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Nano Research 2023, 16(8): 10867-10872 https://doi.org/10.1007/s12274-023-5885-6
Research Article | Issue | Published: 17 July 2023

Atomically precise alkynyl-protected Ag20Cu12 nanocluster: Structure analysis and electrocatalytic performance toward nitrate reduction for NH3 synthesis

Show Author's Information Guanyu Ma1,§,  Fang Sun2,§,  Liang Qiao3,§,  Quanli Shen1,  Lei Wang1,  Qing Tang2( ),  Zhenghua Tang1 ( )
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

§ Guanyu Ma, Fang Sun, and Liang Qiao contributed equally to this work.

Keywords:
ammonia synthesis, density functional theory (DFT) calculations, alkynyl ligand, Ag20Cu12 nanocluster, nitrate reduction reaction (NtrRR)
Topics:
Nitrate reduction reaction
Cite this article:
Ma G, Sun F, Qiao L, et al. Atomically precise alkynyl-protected Ag20Cu12 nanocluster: Structure analysis and electrocatalytic performance toward nitrate reduction for NH3 synthesis. Nano Research, 2023, 16(8): 10867-10872. https://doi.org/10.1007/s12274-023-5885-6
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Abstract Full text Electronic supplementary material About this article

Electrochemical nitrate reduction reaction (NtrRR) has been emerging as an appealing route for both water treatment and NH3 synthesis. Herein, we report the structure analysis and electrocatalytic performance of a novel homoleptic alkynyl-protected Ag20Cu12 nanocluster (Ag20Cu12 in short) with atomic precision, which has eight free electrons and displays characteristic absorbance feature. Single crystal X-ray diffraction (SC-XRD) discloses that, it adopts a Ag14 kernel capped by three Ag2Cu4(C≡CArF)8 metal–ligand binding motifs in the outer shell. Ag20Cu12 exhibited excellent catalytic performance toward NtrRR, as manifested by the superior NH3 Faradaic efficiency (FE, 84.6%) and yield rate (0.138 mmol·h−1·mg−1) than the homoleptic alkynyl-protected Ag32 nanoclusters. Additionally, it demonstrates good catalytic recycling capability. Density functional theory (DFT) calculations revealed that, the de-ligated Ag20Cu12 cluster can expose the available AgCu bimetallic sites as the efficient active sites for NH3 formation. In particular, the participation of Cu sites greatly facilitates the initial capture of NO3− and simultaneously promotes the selectivity of the final product. This study discovers a novel homoleptic alkynyl-protected AgCu superatom, and offers a great example to elucidate the structure–performance relationship of bimetallic catalyst for NtrRR and other multiple protons/electrons coupled electrocatalytic reactions.


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Electronic supplementary material
About this article

Atomically precise alkynyl-protected Ag20Cu12 nanocluster: Structure analysis and electrocatalytic performance toward nitrate reduction for NH3 synthesis

Show Author's information Guanyu Ma1,§, Fang Sun2,§, Liang Qiao3,§, Quanli Shen1, Lei Wang1, Qing Tang2( ), Zhenghua Tang1 ( )
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

§ Guanyu Ma, Fang Sun, and Liang Qiao contributed equally to this work.

Abstract

Electrochemical nitrate reduction reaction (NtrRR) has been emerging as an appealing route for both water treatment and NH3 synthesis. Herein, we report the structure analysis and electrocatalytic performance of a novel homoleptic alkynyl-protected Ag20Cu12 nanocluster (Ag20Cu12 in short) with atomic precision, which has eight free electrons and displays characteristic absorbance feature. Single crystal X-ray diffraction (SC-XRD) discloses that, it adopts a Ag14 kernel capped by three Ag2Cu4(C≡CArF)8 metal–ligand binding motifs in the outer shell. Ag20Cu12 exhibited excellent catalytic performance toward NtrRR, as manifested by the superior NH3 Faradaic efficiency (FE, 84.6%) and yield rate (0.138 mmol·h−1·mg−1) than the homoleptic alkynyl-protected Ag32 nanoclusters. Additionally, it demonstrates good catalytic recycling capability. Density functional theory (DFT) calculations revealed that, the de-ligated Ag20Cu12 cluster can expose the available AgCu bimetallic sites as the efficient active sites for NH3 formation. In particular, the participation of Cu sites greatly facilitates the initial capture of NO3− and simultaneously promotes the selectivity of the final product. This study discovers a novel homoleptic alkynyl-protected AgCu superatom, and offers a great example to elucidate the structure–performance relationship of bimetallic catalyst for NtrRR and other multiple protons/electrons coupled electrocatalytic reactions.

Keywords: ammonia synthesis, density functional theory (DFT) calculations, alkynyl ligand, Ag20Cu12 nanocluster, nitrate reduction reaction (NtrRR)

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Acknowledgements

Publication history

Received: 28 April 2023
Revised: 29 May 2023
Accepted: 30 May 2023
Published: 17 July 2023
Issue date: August 2023

Copyright

© Tsinghua University Press 2023

Acknowledgements

Acknowledgements

Z. H. T. acknowledges the financial support from the Guangdong Natural Science Funds (No. 2022A1515011840). 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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