et al. Homoleptic alkynyl-protected Ag32 nanocluster with atomic precision: Probing the ligand effect toward CO2 electroreduction and 4-nitrophenol reduction. Nano Research, 2022, 15(10): 8908-8913. https://doi.org/10.1007/s12274-022-4812-6
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