Citation: Sanmei Wang, Yong Zhou, Hengxin Fang, Chunyang Nie, Chang Q Sun, Biao Wang. Constant-potential simulation of electrocatalytic N₂ reduction over atomic metal-N-graphene catalysts[J]. Chinese Chemical Letters, ;2025, 36(3): 110476. doi: 10.1016/j.cclet.2024.110476 shu

Constant-potential simulation of electrocatalytic N₂ reduction over atomic metal-N-graphene catalysts

Sanmei Wang ^a ,
Yong Zhou ^{a, *,} ,
Hengxin Fang ^a ,
Chunyang Nie ^{a, *,} ,
Chang Q Sun ^{a, c, d} ,
Biao Wang ^{a, b, *,}

a.
Research Institute of Interdisciplinary Sciences (RISE) and School of Materials Science & Engineering, Dongguan University of Technology, Dongguan 523808, China
b.
Sino-French Institute of Nuclear Engineering and Technology, Sun Yat-sen University, Zhuhai 519082, China
c.
Guangdong Provincial Key Laboratory of Extreme Conditions, Dongguan 523803, China
d.
School of Science, Nanyang Technological University, Singapore 639798, Singapore

zhouyong@dgut.edu.cn

niechunyang@dgut.edu.cn

wangbiao@mail.sysu.edu.cn

Received Date: 1 July 2024
Revised Date: 18 September 2024
Accepted Date: 19 September 2024
Available Online: 19 September 2024

Figures(6)

Charge-neutral method (CNM) is extensively used in investigating the performance of catalysts and the mechanism of N₂ electrochemical reduction (NRR). However, disparities remain between the predicted potentials required for NRR by the CNM methods and those observed experimentally, as the CNM method neglects the charge effect from the electrode potential. To address this issue, we employed the constant electrode potential (CEP) method to screen atomic transition metal-N-graphene (M₁/N-graphene) as NRR electrocatalysts and systematically investigated the underlying catalytic mechanism. Among eight types of M₁/N-graphene (M₁ = Mo, W, Fe, Re, Ni, Co, V, Cr), W₁/N-graphene emerges as the most promising NRR electrocatalyst with a limiting potential as low as −0.13 V. Additionally, the W₁/N-graphene system consistently maintains a positive charge during the reaction due to its Fermi level being higher than that of the electrode. These results better match with the actual circumstances compared to those calculated by conventional CNM method. Thus, our work not only develops a promising electrocatalyst for NRR but also deepens the understanding of the intrinsic electrocatalytic mechanism.
- N₂ reduction,
- Single-atom catalysts,
- Constant potential,
- Graphene,
- DFT
1. [1]
  N. Gruber, J.N. Galloway, Nature 451 (2008) 293–296. doi: 10.1038/nature06592
2. [2]
  L.F. Greenlee, Nat. Energy 5 (2020) 557–558. doi: 10.1038/s41560-020-0670-1
3. [3]
  D.R. MacFarlane, P.V. Cherepanov, J. Choi, et al., Joule 4 (2020) 1186–1205. doi: 10.1016/j.joule.2020.04.004
4. [4]
  C. Tang, S.Z. Qiao, Joule 3 (2019) 1573–1575. doi: 10.1016/j.joule.2019.06.020
5. [5]
  J.N. Galloway, A.R. Townsend, J.W. Erisman, et al., Science 320 (2008) 889–892. doi: 10.1126/science.1136674
6. [6]
  J.W. Erisman, M.A. Sutton, J. Galloway, et al., Nat. Geosci. 1 (2008) 636–639. doi: 10.1038/ngeo325
7. [7]
  R. Schlögl, Angew. Chem. Int. Ed. 42 (2003) 2004–2008. doi: 10.1002/anie.200301553
8. [8]
  C. Liu, K.K. Sakimoto, B.C. Colón, et al., Proc. Natl. Acad. Sci. U. S. A. 114 (2017) 6450–6455. doi: 10.1073/pnas.1706371114
9. [9]
  K.T. Shanmugam, R.C. Valentine, Proc. Natl. Acad. Sci. U. S. A. 72 (1975) 136–139. doi: 10.1073/pnas.72.1.136
10. [10]
  Y. Xiong, B. Li, Y. Gu, et al., Nat. Chem. 15 (2023) 286–293. doi: 10.1038/s41557-022-01088-8
11. [11]
  W. Zhang, T. Liu, Q. Tan, et al., ACS Catal. 13 (2023) 3242–3253. doi: 10.1021/acscatal.2c05129
12. [12]
  G.F. Chen, Y. Yuan, H. Jiang, et al., Nat. Energy 5 (2020) 605–613. doi: 10.1038/s41560-020-0654-1
13. [13]
  K. Qi, X.Q. Cui, L. Gu, et al., Nat. Commun. 10 (2019) 5. doi: 10.1038/s41467-018-07830-6
14. [14]
  J. Wang, M. Shi, G. Yi, et al., Chin. Chem. Lett. 33 (2022) 4623–4627. doi: 10.1016/j.cclet.2021.12.040
15. [15]
  C. Cai, K. Liu, L. Zhang, et al., Angew. Chem. Int. Ed. 62 (2023) e202300873. doi: 10.1002/anie.202300873
16. [16]
  Y. Wang, W. Zhou, R. Jia, et al., Angew. Chem. Int. Ed. 59 (2020) 5350–5354. doi: 10.1002/anie.201915992
17. [17]
  X. Li, P. Shen, Y. Luo, et al., Angew. Chem. Int. Ed. 61 (2022) e202205923. doi: 10.1002/anie.202205923
18. [18]
  F. Lü, S. Zhao, R. Guo, et al., Nano Energy 61 (2019) 420–427. doi: 10.1016/j.nanoen.2019.04.092
19. [19]
  Y. Zhao, S. Zhang, C. Han, et al., Chem. Eng. J. 468 (2023) 143517. doi: 10.1016/j.cej.2023.143517
20. [20]
  W. Zang, T. Yang, H. Zou, et al., ACS Catal. 9 (2019) 10166–10173. doi: 10.1021/acscatal.9b02944
21. [21]
  H.P. Jia, E.A. Quadrelli, Chem. Soc. Rev. 43 (2014) 547–564. doi: 10.1039/C3CS60206K
22. [22]
  S. Zhang, M. Jin, T. Shi, et al., Angew. Chem. Int. Ed. 59 (2020) 13423–13429. doi: 10.1002/anie.202005930
23. [23]
  L. Han, X. Liu, J. Chen, et al., Angew. Chem. Int. Ed. 58 (2019) 2321–2325. doi: 10.1002/anie.201811728
24. [24]
  L. Chen, C. He, R. Wang, et al., Chin. Chem. Lett. 32 (2021) 53–56. doi: 10.1016/j.cclet.2020.11.013
25. [25]
  J. Guo, T. Tadesse Tsega, I. Ul Islam, et al., Chin. Chem. Lett. 31 (2020) 2487–2490. doi: 10.1016/j.cclet.2020.02.019
26. [26]
  Y. Ma, T. Yang, H. Zou, et al., Adv. Mater. 32 (2020) 2002177. doi: 10.1002/adma.202002177
27. [27]
  J. Chen, Y. Kang, W. Zhang, et al., Angew. Chem. Int. Ed. 61 (2022) e202203022. doi: 10.1002/anie.202203022
28. [28]
  H. Yin, S.L. Li, L.Y. Gan, P. Wang, J. Mater. Chem. A 7 (2019) 11908–11914. doi: 10.1039/c9ta01624d
29. [29]
  N. Saeidi, M.D. Esrafili, J.J. Sardroodi, ChemistrySelect 4 (2019) 12216–12226. doi: 10.1002/slct.201903206
30. [30]
  P. Ou, X. Zhou, F. Meng, et al., Nanoscale 11 (2019) 13600–13611. doi: 10.1039/c9nr02586c
31. [31]
  S. Surendralal, M. Todorova, M.W. Finnis, J. Neugebauer, Phys. Rev. Lett. 120 (2018) 246801. doi: 10.1103/PhysRevLett.120.246801
32. [32]
  G. Kastlunger, P. Lindgren, A.A. Peterson, J. Phys. Chem. C 122 (2018) 12771–12781. doi: 10.1021/acs.jpcc.8b02465
33. [33]
  C. He, Z.Y. Wu, L. Zhao, et al., ACS Catal. 9 (2019) 7311–7317. doi: 10.1021/acscatal.9b00959
34. [34]
  Y. Wang, X. Cui, J. Zhao, et al., ACS Catal. 9 (2019) 336–344. doi: 10.1021/acscatal.8b03802
35. [35]
  X. Zhao, Y. Liu, J. Am. Chem. Soc. 143 (2021) 9423–9428. doi: 10.1021/jacs.1c02186
36. [36]
  S. Yu, Z. Levell, Z. Jiang, et al., J. Am. Chem. Soc. 145 (2023) 25352–25356. doi: 10.1021/jacs.3c09193
37. [37]
  X. Bai, X. Zhao, Y. Zhang, et al., J. Am. Chem. Soc. 144 (2022) 17140–17148. doi: 10.1021/jacs.2c07178
38. [38]
  G. Gao, L.W. Wang, Chem. Catal. 1 (2021) 1331–1345. doi: 10.1016/j.checat.2021.10.006
39. [39]
  C. He, J. Ma, S. Xi, W. Zhang, J. Energy Chem. 97 (2024) 68–78. doi: 10.1016/j.jechem.2024.05.040
40. [40]
  C. He, S. Yan, W. Zhang, J. Energy Chem. 96 (2024) 437–447. doi: 10.1016/j.jechem.2024.04.047
41. [41]
  C. He, J. Ma, Y. Wu, W. Zhang, J. Energy Chem. 84 (2023) 131–139. doi: 10.1016/j.jechem.2023.05.022
42. [42]
  D. Kim, J. Shi, Y. Liu, J. Am. Chem. Soc. 140 (2018) 9127–9131. doi: 10.1021/jacs.8b03002
43. [43]
  S. Chung, H. Ju, M. Choi, et al., Angew. Chem. Int. Ed. 61 (2022) e202212676. doi: 10.1002/anie.202212676
44. [44]
  N. Zhang, A. Jalil, D. Wu, et al., J. Am. Chem. Soc. 140 (2018) 9434–9443. doi: 10.1021/jacs.8b02076
45. [45]
  Z.Y. Wu, M. Karamad, X. Yong, et al., Nat. Commun. 12 (2021) 2870. doi: 10.1038/s41467-021-23115-x
46. [46]
  T.N. Ye, S.W. Park, Y. Lu, et al., Nature 583 (2020) 391–395. doi: 10.1038/s41586-020-2464-9
47. [47]
  C. Ling, Y. Ouyang, Q. Li, et al., Small Methods 3 (2019) 1800376. doi: 10.1002/smtd.201800376
48. [48]
  C. He, C. Xu, W. Zhang, ACS Appl. Mater. Interfaces 15 (2023) 57015–57028.
49. [49]
  Y. Wu, C. He, W. Zhang, J. Am. Chem. Soc. 144 (2022) 9344–9353. doi: 10.1021/jacs.2c01245
50. [50]
  S. Han, X. Wei, Y. Huang, et al., Nano Energy 99 (2022) 107363. doi: 10.1016/j.nanoen.2022.107363
51. [51]
  X. Zhai, L. Li, X. Liu, et al., Nanoscale 12 (2020) 10035–10043. doi: 10.1039/d0nr00030b
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2. [2]
  Tsegaye Tadesse Tsega , Jiantao Zai , Chin Wei Lai , Xin-Hao Li , Xuefeng Qian . Earth-abundant CuFeS2 nanocrystals@graphite felt electrode for high performance aqueous polysulfide/iodide redox flow batteries. Chinese Journal of Structural Chemistry, 2024, 43(1): 100192-100192. doi: 10.1016/j.cjsc.2023.100192
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4. [4]
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  Zeyu Jiang , Yadi Wang , Changwei Chen , Chi He . Progress and challenge of functional single-atom catalysts for the catalytic oxidation of volatile organic compounds. Chinese Chemical Letters, 2024, 35(9): 109400-. doi: 10.1016/j.cclet.2023.109400
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Constant-potential simulation of electrocatalytic N2 reduction over atomic metal-N-graphene catalysts

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通讯作者: 陈斌, bchen63@163.com

Constant-potential simulation of electrocatalytic N₂ reduction over atomic metal-N-graphene catalysts