English

S-Scheme MnCo₂S₄/g-C₃N₄ Heterojunction Photocatalyst for H₂ Production

• Tao Sun ^{†, ,} ,
• Chenxi Li ^†, ,
• Yupeng Bao ,
• Jun Fan ,
• Enzhou Liu ^,

• School of Chemical Engineering, Xi'an Key Laboratory of Special Energy Materials, Northwest University, Xi'an, 710069, China

• ^† These authors contributed equally to this paper.

Corresponding author: Tao Sun, chemstst@nwu.edu.cn Enzhou Liu, liuenzhou@nwu.edu.cn

• Received Date: 04 December 2022
  Accepted Date: 03 January 2023
  Revised Date: 02 January 2023
  Available Online: 15 June 2023
• Fund Project:

Abstract: The increased global demand for energy and the enhanced deterioration of the environment are the two urgent challenges of the 21st century on the way to sustainable development for human society. Currently, green and renewable energy conversion technology has received much attention as a substitute for limited and non-renewable fossil fuels. Hydrogen energy is advantageous because of its high energy capacity (142 MJ·kg⁻¹) and its production by green conversion technology, consisting of H₂ reacting with O₂ to generate H₂O. It can establish a clean and sustainable hydrogen economic system, as well as reduce the utilization of fossil fuels and carbon dioxide emissions. Water splitting technology is an efficient approach to acquire the featured H₂ energy of the green reaction (2H₂O → 2H₂ + O₂) through electrocatalytic and photocatalytic reactions. Photocatalysis technology, with the advantage of huge solar energy utilization, has been widely regarded as a promising method for the realization of this chemical synthesis. Among photocatalysis technologies, photocatalytic H₂ production from water is considered a promising approach to obtain H₂ energy due to its environmentally friendly energy conversion. However, the effectiveness of acquiring H₂ energy through photocatalytic water splitting is intimately related with photocatalysts. In general, photocatalysts still face the big challenge of their low solar energy utilization efficiency, which restricts the large-scale application of photocatalytic technology to obtain H₂ energy. Thus, developing highly efficient photocatalysts for H₂ production is critical in promoting this technology moving forward, and obtaining renewable energy. Herein, we successfully construct the S-scheme MnCo₂S₄/g-C₃N₄ heterojunction through an expedient physical mixing process at a low temperature, which can be separately obtained via the pyrolysis process and hydrothermal method. The H₂ production rate of MnCo₂S₄/g-C₃N₄ heterojunction can achieve up to 2979 µmol·g⁻¹·h⁻¹, which is 26.4 and 8.7 times higher than those of g-C₃N₄ (113 µmol·g⁻¹·h⁻¹) and MnCo₂S₄ (341 µmol·g⁻¹·h⁻¹), respectively, and presents a superior stability in three continuous cycles during H₂ production tests. The high H₂ production of MnCo₂S₄/g-C₃N₄ heterojunction is mainly ascribed to the following three reasons: i) The light absorption region of the heterojunction is extended to visible light. ii) MnCo₂S₄/g-C₃N₄ possesses low impedance during the reaction, high photocurrent density, and more exposed sites in solution. iii) The efficient reservation of active electron-hole pairs greatly enhances the ratio of electrons reacting with H* species to generate H₂ over MnCo₂S₄/g-C₃N₄ heterojunction. This work provides an efficient approach to constructing advanced g-C₃N₄-based photocatalysts through hybridization with metal sulfides to form S-scheme heterojunctions.

Key words:
• MnCo₂S₄
•  /  Carbon nitride
•  /  S-scheme heterojunction
•  /  Photocatalytic H₂ production from water splitting

• 1. [1]

     Bie, C.; Wang, L.; Yu, J. Chem 2022, 8, 1567. doi: 10.1016/j.chempr.2022.04.013

  2. [2]

     Li, A.; Zhu, W.; Li, C.; Wang, T.; Gong, J. Chem. Soc. Rev. 2019, 48, 1874. doi: 10.1039/C8CS00711J

  3. [3]

     Chen, L.; Ren, J.; Yuan, Z. Green Chem. 2022, 24, 713. doi: 10.1039/D1GC03768D

  4. [4]

     Bie, C.; Yu, H.; Cheng, B.; Ho, W.; Fan, J.; Yu, J. Adv. Mater. 2021, 33, 2003521. doi: 10.1002/adma.202003521

  5. [5]

     Xu, Q.; Zhang, J.; Zhang, H.; Zhang, L.; Chen, L.; Hu, Y.; Jiang, H.; Li, C. Energy Environ. Sci. 2021, 14, 5228. doi: 10.1039/D1EE02105B

  6. [6]

     Li, R.; Li, Y.; Yang, P.; Wang, D.; Xu, H.; Wang, B.; Meng, F.; Zhang, J.; An, M. J. Energy Chem. 2021, 57, 547. doi: 10.1016/j.jechem.2020.08.040

  7. [7]

     Tao, X.; Zhao, Y.; Wang, S.; Li, C.; Li, R. Chem. Soc. Rev. 2022, 51, 3561. doi: 10.1039/D1CS01182K

  8. [8]

     Wang, Q.; Domen, K. Chem. Rev. 2020, 120, 919. doi: 10.1021/acs.chemrev.9b00201

  9. [9]

     Yang, L.; Fan, D.; Li, Z.; Cheng, Y.; Yang, X.; Zhang, T. Adv. Sustain. Syst. 2022, 6, 2100477. doi: 10.1002/adsu.202100477

  10. [10]

      Che, S.; Zhang, L.; Wang, T.; Su, D.; Wang, C. Adv. Sustain. Syst. 2022, 6, 2100294. doi: 10.1002/adsu.202100294

  11. [11]

      Ong, W.; Tan, L.; Ng, Y.; Yong, S.; Chai, S. Chem. Rev. 2016, 116, 7159. doi: 10.1021/acs.chemrev.6b00075

  12. [12]

      Zhang, M.; Li, Y.; Chang, W.; Zhu, W.; Zhang, L.; Jin, R.; Xing, Y. Chin. J. Catal. 2022, 43, 526. doi: 10.1016/S1872-2067(21)63872-X

  13. [13]

      Zhang, Q.; Bai, X.; Hu, X.; Fan, J.; Liu, E. Appl. Surf. Sci. 2022, 579, 152224. doi: 10.1016/j.apsusc.2021.152224

  14. [14]

      Liang, J.; Yang, X.; Wang, Y.; He, P.; Fu, H.; Zhao, Y.; Zou, Q.; An, X. J. Mater. Chem. A 2021, 9, 12898. doi: 10.1039/D1TA00890K

  15. [15]

      Jia, J.; Zhang, Q.; Li, K.; Zhang, Y.; Liu, E.; Li, X. Int. J. Hydrog. Energy 2023, 48, 196. doi: 10.1016/j.ijhydene.2022.09.272.

  16. [16]

      Yang, Y.; Wu, J.; Cheng, B.; Zhang, L.; Al-Ghamdi, A.; Wageh, S.; Li, Y. Chin. J. Struc. Chem. 2022, 41, 2206006. doi: 10.14102/j.cnki.0254-5861.2022-0124

  17. [17]

      雷卓楠, 马心怡, 胡晓云, 樊君, 刘恩周. 物理化学学报, 2022, 38 (7), 2110049. doi: 10.3866/PKU.WHXB202110049Lei, Z.; Ma, X.; Hu, X.; Fan, J.; Liu, E. Acta Phys. -Chim. Sin. 2022, 38 (7), 2110049. doi: 10.3866/PKU.WHXB202110049

  18. [18]

      Tao, S.; Wan, S.; Huang, Q.; Li, C.; Yu, J.; Cao, S. Chin. J. Struc. Chem. 2022, 41, 2206048. doi: 10.14102/j.cnki.0254-5861.2022-0068

  19. [19]

      Bie, C.; Zhu, B.; Wang, L.; Yu, H.; Jiang, C.; Chen, T.; Yu, J. Angew. Chem. Int. Ed. 2022, 61, e202212045. doi: 10.1002/anie.202212045

  20. [20]

      Tian, N.; Huang, H.; Du, X.; Dong, F.; Zhang, Y. J. Mater. Chem. A 2019, 7, 11584. doi: 10.1039/C9TA01819K

  21. [21]

      Zhang, J.; Yang, G.; He, B.; Cheng, B.; Li, Y.; Liang, G.; Wang, L. Chin. J. Catal. 2022, 43, 2530. doi: 10.1016/S1872-2067(22)64108-1

  22. [22]

      Zhang, L.; Zhang, J.; Yu, H.; Yu, J. Adv. Mater. 2022, 34, 2107668. doi: 10.1002/adma.202107668

  23. [23]

      Xu, Q.; Zhang, L.; Cheng, B.; Fan, J.; Yu, J. Chem 2020, 6, 1543. doi: 10.1016/j.chempr.2020.06.010

  24. [24]

      Yang, T.; Deng, P.; Wang, L.; Hu, J.; Liu, Q.; Tang, H. Chin. J. Struc. Chem. 2022, 41, 2206023. doi: 10.14102/j.cnki.0254-5861.2022-0062

  25. [25]

      刘珊池, 王凯, 杨梦薛, 靳治良. 物理化学学报, 2022, 38 (7), 2109023. doi: 10.3866/PKU.WHXB202109023Liu, S.; Wang, K.; Yang, M.; Jin, Z. Acta Phys. -Chim. Sin. 2022, 38 (7), 2109023. doi: 10.3866/PKU.WHXB202109023

  26. [26]

      Zhang, J.; Wang, L.; Mousavi, M.; Ghasemi, J.; Yu, J. Chin. J. Struc. Chem. 2022, 41, 2206003. doi: 10.14102/j.cnki.0254-5861.2022-0150

  27. [27]

      Yang, H.; Zhang, J.; Dai, K. Chin. J. Catal. 2022, 43, 255. doi: 10.1016/S1872-2067(20)63784-6

  28. [28]

      Wang, Z.; Liu, R.; Zhang, J.; Dai, K. Chin. J. Struc. Chem. 2022, 41, 2206015. doi: 10.14102/j.cnki.0254-5861.2022-0108

  29. [29]

      Li, C.; Zhao, Y.; Fan, J.; Hu, X.; Liu, E.; Yu, Q. J. Alloy. Compd. 2022, 919, 165752. doi: 10.1016/j.jallcom.2022.165752

  30. [30]

      Sayed, M.; Zhu, B.; Kuang, P.; Liu, X.; Cheng, B.; Al-Ghamdi, A.; Wageh, S.; Zhang, L.; Yu, J. Adv. Sustain. Syst. 2022, 6, 2100264. doi: 10.1002/adsu.202100264

  31. [31]

      Wang, L.; Yang, T.; Peng, L.; Zhang, Q.; She, X.; Tang, H.; Liu, Q. Chin. J. Catal. 2022, 43, 2720. doi: 10.1016/S1872-2067(22)64133-0

  32. [32]

      Li, X.; Kang, B.; Dong, F.; Zhang, Z.; Luo, X.; Han, L.; Huang, J.; Feng, Z.; Chen, Z.; Xu, J.; et al. Nano Energy 2021, 81, 105671. doi: 10.1016/j.nanoen.2020.105671

  33. [33]

      Dong, G.; Zhang, Y.; Wang, Y.; Deng, Q.; Qin, C.; Hu, Y.; Zhou, Y.; Tian, G. ACS Appl. Energy Mater. 2021, 4, 14342. doi: 10.1021/acsaem.1c03019

  34. [34]

      Shang, Y.; Fan, H.; Sun, Y.; Wang, W. Sustain. Energy Fuels 2022, 6, 3729. doi: 10.1039/D2SE00916A

  35. [35]

      Shang, Y.; Fang, H.; Sun, Y.; Wang, W. J. Mater. Chem. A 2022, 10, 20248. doi: 10.1039/D2TA06372G

  36. [36]

      Zhao, Z.; Dai, K.; Zhang, J.; Dawson, G. Adv. Sustain. Syst. 2022, 6, 2100498. doi: 10.1002/adsu.202100498

  37. [37]

      沈荣晨, 郝磊, 陈晴, 郑巧清, 张鹏, 李鑫. 物理化学学报, 2022, 38 (7), 2110014. doi: 10.3866/PKU.WHXB202110014Shen, R.; Hao, L.; Chen, Q.; Zheng, Q.; Zhang, P.; Li, X. Acta Phys. -Chim. Sin. 2022, 38 (7), 2110014. doi: 10.3866/PKU.WHXB202110014

  38. [38]

      黄悦, 梅飞飞, 张金锋, 代凯, Dawson, G. 物理化学学报, 2022, 38 (7), 2108028. doi: 10.3866/PKU.WHXB202108028Huang, Y.; Mei, F.; Zhang, J.; Dai, K.; Dawson, G. Acta Phys. -Chim. Sin. 2022, 38 (7), 2108028. doi: 10.3866/PKU.WHXB202108028

  39. [39]

      Huang, W.; Xue, W.; Hu, X.; Fan, J.; Tang, C.; Shi, Y.; Liu, E.; Sun, T. J. Alloy. Compd. 2023, 930, 167368. doi: 10.1016/j.jallcom.2022.167368

  40. [40]

      Ren, D.; Zhang, W.; Ding, Y.; Shen, R.; Jiang, Z.; Lu, X.; Li, X. RRL Sol. 2020, 4, 1900423. doi: 10.1002/solr.201900423

  41. [41]

      Zhu, Q.; Xu, Q.; Du, M.; Zeng, X.; Zhong, G.; Qiu, B.; Zhang, J. Adv. Mater. 2022, 34, 2202929. doi: 10.1002/adma.202202929

  42. [42]

      Zhang, G.; Guan, Z.; Yang, J.; Li, Q.; Zhou, Y.; Zou, Z. RRL Sol. 2022, 6, 2200587. doi: 10.1002/solr.202200587

  43. [43]

      Jia, L.; Tan, X.; Yu, T.; Ye, J. Energy Fuel. 2022, 36, 11308. doi: 10.1021/acs.energyfuels.2c01137

  44. [44]

      Qiu, B.; Zhu, Q.; Du, M.; Fan, L.; Xing, M.; Zhang, J. Angew. Chem. Int. Ed. 2017, 56, 2684. doi: 10.1002/ange.201612551

  45. [45]

      Jiang, L.; Wang, K.; Wu, X.; Zhang, G.; Yin, S. ACS Appl. Mater. Interfaces 2019, 11, 26898. doi: 10.1021/acsami.9b07311

  46. [46]

      Zhang, Y.; Shi, J.; Huang, Z.; Guan, X.; Zong, S.; Cheng, C.; Zheng, B.; Guo, L. Chem. Eng. J. 2020, 401, 126135. doi: 10.1016/j.cej.2020.126135

  47. [47]

      Wang, X.; Li, Y.; Li, T.; Jin, Z. Adv. Sustain. Syst. 2022, 6, 2200139. doi: 10.1002/adsu.202200139

  48. [48]

      Tian, J.; Xue, W.; Li, M.; Sun, T.; Hu, X.; Fan, J.; Liu, E. Catal. Sci. Technol. 2022, 12, 3165. doi: 10.1039/D2CY00174H

  49. [49]

      Yendrapati, T.; Soumya, J.; Bojja, S.; Pal, U. J. Phys. Chem. C 2021, 125, 5099. doi: 10.1021/acs.jpcc.0c11554

  50. [50]

      Ma, M.; Cui, F.; Huang, Y.; Zhao, Y.; Lian, J.; Bao, J.; Zhang, B.; Yuan, S.; Li, H. Electrochim. Acta 2019, 323, 134770. doi: 10.1016/j.electacta.2019.134770

  51. [51]

      Liu, S.; Jun, S. J. Power Sources 2017, 342, 629. doi: 10.1016/j.jpowsour.2016.12.057

  52. [52]

      Lee, D.; Lee, H.; Mathur, S.; Kim, K. J. Alloy. Compd. 2021, 868, 158850. doi: 10.1016/j.jallcom.2021.158850

  53. [53]

      Liu, T.; Li, Y.; Sun, H.; Zhang, M.; Xia, Z.; Yang, Q. Chin. J. Struc. Chem. 2022, 41, 2206055. doi: 10.14102/j.cnki.0254-5861.2022-0152

  54. [54]

      Cheng, L.; Zhang, P.; Wenm, Q.; Fan, J.; Xiang, Q. Chin. J. Catal. 2022, 43, 451. doi: 10.1016/S1872-2067(21)63879-2

  55. [55]

      Zhang, J.; Pan, Z.; Yang, Y.; Wang, P.; Pei, C.; Chen, W.; Huang, G. Chin. J. Catal. 2022, 43, 265. doi: 10.1016/S1872-2067(21)63801-9

  56. [56]

      Bai, J.; Shen, R.; Jiang, Z.; Zhang, P.; Li, Y.; Li, X. Chin. J. Catal. 2022, 43, 359. doi: 10.1016/S1872-2067(21)63883-4

  57. [57]

      熊壮, 侯乙东, 员汝胜, 丁正新, 王伟俊, 汪思波. 物理化学学报, 2022, 38 (7), 2111021. doi: 10.3866/PKU.WHXB202111021Xiong, Z.; Hou, Y.; Yuan, R.; Ding, Z.; Ong, W.; Wang, S. Acta Phys. -Chim. Sin. 2022, 38 (7), 2111021. doi: 10.3866/PKU.WHXB202111021

  58. [58]

      Jin, Z.; Li, H.; Li, J. Chin. J. Catal. 2022, 43, 303. doi: 10.1016/S1872-2067(21)63818-4

  59. [59]

      Qi, K.; Wang, Y.; Rengaraj, S.; Wahaibi, B.; Jahangir, A. Mater. Chem. Phys. 2017, 193, 177. doi: 10.1016/j.matchemphys.2017.02.023

  60. [60]

      Arul, N.; Cavalcante, L.; Han, J. J. Solid State Electr. 2018, 22, 303. doi: 10.1007/s10008-017-3782-1

  61. [61]

      Hua, S.; Qu, D.; An, L.; Jiang, W.; Wen, Y.; Wang, X.; Sun, Z. Appl. Catal. B: Environ. 2019, 240, 253. doi: 10.1016/j.apcatb.2018.09.010

  62. [62]

      Liao, Y.; Wang, G.; Wang, J.; Wang, K.; Yan, S.; Su, Y. J. Colloid Interface Sci. 2021, 587, 110. doi: 10.1016/j.jcis.2020.12.009

  63. [63]

      Huang, W.; Xue, W.; Hu, X.; Fan, J.; Tang, C.; Liu, E. Appl. Surf. Sci. 2022, 599, 153900. doi: 10.1016/j.apsusc.2022.153900

  64. [64]

      Sun, T.; Wang, J.; Chi, X.; Lin, Y.; Chen, Z.; Ling, X.; Qiu, C.; Xu, Y.; Song, L.; Chen, W.; et al. ACS Catal. 2018, 8, 7585. doi: 10.1021/acscatal.8b00783

  65. [65]

      Feng, K.; Sun, T.; Hu, X.; Fan, J.; Yang, D.; Liu, E. Catal. Sci. Technol. 2022, 12, 4893. doi: 10.1039/D2CY00858K

  66. [66]

      Chu, S.; Hu, Y.; Zhang, J.; Cui, Z.; Shi, J.; Wang, Y.; Zou, Z. Int. J. Hydrog. Energy 2021, 46, 9064. doi: 10.1016/j.ijhydene.2020.12.225

  67. [67]

      Zhang, W.; Xu, C.; Liu, E.; Fan, J.; Hu, X. Appl. Surf. Sci. 2020, 515, 146039. doi: 10.1016/j.apsusc.2020.146039

  68. [68]

      Wang, L.; Fei, X.; Zhang, L.; Yu, J.; Cheng, B.; Ma, Y. J. Mater. Sci. Technol. 2022, 112, 1. doi: 10.1016/j.jmst.2021.10.016

  69. [69]

      Zhang, J.; Zhang, L.; Wang, W.; Yu, J. J. Phys. Chem. Lett. 2022, 13, 8462. doi: 10.1021/acs.jpclett.2c02125

  70. [70]

      Shao, X.; Wang, K.; Peng, L.; Li, K.; Wen, H.; Le, X.; Wu, X.; Wang, G. Colloid Surface A 2022, 652, 129846. doi: 10.1016/j.colsurfa.2022.129846

•