Heteroatom Doping Modulates the Electronic Environment of Bi for Efficient Electroreduction of CO2 to Formic Acid

doi:10.1007/s40242-025-5019-7

高等学校化学研究 ›› 2025, Vol. 41 ›› Issue (2): 273-280.doi: 10.1007/s40242-025-5019-7

Heteroatom Doping Modulates the Electronic Environment of Bi for Efficient Electroreduction of CO₂ to Formic Acid

ZHAO Sirui¹, ZHOU Heng¹, CAO Dengfeng¹, SHENG Beibei², QIAN Fangren¹, LIU Chongjing¹, CHU Yongheng¹, LI Rongyao¹, SONG Li¹, CHEN Shuangming¹

1. National Synchrotron Radiation Laboratory, Key Laboratory of Precision and Intelligent Chemistry, University of Science and Technology of China, Hefei 230029, P. R. China;
2. SINOPEC Shanghai Research Institute of Petrochemical Technology Co., Ltd., Shanghai 201208, P. R. China

收稿日期:2025-01-24 接受日期:2025-03-10 出版日期:2025-04-01 发布日期:2025-03-31
通讯作者: CHEN Shuangming,csmp@ustc.edu.cn E-mail:csmp@ustc.edu.cn
基金资助:
This work was supported by the National Key Research and Development Program of China (No. 2024YFA1509501), the National Natural Science Foundation of China (Nos.12322515, U23A20121, 12225508, 12305370), the Youth Innovation Promotion Association of CAS (No. 2022457), the China Postdoctoral Science Foundation (Nos. BX20220282, 2022M720136), and the Anhui Provincial Natural Science Foundation, China (No. 2308085QA16). We thank the Beijing Synchrotron Radiation Facility (1W1B, BSRF), the Shanghai Synchrotron Radiation Facility (BL14W1, SSRF), the Hefei Synchrotron Radiation Facility (MCD-A and MCD-B Soochow Beamline for Energy Materials at NSRL), and the USTC Center for Micro and Nanoscale Research and Fabrication for help in characterizations. This work was partially carried out at the Instruments Center for Physical Science, University of Science and Technology of China.

Heteroatom Doping Modulates the Electronic Environment of Bi for Efficient Electroreduction of CO₂ to Formic Acid

ZHAO Sirui¹, ZHOU Heng¹, CAO Dengfeng¹, SHENG Beibei², QIAN Fangren¹, LIU Chongjing¹, CHU Yongheng¹, LI Rongyao¹, SONG Li¹, CHEN Shuangming¹

1. National Synchrotron Radiation Laboratory, Key Laboratory of Precision and Intelligent Chemistry, University of Science and Technology of China, Hefei 230029, P. R. China;
2. SINOPEC Shanghai Research Institute of Petrochemical Technology Co., Ltd., Shanghai 201208, P. R. China

Received:2025-01-24 Accepted:2025-03-10 Online:2025-04-01 Published:2025-03-31
Contact: CHEN Shuangming,csmp@ustc.edu.cn E-mail:csmp@ustc.edu.cn
Supported by:
This work was supported by the National Key Research and Development Program of China (No. 2024YFA1509501), the National Natural Science Foundation of China (Nos.12322515, U23A20121, 12225508, 12305370), the Youth Innovation Promotion Association of CAS (No. 2022457), the China Postdoctoral Science Foundation (Nos. BX20220282, 2022M720136), and the Anhui Provincial Natural Science Foundation, China (No. 2308085QA16). We thank the Beijing Synchrotron Radiation Facility (1W1B, BSRF), the Shanghai Synchrotron Radiation Facility (BL14W1, SSRF), the Hefei Synchrotron Radiation Facility (MCD-A and MCD-B Soochow Beamline for Energy Materials at NSRL), and the USTC Center for Micro and Nanoscale Research and Fabrication for help in characterizations. This work was partially carried out at the Instruments Center for Physical Science, University of Science and Technology of China.

摘要/Abstract

摘要： Electrocatalytic reduction reaction of carbon dioxide (CO₂RR) to formic acid is widely considered an effective strategy for addressing the greenhouse effect and enhancing energy conversion efficiency. However, existing catalytic systems are severely hampered by insufficient activity and significant hydrogen evolution reaction (HER), which substantially compromises the selectivity and stability of CO₂RR, necessitating the development of highly efficient and stable electrocatalysts. Herein, we present a heteroatomic modification strategy to synthesize B-doped Bi and N-doped Bi electrocatalysts, and systematically investigate the regulation mechanism of incorporated elements on the electronic environment using X-ray absorption fine structure (XAFS) spectroscopy and other characterization techniques. The optimized B-doped Bi catalyst demonstrates exceptional catalytic performance, achieving a remarkable Faradaic efficiency of 95% for formic acid production at a high current density of −190 mA/cm² under alkaline conditions, while maintaining excellent stability for 20 h. Through comprehensive experimental characterization and theoretical calculations, we reveal that the B-doping-induced electron-rich structure significantly promotes CO₂ molecule activation and facilitates the formation of the key intermediate ^*OCHO, thereby achieving high selectivity and stability in CO₂RR. This work not only elucidates the crucial role of electronic environment in CO₂ electrocatalytic conversion but also provides innovative insights into the rational design of high-performance electrocatalysts.

关键词: Electrocatalytic carbon dioxide reduction reaction, Synchrotron radiation spectroscopy, Heteroatom doping, Electronic environment modulation

Abstract: Electrocatalytic reduction reaction of carbon dioxide (CO₂RR) to formic acid is widely considered an effective strategy for addressing the greenhouse effect and enhancing energy conversion efficiency. However, existing catalytic systems are severely hampered by insufficient activity and significant hydrogen evolution reaction (HER), which substantially compromises the selectivity and stability of CO₂RR, necessitating the development of highly efficient and stable electrocatalysts. Herein, we present a heteroatomic modification strategy to synthesize B-doped Bi and N-doped Bi electrocatalysts, and systematically investigate the regulation mechanism of incorporated elements on the electronic environment using X-ray absorption fine structure (XAFS) spectroscopy and other characterization techniques. The optimized B-doped Bi catalyst demonstrates exceptional catalytic performance, achieving a remarkable Faradaic efficiency of 95% for formic acid production at a high current density of −190 mA/cm² under alkaline conditions, while maintaining excellent stability for 20 h. Through comprehensive experimental characterization and theoretical calculations, we reveal that the B-doping-induced electron-rich structure significantly promotes CO₂ molecule activation and facilitates the formation of the key intermediate ^*OCHO, thereby achieving high selectivity and stability in CO₂RR. This work not only elucidates the crucial role of electronic environment in CO₂ electrocatalytic conversion but also provides innovative insights into the rational design of high-performance electrocatalysts.

Key words: Electrocatalytic carbon dioxide reduction reaction, Synchrotron radiation spectroscopy, Heteroatom doping, Electronic environment modulation

ZHAO Sirui, ZHOU Heng, CAO Dengfeng, SHENG Beibei, QIAN Fangren, LIU Chongjing, CHU Yongheng, LI Rongyao, SONG Li, CHEN Shuangming. Heteroatom Doping Modulates the Electronic Environment of Bi for Efficient Electroreduction of CO₂ to Formic Acid[J]. 高等学校化学研究, 2025, 41(2): 273-280.

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Heteroatom Doping Modulates the Electronic Environment of Bi for Efficient Electroreduction of CO₂ to Formic Acid

Heteroatom Doping Modulates the Electronic Environment of Bi for Efficient Electroreduction of CO₂ to Formic Acid

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