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Nano Research 2022, 15(10): 8908-8913 https://doi.org/10.1007/s12274-022-4812-6
Research Article | Issue | Published: 20 August 2022

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

Show Author's Information 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.

Keywords:
4-nitrophenol reduction, CO2 electroreduction, ligand effect, alkynyl ligand, Ag32 nanocluster
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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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Abstract Full text Electronic supplementary material About this article

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.


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About this article

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

Show Author's information 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.

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: 4-nitrophenol reduction, CO2 electroreduction, ligand effect, alkynyl ligand, Ag32 nanocluster

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Publication history
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Acknowledgements

Publication history

Received: 12 June 2022
Revised: 24 July 2022
Accepted: 25 July 2022
Published: 20 August 2022
Issue date: October 2022

Copyright

© Tsinghua University Press 2022

Acknowledgements

Acknowledgements

This study was supported by the Open Fund of Guangdong Provincial Key Laboratory of Functional Supramolecular Coordination Materials and Applications (No. 2021A07). Z. H. T. acknowledges the financial support from Guangdong Natural Science Funds (No. 2022A1515011840). L. K. W. acknowledges the funding from the National Natural Science Foundation of China (No. 21805170). Q. T. thanks the grants from the National Natural Science Foundation of China (No. 21903008) and the Chongqing Science and Technology Commission (No. cstc2020jcyj-msxmX0382).

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