Citation: Cuiping Lin, Chenchen Wang, Shaoqi Li, Qi Shen, Xiaodong Yang, Zengsheng Guo, Haiming Feng, Cuncheng Li, Yiqing Sun, Lifeng Hang. Pd@PtNiCoRuIr core-shell high-entropy alloys mesoporous nanospheres for temporally decoupled ammonia splitting by a Zn-NH₃ battery[J]. Chinese Chemical Letters, ;2026, 37(1): 111826. doi: 10.1016/j.cclet.2025.111826 shu

Pd@PtNiCoRuIr core-shell high-entropy alloys mesoporous nanospheres for temporally decoupled ammonia splitting by a Zn-NH₃ battery

Cuiping Lin ^a ,
Chenchen Wang ^a ,
Shaoqi Li ^a ,
Qi Shen ^{a, *,} ,
Xiaodong Yang ^a ,
Zengsheng Guo ^a ,
Haiming Feng ^b ,
Cuncheng Li ^{a, *,} ,
Yiqing Sun ^{a, *,} ,
Lifeng Hang ^{b, *,}

a.
School of Chemistry and Chemical Engineering, University of Jinan, Ji'nan 250022, China
b.
The Department of Medical Imaging, the Affiliated Guangdong Second Provincial General Hospital of Jinan University, Guangzhou 518037, China

Received Date: 16 April 2025
Revised Date: 9 September 2025
Accepted Date: 11 September 2025
Available Online: 11 September 2025

Figures(5)

Conversion of ammonia into hydrogen, a crucial pathway for the hydrogen economy, is severely constrained by the intricacy of the required equipment and the low efficiency. Herein, Pd@PtNiCoRuIr core-shell mesoporous bifunctional electrocatalysts were fabricated via a one-step wet-chemical reduction approach. By utilizing the limiting effect of triblock copolymers, gradient distribution control of six metal elements (Pd core and Pt/Ni/Co/Ru/Ir high-entropy alloys shell) was achieved, where the high-entropy alloy shell forms high-density active sites through lattice distortion effect. With the help of lattice distortion and mesoporous-confinement-enabled interfacial coupling effects, Pd@PtNiCoRuIr catalyst exhibited exceptional bifunctional performance in alkaline media: A low hydrogen evolution reaction (HER) overpotential of 30.5 mV at 10 mA/cm² and a high ammonia oxidation reaction (AOR) peak current density of 19.6 mA/cm² at 0.7 V vs. RHE, representing a 3.83-fold enhancement over commercial Pt/C. Moreover, a rechargeable Zn-NH₃ battery system was constructed and achieved 92.3% Faradaic efficiency (FE) for NH₃-to-H₂ conversion with outstanding stability at 16 mA/cm², thereby providing an innovative solution for efficient ammonia decomposition-based hydrogen production.
- Lattice distortion,
- High entropy alloy,
- Mesoporous architectures,
- Core-shell configurations,
- Zn-NH₃ battery
1. [1]
  F. Chang, W. Gao, J. Guo, et al., Adv. Mater. 33 (2021) 2005721. doi: 10.1002/adma.202005721
2. [2]
  X. Gao, Y. Zhang, S. Yin, et al., Adv. Funct. Mater. 32 (2022) 2204833. doi: 10.1002/adfm.202204833
3. [3]
  Y. Sun, K. Xu, Z. Wei, et al., Adv. Mater. 30 (2018) 1802121. doi: 10.1002/adma.201802121
4. [4]
  D. Khan, W.J. Ong, Interdiscip. Mater. 4 (2025) 249–283.
5. [5]
  H. Pan, J. Li, Y. Wang, et al., Adv. Sci. 11 (2024) 2402651. doi: 10.1002/advs.202402651
6. [6]
  Y. Fu, H. Wang, N. Li, et al., Chin. Chem. Lett. 36 (2025) 110890. doi: 10.1016/j.cclet.2025.110890
7. [7]
  C. Wang, D. Astruc, Chem. Soc. Rev. 50 (2021) 3437–3484. doi: 10.1039/D0CS00515K
8. [8]
  M.D. Allendorf, V. Stavila, J.L. Snider, et al., Nat. Chem. 14 (2022) 1214–1223. doi: 10.1038/s41557-022-01056-2
9. [9]
  J.H. Shin, U. Jung, J. Kim, et al., Appl. Catal. B: Environ. 340 (2024) 123234. doi: 10.1016/j.apcatb.2023.123234
10. [10]
  M. Monge-Palacios, X. Zhang, N. Morlanes, et al., Prog. Energy Combust. 105 (2024) 101177. doi: 10.1016/j.pecs.2024.101177
11. [11]
  R. Chen, H. Pan, Z. Meng, et al., Adv. Compos. Hybrid Mater. 8 (2025) 164. doi: 10.1007/s42114-025-01252-x
12. [12]
  A.M. Beiler, W.H. Li, A. Denisiuk, E. Palomares, A. Llobet, J. Energy Chem. 92 (2024) 292–295. doi: 10.1016/j.jechem.2023.12.032
13. [13]
  Y. Li, Q. Guan, G. Huang, et al., Adv. Energy. Mater. 12 (2022) 2202459. doi: 10.1002/aenm.202202459
14. [14]
  J. Lee, S.A. Lee, J. Kim, et al., Appl. Catal. B: Environ. 371 (2025) 125251. doi: 10.1016/j.apcatb.2025.125251
15. [15]
  G. Qing, T.W. Hamann, Joule 3 (2019) 634–636. doi: 10.1016/j.joule.2019.02.013
16. [16]
  J. Łuczak, M. Lieder, Adv. Colloid Interface Sci. 319 (2023) 102963. doi: 10.1016/j.cis.2023.102963
17. [17]
  X. Yang, H. Sun, C. Liu, L. Yu, H. Chen, Chem. Eng. J. 442 (2022) 136167. doi: 10.1016/j.cej.2022.136167
18. [18]
  F. Sarabia, C.G. Rodellar, B.R. Cuenya, S.Z. Oener, Nat. Commun. 15 (2025) 8204.
19. [19]
  X. Du, A. Du, D. Wang, et al., J. Am. Chem. Soc. 147 (2025) 8083–8087. doi: 10.1021/jacs.4c15489
20. [20]
  D. Yoon, S. Chung, M. Choi, E. Yang, J. Lee, J. Energy Chem. 93 (2024) 352–360. doi: 10.1016/j.jechem.2024.01.065
21. [21]
  Y. Feng, S. Yan, X. Zhang, Y. Wang, Acc. Chem. Res. 56 (2023) 1645–1655. doi: 10.1021/acs.accounts.3c00177
22. [22]
  S. Yan, Y. Feng, J. Lin, Y. Wang, et al., Adv. Mater. 5 (2023) 2212078.
23. [23]
  P. Jiang, Y. Xu, Z. Gong, et al., Angew. Chem. Int. Ed. 64 (2025) e202504188. doi: 10.1002/anie.202504188
24. [24]
  H. Wang, J. Ren, M. Sun, et al., Adv. Energy. Mater. 14 (2023) 2302515.
25. [25]
  Y. Feng, L. Huang, Z. Xiao, et al., J. Am. Chem. Soc. 146 (2024) 7771–7778. doi: 10.1021/jacs.4c00369
26. [26]
  S. Liu, Y. Jiang, M. Wang, et al., Adv. Funct. Mater. 33 (2023) 2306204. doi: 10.1002/adfm.202306204
27. [27]
  X. Yang, L. Sun, X. Liu, et al., ACS Catal. 14 (2024) 6236–6246. doi: 10.1021/acscatal.4c00209
28. [28]
  Y. Wang, Y. Ji, C. Li, et al., Chin. Chem. Lett. 36 (2025) 110370. doi: 10.1016/j.cclet.2024.110370
29. [29]
  R. Rizo, J. Fernández-Vidal, L.J. Hardwick, et al., Nat. Commun. 13 (2022) 2550. doi: 10.1038/s41467-022-30241-7
30. [30]
  Y. Sun, C. Wang, Y. Wang, et al., Appl. Surf. Sci. 651 (2024) 159222. doi: 10.1016/j.apsusc.2023.159222
31. [31]
  L. Gao, Z. Yang, T. Sun, et al., Adv. Energy Mater. 12 (2022) 2103943. doi: 10.1002/aenm.202103943
32. [32]
  J. Mahin, K. Kusada, T. Yamamoto, et al., Angew. Chem. Int. Ed. 64 (2025) e202502552. doi: 10.1002/anie.202502552
33. [33]
  H. Lv, H. Qin, K. Ariga, et al., Angew. Chem. Int. Ed. 61 (2022) e202116179. doi: 10.1002/anie.202116179
34. [34]
  Y. Wang, H. Lv, L. Sun, F. Jia, B. Liu, Adv. Energy Mater. 12 (2022) 2201478. doi: 10.1002/aenm.202201478
35. [35]
  D. Fan, H. Yao, L. Sun, H. Lv, B. Liu, Adv. Mater. 36 (2024) 2407940. doi: 10.1002/adma.202407940
36. [36]
  P. Kuang, Z. Ni, B. Zhu, Y. Lin, J. Yu, Adv. Mater. 35 (2023) 2303030. doi: 10.1002/adma.202303030
37. [37]
  X. Zhu, W. Huang, L. Tan, et al., Chin. Chem. Lett. (2025), doi:10.1016/j.cclet. 2025.110852. doi: 10.1016/j.cclet.2025.110852
38. [38]
  S. Moniri, Y. Yang, J. Ding, et al., Nature 624 (2023) 564–569. doi: 10.1038/s41586-023-06785-z
39. [39]
  A. Selmani, D. Kovačevič, K. Bohinc, et al., Adv. Colloid Interf. Sci. 303 (2022) 102640. doi: 10.1016/j.cis.2022.102640
40. [40]
  J. Yu, Y. Zhang, N. Zhang, et al., Chin. Chem. Lett. (2025), doi:10.1016/j.cclet. 2025.110830. doi: 10.1016/j.cclet.2025.110830
41. [41]
  Y. Zhang, T. Liu, J. Yu, et al., Chin. Chem. Lett. 36 (2025) 110275. doi: 10.1016/j.cclet.2024.110275
42. [42]
  Z. Zhang, P. Yu, Z. Liu, et al., J. Am. Chem. Soc. 147 (2022) 9640–9652.
43. [43]
  A. Lavoratti, O.A. Diejomaoh, A.M. Seddon, et al., Carbohydr. Polym. 352 (2025) 123156. doi: 10.1016/j.carbpol.2024.123156
44. [44]
  X. Yang, B. yang, P. Shen, et al., J. Am. Chem. Soc. 144 (2022) 11138–11147. doi: 10.1021/jacs.2c00793
45. [45]
  Q. Liang, J. Chen, F. Wang, Y. Li, Coord. Chem. Rev. 424 (2020) 213488. doi: 10.1016/j.ccr.2020.213488
46. [46]
  S. Liu, Y. Jiang, M. Wang, et al., Adv. Funct. Mater. 33 (2023) 2306204. doi: 10.1002/adfm.202306204
47. [47]
  M. Long, S. Lai, K. Miao, et al., Angew. Chem. Int. Ed. 64 (2025) e202419956. doi: 10.1002/anie.202419956
48. [48]
  H. Wang, H.D. Abruña, J. Am. Chem. Soc. 147 (2025) 9352–9364. doi: 10.1021/jacs.4c16057
49. [49]
  Y. Tian, H. Tan, X. Li, et al., Chin. J. Catal. 56 (2024) 25–50. doi: 10.1016/S1872-2067(23)64576-0
50. [50]
  H. Wang, D.R. Dekel, H.D. Abruña, J. Am. Chem. Soc. 146 (2024) 15926–15940. doi: 10.1021/jacs.4c02621
51. [51]
  K. Siddhartha, Y. Hong, X. Qin, et al., App. Catal. B: Environ. 269 (2020) 118821. doi: 10.1016/j.apcatb.2020.118821
52. [52]
  Z. Hua, S. Lu, F. Tang, et al., App. Catal. B: Environ. 334 (2023) 122856. doi: 10.1016/j.apcatb.2023.122856
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2. [2]
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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

Pd@PtNiCoRuIr core-shell high-entropy alloys mesoporous nanospheres for temporally decoupled ammonia splitting by a Zn-NH3 battery

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通讯作者: 陈斌, bchen63@163.com

Pd@PtNiCoRuIr core-shell high-entropy alloys mesoporous nanospheres for temporally decoupled ammonia splitting by a Zn-NH₃ battery