Citation: Yueting Ma, Zhiyan Feng, Yuxin Dong, Zhiyong Yan, Hou Wang, Yan Wu. Harnessing the interfacial sulfur-edge and metal-edge sites in ZnIn₂S₄/MnS heterojunctions boosts charge transfer for photocatalytic hydrogen production[J]. Chinese Chemical Letters, ;2025, 36(6): 110922. doi: 10.1016/j.cclet.2025.110922 shu

Harnessing the interfacial sulfur-edge and metal-edge sites in ZnIn₂S₄/MnS heterojunctions boosts charge transfer for photocatalytic hydrogen production

Yueting Ma ^{a, b} ,
Zhiyan Feng ^b ,
Yuxin Dong ^a ,
Zhiyong Yan ^a ,
Hou Wang ^{b, *,} ,
Yan Wu ^{a, *,}

a.
College of Environment and Ecology, Hunan Agricultural University, Changsha 410128, China
b.
Key Laboratory of Environment Biology and Pollution Control, College of Environmental Science and Engineering, Hunan University, Changsha 410082, China

wangh@hnu.edu.cn

wu_yan@hunau.edu.cn

Received Date: 6 December 2024
Revised Date: 27 January 2025
Accepted Date: 5 February 2025
Available Online: 5 February 2025

Figures(5)

Rapid carrier recombination and slow charge transfer dynamics have significantly reduced the performance of photocatalytic hydrogen production. Construction of heterojunctions via utilizing the sulfur-edge and metal-edge sites of metal sulfide semiconductor for improving photocatalytic activity remains a significant challenge. Herein, a novel ZnIn₂S₄/MnS S-scheme heterojunction was prepared by hydrothermal synthesis to accelerate charge carrier transfer for efficient photocatalysis. Notably, ZnIn₂S₄/MnS exhibited excellent photocatalytic hydrogen evolution activity (7.95 mmol g⁻¹ h⁻¹) under visible light irradiation (≥420 nm), up to 4.7 times higher than that of pure ZnIn₂S₄. Additionally, cycling experiments showed that ZM-2 remained high stability after four cycles. Density-functional theory (DFT) calculations and in situ XPS results confirm the formation of S-scheme heterojunction, indicating that the tight interfacial contact between ZnIn₂S₄ and MnS with the presence of Mn-S bonds (the unsaturated Mn edges of MnS and the uncoordinated S atoms in the edge of ZnIn₂S₄) promoted faster charge transfer. Besides, the unsaturated S atom on the surface of MnS is an active site with strong H⁺ binding ability, which can effectively reduce the overpotential or activation barrier for hydrogen evolution. This study illustrates the critical influence of the interfacial Mn-S bond on the ZnIn₂S₄/MnS S-scheme heterojunction to achieve efficient photocatalytic hydrogen production and provides relevant guidance for carrying out rational structural/interfacial modulation.
- ZnIn₂S₄/MnS,
- S-scheme,
- Photocatalysis,
- M-S bonds
1. [1]
  Z. Wei, J. Liu, W. Shangguan, Chin. J. Catal. 41 (2020) 1440–1450. doi: 10.1016/S1872-2067(19)63448-0
2. [2]
  Y.S. Ouyang, Y. Jiang, S. Ni, et al., ACS Appl. Mater. Interfaces 15 (2023) 32329–32340. doi: 10.1021/acsami.3c04081
3. [3]
  W.K. Chong, B.J. Ng, X.Y. Kong, et al., Appl. Catal. B: Environ. 325 (2023) 122372. doi: 10.1016/j.apcatb.2023.122372
4. [4]
  X. Zheng, L. Feng, Y. Dou, et al., Angew. Chem. Int. Ed. 15 (2021) 13209–13219. doi: 10.1021/acsnano.1c02884
5. [5]
  S. Zhang, G. Zhang, S. Wu, et al., J. Colloid Interface Sci. 650 (2023) 1974–1982. doi: 10.1016/j.jcis.2023.07.147
6. [6]
  A. Alamiery, ChemPhysMater 3 (2023) 64–73.
7. [7]
  X. Zheng, Y. Song, Y. Liu, et al., Coord. Chem. Rev. 475 (2023) 214898. doi: 10.1016/j.ccr.2022.214898
8. [8]
  Y. Wu, Y. Qi, G. Zhou, et al., Int. J. Hydrogen Energy 72 (2024) 179–188. doi: 10.1016/j.ijhydene.2024.05.402
9. [9]
  S.B. Wang, Y. Wang, S.L. Zhang, et al., Adv. Mater. 31 (2019) 1903404. doi: 10.1002/adma.201903404
10. [10]
  Z. Xiong, Y.D. Hou, R.S. Yuan, et al., Acta Phys. Chim. Sin. 38 (2022) 1903404.
11. [11]
  S. Wang, B.Y. Guan, X. Wang, X.W.D. Lou, J. Am. Chem. Soc. 140 (2018) 15145–15148. doi: 10.1021/jacs.8b07721
12. [12]
  C. Li, H. Che, Y. Yan, et al., Chem. Eng. J. 398 (2020) 125523. doi: 10.1016/j.cej.2020.125523
13. [13]
  J. He, G. Zhang, Y. Jiang, et al., Prog. Nat. Sci.: Mater. 33 (2023) 607–615. doi: 10.1016/j.pnsc.2023.11.005
14. [14]
  W. Zhang, S. Zhao, Y. Xing, et al., Chem. Eng. J. 442 (2022) 136151. doi: 10.1016/j.cej.2022.136151
15. [15]
  S. Zhang, Y. Yang, Y. Zhai, et al., Chin. Chem. Lett. 34 (2023) 107652. doi: 10.1016/j.cclet.2022.06.075
16. [16]
  V.N. Pham, S. Lee, D.T. Hoang, et al., Inorg. Chem. 62 (2023) 12913–12919. doi: 10.1021/acs.inorgchem.3c01607
17. [17]
  Y. Geng, X. Zou, Y. Lu, L. Wang, Int. J. Hydrogen Energy 47 (2022) 11520–11527. doi: 10.1016/j.ijhydene.2022.01.176
18. [18]
  H. Fang, J. Cai, H. Li, et al., ACS Appl. Energy Mater. 5 (2022) 8232–8240. doi: 10.1021/acsaem.2c00767
19. [19]
  S. Liu, Y. Mao, Z. Su, et al., Catal. Sci. Technol. 13 (2023) 3351–3357. doi: 10.1039/d3cy00298e
20. [20]
  X. Ren, J. Shi, R. Duan, et al., Chin. Chem. Lett. 33 (2022) 4700–4704. doi: 10.1016/j.cclet.2021.12.076
21. [21]
  H. Song, L. Wei, C. Chen, et al., J. Catal. 376 (2019) 198–208. doi: 10.1016/j.jcat.2019.06.015
22. [22]
  X. Fang, L. Cui, T. Pu, et al., Appl. Surf. Sci. 457 (2018) 863–869. doi: 10.1016/j.apsusc.2018.07.012
23. [23]
  C. Ouyang, W. Huang, H. Tang, et al., ACS Appl. Energy Mater. 5 (2022) 12739–12751. doi: 10.1021/acsaem.2c02352
24. [24]
  X. Wang, X. Wang, J. Huang, et al., Nat. Commun. 12 (2021) 4112. doi: 10.1038/s41467-021-24511-z
25. [25]
  B. Zhu, W. Fu, J. Qu, et al., Chem. Eng. J. 497 (2024) 154712. doi: 10.1016/j.cej.2024.154712
26. [26]
  J. Song, Y. Chen, H. Huang, et al., Adv. Sci. 9 (2022) 2104522. doi: 10.1002/advs.202104522
27. [27]
  J. Wang, X. Niu, Q. Hao, et al., Chem. Eng. J. 493 (2024) 152534. doi: 10.1016/j.cej.2024.152534
28. [28]
  Y. Qi, G. Zhou, Y. Wu, et al., J. Colloid Interface Sci. 664 (2024) 107–116. doi: 10.1016/j.jcis.2024.03.033
29. [29]
  Z. Jin, T. Wei, J. Huang, et al., Int. J. Hydrogen Energy 45 (2020) 22711–22721. doi: 10.1016/j.ijhydene.2020.06.093
30. [30]
  G. Li, H. Liang, X. Fan, et al., J. Mater. 11 (2023) 14809–14818. doi: 10.1039/d3ta02519e
31. [31]
  Y. Liu, L. Li, J. Zhu, et al., ACS Appl. Mater. Interfaces 10 (2018) 27911–27919. doi: 10.1021/acsami.8b05688
32. [32]
  A.M.A. Omar, H.S.H. Mohamed, G. Khabiri, Sep. Purif. Technol. 339 (2024) 126712. doi: 10.1016/j.seppur.2024.126712
33. [33]
  S.H. Chen, X.Y. Xiao, P.H. Li, et al., Environ. Sci. Nano 7 (2020) 753–763. doi: 10.1039/C9EN01265F
34. [34]
  M. Tan, Y. Ma, C. Yu, et al., Adv. Funct. Mater. 32 (2021) 2111740.
35. [35]
  G. Zhang, D. Chen, N. Li, et al., Appl. Catal. B: Environ. 232 (2018) 164–174. doi: 10.1016/j.apcatb.2018.03.017
36. [36]
  Y. Xiao, H. Wang, Y. Jiang, et al., J. Colloid Interface Sci. 623 (2022) 109–123. doi: 10.1016/j.jcis.2022.04.137
37. [37]
  J.J. Li, W. Li, Z.F. Liu, et al., ACS Appl. Nano Mater. 6 (2023) 16927–16937. doi: 10.1021/acsanm.3c03085
38. [38]
  T. Gao, Y. Li, J. Tian, et al., J. Alloys Compd. 951 (2023) 169939. doi: 10.1016/j.jallcom.2023.169939
39. [39]
  Z.Y. Peng, Y.H. Jiang, X.Q. Wang, et al., Ceram. Int. 45 (2019) 15942–15953. doi: 10.1016/j.ceramint.2019.05.103
40. [40]
  Z. Huang, P. Sun, H. Zhang, et al., ACS Catal. 14 (2024) 4581–4592. doi: 10.1021/acscatal.3c05826
41. [41]
  S. Liu, D. Chi, R. Chen, et al., Renew. Energy 219 (2023) 119494. doi: 10.1016/j.renene.2023.119494
42. [42]
  L. Yi, R. Zhu, H. Jiang, G. Zhang, Sep. Purif. Technol. 349 (2024) 127885. doi: 10.1016/j.seppur.2024.127885
43. [43]
  M. Tan, Y. Ma, C. Yu, et al., Adv. Funct. Mater. 32 (2021) 2111740.
44. [44]
  V.N. Rao, N.L. Reddy, V. Preethi, et al., Int. J. Hydrogen Energy 48 (2023) 11754–11774. doi: 10.1016/j.ijhydene.2023.01.059
45. [45]
  X. Li, W. Bi, L. Zhang, et al., Adv Mater. 28 (2016) 2427–2431. doi: 10.1002/adma.201505281
46. [46]
  H.S. Moon, K.C. Hsiao, M.C. Wu, et al., Adv. Mater. 35 (2023) e2200172. doi: 10.1002/adma.202200172
47. [47]
  R. Wang, W. Yu, N. Fang, et al., Appl. Catal. B: Environ. 341 (2024) 123284. doi: 10.1016/j.apcatb.2023.123284
48. [48]
  H. Wang, J. Liu, X. Xiao, et al., Chin. Chem. Lett. 34 (2023) 107125. doi: 10.1016/j.cclet.2022.01.018
49. [49]
  W.J. Ong, L.K. Putri, Y.C. Tan, et al., Nano Res. 10 (2017) 1673–1696. doi: 10.1007/s12274-016-1391-4
50. [50]
  Z. Sun, X. Yang, X.F. Yu, et al., Appl. Catal. B: Environ. 285 (2021) 119790. doi: 10.1016/j.apcatb.2020.119790
51. [51]
  Z. Shi, W. Chen, Y. Hu, et al., Molecules 29 (2024) 1362. doi: 10.3390/molecules29061362
52. [52]
  Z. Chen, M. Li, Y. Cui, Y. Wang, Mater. Today Sustainability 24 (2023) 100591. doi: 10.1016/j.mtsust.2023.100591
53. [53]
  H. Wang, Y. Sun, Y. Wu, et al., Appl. Catal. B: Environ. 245 (2019) 290–301. doi: 10.1016/j.apcatb.2018.12.051
54. [54]
  L. Wang, G. Tang, S. Liu, et al., Chem. Eng. J. 428 (2022) 131338. doi: 10.1016/j.cej.2021.131338
55. [55]
  C. Qin, Y. Yang, G. Zhou, et al., Chem. Eng. J. 487 (2024) 150571. doi: 10.1016/j.cej.2024.150571
56. [56]
  J. Huang, B. Chai, J. Xiao, et al., Chem. Eng. J. 481 (2024) 148501. doi: 10.1016/j.cej.2023.148501
57. [57]
  X. Wang, T. Shi, X. Wang, et al., J. Energy Chem. 92 (2024) 151–161. doi: 10.1016/j.jechem.2023.12.040
58. [58]
  C.H. Shen, X.J. Wen, Z.H. Fei, et al., J. Colloid Interface Sci. 579 (2020) 297–306. doi: 10.1016/j.jcis.2020.06.075
59. [59]
  Q. Zhang, H. Gu, X. Wang, et al., Appl. Catal. B: Environ. 298 (2021) 120632. doi: 10.1016/j.apcatb.2021.120632
60. [60]
  W. Tu, Y. Li, L. Kuai, et al., Nanoscale 9 (2017) 9065–9070. doi: 10.1039/C7NR03238B
61. [61]
  M. Xiong, B. Chai, J. Yan, et al., Appl. Surf. Sci. 514 (2020) 145965. doi: 10.1016/j.apsusc.2020.145965
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Harnessing the interfacial sulfur-edge and metal-edge sites in ZnIn2S4/MnS heterojunctions boosts charge transfer for photocatalytic hydrogen production

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通讯作者: 陈斌, bchen63@163.com

Harnessing the interfacial sulfur-edge and metal-edge sites in ZnIn₂S₄/MnS heterojunctions boosts charge transfer for photocatalytic hydrogen production