Citation: Yidan Mao, Bingyu Li, Shuailing Ma, Siwen Cui, Zihan Zhang, Pinwen Zhu, Kongsheng Qi, Xiaodong Li, Weiwei Dong, Wei Luo, Rajeev Ahuja, Dexin Yang, Tian Cui. Metal diborides as robust and highly stable electrodes for efficient electrocatalytic reduction of CO₂ to CO in ionic liquid-based electrolytes[J]. Chinese Chemical Letters, ;2026, 37(4): 111675. doi: 10.1016/j.cclet.2025.111675 shu

Metal diborides as robust and highly stable electrodes for efficient electrocatalytic reduction of CO₂ to CO in ionic liquid-based electrolytes

Yidan Mao ^{a, 1} ,
Bingyu Li ^{a, 1} ,
Shuailing Ma ^{b, *,} ,
Siwen Cui ^d ,
Zihan Zhang ^e ,
Pinwen Zhu ^d ,
Kongsheng Qi ^a ,
Xiaodong Li ^c ,
Weiwei Dong ^{c, *,} ,
Wei Luo ^e ,
Rajeev Ahuja ^e ,
Dexin Yang ^{a, *,} ,
Tian Cui ^{b, *,}

a.
College of Chemistry, Zhengzhou University, Zhengzhou 450001, China
b.
Institute of High-Pressure Physics, School of Physical Scientific and Technology, Ningbo University, Ningbo 315211, China
c.
Beijing Synchrotron Radiation Facility (BSRF), Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China
d.
Synergetic Extreme Condition High-Pressure Science Center, State Key Laboratory of Superhard Materials, College of Physics, Jilin University, Changchun 130012, China
e.
Condensed Matter Theory, Department of Physics and Astronomy, Uppsala University, Uppsala 75120, Sweden

mashuailing@nbu.edu.cn

dongww@ihep.ac.cn

yangdx@zzu.edu.cn

cuitian@nbu.edu.cn

Received Date: 8 March 2025
Revised Date: 30 July 2025
Accepted Date: 5 August 2025
Available Online: 6 August 2025

Figures(4)

The electrocatalytic reduction of carbon dioxide (CO₂) into fuels holds significant promise for addressing energy and environmental challenges, albeit hindered by constraints in conversion efficiency, production rates, and electrode stability. Metal diborides are considered as promising electrocatalysts that may demonstrate superior CO₂ electroreduction performance due to their distinctive electronic properties. Herein, a series of novel bulk metal diborides, encompassing transition metals from group IVB to group VIIB elements, were fabricated using a high pressure-high temperature technique, which were directly utilized as self-supporting electrodes for electrocatalytic reduction of CO₂. The zirconium diboride (ZrB₂) electrode stood out in metal diborides with superior electrocatalytic activity in generating carbon monoxide (CO), achieving a Faradaic efficiency of 92.2% at −2.2 V vs. Ag/Ag⁺ in ionic liquid-based electrolytes. Impressively, the ZrB₂ electrode demonstrated stable catalysis of CO₂ reduction to CO over a nearly 60-h electrolysis period. Furthermore, the ZrB₂ electrode and ionic liquid-based electrolytes could synergistically catalyze the reduction of CO₂ to CO. Experimental results and density functional theory calculations support the notion that exposed metal sites on the ZrB₂ (001) surface could enhance *CO desorption and restrain the hydrogen evolution reaction, thereby facilitating the conversion of CO₂ into CO.
- Metal diborides,
- Electrocatalytic reduction of CO₂,
- Ionic liquids,
- CO,
- Self-supporting electrodes
1. [1]
  B. Ekwurzel, J. Boneham, M.W. Dalton, et al., Clim. Change 144 (2017) 579–590. doi: 10.1007/s10584-017-1978-0
2. [2]
  D. Johnson, Z. Qiao, A. Djire, ACS Appl. Energy Mater. 4 (2021) 8661–8684. doi: 10.1021/acsaem.1c01624
3. [3]
  G. Xie, W. Guo, Z. Fang, et al., Angew. Chem. Int. Ed. 63 (2024) e202412568. doi: 10.1002/anie.202412568
4. [4]
  M. Melchionna, P. Fornasiero, M. Prato, M. Bonchio, Energy Environ. Sci. 14 (2021) 5816–5833. doi: 10.1039/D1EE00228G
5. [5]
  S. Das, J. Pérez-Ramírez, J. Gong, et al., Chem. Soc. Rev. 49 (2020) 2937–3004. doi: 10.1039/C9CS00713J
6. [6]
  J. Zhu, Q. Zhang, C. Wang, et al., Nanoscale 17 (2025) 2709–2717. doi: 10.1039/D4NR04843A
7. [7]
  K. Lian, J. Ding, J. Zhang, et al., J. Mater. Chem. A 13 (2025) 2010–2018. doi: 10.1039/D4TA06503D
8. [8]
  S. Gao, H. Li, Z. Lu, et al., Carbon Energy 7 (2025) e637. doi: 10.1002/cey2.637
9. [9]
  Y. Liu, Y. Fang, Q. Yuan, J. Lu, H. Wang, Green Chem. 25 (2023) 1339–1344. doi: 10.1039/D2GC04659H
10. [10]
  X. Ma, J. Du, H. Sun, et al., Appl. Catal. B: Environ. 298 (2021) 120543. doi: 10.1016/j.apcatb.2021.120543
11. [11]
  X. Song, W. Guo, X. Ma, et al., Green Chem. 24 (2022) 1488–1493. doi: 10.1039/D1GC04146K
12. [12]
  T. Shao, D. Duan, S. Liu, et al., Nanoscale 14 (2022) 833–841. doi: 10.1039/D1NR06545A
13. [13]
  C. Jia, W. Ren, X. Chen, W. Yang, C. Zhao, ACS Sustain. Chem. Eng. 8 (2020) 6003–6010. doi: 10.1021/acssuschemeng.0c00739
14. [14]
  J. Song, X. Lei, J. Mu, et al., Small 19 (2023) 2305666. doi: 10.1002/smll.202305666
15. [15]
  X. Liu, Y. Jiao, Y. Zheng, S.Z. Qiao, ACS Catal. 10 (2020) 1847–1854. doi: 10.1021/acscatal.9b04103
16. [16]
  D. Wu, R. Feng, C. Xu, et al., Nano-Micro Lett. 14 (2021) 38.
17. [17]
  Y. Zhou, F. Che, M. Liu, et al., Nat. Chem. 10 (2018) 974–980. doi: 10.1038/s41557-018-0092-x
18. [18]
  B. Jiang, X.G. Zhang, K. Jiang, D.Y. Wu, W.B. Cai, J. Am. Chem. Soc. 140 (2018) 2880–2889. doi: 10.1021/jacs.7b12506
19. [19]
  X. Lu, Y. Hu, S. Cao, et al., Phys. Chem. Chem. Phys. 25 (2023) 18952–18959. doi: 10.1039/D2CP05449C
20. [20]
  S.H. Mir, V.K. Yadav, J.K. Singh, ACS Appl. Mater. Interfaces 14 (2022) 29703–29710. doi: 10.1021/acsami.2c02469
21. [21]
  H. Chen, X. Zou, Inorg. Chem. Front. 7 (2020) 2248–2264. doi: 10.1039/D0QI00146E
22. [22]
  F. Ling, K. Luo, L. Hao, et al., ACS Omega 5 (2020) 4620–4625. doi: 10.1021/acsomega.9b04260
23. [23]
  Z. Pu, T. Liu, G. Zhang, et al., Small Methods 5 (2021) 2100699. doi: 10.1002/smtd.202100699
24. [24]
  P.R. Jothi, Y. Zhang, K. Yubuta, et al., ACS Appl. Energy Mater. 2 (2018) 176–181.
25. [25]
  V. Mazánek, H. Nahdi, J. Luxa, Z. Sofer, M. Pumera, Nanoscale 10 (2018) 11544–11552. doi: 10.1039/C8NR02142B
26. [26]
  H. Yuan, Z. Li, J. Yang, J. Phys. Chem. C 123 (2019) 16294–16299. doi: 10.1021/acs.jpcc.9b04221
27. [27]
  M. Wallace, High-pressure high-temperature (HPHT) synthesis of functional materials, in: S. Igor (Ed. ), Sintering of Functional Materials, IntechOpen, Rijeka, 2017, pp. 166–182.
28. [28]
  B. Ren, H. Cui, C. Wang, Electrochem. Energy Rev. 5 (2022) 32.
29. [29]
  Y. Chen, Y. Yao, Y. Xia, et al., Nano Res. 13 (2020) 2777–2783. doi: 10.1007/s12274-020-2928-0
30. [30]
  H. Li, L. Zhang, Q. Zeng, et al., Comp. Mater. Sci. 49 (2010) 814–819. doi: 10.1016/j.commatsci.2010.06.027
31. [31]
  C. Zhou, P. Wang, C. Wei, et al., J. Alloys Compd. 698 (2017) 27–32. doi: 10.1016/j.jallcom.2016.12.244
32. [32]
  P. Wang, Y. Qi, S. Zhou, et al., Phys. Status Solidi B 253 (2016) 1590. doi: 10.1002/pssb.201552752
33. [33]
  L. Scatteia, R. Borrelli, G. Cosentino, et al., J. Spacecr. Rockets 43 (2006) 1004–1012. doi: 10.2514/1.21156
34. [34]
  S.H. Lee, Y. Sakka, Y. Kagawa, J. Am. Ceram. Soc. 91 (2008) 1715–1717. doi: 10.1111/j.1551-2916.2008.02343.x
35. [35]
  Y. Panayiotatos, Diam. Relat. Mater. 12 (2003) 1151–1156. doi: 10.1016/S0925-9635(02)00318-7
36. [36]
  F. Guo, Y. Wu, H. Chen, et al., Energy Environ. Sci. 12 (2019) 684–692. doi: 10.1039/C8EE03405B
37. [37]
  B. Qin, Y. Li, H. Wang, et al., Nano Energy 60 (2019) 43–51. doi: 10.1016/j.nanoen.2019.03.024
38. [38]
  P.P. Guo, Z.H. He, S.Y. Yang, et al., Green Chem. 24 (2022) 1527–1533. doi: 10.1039/D1GC04284J
39. [39]
  D. Yang, Q. Zhu, B. Han, The Innovation 1 (2020) 100016.
40. [40]
  X. Tan, X. Sun, B. Han, Natl. Sci. Rev. 9 (2022) nwab022. doi: 10.1093/nsr/nwab022
41. [41]
  B.A. Rosen, A. Salehi-Khojin, M.R. Thorson, et al., Science 334 (2011) 643–644. doi: 10.1126/science.1209786
42. [42]
  C. Cadena, J.L. Anthony, J.K. Shah, et al., J. Am. Chem. Soc 126 (2004) 5300–5308. doi: 10.1021/ja039615x
43. [43]
  G. Hong, J. Jacquemin, P. Husson, et al., Ind. Eng. Chem. Res. 45 (2006) 8180–8188. doi: 10.1021/ie0605377
44. [44]
  D. Faggion, W.D.G. Gonçalves, J. Dupont, Front. Chem. 7 (2019) 1–8. doi: 10.3389/fchem.2019.00001
45. [45]
  J. Pei, T. Wang, R. Sui, et al., Energy Environ. Sci. 14 (2021) 3019–3028. doi: 10.1039/D0EE03947K
46. [46]
  B. Ratschmeier, B. Braunschweig, J. Phys. Chem. C 125 (2021) 16498–16507. doi: 10.1021/acs.jpcc.1c02898
47. [47]
  N.J. Firet, W.A. Smith, ACS Catal. 7 (2016) 606–612.
48. [48]
  Y. Katayama, F. Nattino, L. Giordano, et al., J. Phys. Chem. C 123 (2018) 5951–5963.
49. [49]
  H. Chang, F. Gao, A. Luo, et al., Chem. Commun. 59 (2023) 7647–7650. doi: 10.1039/D3CC01834B
50. [50]
  K. Yao, J. Li, H. Wang, et al., J. Am. Chem. Soc. 144 (2022) 14005–14011. doi: 10.1021/jacs.2c01044
51. [51]
  M. Dai, W. Ni, Z. Zeng, et al., Energy Environ. Sci. 17 (2024) 1531–1539. doi: 10.1039/D3EE03226D
52. [52]
  X. Li, W. Bi, M. Chen, et al., J. Am. Chem. Soc. 139 (2017) 14889–14892. doi: 10.1021/jacs.7b09074
1. [1]
  Zelong LIANG , Shijia QIN , Pengfei GUO , Hang XU , Bin ZHAO . Synthesis and electrocatalytic CO₂ reduction performance of metal-organic framework catalysts loaded with silver particles. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 165-173. doi: 10.11862/CJIC.20240409
2. [2]
  Luyu Zhang , Zirong Dong , Shuai Yu , Guangyue Li , Weiwen Kong , Wenjuan Liu , Haisheng He , Yi Lu , Wei Wu , Jianping Qi . Ionic liquid-based in situ dynamically self-assembled cationic lipid nanocomplexes (CLNs) for enhanced intranasal siRNA delivery. Chinese Chemical Letters, 2024, 35(7): 109101-. doi: 10.1016/j.cclet.2023.109101
3. [3]
  Hao-Cong Li , Ming Zhang , Qiyan Lv , Kai Sun , Xiao-Lan Chen , Lingbo Qu , Bing Yu . Homogeneous catalysis and heterogeneous separation: Ionic liquids as recyclable photocatalysts for hydroacylation of olefins. Chinese Chemical Letters, 2025, 36(2): 110579-. doi: 10.1016/j.cclet.2024.110579
4. [4]
  Jiajia Wang , XinXin Ge , Yajing Xiang , Xiaoliang Qi , Ying Li , Hangbin Xu , Erya Cai , Chaofan Zhang , Yulong Lan , Xiaojing Chen , Yizuo Shi , Zhangping Li , Jianliang Shen . An ionic liquid functionalized sericin hydrogel for drug-resistant bacteria-infected diabetic wound healing. Chinese Chemical Letters, 2025, 36(2): 109819-. doi: 10.1016/j.cclet.2024.109819
5. [5]
  Mengyu Chen , Qinglin Zhou , Tianyun Qin , Ningyao Sun , Yuxi Chen , Yuwei Gong , Xingyi Li , Jinsong Liu . An ionic liquid-reinforced gelatin hydrogel with strong adhesion, antibacterial and anti-inflammatory properties for treating oral ulcers. Chinese Chemical Letters, 2025, 36(7): 110441-. doi: 10.1016/j.cclet.2024.110441
6. [6]
  Mingming Zhang , Ting Xu , Ruonan Yin , Xueqiu Chen , Zheng-Jun Wang , Jun Li , Xin Wang , Huile Jin , Haibo Ke , Shun Wang , Jing-Jing Lv . Anode engineering for electrocatalytic CO₂ reduction reaction. Chinese Chemical Letters, 2026, 37(3): 110665-. doi: 10.1016/j.cclet.2024.110665
7. [7]
  Xueyang Zhao , Bangwei Deng , Hongtao Xie , Yizhao Li , Qingqing Ye , Fan Dong . Recent process in developing advanced heterogeneous diatomic-site metal catalysts for electrochemical CO₂ reduction. Chinese Chemical Letters, 2024, 35(7): 109139-. doi: 10.1016/j.cclet.2023.109139
8. [8]
  Tinghui Yang , Min Kuang , Jianping Yang . Mesoporous CuCe dual-metal catalysts for efficient electrochemical reduction of CO2 to methane. Chinese Journal of Structural Chemistry, 2024, 43(8): 100350-100350. doi: 10.1016/j.cjsc.2024.100350
9. [9]
  Xiangyu Chen , Aihao Xu , Dong Wei , Fang Huang , Junjie Ma , Huibing He , Jing Xu . Atomic cerium-doped CuO_x catalysts for efficient electrocatalytic CO₂ reduction to CH₄. Chinese Chemical Letters, 2025, 36(1): 110175-. doi: 10.1016/j.cclet.2024.110175
10. [10]
  Maomao Liu , Guizeng Liang , Ningce Zhang , Tao Li , Lipeng Diao , Ping Lu , Xiaoliang Zhao , Daohao Li , Dongjiang Yang . Electron-rich Ni2+ in Ni3S2 boosting electrocatalytic CO2 reduction to formate and syngas. Chinese Journal of Structural Chemistry, 2024, 43(8): 100359-100359. doi: 10.1016/j.cjsc.2024.100359
11. [11]
  Dong-Ling Kuang , Song Chen , Shaoru Chen , Yong-Jie Liao , Ning Li , Lai-Hon Chung , Jun He . 2D Zirconium-based metal-organic framework/bismuth(III) oxide nanorods composite for electrocatalytic CO2-to-formate reduction. Chinese Journal of Structural Chemistry, 2024, 43(7): 100301-100301. doi: 10.1016/j.cjsc.2024.100301
12. [12]
  Lili Wang , Xujie Han , Baichuan Xiong , Ya Yan , Cheng Zhang , Yuning Qu , Yiran Zhang , Linlin Zheng , Zirui Gao , Shuheng Tian , Wenjing Dai , Bowen Cheng , Hang Zhang , Zhen Yin . 1D self-supporting NiFe₂O₄/NiMoO₄ heterostructure as bifunctional electrocatalyst via interface engineering for highly efficient seawater splitting. Chinese Chemical Letters, 2025, 36(12): 111437-. doi: 10.1016/j.cclet.2025.111437
13. [13]
  Peiyang Du , Ling Yuan , Tong Bao , Yamin Xi , Jiaxin Li , Yin Bi , Luli Yin , Jing Wang , Chao Liu . Facet effect of metal-organic frameworks on supporting co-catalysts for photocatalytic hydrogen peroxide production. Chinese Chemical Letters, 2025, 36(11): 110472-. doi: 10.1016/j.cclet.2024.110472
14. [14]
  Hong Dong , Feng-Ming Zhang . Covalent organic frameworks for artificial photosynthetic diluted CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(7): 100307-100307. doi: 10.1016/j.cjsc.2024.100307
15. [15]
  Ping Wang , Tianbao Zhang , Zhenxing Li . Reconstruction mechanism of Cu surface in CO2 reduction process. Chinese Journal of Structural Chemistry, 2024, 43(8): 100328-100328. doi: 10.1016/j.cjsc.2024.100328
16. [16]
  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
17. [17]
  Xiaofan ZHANG , Yu DUAN , Meijie SHI , Nan LU , Renhong LI , Xiaoqing YAN . Z-scheme Co₃O₄/BiOBr heterojunction for efficient photoreduction CO₂ reduction. Chinese Journal of Inorganic Chemistry, 2025, 41(9): 1878-1888. doi: 10.11862/CJIC.20250079
18. [18]
  Shu-Ran Xu , Fang-Xing Xiao . Metal halide perovskites quantum dots: Synthesis, and modification strategies for solar CO2 conversion. Chinese Journal of Structural Chemistry, 2023, 42(12): 100173-100173. doi: 10.1016/j.cjsc.2023.100173
19. [19]
  Yuhao Guo , Na Li , Tingjiang Yan . Tandem catalysis for photoreduction of CO2 into multi-carbon fuels on atomically thin dual-metal phosphochalcogenides. Chinese Journal of Structural Chemistry, 2024, 43(7): 100320-100320. doi: 10.1016/j.cjsc.2024.100320
20. [20]
  Ruolin CHENG , Yue WANG , Fei YANG , Huagen LIANG , Shijian LU . Application of metal-organic frameworks (MOFs) in photocatalytic CO₂ cycloaddition reaction: A mini review. Chinese Journal of Inorganic Chemistry, 2025, 41(12): 2429-2440. doi: 10.11862/CJIC.20250242

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(97)
HTML views(11)

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

Metal diborides as robust and highly stable electrodes for efficient electrocatalytic reduction of CO2 to CO in ionic liquid-based electrolytes

Metrics

通讯作者: 陈斌, bchen63@163.com

Metal diborides as robust and highly stable electrodes for efficient electrocatalytic reduction of CO₂ to CO in ionic liquid-based electrolytes