Citation: Hao-Nan Zhou, Lan-Yan Li, Hong-Bing Mo, Yi-Xin Li, Jun Yan, Chao Liu. Ligand-engineered octanuclear bismuth-oxo clusters with exposed active sites for enhanced CO₂-to-HCOOH electroreduction[J]. Chinese Chemical Letters, ;2025, 36(10): 111269. doi: 10.1016/j.cclet.2025.111269 shu

Ligand-engineered octanuclear bismuth-oxo clusters with exposed active sites for enhanced CO₂-to-HCOOH electroreduction

Hao-Nan Zhou ^{a, 1} ,
Lan-Yan Li ^{b, 1} ,
Hong-Bing Mo ^{a, *,} ,
Yi-Xin Li ^c ,
Jun Yan ^a ,
Chao Liu ^{a, *,}

a.
College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China
b.
School of Resources and Environment, Hunan University of Technology and Business, Changsha 410205, China
c.
Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University, Tianjin 300071, China

135296@csu.edu.cn

chaoliu@csu.edu.cn

Received Date: 14 March 2025
Revised Date: 22 April 2025
Accepted Date: 27 April 2025
Available Online: 1 May 2025

Figures(8)

The atomic-level exploration of structure-property correlations poses significant challenges in establishing precise design principles for electrocatalysts targeting efficient CO₂ conversion. This study demonstrates how controlled exposure of metal sites governs CO₂ electroreduction performance through two octanuclear bismuth-oxo clusters with distinct architectures. The Bi₈-DMF cluster, constructed using tert-butylthiacalix^[4]arene (TC4A) as the sole ligand, features two surface-exposed Bi active sites, while the dual-ligand Bi₈-Fc (with TC4A/ferrocene carboxylate) forms a fully encapsulated structure. Electrocatalytic tests reveal Bi₈-DMF achieves exceptional formate selectivity (> 90% Faradaic efficiency) across a broad potential window (-0.9 V to -1.6 V vs. RHE) with 20 h stability, outperforming Bi₈-Fc (60% efficiency at -1.5 V). Theoretical calculations attribute Bi₈-DMF's superiority to exposed Bi sites that stabilize the critical *OCHO intermediate via optimized orbital interactions. This work provides crucial guidance for polynuclear catalyst design: moderate exposure of metal active sites significantly enhances CO₂ reduction performance.
- Nanocluster,
- Bismuth-oxo clusters,
- CO₂ electroreduction,
- Formic acid,
- Ligand engineering
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沈阳化工大学材料科学与工程学院沈阳 110142

Ligand-engineered octanuclear bismuth-oxo clusters with exposed active sites for enhanced CO2-to-HCOOH electroreduction

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通讯作者: 陈斌, bchen63@163.com

Ligand-engineered octanuclear bismuth-oxo clusters with exposed active sites for enhanced CO₂-to-HCOOH electroreduction