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Nano Research 2024, 17(5): 3644-3652 https://doi.org/10.1007/s12274-023-6247-0
Research Article | Issue | Published: 25 November 2023

Hierarchical Bi/S-modified Cu/brass mesh used as structured highly performance catalyst for CO2 electroreduction to formate

Show Author's Information Tong Dou,  Dian Song,  Yiping Wang( ),  Xuhui Zhao,  Fazhi Zhang,  Xiaodong Lei( )
State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China
Keywords:
CO2 electroreduction, formate, Cu-Bi-based catalyst, S-modified Cu catalyst
Topics:
ElectrocatalystsElectrolytic reduction
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Dou T, Song D, Wang Y, et al. Hierarchical Bi/S-modified Cu/brass mesh used as structured highly performance catalyst for CO2 electroreduction to formate. Nano Research, 2024, 17(5): 3644-3652. https://doi.org/10.1007/s12274-023-6247-0
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Abstract Full text Electronic supplementary material About this article

Electrocatalytic CO2 reduction reaction (ECO2RR) converts CO2 to high-value chemical products and promotes the carbon cycle. Sulfur (S)-modified copper (Cu) and bismuth (Bi)-based catalysts have been recognized as promising catalysts for ECO2RR. Both of them are highly active for selective formate generation, however, their poor stability and severe competing hydrogen evolution reaction (HER) remain challenging. Herein, S-doped Cu coated with Bi (Bi/Cu-S) is developed to improve ECO2RR selectivity to formate. Bi/Cu-S/brass mesh (BM) electrode material for ECO2RR was prepared by electrodepositing Bi on the surface of Cu-S/BM nanowires obtained from CuS/BM after the electroreduction. The Faradaic efficiency (FE) of the formate reaches the maximum of 94.3% at −0.9 V vs. reversible hydrogen electrode (RHE) with a partial current density as high as −50.7 mA·cm−2 and a yield of 30.7 mmol·h−1·cm−2 under 0.5 M KHCO3 electrolyte. Meanwhile, the FE of formate is higher than 90% in the voltage range of −0.8 to −1.0 V vs. RHE. It also shows good stability at −0.9 V vs. RHE with the FE of formate remaining above 93% after a 10 h reaction. Density functional theory (DFT) calculations demonstrate that the Bi/Cu-S structure promotes the adsorption of CO2 and effectively inhibits HER by enhancing the adsorption of *H to a great extent, improving the selective conversion of CO2 to formate. This work deepens the understanding of the mechanism of Cu-Bi-based catalysts and S-modified Cu-based catalysts in selective ECO2RR to formate, and also provides a new strategy for catalyst design.


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Electronic supplementary material
About this article

Hierarchical Bi/S-modified Cu/brass mesh used as structured highly performance catalyst for CO2 electroreduction to formate

Show Author's information Tong Dou, Dian Song, Yiping Wang( ), Xuhui Zhao, Fazhi Zhang, Xiaodong Lei( )
State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China

Abstract

Electrocatalytic CO2 reduction reaction (ECO2RR) converts CO2 to high-value chemical products and promotes the carbon cycle. Sulfur (S)-modified copper (Cu) and bismuth (Bi)-based catalysts have been recognized as promising catalysts for ECO2RR. Both of them are highly active for selective formate generation, however, their poor stability and severe competing hydrogen evolution reaction (HER) remain challenging. Herein, S-doped Cu coated with Bi (Bi/Cu-S) is developed to improve ECO2RR selectivity to formate. Bi/Cu-S/brass mesh (BM) electrode material for ECO2RR was prepared by electrodepositing Bi on the surface of Cu-S/BM nanowires obtained from CuS/BM after the electroreduction. The Faradaic efficiency (FE) of the formate reaches the maximum of 94.3% at −0.9 V vs. reversible hydrogen electrode (RHE) with a partial current density as high as −50.7 mA·cm−2 and a yield of 30.7 mmol·h−1·cm−2 under 0.5 M KHCO3 electrolyte. Meanwhile, the FE of formate is higher than 90% in the voltage range of −0.8 to −1.0 V vs. RHE. It also shows good stability at −0.9 V vs. RHE with the FE of formate remaining above 93% after a 10 h reaction. Density functional theory (DFT) calculations demonstrate that the Bi/Cu-S structure promotes the adsorption of CO2 and effectively inhibits HER by enhancing the adsorption of *H to a great extent, improving the selective conversion of CO2 to formate. This work deepens the understanding of the mechanism of Cu-Bi-based catalysts and S-modified Cu-based catalysts in selective ECO2RR to formate, and also provides a new strategy for catalyst design.

Keywords: CO2 electroreduction, formate, Cu-Bi-based catalyst, S-modified Cu catalyst

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Publication history
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Acknowledgements

Publication history

Received: 17 August 2023
Revised: 30 September 2023
Accepted: 06 October 2023
Published: 25 November 2023
Issue date: May 2024

Copyright

© Tsinghua University Press 2023

Acknowledgements

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Nos. 22278020 and 2177060378), the Program for Changjiang Scholars, Innovative Research Teams in Universities (No. IRT1205), and the Fundamental Research Funds for the Central Universities (Nos. 12060093063 and XK1803-05).

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