Citation: Xiao Li, Chaoqiong Fang, Riming Hu, Jiayuan Yu. Regulating the proton supply effect on chlorine-doped bismuth for enhanced electroreduction CO₂ to formate[J]. Chinese Chemical Letters, ;2026, 37(1): 111307. doi: 10.1016/j.cclet.2025.111307 shu

Regulating the proton supply effect on chlorine-doped bismuth for enhanced electroreduction CO₂ to formate

Xiao Li ^{a, b} ,
Chaoqiong Fang ^{b, *,} ,
Riming Hu ^{c, *,} ,
Jiayuan Yu ^{b, *,}

a.
School of Materials Science and Physics, China University of Mining and Technology, Xuzhou 221116, China
b.
Institute for Advanced Interdisciplinary Research (iAIR), School of Chemistry and Chemical Engineering, University of Jinan, Ji'nan 250022, China
c.
Institute for Smart Materials & Engineering, University of Jinan, Ji'nan 250022, China

18160080351@163.com

ism_hurm@ujn.edu.cn

ifc_yujy@ujn.edu.cn

Received Date: 23 December 2024
Revised Date: 9 May 2025
Accepted Date: 12 May 2025
Available Online: 13 May 2025

Figures(6)

Electrochemical CO₂ reduction reaction (CO₂RR) into valuable formate provides a strategy for carbon neutrality. Bismuth (Bi) catalysts, attributed to their appropriate energy barrier of OCHO* intermediate, have demonstrated substantial potential for the advancement of electrocatalytic CO₂ reduction to formate. However, due to the weak bonding of protons (H*) of Bi, the available protonate of CO₂ on Bi is insufficient, which limits the formation of OCHO*. Prediction by theoretical calculation, chlorine doping can effectively promote the dissociation of H₂O and thus achieve effective proton supply. We prepare chlorine-doped Bi (Cl-Bi) via an electrochemical conversion strategy for electroreduction of CO₂. An obvious improvement of faradaic efficiency (FE) of formate (96.7% at −0.95 V vs. RHE) can be achieved on Cl-Bi, higher than that of Bi (89.4%). Meanwhile, Cl-Bi has the highest formate production rate of 275 µmol h⁻¹ cm⁻² at −0.95 V vs. RHE, which is 1.2 times higher than that of Bi (224 µmol h⁻¹ cm⁻²). In situ characterizations and kinetic analysis reveal that chlorine doping promotes the activation of H₂O and supply sufficient protons to promote the protonation of CO₂ to OCHO*, which is consistent with theoretical calculation. The study presents an effective strategy for rational design of highly efficient electrocatalysts to promote green chemical production.
- CO₂ electroreduction,
- Heteroatom doping,
- Proton supply effect,
- Reaction kinetics,
- Bismuth-based catalysts
1. [1]
  P. Sui, C. Xu, M. Zhu, et al., Small 18 (2022) 2105682.
2. [2]
  S. Nitopi, E. Bertheussen, S. Scott, et al., Chem. Rev. 119 (2019) 7610-7672. doi: 10.1021/acs.chemrev.8b00705
3. [3]
  G. Wang, J. Chen, Y. Ding, et al., Chem. Soc. Rev. 50 (2021) 4993-5061. doi: 10.1039/d0cs00071j
4. [4]
  C. Sun, J. Hao, B. Wei, et al., Chin. Chem. Lett. 34 (2023) 108520.
5. [5]
  N. Han, P. Ding, L. He, Y. Li, Y. Li, Adv. Energy Mater. 10 (2020) 1902338.
6. [6]
  P. Li, F. Yang, J. Li, et al., Adv. Energy Mater. 13 (2023) 2301597.
7. [7]
  S. Liu, L. Song, R. Liu, et al., Small 19 (2023) 2304808.
8. [8]
  J. Lu, Y. Ren, J. Liang, et al., Small 20 (2024) 2402879.
9. [9]
  C. Wang, Z. Lv, X. Feng, W. Yang, B. Wang, Adv. Energy Mater. 14 (2024) 2400160.
10. [10]
  H. Sun, J. Liu, Chin. Chem. Lett. 34 (2023) 108018.
11. [11]
  S. Yang, M. Jiang, W. Zhang, et al., Adv. Funct. Mater. 33 (2023) 2301984.
12. [12]
  P. Deng, H. Wang, R. Qi, et al., ACS Catal. 10 (2020) 743-750. doi: 10.1021/acscatal.9b04043
13. [13]
  N. Han, Y. Wang, H. Yang, et al., Nat. Commun. 9 (2018) 1320.
14. [14]
  C. Zhang, X. Hao, J. Wang, et al., Angew. Chem. Int. Ed. 63 (2024) e202317628.
15. [15]
  Y. Liu, L. Gong, J. Liu, et al., Appl. Catal. B: Environ. Energy 362 (2025) 124760.
16. [16]
  Z. Yang, Y. Jin, Z. Feng, et al., ChemSusChem 18 (2025) e202401181.
17. [17]
  Y. Liu, Z. Wei, X. Su, et al., Adv. Funct. Mater. 35 (2025) 2403547. doi: 10.1002/adfm.202403547
18. [18]
  R. Cui, Q. Yuan, C. Zhang, et al., ACS Catal. 12 (2022) 11294-11300. doi: 10.1021/acscatal.2c03369
19. [19]
  S. Liu, M. Gao, S. Wu, et al., Energy Environ. Sci. 16 (2023) 5305-5314. doi: 10.1039/d3ee01999c
20. [20]
  P. Lei, S. Liu, Q. Wen, et al., Angew. Chem. Int. Ed. 64 (2025) e202415726.
21. [21]
  D. Cha, T. Singh, A. Maibam, et al., Small 19 (2023) 2301405.
22. [22]
  B. Yan, X. Qin, T. Chen, et al., Adv. Funct. Mater. 34 (2024) 2309264.
23. [23]
  R. Shen, Y. Liu, H. Wen, et al., Small 18 (2022) 2105588.
24. [24]
  W. Ma, S. Xie, X. Zhang, et al., Nat. Commun. 10 (2019) 892.
25. [25]
  K. Yan, L. Chen, Y. Hu, et al., Nano Res. 17 (2024) 1056-1065. doi: 10.1007/s12274-023-5888-3
26. [26]
  Z. Jiang, S. Ren, X. Cao, et al., Angew. Chem. Int. Ed. 63 (2024) e202408412.
27. [27]
  A. Fan, C. Qin, R. Zhao, et al., Nano Res. 15 (2022) 6961-6968. doi: 10.1007/s12274-022-4210-0
28. [28]
  Q. Guan, W. Ran, D. Zhang, et al., Adv. Sci. 11 (2024) 2401990.
29. [29]
  T. Liu, Y. Zhao, L. Gao, J. Ni, Sci. Rep. 5 (2015) 9307.
30. [30]
  H. Jiang, S. Huang, H. Lv, et al., Water Res. 225 (2022) 119134.
31. [31]
  J. Yang, X. Wang, Y. Qu, et al., Adv. Energy Mater. 10 (2020) 2001709.
32. [32]
  X. Wang, M. Zhou, M. Wang, et al., Nano Lett. 2023, 23, 10946-10954. doi: 10.1021/acs.nanolett.3c03173
33. [33]
  Y. Meng, M. Wang, J. Xu, et al., Angew. Chem. Int. Ed. 62 (2023) e202308454.
34. [34]
  C. Liu, T. Zhang, R. Wang, et al., Adv. Funt. Mater. 35 (2025) 2412144.
35. [35]
  E. Corson, R. Kas, R. Kostecki, et al., J. Am. Chem. Soc. 142 (2020) 11750-11762. doi: 10.1021/jacs.0c01953
36. [36]
  C. Liu, Y. Wu, K. Sun, et al., Chem 7 (2021) 1297-1307.
37. [37]
  Y. Shi, Y. Wang, J. Yu, et al., Adv. Energy Mater. 13 (2023) 2203506.
38. [38]
  J. Xue, X. Fu, S. Geng, et al., J. Environ. Manage. 342 (2023) 118354.
39. [39]
  X. Cao, Y. Tian, J. Ma, et al., Adv. Mater. 36 (2024) 2309648.
40. [40]
  Z. Wei, J. Ding, Z. Wang, et al., Angew. Chem. Int. Ed. 63 (2024) e202402070.
41. [41]
  J. Chen, Z. Li, X. Wang, et al., Angew. Chem. Int. Ed. 61 (2022) e202111683.
42. [42]
  X. Ren, F. Liu, H. Wu, et al., Angew. Chem. Int. Ed. 63 (2024) e202316640.
43. [43]
  J. Li, H. Liu, W. Gou, et al., Energy Environ. Sci. 12 (2019) 2298-2304. doi: 10.1039/c9ee00752k
44. [44]
  S. Chen, X. Li, C. Kao, et al., Angew. Chem. Int. Ed. 61 (2022) e202206233.
45. [45]
  Z. Guo, H. Zhu, Z. Yan, et al., Appl. Catal. B: Environ. Energy 364 (2025) 124839.
1. [1]
  Yi Zhang , Biao Wang , Chao Hu , Muhammad Humayun , Yaping Huang , Yulin Cao , Mosaad Negem , Yigang Ding , Chundong Wang . Fe–Ni–F electrocatalyst for enhancing reaction kinetics of water oxidation. Chinese Journal of Structural Chemistry, 2024, 43(2): 100243-100243. doi: 10.1016/j.cjsc.2024.100243
2. [2]
  Yi Herng Chan , Zhe Phak Chan , Serene Sow Mun Lock , Chung Loong Yiin , Shin Ying Foong , Mee Kee Wong , Muhammad Anwar Ishak , Ven Chian Quek , Shengbo Ge , Su Shiung Lam . Thermal pyrolysis conversion of methane to hydrogen (H₂): A review on process parameters, reaction kinetics and techno-economic analysis. Chinese Chemical Letters, 2024, 35(8): 109329-. doi: 10.1016/j.cclet.2023.109329
3. [3]
  Xingxing Jiang , Yuxin Zhao , Yan Kong , Jianju Sun , Shangzhao Feng , Xin Lu , Qi Hu , Hengpan Yang , Chuanxin He . Support effect and confinement effect of porous carbon loaded tin dioxide nanoparticles in high-performance CO₂ electroreduction towards formate. Chinese Chemical Letters, 2025, 36(1): 109555-. doi: 10.1016/j.cclet.2024.109555
4. [4]
  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. Chinese Chemical Letters, 2025, 36(10): 111269-. doi: 10.1016/j.cclet.2025.111269
5. [5]
  Qian-Qian Tang , Li-Fang Feng , Zhi-Peng Li , Shi-Hao Wu , Long-Shuai Zhang , Qing Sun , Mei-Feng Wu , Jian-Ping Zou . Single-atom sites regulation by the second-shell doping for efficient electrochemical CO₂ reduction. Chinese Chemical Letters, 2024, 35(9): 109454-. doi: 10.1016/j.cclet.2023.109454
6. [6]
  Zuyou Song , Yong Jiang , Qiao Gou , Yini Mao , Yimin Jiang , Wei Shen , Ming Li , Rongxing He . Promoting the generation of active sites through "Co-O-Ru" electron transport bridges for efficient water splitting. Chinese Chemical Letters, 2025, 36(4): 109793-. doi: 10.1016/j.cclet.2024.109793
7. [7]
  Tingting Huang , Zhuanlong Ding , Hao Liu , Ping-An Chen , Longfeng Zhao , Yuanyuan Hu , Yifan Yao , Kun Yang , Zebing Zeng . Electron-transporting boron-doped polycyclic aromatic hydrocarbons: Facile synthesis and heteroatom doping positions-modulated optoelectronic properties. Chinese Chemical Letters, 2024, 35(4): 109117-. doi: 10.1016/j.cclet.2023.109117
8. [8]
  Xiangyang Ji , Yishuang Chen , Peng Zhang , Shaojia Song , Jian Liu , Weiyu Song . Boosting the first C–H bond activation of propane on rod-like V/CeO₂ catalyst by photo-assisted thermal catalysis. Chinese Chemical Letters, 2025, 36(5): 110719-. doi: 10.1016/j.cclet.2024.110719
9. [9]
  Longsheng Zhan , Yuchao Wang , Mengjie Liu , Xin Zhao , Danni Deng , Xinran Zheng , Jiabi Jiang , Xiang Xiong , Yongpeng Lei . BiVO₄ as a precatalyst for CO₂ electroreduction to formate at large current density. Chinese Chemical Letters, 2025, 36(3): 109695-. doi: 10.1016/j.cclet.2024.109695
10. [10]
  Xiaoxu Duan , Junli Xu , Jiwei Li , Congcong Du , Kai Chen , Teng Xu , Yifei Sun , Haifeng Xiong . Enhancing CO₂ reduction efficiency with axial oxygen coordinated Ni-N₄ active sites on hierarchical pore N-doped carbon. Chinese Chemical Letters, 2025, 36(7): 110340-. doi: 10.1016/j.cclet.2024.110340
11. [11]
  Haoyu Sun , Dun Li , Yuanyuan Min , Yingying Wang , Yanyun Ma , Yiqun Zheng , Hongwen Huang . Hierarchical Palladium-Copper-Silver Porous Nanoflowers as Efficient Electrocatalysts for CO₂ Reduction to C₂₊ Products. Acta Physico-Chimica Sinica, 2024, 40(6): 2307007-0. doi: 10.3866/PKU.WHXB202307007
12. [12]
  Pan Liu , Yanming Sun , Alberto J. Fernández-Carrión , Bowen Zhang , Hui Fu , Lunhua He , Xing Ming , Congling Yin , Xiaojun Kuang . Bismuth-based halide double perovskite Cs₂KBiCl₆: Disorder and luminescence. Chinese Chemical Letters, 2024, 35(5): 108641-. doi: 10.1016/j.cclet.2023.108641
13. [13]
  Yuxiang Zhang , Jia Zhao , Sen Lin . Nitrogen doping retrofits the coordination environment of copper single-atom catalysts for deep CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(11): 100415-100415. doi: 10.1016/j.cjsc.2024.100415
14. [14]
  Zixuan Zhu , Xianjin Shi , Yongfang Rao , Yu Huang . Recent progress of MgO-based materials in CO₂ adsorption and conversion: Modification methods, reaction condition, and CO₂ hydrogenation. Chinese Chemical Letters, 2024, 35(5): 108954-. doi: 10.1016/j.cclet.2023.108954
15. [15]
  Xiujuan Wang , Yijie Wang , Luyun Cui , Wenqiang Gao , Xiao Li , Hong Liu , Weijia Zhou , Jingang Wang . Coordination-based synthesis of Fe single-atom anchored nitrogen-doped carbon nanofibrous membrane for CO₂ electroreduction with nearly 100% CO selectivity. Chinese Chemical Letters, 2024, 35(12): 110031-. doi: 10.1016/j.cclet.2024.110031
16. [16]
  Jiawei Ge , Xian Wang , Heyuan Tian , Hao Wan , Wei Ma , Jiangying Qu , Junjie Ge . Iridium-based catalysts for oxygen evolution reaction in proton exchange membrane water electrolysis. Chinese Chemical Letters, 2025, 36(5): 109906-. doi: 10.1016/j.cclet.2024.109906
17. [17]
  Jaeyong Ahn , Zhenping Li , Zhiwei Wang , Ke Gao , Huagui Zhuo , Wanuk Choi , Gang Chang , Xiaobo Shang , Joon Hak Oh . Surface doping effect on the optoelectronic performance of 2D organic crystals based on cyano-substituted perylene diimides. Chinese Chemical Letters, 2024, 35(9): 109777-. doi: 10.1016/j.cclet.2024.109777
18. [18]
  Yufei Jia , Fei Li , Ke Fan . Surface reconstruction of Cu-based bimetallic catalysts for electrochemical CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(3): 100255-100255. doi: 10.1016/j.cjsc.2024.100255
19. [19]
  Qiang Zhang , Yuanbiao Huang , Rong Cao . Imidazolium-Based Materials for CO₂ Electroreduction. Acta Physico-Chimica Sinica, 2024, 40(4): 2306040-0. doi: 10.3866/PKU.WHXB202306040
20. [20]
  Muhammad Humayun , Mohamed Bououdina , Abbas Khan , Sajjad Ali , Chundong Wang . Designing single atom catalysts for exceptional electrochemical CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(1): 100193-100193. doi: 10.1016/j.cjsc.2023.100193

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(6)
HTML views(1)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Regulating the proton supply effect on chlorine-doped bismuth for enhanced electroreduction CO2 to formate

Metrics

通讯作者: 陈斌, bchen63@163.com

Regulating the proton supply effect on chlorine-doped bismuth for enhanced electroreduction CO₂ to formate