Citation: Zilin Li, Dongjie Zuo, Zhimin Chen, Huifang Guo, Qingyuan Wu, Simin Li, Jiangwei Zhang, Jing Sun, Limin Zhang, Qing Tang, Hui Shen. Atomically dynamic surfaces enable efficient electrochemical hydrogen evolution on ligand-protected non-platinum clusters[J]. Chinese Chemical Letters, ;2026, 37(11): 111697. doi: 10.1016/j.cclet.2025.111697 shu

Atomically dynamic surfaces enable efficient electrochemical hydrogen evolution on ligand-protected non-platinum clusters

Zilin Li ^{a, 1} ,
Dongjie Zuo ^{a, 1} ,
Zhimin Chen ^{b, 1} ,
Huifang Guo ^a ,
Qingyuan Wu ^{c, d} ,
Simin Li ^a ,
Jiangwei Zhang ^a ,
Jing Sun ^a ,
Limin Zhang ^{e, *,} ,
Qing Tang ^{b, *,} ,
Hui Shen ^{a, *,}

a.
College of Energy Materials and Chemistry, Inner Mongolia University, Hohhot 010021, China
b.
School of Chemistry and Chemical Engineering, Chongqing Key Laboratory of Chemical Theory and Mechanism, Chongqing University, Chongqing 401331, China
c.
New Cornerstone Science Laboratory, State Key Laboratory for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, and National & Local Joint Engineering Research Center of Preparation Technology of Nanomaterials, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
d.
Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Xiamen 361102, China
e.
Key Laboratory of Magnetic Molecules and Magnetic Information Materials of the Ministry of Education & School of Chemistry and Materials Science of Shanxi Normal University, Taiyuan 030032, China

zhanglm@sxnu.edu.cn

qingtang@cqu.edu.cn

shen@imu.edu.cn

Received Date: 18 April 2025
Revised Date: 3 August 2025
Accepted Date: 9 August 2025
Available Online: 10 August 2025

Figures(4)

Atomically precise metal nanoclusters stabilised by organic ligands represent a distinct class of catalyst materials. However, the synthesis of efficient ligated cluster catalysts and understanding how they work, especially under the full exposure of surface ligands, remains challenging. In this study, we describe a stable ligand-protected [Au₅Cu₂(dppm)₂(C₇H₇S)₆]⁺ (dppm is bis(diphenylphosphino)methane, and RSH is 4-methylbenzenethiol) cluster that exhibits exceptional activity in the electrocatalytic hydrogen evolution (HER) reaction. The cluster demonstrates HER activity comparable to commercial Pt/C in acidic media and retains its performance over extended operation. Mechanism studies using theoretical computations reveal that the thiolate ligands in the cluster undergo protonation-induced removal and reconstruction. These atomically dynamic surfaces transiently expose active metal sites, leading to a substantial enhancement in HER activity. The dynamic catalysis mechanism of the cluster has also been validated by X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) experiments. This study not only rationalises the controversial issue of how ligated metal clusters drive chemical transformations with high activity but also highlights the importance of surface dynamics in governing the catalysis of metal nanoclusters.
- Dynamic surface,
- Nanoclusters,
- Ligands,
- Crystal structure,
- Electrocatalytic hydrogen evolution
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