Citation: Lin Xu, Lifen Liu, Guohua Chen, Deming Xia. In-situ grown high-load single-atom Fe on MoS₂/CFC with super high activity in ammonia synthesis via electrochemical nitrate reduction[J]. Chinese Chemical Letters, ;2026, 37(3): 111188. doi: 10.1016/j.cclet.2025.111188 shu

In-situ grown high-load single-atom Fe on MoS₂/CFC with super high activity in ammonia synthesis via electrochemical nitrate reduction

Lin Xu ^a ,
Lifen Liu ^{b, *,} ,
Guohua Chen ^c ,
Deming Xia ^a

a.
School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024, China
b.
School of Chemical Engineering, Ocean and Life Sciences, Dalian University of Technology, Panjin 124221, China
c.
School of Energy and Environment, City University of Hong Kong, Hong Kong, China

lifenliu@dlut.edu.cn

Received Date: 9 October 2024
Revised Date: 10 February 2025
Accepted Date: 8 April 2025
Available Online: 16 June 2025

Figures(3)

Electrochemically converting nitrate to ammonia under ambient conditions is a hot topic. However, it suffers from low efficiency because of the multi-electron/proton transfer. Herein, high-load atomic Fe (16.45 wt%) in-situ grown on carbon fiber cloth (Fe₁@MoS₂/CFC) demonstrates super high activity and selectivity in electrochemical nitrate reduction to ammonia at -0.73 V vs. RHE. The maximum NH₃ yield is 28.59 mg h^-1 cm^-2, and the corresponding NH₃-Faradaic efficiency is 96.65% at 360 mA/cm² partial current density. The electrode exhibits good durability during ten cycled tests of 1 h each. The X-ray absorption near-edge structure (XANES), extended X-ray absorption fine structure (EXAFS), in-situ Raman analysis, and electron paramagnetic resonance (EPR) measurements reveal that the super high activity derives from the rich presence of active sites related to Fe-S and surrounding unsaturated Mo-S. Density functional theory (DFT) calculations show that the atomic Fe facilitates the water dissociation and provides sufficient active hydrogen for the edge Mo to boost nitrate reduction reaction (NO₃^-RR) activity, enhances NH₃ selectivity, and decreases the energy barrier of NH₃ desorption (rate-determining step) by regulating the coordination environment and electronic structure of the active Mo site. This stable and binder-free electrode with high dosage atomic Fe and rich edge Mo active sites is an attractive cathode for NO₃^-RR.
- Nitrate reduction reaction,
- Electrocatalytic ammonia synthesis,
- Single-atom catalysts,
- Molybdenum disulfide,
- Binder-free electrode
1. [1]
  Y. Cui, A. Dong, Y. Zhou, et al., Small 19 (2023) 2207661. doi: 10.1002/smll.202207661
2. [2]
  W. Chen, X. Yang, Z. Chen, et al., Adv. Funct. Mater. 33 (2023) 2300512. doi: 10.1002/adfm.202300512
3. [3]
  S. Dong, A. Niu, K. Wang, et al., Appl. Catal. B 333 (2023) 122772. doi: 10.1016/j.apcatb.2023.122772
4. [4]
  S.L. Foster, S.I.P. Bakovic, R.D. Duda, et al., Nat. Catal. 1 (2018) 490–500. doi: 10.1038/s41929-018-0092-7
5. [5]
  W. He, J. Zhang, S. Dieckhöfer, et al., Nat. Commun. 13 (2022) 1129. doi: 10.1038/s41467-022-28728-4
6. [6]
  S. Zhang, M. Han, T. Shi, et al., Nat. Sustain. 6 (2023) 169–179.
7. [7]
  Y.X. Lin, S.N. Zhang, Z.H. Xue, et al., Nat. Commun. 10 (2019) 4380. doi: 10.1038/s41467-019-12312-4
8. [8]
  S. Liu, T. Qian, M. Wang, et al., Nat. Catal. 4 (2021) 322–331. doi: 10.1038/s41929-021-00599-w
9. [9]
  F.Y. Chen, Z.Y. Wu, S. Gupta, et al., Nat. Nanotechnol. 17 (2022) 759–767. doi: 10.1038/s41565-022-01121-4
10. [10]
  Y. Wang, S. Wang, Y. Fu, et al., Chin. J. Catal. 56 (2024) 104–113. doi: 10.1016/S1872-2067(23)64578-4
11. [11]
  E. Murphy, B. Sun, M. Rüscher, et al., Adv. Mater. 36 (2024) 2401133. doi: 10.1002/adma.202401133
12. [12]
  K. Chen, D. Ma, Y. Zhang, et al., Adv. Mater. 36 (2024) 2402160. doi: 10.1002/adma.202402160
13. [13]
  K. Fan, W. Xie, J. Li, et al., Nat. Commun. 13 (2022) 7958. doi: 10.1038/s41467-022-35664-w
14. [14]
  R. Jia, Y. Wang, C. Wang, et al., ACS Catal. 10 (2020) 3533–3540. doi: 10.1021/acscatal.9b05260
15. [15]
  R. Chen, S. Shen, K. Wang, et al., Proc. Natl. Acad. Sci. U. S. A. 120 (2023) e2312550120. doi: 10.1073/pnas.2312550120
16. [16]
  Y. Liu, X. Zhao, C. Long, et al., Chin. J. Catal. 52 (2023) 196–206. doi: 10.1016/S1872-2067(23)64506-1
17. [17]
  J. Li, G. Zhan, J. Yang, et al., J Am. Chem. Soc. 142 (2020) 7036–7046. doi: 10.1021/jacs.0c00418
18. [18]
  S. Garcia-Segura, M. Lanzarini-Lopes, K. Hristovski, P. Westerhoff, Appl. Catal. B 236 (2018) 546–568. doi: 10.1016/j.apcatb.2018.05.041
19. [19]
  A. Wang, J. Li, T. Zhang, Nat. Rev. Chem. 2 (2018) 65–81. doi: 10.1038/s41570-018-0010-1
20. [20]
  Y. Ren, Y. Tang, L. Zhang, et al., Nat. Commun. 10 (2019) 4500. doi: 10.1038/s41467-019-12459-0
21. [21]
  F. Chen, X.-L. Wu, C. Shi, et al., Adv. Funct. Mater. 31 (2021) 2007877. doi: 10.1002/adfm.202007877
22. [22]
  Y. Jiang, J. Yang, M.-L. Li, et al., Chin. J. Catal. 59 (2024) 195–203. doi: 10.1016/S1872-2067(23)64634-0
23. [23]
  C. Wang, Y. Zhang, H. Luo, et al., Small Methods 6 (2022) 2200790. doi: 10.1002/smtd.202200790
24. [24]
  S. Zhang, J. Wu, M. Zheng, et al., Nat. Commun. 14 (2023) 3634. doi: 10.1007/978-981-99-1964-2_313
25. [25]
  S. Zhang, M. Li, J. Li, Q. Song, X. Liu, Proc. Natl. Acad. Sci. U. S. A. 119 (2022) e2115504119. doi: 10.1073/pnas.2115504119
26. [26]
  C. Liu, G. Zhang, W. Zhang, Z. Gu, G. Zhu, Proc. Natl. Acad. Sci. U. S. A. 120 (2023) e2209979120. doi: 10.1073/pnas.2209979120
27. [27]
  Z.-Y. Wu, M. Karamad, X. Yong, et al., Nat. Commun. 12 (2021) 2870. doi: 10.1038/s41467-021-23115-x
28. [28]
  W.-D. Zhang, H. Dong, L. Zhou, et al., Appl. Catal. B 317 (2022) 121750. doi: 10.1016/j.apcatb.2022.121750
29. [29]
  A. Khorshidi, J. Violet, J. Hashemi, A.A. Peterson, Nat. Catal. 1 (2018) 263–268. doi: 10.1038/s41929-018-0054-0
30. [30]
  V. Fourmond, M. Sabaty, P. Arnoux, et al., J. Phys. Chem. B 114 (2010) 3341–3347. doi: 10.1021/jp911443y
31. [31]
  C. Sparacino-Watkins, J.F. Stolz, P. Basu, Chem. Soc. Rev. 43 (2014) 676–706. doi: 10.1039/C3CS60249D
32. [32]
  E. Murphy, Y. Liu, I. Matanovic, S. Guo, et al., ACS Catal. 12 (2022) 6651–6662. doi: 10.1021/acscatal.2c01367
33. [33]
  J. Zhang, J. Wu, H. Guo, et al., Adv. Mater. 29 (2017) 1701955. doi: 10.1002/adma.201701955
34. [34]
  I.S. Amiinu, Z. Pu, X. Liu, et al., Adv. Funct. Mater. 27 (2017) 1702300. doi: 10.1002/adfm.201702300
35. [35]
  L. Zhang, X. Ji, X. Ren, et al., Adv. Mater. 30 (2018) 1800191. doi: 10.1002/adma.201800191
36. [36]
  S. Jiao, Z. Yao, F. Xue, et al., Appl. Catal. B 258 (2019) 117964. doi: 10.1016/j.apcatb.2019.117964
37. [37]
  J. Ge, D. Zhang, Y. Qin, et al., Appl. Catal. B 298 (2021) 120557. doi: 10.1016/j.apcatb.2021.120557
38. [38]
  J. Li, Y. Zhang, C. Liu, et al., Adv. Funct. Mater. 32 (2022) 2108316. doi: 10.1002/adfm.202108316
39. [39]
  L. Xu, L. Liu, Appl. Catal. B 304 (2022) 120953. doi: 10.1016/j.apcatb.2021.120953
40. [40]
  X. Li, G. Zhang, Y. Chang, et al., Chem. Eng. J. 499 (2024) 156337. doi: 10.1016/j.cej.2024.156337
41. [41]
  X. Chen, R. Pan, H. Xu, et al., Appl. Catal. B 361 (2025) 124688. doi: 10.1016/j.apcatb.2024.124688
42. [42]
  M.K. Kim, B. Lamichhane, B. Song, et al., Appl. Catal. B 352 (2024) 124037. doi: 10.1016/j.apcatb.2024.124037
43. [43]
  X. Sun, Y. Qiu, B. Jiang, et al., Nat. Commun. 14 (2023) 291. doi: 10.1007/s11770-023-1069-0
44. [44]
  J. Xu, S. Zhang, H. Liu, et al., Angew. Chem. Int. Ed. 62 (2023) e202308044. doi: 10.1002/anie.202308044
45. [45]
  W. Wan, Y. Zhao, S. Wei, et al., Nat. Commun. 12 (2021) 5589. doi: 10.1038/s41467-021-25811-0
46. [46]
  Z. Jin, P. Li, Y. Meng, et al., Nat. Catal. 4 (2021) 615–622. doi: 10.1038/s41929-021-00650-w
47. [47]
  Y. Sun, R. Li, C. Song, et al., Appl. Catal. B 298 (2021) 120537. doi: 10.1016/j.apcatb.2021.120537
48. [48]
  Y. Yan, S. Liang, X. Wang, et al., Proc. Natl. Acad. Sci. U. S. A. 118 (2021) e2110036118. doi: 10.1073/pnas.2110036118
49. [49]
  K. Chen, J. Wang, J. Kang, et al., Appl. Catal. B 324 (2023) 122241. doi: 10.1016/j.apcatb.2022.122241
50. [50]
  A. Paliwal, C.D. Bandas, E.S. Thornburg, R.T. Haasch, A.A. Gewirth, ACS Catal. 13 (2023) 6754–6762. doi: 10.1021/acscatal.3c00999
51. [51]
  Y.Y. Lou, Q.Z. Zheng, S.Y. Zhou, et al., ACS Catal. 14 (2024) 5098–5108. doi: 10.1021/acscatal.4c00479
52. [52]
  Y. Liu, J. Ma, S. Huang, S. Niu, S. Gao, Nano Energy 117 (2023) 108840. doi: 10.1016/j.nanoen.2023.108840
53. [53]
  Z. Gu, Y. Zhang, Y. Fu, et al., Angew. Chem. Int. Ed. 63 (2024) e202409125. doi: 10.1002/anie.202409125
54. [54]
  C. Wang, K. Li, M. Zhao, Z. Li, J. Zheng, Sep. Purif. Technol. 340 (2024) 126641. doi: 10.1016/j.seppur.2024.126641
55. [55]
  N. Pu, A. Hu, Q. Yang, et al., Chem. Eng. J. 499 (2024) 156100. doi: 10.1016/j.cej.2024.156100
56. [56]
  X. Lv, Y. Li, F. Deng, et al., Chem. Eng. J. 475 (2023) 146128. doi: 10.1016/j.cej.2023.146128
57. [57]
  X. Shi, M. Xie, K. Yang, et al., Angew. Chem. Int. Ed. 63 (2024) e202406750. doi: 10.1002/anie.202406750
58. [58]
  S. Xu, Y. Shi, Z. Wen, et al., Appl. Catal. B 323 (2023) 122192. doi: 10.1016/j.apcatb.2022.122192
59. [59]
  N. Zhou, Z. Wang, N. Zhang, et al., ACS Catal. 13 (2023) 7529–7537. doi: 10.1021/acscatal.3c01315
60. [60]
  K. Chen, G. Wang, Y. Guo, D. Ma, K. Chu, Nano Res. 16 (2023) 8737–8742. doi: 10.1007/s12274-023-5556-7
61. [61]
  Z. Zhang, Y. Liu, X. Su, et al., Nano Res. 16 (2023) 6632–6641. doi: 10.1007/s12274-023-5402-y
62. [62]
  L. Xiao, C. Cheng, T. Yang, et al., Adv. Mater. 36 (2024) 2411134. doi: 10.1002/adma.202411134
63. [63]
  Y. Zhu, K. Fan, C.-S. Hsu, et al., Adv. Mater. 35 (2023) 2301133. doi: 10.1002/adma.202301133
64. [64]
  S. Luo, H. Guo, T. Li, et al., Appl. Catal. B 351 (2024) 123967. doi: 10.1016/j.apcatb.2024.123967
65. [65]
  H. Lin, J. Wei, Y. Guo, et al., Adv. Funct. Mater. 34 (2024) 2409696. doi: 10.1002/adfm.202409696
66. [66]
  D. Wu, K. Chen, P. Lv, et al., Nano Lett. 24 (2024) 8502–8509. doi: 10.1021/acs.nanolett.4c00576
67. [67]
  Y. Wang, F. Hao, M. Sun, et al., Adv. Mater. 36 (2024) 2313548. doi: 10.1002/adma.202313548
68. [68]
  G. Zhang, X. Li, K. Chen, et al., Angew. Chem. Int. Ed. 62 (2023) e202300054. doi: 10.1002/anie.202300054
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2. [2]
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3. [3]
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4. [4]
  Doudou Liu , Weiwei Guo , Guoliang Mei , Youpeng Dan , Rong Yang , Chao Huang , Yanling Zhai , Xiaoquan Lu . Application of catalyst Cu-t-ZrO₂ based on the electronic metal-support interaction in electrocatalytic nitrate reduction. Chinese Chemical Letters, 2025, 36(8): 110578-. doi: 10.1016/j.cclet.2024.110578
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  Mingxing Chen , Xue Li , Nian Liu , Zihe Du , Zhitao Wang , Jing Qi . A zinc-nitrate battery for efficient ammonia electrosynthesis and energy output by a high entropy hydroxide catalyst. Chinese Chemical Letters, 2025, 36(10): 111294-. doi: 10.1016/j.cclet.2025.111294
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沈阳化工大学材料科学与工程学院沈阳 110142

In-situ grown high-load single-atom Fe on MoS2/CFC with super high activity in ammonia synthesis via electrochemical nitrate reduction

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通讯作者: 陈斌, bchen63@163.com

In-situ grown high-load single-atom Fe on MoS₂/CFC with super high activity in ammonia synthesis via electrochemical nitrate reduction