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Research Article

Boosting CO2 electroreduction to formate via bismuth oxide clusters

Xiaole Jiang1,§( ), Le Lin2,§, Youwen Rong2,3,§, Rongtan Li2,4, Qike Jiang2, Yaoyue Yang1, Dunfeng Gao2( )
Key Laboratory of Fundamental Chemistry of the State Ethnic Commission, School of Chemistry and Environment, Southwest Minzu University, Chengdu 610041, China
State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
School of Science, Dalian Maritime University, Dalian 116026, China
University of Chinese Academy of Sciences, Beijing 100049, China

§ Xiaole Jiang, Le Lin, and Youwen Rong contributed equally to this work.

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Graphical Abstract

A BiOn cluster catalyst achieves a formate Faradaic efficiency of over 90% at a current density up to 500 mA·cm−2 and a remarkable mass activity as high as 3,750 A·gBi−1, owing to the stabilization of HCOO*, a key intermediate forformate formation.

Abstract

Supported metal (oxide) clusters, with both rich surface sites and high atom utilization efficiency, have shown improved activity and selectivity for many catalytic reactions over nanoparticle and single atom catalysts. Yet, the role of cluster catalysts has been rarely reported in CO2 electroreduction reaction (CO2RR), which is a promising route for converting CO2 to liquid fuels like formic acid with renewable electricity. Here we develop a bismuth oxide (BiOn) cluster catalyst for highly efficient CO2RR to formate. The BiOn cluster catalyst exhibits excellent activity, selectivity, and stability towards formate production, with a formate Faradaic efficiency of over 90% at a current density up to 500 mA·cm−2 in an alkaline membrane electrode assembly electrolyzer, corresponding to a mass activity as high as 3,750 A·gBi−1. The electrolyzer with the BiOn cluster catalyst delivers a remarkable formate production rate of 0.56 mmol·min−1 at a high single-pass CO2 conversion of 44%. Density functional theory calculations indicate that Bi4O3 cluster is more favorable for stabilizing the HCOO* intermediate than Bi(001) surface and single site BiC4 motif, rationalizing the improved formate production over the BiOn cluster catalyst. This work highlights the great importance of cluster catalysts in activity and selectivity control in electrocatalytic CO2 conversion.

Keywords

CO2 electroreduction reactionformatebismuth oxidecluster catalystmembrane electrode assembly

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Nano Research
Volume 16 Issue 10,
October 2023
Pages 12050-12057
DOI: 10.1007/s12274-022-5073-0
Cite this article:
Jiang X, Lin L, Rong Y, et al. Boosting CO2 electroreduction to formate via bismuth oxide clusters. Nano Research, 2023, 16(10): 12050-12057. https://doi.org/10.1007/s12274-022-5073-0
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Electrocatalysis
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Received: 01 July 2022
Revised: 31 August 2022
Accepted: 19 September 2022
Published: 09 November 2022
© Tsinghua University Press 2022
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