Citation: 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[J]. Chinese Chemical Letters, ;2025, 36(10): 111294. doi: 10.1016/j.cclet.2025.111294 shu

A zinc-nitrate battery for efficient ammonia electrosynthesis and energy output by a high entropy hydroxide catalyst

Henan Engineering Research Center of Design and Recycle for Advanced Electrochemical Energy Storage Materials, School of Materials Science and Engineering, Henan Normal University, Xinxiang 453007, China

chenmingxing@htu.edu.cn

qijing2020@htu.edu.cn

Received Date: 26 October 2024
Revised Date: 6 May 2025
Accepted Date: 9 May 2025
Available Online: 9 May 2025

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Zinc-nitrate battery could produce electrical power, remove pollutant nitrate and obtain value-added ammonia, where the cathodic reaction of converting nitrate to ammonia is sluggish and complex due to the involvement of multi-electron transfer. Thus, highly efficient catalysts for nitrate reduction reaction (NO₃RR) are greatly needed. In this work, we report a high entropy hydroxide (HE-OH) as an excellent NO₃RR catalyst, which could achieve high NH₃ Faradaic efficiencies (e.g., nearly 100% at −0.3 V versus reversible hydrogen electrode) and high yield rates (e.g., 30.4 mg h⁻¹cm⁻² at −0.4 V). Moreover, HE-OH could also deliver a current density of 10 mA/cm² at an overpotential of 260 mV for oxygen evolution reaction. The assembled zinc-nitrate battery using HE-OH as the cathode demonstrates a high power density (e.g., 3.62 mW/cm²), rechargeability and stability.
- Nitrate reduction reaction,
- High entropy hydroxide,
- Ammonia synthesis,
- Electrocatalysis,
- Zinc-nitrate battery
1. [1]
  C. Ma, L. Bao, X. Fan, et al., Catal. Sci. Technol. 14 (2024) 3007–3011. doi: 10.1039/d4cy00392f
2. [2]
  P. Hu, X. Zhang, M. Xu, et al., Appl. Catal. B 357 (2024) 124267. doi: 10.1016/j.apcatb.2024.124267
3. [3]
  Z. Zhang, T. Wang, J.S. Chen, et al., J. Colloid. Interface Sci. 648 (2023) 693–700. doi: 10.1016/j.jcis.2023.05.186
4. [4]
  Y. Li, L. Ouyang, J. Chen, et al., J. Colloid. Interface Sci. 663 (2024) 405–412. doi: 10.1016/j.jcis.2024.02.153
5. [5]
  K. Chen, G. Wang, Y. Guo, et al., Nano Res. 16 (2023) 8737–8742. doi: 10.1007/s12274-023-5556-7
6. [6]
  D. Wu, K. Chen, P. Lv, et al., Nano Lett. 24 (2024) 8502–8509. doi: 10.1021/acs.nanolett.4c00576
7. [7]
  V. Kyriakou, I. Garagounis, A. Vourros, et al., Joule 4 (2020) 142–158. doi: 10.1016/j.joule.2019.10.006
8. [8]
  K. Dong, Y. Yao, H. Li, et al., Nat. Synth. 3 (2024) 763–773. doi: 10.1038/s44160-024-00522-8
9. [9]
  K. Chen, D. Ma, Y. Zhang, et al., Adv. Mater. 36 (2024) 2402160. doi: 10.1002/adma.202402160
10. [10]
  H. Wu, H. Guo, F. Zhang, et al., J. Mater. Chem. A 11 (2023) 22466–22477. doi: 10.1039/d3ta04155g
11. [11]
  S. Luo, H. Guo, T. Li, et al., Appl. Catal. B 351 (2024) 123967. doi: 10.1016/j.apcatb.2024.123967
12. [12]
  Y. Xiong, Y. Wang, J. Zhou, et al., Adv. Mater. 36 (2023) e2304021.
13. [13]
  L. Xie, Q. Liu, X. Li, et al., ACS. Appl. Nano Mater. 7 (2023) 951–956.
14. [14]
  J. Miao, Q. Hong, L. Liang, et al., Chin. Chem. Lett. 35 (2024) 108935. doi: 10.1016/j.cclet.2023.108935
15. [15]
  Z. Tao, H. Yin, Y. Lv, et al., Chem. Commun. 60 (2024) 5554–5557. doi: 10.1039/d4cc01399a
16. [16]
  K. Wang, J. Pan, J. Hu, et al., Chem. Eng. J. 482 (2024) 148883. doi: 10.1016/j.cej.2024.148883
17. [17]
  G. Zhang, X. Li, K. Chen, et al., Angew. Chem. Int. Ed. 62 (2023) e202300054. doi: 10.1002/anie.202300054
18. [18]
  Y. Zhang, Z. Li, K. Chen, et al., Adv. Energy Mater. 14 (2024) 2402309. doi: 10.1002/aenm.202402309
19. [19]
  T. Zhu, Q. Chen, P. Liao, et al., Small 16 (2020) 2004526. doi: 10.1002/smll.202004526
20. [20]
  R. Zhao, Q. Yan, L. Yu, et al., Adv. Mater. 35 (2023) e2306633. doi: 10.1002/adma.202306633
21. [21]
  X. Deng, Y. Yang, L. Wang, et al., Adv. Sci. 8 (2021) 2004523. doi: 10.1002/advs.202004523
22. [22]
  H. Xu, Y. Ma, J. Chen, et al., Chem. Soc. Rev. 51 (2022) 2710–2758. doi: 10.1039/d1cs00857a
23. [23]
  W. Zhong, Q.L. Hong, X. Ai, et al., Adv. Mater. 36 (2024) 2314351. doi: 10.1002/adma.202314351
24. [24]
  Z. Zhang, A. Niu, Y. Lv, et al., Angew. Chem. Int. Ed. 63 (2024) e202406441. doi: 10.1002/anie.202406441
25. [25]
  R. Zhang, Y. Guo, S. Zhang, et al., Adv. Energy Mater. 12 (2022) 2103872. doi: 10.1002/aenm.202103872
26. [26]
  W. Lin, E. Zhou, J.F. Xie, et al., Adv. Funct. Mater. 32 (2022) 2209464. doi: 10.1002/adfm.202209464
27. [27]
  X. He, T. Xie, K. Dong, et al., Sci. China Mater. 68 (2025) 2756–2763. doi: 10.1007/s40843-024-2798-5
28. [28]
  X.P. Zhang, A. Chandra, Y.M. Lee, et al., Chem. Soc. Rev. 50 (2021) 4804–4811. doi: 10.1039/d0cs01456g
29. [29]
  J.Y. Zhu, Q. Xue, Y.Y. Xue, et al., ACS. Appl. Mater. Interfaces 12 (2020) 14064–14070. doi: 10.1021/acsami.0c01937
30. [30]
  Z. Chang, G. Meng, Y. Chen, et al., Adv. Mater. 35 (2023) e2304508. doi: 10.1002/adma.202304508
31. [31]
  K. Fan, W. Xie, J. Li, et al., Nat. Commun. 13 (2022) 7958. doi: 10.1038/s41467-022-35664-w
32. [32]
  H. Jiang, G.F. Chen, O. Savateev, et al., Angew. Chem. Int. Ed. 62 (2023) e202218717. doi: 10.1002/anie.202218717
33. [33]
  Y. Fu, S. Wang, Y. Wang, et al., Angew. Chem. Int. Ed. 62 (2023) e202303327. doi: 10.1002/anie.202303327
34. [34]
  H. Liu, X. Lang, C. Zhu, et al., Angew. Chem. Int. Ed. 61 (2022) e202202556. doi: 10.1002/anie.202202556
35. [35]
  N. Zhou, Z. Wang, N. Zhang, et al., ACS. Catal. 13 (2023) 7529–7537. doi: 10.1021/acscatal.3c01315
36. [36]
  Y. Ma, Y. Ma, Q. Wang, et al., Energy Environ. Sci. 14 (2021) 2883–2905. doi: 10.1039/d1ee00505g
37. [37]
  H. Xu, Z. Jin, Y. Zhang, et al., Chem. Sci. 14 (2023) 771–790. doi: 10.1039/d2sc06403k
38. [38]
  R. Nandan, M.Y. Rekha, H.R. Devi, et al., Chem. Commun. 57 (2021) 611–614. doi: 10.1039/d0cc06485h
39. [39]
  X. Miao, Z. Peng, L. Shi, et al., ACS. Catal. 13 (2023) 3983–3989. doi: 10.1021/acscatal.2c06276
40. [40]
  M. Cui, C. Yang, B. Li, et al., Adv. Energy Mater. 11 (2020) 2002887.
41. [41]
  F. Wang, P. Zou, Y. Zhang, et al., Nat. Commun. 14 (2023) 6019. doi: 10.1038/s41467-023-41706-8
42. [42]
  M. Shi, T. Tang, L. Xiao, et al., Chem. Commun. 59 (2023) 11971–11974. doi: 10.1039/d3cc04023b
43. [43]
  R. Zhang, Y. Zhang, B. Xiao, et al., Angew. Chem. Int. Ed. 63 (2024) e202407589. doi: 10.1002/anie.202407589
44. [44]
  M. Chen, H. Li, C. Wu, et al., Adv. Funct. Mater. 32 (2022) 2206407. doi: 10.1002/adfm.202206407
45. [45]
  X. Bo, R.K. Hocking, S. Zhou, et al., Energy Environ. Sci. 13 (2020) 4225–4237. doi: 10.1039/d0ee01609h
46. [46]
  J.Y. Fang, Q.Z. Zheng, Y.Y. Lou, et al., Nat. Commun. 13 (2022) 7899. doi: 10.1038/s41467-022-35533-6
47. [47]
  S. Zhang, J. Wu, M. Zheng, et al., Nat. Commun. 14 (2023) 3634. doi: 10.1007/978-981-99-1964-2_313
48. [48]
  T. Sun, S. Zhang, L. Xu, et al., Chem. Commun. 54 (2018) 12101–12104. doi: 10.1039/c8cc06566g
49. [49]
  Y. Li, X. Tan, R.K. Hocking, et al., Nat. Commun. 11 (2020) 2720. doi: 10.1038/s41467-020-16554-5
50. [50]
  Z. Cai, L. Li, Y. Zhang, et al., Angew. Chem. Int. Ed. 58 (2019) 4189–4194. doi: 10.1002/anie.201812601
51. [51]
  Y. Chen, S. Yang, H. Liu, et al., Chin. J. Catal. 42 (2021) 1724–1731. doi: 10.1016/S1872-2067(21)63793-2
52. [52]
  J. He, X. Liu, H. Liu, et al., J. Catal. 364 (2018) 125–130. doi: 10.1016/j.jcat.2018.05.005
53. [53]
  A. Sarkar, Q. Wang, A. Schiele, et al., Adv. Mater. 31 (2019) 1806236. doi: 10.1002/adma.201806236
54. [54]
  Y. Xin, S. Li, Y. Qian, et al., ACS. Catal. 10 (2020) 11280–11306. doi: 10.1021/acscatal.0c03617
55. [55]
  G. Zhang, F. Wang, K. Chen, et al., Adv. Funct. Mater. 34 (2023) 2305372.
56. [56]
  R.Z. Snitkoff-Sol, A. Friedman, H.C. Honig, et al., Nat. Catal. 5 (2022) 163–170. doi: 10.1038/s41929-022-00748-9
57. [57]
  Y. Zhang, A.N. Simonov, J. Zhang, et al., Curr. Opin. Electrochem. 10 (2018) 72–81. doi: 10.1016/j.coelec.2018.04.016
58. [58]
  M.E.G. Lyons, R.L. Doyle, M.P. Brandon, et al., Phys. Chem. Chem. Phys. 13 (2011) 21530–21551. doi: 10.1039/c1cp22470k
59. [59]
  W. Luo, Z. Guo, L. Ye, et al., Small 20 (2024) 2311336. doi: 10.1002/smll.202311336
60. [60]
  C. Choi, S. Kwon, T. Cheng, et al., Nat. Catal. 3 (2020) 804–812. doi: 10.1038/s41929-020-00504-x
61. [61]
  W. He, J. Zhang, S. Dieckhofer, et al., Nat. Commun. 13 (2022) 1129. doi: 10.1038/s41467-022-28728-4
62. [62]
  L. Fang, S. Wang, S. Lu, et al., Chin. Chem. Lett. 35 (2024) 108864. doi: 10.1016/j.cclet.2023.108864
63. [63]
  W. Jang, D. Oh, J. Lee, et al., J. Am. Chem. Soc. 146 (2024) 27417–27428. doi: 10.1021/jacs.4c07061
64. [64]
  S. Ye, Z. Chen, G. Zhang, et al., Energy Environ. Sci. 15 (2022) 760–770. doi: 10.1039/d1ee03097c
65. [65]
  T.T.H. Hoang, S. Verma, S. Ma, et al., J. Am. Chem. Soc. 140 (2018) 5791–5797. doi: 10.1021/jacs.8b01868
66. [66]
  F. Lei, K. Li, M. Yang, et al., Inorg. Chem. Front. 9 (2022) 2734–2740. doi: 10.1039/d2qi00489e
67. [67]
  L.H. Zhang, Y. Jia, J. Zhan, et al., Angew. Chem. Int. Ed. 62 (2023) e202303483. doi: 10.1002/anie.202303483
68. [68]
  J.J. Zhang, Y.Y. Lou, Z. Wu, et al., J. Am. Chem. Soc. 146 (2024) 24966–24977. doi: 10.1021/jacs.4c06657
69. [69]
  J. Yu, Y. Qin, X. Wang, et al., Nano Energ. 103 (2022) 107705. doi: 10.1016/j.nanoen.2022.107705
70. [70]
  J. Ma, Y. Zhang, B. Wang, et al., ACS. Nano 17 (2023) 6687–6697. doi: 10.1021/acsnano.2c12491
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