Citation: Peipei Sun, Jinyuan Zhang, Yanhua Song, Zhao Mo, Zhigang Chen, Hui Xu. Built-in Electric Fields Enhancing Photocarrier Separation and H₂ Evolution[J]. Acta Physico-Chimica Sinica, ;2024, 40(11): 231100. doi: 10.3866/PKU.WHXB202311001 shu

Built-in Electric Fields Enhancing Photocarrier Separation and H₂ Evolution

Peipei Sun ¹ ,
Jinyuan Zhang ¹ ,
Yanhua Song ^2,, ,
Zhao Mo ^1,, ,
Zhigang Chen ¹ ,
Hui Xu ^1,,

1.
School of the Environment and Safety Engineering, Jingjiang College, Jiangsu University, Zhenjiang 212013, Jiangsu Province, China
2.
School of Environmental and Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, Jiangsu Province, China

Corresponding author: Yanhua Song, songyh@just.edu.cn Zhao Mo, zhaomo@ujs.edu.cn Hui Xu, xh@ujs.edu.cn
Received Date: 1 November 2023
Revised Date: 13 December 2023
Accepted Date: 14 December 2023
Available Online: 25 December 2023
Fund Project: the National Natural Science Foundation of China 22378174the National Natural Science Foundation of China 21878134the National Natural Science Foundation of China 22208129the National Natural Science Foundation of China 22108110

The construct of the internal electric field (IEF) is recognized as an effective driver for promoting charge migration and separation to enhance photocatalytic performance. In this study, one-dimensional nanorods of Mn_0.2Cd_0.8S (MCS) co-doped with interstitial chlorine (Cl_int) and substitutional chlorine (Cl_sub) were designed and synthesized using a one-step solvothermal method. The incorporation of Cl_int and Cl_sub led to an unbalanced charge distribution and the formation of IEF in the MCS nanorods, contributing to the improvement of photogenerated carrier kinetic behavior. Through density functional theory (DFT) calculations, the effect of Cl_int and Cl_sub doping on the activity of the MCS was visually explained by examining differences in electronic structure, charge distribution and H₂ adsorption/desorption balance. Interestingly, the modulation of the energy band structure of MCS primarily resulted from the contribution of Cl_int, while Cl_sub playing a negligible role. Moreover, the Cl_sub further facilitated the optimization of Cl_int concerning the H₂ adsorption-desorption Gibbs free energy (ΔG_H*) of MCS. Ultimately, the ΔG_H* of 0.9 Cl-MCS favored H₂ production (1.14 vs. 0.17 eV), leading to a 9 times increase in photocatalytic H₂ production activity compared to MCS. This investigation presents a valuable approach for constructing IEF in bimetallic sulfide photocatalysts.
- Photocatalysis,
- H₂ production,
- Bimetallic sulfides,
- Internal electric fields,
- Gibbs free energy
1. [1]
  Hansora, D. Matter 2023, 6, 2501. doi: 10.1016/j.matt.2023.05.006 doi: 10.1016/j.matt.2023.05.006
2. [2]
  Rahman, M. Z.; Raziq, F.; Zhang, H.; Gascon, J. Angew. Chem. Int. Ed. 2023, e202305385. doi: 10.1002/anie.202305385 doi: 10.1002/anie.202305385
3. [3]
  Li, Y.; Yu, S.; Xiang, J.; Zhang, F.; Jiang, A.; Duan, Y.; Tang, C.; Cao, Y.; Guo, H.; Zhou, Y. ACS Catal. 2023, 13, 8281. doi: 10.1021/acscatal.3c01210 doi: 10.1021/acscatal.3c01210
4. [4]
  Yan, Z.; Yin, K.; Xu, M.; Fang, N.; Yu, W.; Chu, Y.; Shu, S. Chem. Eng. J. 2023, 472, 145066. doi: 10.1016/j.cej.2023.145066 doi: 10.1016/j.cej.2023.145066
5. [5]
  Zhang, J.; Pan, Y.; Feng, D.; Cui, L.; Zhao, S.; Hu, J.; Wang, S.; Qin, Y. Adv. Mater. 2023, 35, e2300902. doi: 10.1002/adma.202300902 doi: 10.1002/adma.202300902
6. [6]
  Zhu, Y.; Deng, W.; Tan, Y.; Shi, J.; Wu, J.; Lu, W.; Jia, J.; Wang, S.; Zou, Y. Adv. Funct. Mater. 2023, 33, 2304985. doi: 10.1002/adfm.202304985 doi: 10.1002/adfm.202304985
7. [7]
  Khan, K.; Tao, X.; Shi, M.; Zeng, B.; Feng, Z.; Li, C.; Li, R. Adv. Funct. Mater. 2020, 30, 2003731. doi: 10.1002/adfm.202003731 doi: 10.1002/adfm.202003731
8. [8]
  Sun, B.; Bu, J.; Chen, X.; Fan, D.; Li, S.; Li, Z.; Zhou, W.; Du, Y. Chem. Eng. J. 2022, 435, 135074. doi: 10.1016/j.cej.2022.135074 doi: 10.1016/j.cej.2022.135074
9. [9]
  Liu, W.; Wang, Y.; Huang, H.; Wang, J.; He, G.; Feng, J.; Yu, T.; Li, Z.; Zou, Z. J. Am. Chem. Soc. 2023, 145, 7181. doi: 10.1021/jacs.2c12182 doi: 10.1021/jacs.2c12182
10. [10]
  Du, C.; Zhang, Q.; Lin, Z.; Yan, B.; Xia, C.; Yang, G. Appl. Catal. B Environ. 2019, 248, 193. doi: 10.1016/j.apcatb.2019.02.027 doi: 10.1016/j.apcatb.2019.02.027
11. [11]
  Hua, W.; Xia, J.; Hu, Z.; Li, H.; Lv, W.; Yang, Q. J. Electrochem. 2023, 29, 2217006. doi: 10.13208/j.electrochem.2217006 doi: 10.13208/j.electrochem.2217006
12. [12]
  Cao, S.; Zhong, B.; Bie, C.; Cheng, B.; Xu, F. Acta Phys. -Chim. Sin. 2024, 40, 2307016. doi: 10.3866/PKU.WHXB202307016 doi: 10.3866/PKU.WHXB202307016
13. [13]
  Liu, S.; Wang, K.; Yang, M.; Jin, Z. Acta Phys. -Chim. Sin. 2022, 38, 2109023. doi: 10.3866/PKU.WHXB202109023 doi: 10.3866/PKU.WHXB202109023
14. [14]
  Jiang, Z.; Chen, Q.; Zheng, Q.; Shen, R.; Zhang, P.; Li, X. Acta Phys. -Chim. Sin. 2021, 37, 2010059. doi: 10.3866/PKU.WHXB202010059 doi: 10.3866/PKU.WHXB202010059
15. [15]
  Huang, W.; Li, Z.; Wu, C.; Zhang, H.; Sun, J.; Li, Q. J. Mater. Sci. Technol. 2022, 120, 89. doi: 10.1016/j.jmst.2021.12.028 doi: 10.1016/j.jmst.2021.12.028
16. [16]
  Ikeue, K.; Shinmura, Y.; Machida, M. Appl. Catal. B-Environ. 2012, 123–124, 84. doi: 10.1016/j.apcatb.2012.04.019 doi: 10.1016/j.apcatb.2012.04.019
17. [17]
  Wu, L.; Li, M.; Zhou, B.; Xu, S.; Yuan, L.; Wei, J.; Wang, J.; Zou, S.; Xie, W.; Qiu, Y.; et al. Small 2023, e2303821. doi: 10.1002/smll.202303821 doi: 10.1002/smll.202303821
18. [18]
  Xiong, M.; Qin, Y.; Chai, B.; Yan, J.; Fan, G.; Xu, F.; Wang, C.; Song, G. Chem. Eng. J. 2022, 428, 131069. doi: 10.1016/j.cej.2021.131069 doi: 10.1016/j.cej.2021.131069
19. [19]
  Li, Z.; Huang, W.; Liu, J.; Lv, K.; Li, Q. ACS Catal. 2021, 11, 8510. doi: 10.1021/acscatal.1c02018 doi: 10.1021/acscatal.1c02018
20. [20]
  Wu, C.; Huang, W.; Liu, H.; Lv, K.; Li, Q. Appl. Catal. B Environ. 2023, 330, 122653. doi: 10.1016/j.apcatb.2023.122653 doi: 10.1016/j.apcatb.2023.122653
21. [21]
  Zhao, D.; Wang, Y.; Dong, C. L.; Huang, Y. C.; Chen, J.; Xue, F.; Shen, S.; Guo, L. Nat. Energy 2021, 6, 388. doi: 10.1038/s41560-021-00795-9 doi: 10.1038/s41560-021-00795-9
22. [22]
  Zhang, Z.; Jia, F.; Kong, F.; Wang, M. Small 2023, 19, e2300810. doi: 10.1002/smll.202300810 doi: 10.1002/smll.202300810
23. [23]
  Wang, J.; Zhang, Y.; Jiang, S.; Sun, C.; Song, S. Angew. Chem. Int. Ed. 2023, 62, e202307808. doi: 10.1002/anie.202307808 doi: 10.1002/anie.202307808
24. [24]
  Li, F.; Yue, X.; Liao, Y.; Qiao, L.; Lv, K.; Xiang, Q. Nat. Commun. 2023, 14, 3901. doi: 10.1038/s41467-023-39578-z doi: 10.1038/s41467-023-39578-z
25. [25]
  Liu, S.; Qi, W.; Liu, J.; Meng, X.; Adimi, S.; Attfield, J. P.; Yang, M. ACS Catal. 2023, 13, 2214. doi: 10.1021/acscatal.2c05075 doi: 10.1021/acscatal.2c05075
26. [26]
  Li, L.; Song, L.; Zhang, X.; Zhu, S.; Wang, Y. ACS Appl. Energy Mater. 2022, 5, 2505. doi: 10.1021/acsaem.1c04033 doi: 10.1021/acsaem.1c04033
27. [27]
  Wang, W.; Jiang, Y.; Yang, Y.; Xiong, F.; Zhu, S.; Wang, J.; Du, L.; Chen, J.; Cui, L.; Xie, J.; et al. ACS Nano 2022, 16, 17097. doi: 10.1021/acsnano.2c07399 doi: 10.1021/acsnano.2c07399
28. [28]
  Li, H.; Qin, X.; Zhang, X.; Jiang, K.; Cai, W. ACS Catal. 2022, 12, 12750. doi: 10.1021/acscatal.2c04358 doi: 10.1021/acscatal.2c04358
29. [29]
  Jiao, W.; Li, N.; Wang, L.; Wen, L.; Li, F.; Liu, G.; Cheng, H. M. Chem. Commun. 2013, 49, 3461. doi: 10.1039/c3cc40568k doi: 10.1039/c3cc40568k
30. [30]
  Khan, S.; Ruwer, T. L.; Khan, N.; Köche, A.; Lodge, R. W.; Coelho-Júnior, H.; Sommer, R. L.; Santos, M. J. L.; Malfatti, C. F.; Bergmann, C. P.; et al. J. Mater. Chem. A 2021, 9, 12214. doi: 10.1039/D0TA11494D doi: 10.1039/D0TA11494D
31. [31]
  Mee Rahn, K.; Karol, M.; Mauro, P.; Rosaria, B.; Sotirios, C.; Mirko, P.; Sergio, M.; Liberato, M. ACS Nano 2012, 6, 11088. doi: 10.1021/nn3048846 doi: 10.1021/nn3048846
32. [32]
  Liu, K.; Wang, J.; Yang, J.; Zhao, D.; Chen, P.; Man, J.; Yu, X.; Wen, Z.; Sun, J. Chem. Eng. J. 2021, 407, 127190. doi: 10.1016/j.cej.2020.127190 doi: 10.1016/j.cej.2020.127190
33. [33]
  Huang, H.; Dai, B.; Wang, W.; Lu, C.; Kou, J.; Ni, Y.; Wang, L.; Xu, Z. Nano Lett. 2017, 17, 3803. doi: 10.1021/acs.nanolett.7b01147 doi: 10.1021/acs.nanolett.7b01147
34. [34]
  Zhang, Q.; Chen, X.; Yang, Z.; Yu, T.; Liu, L.; Ye, J. ACS Appl. Mater. Interfaces 2022, 14, 3970. doi: 10.1021/acsami.1c19638 doi: 10.1021/acsami.1c19638
35. [35]
  Zhang, Y.; Cheng, C.; Xing, F.; Li, Z.; Huang, C. ACS Appl. Mater. Interfaces 2023, 15, 31364. doi: 10.1021/acsami.3c02662 doi: 10.1021/acsami.3c02662
36. [36]
  Zhong, W.; Huang, Y.; Wang, X.; Fan, J.; Yu, H. Chem. Commun. 2020, 56, 9316. doi: 10.1039/d0cc01191f doi: 10.1039/d0cc01191f
37. [37]
  Li, W.; Wang, F.; Liu, X.; Dang, Y.; Li, J.; Ma, T.; Wang, C. Appl. Catal. B-Environ. 2022, 313, 121470. doi: 10.1016/j.apcatb.2022.121470 doi: 10.1016/j.apcatb.2022.121470
38. [38]
  Vaquero, F.; Navarro, R. M.; Fierro, J. L. G. Appl. Catal. B-Environ. 2017, 203, 753. doi: 10.1016/j.apcatb.2016.10.073 doi: 10.1016/j.apcatb.2016.10.073
39. [39]
  Prabhu, R. R.; Khadar, M. A. Bull. Mater. Sci. 2008, 31, 511. doi: 10.1007/s12034-008-0080-7 doi: 10.1007/s12034-008-0080-7
40. [40]
  Cao, M.; Wang, K.; Tudela, I.; Fan, X. Appl. Surf. Sci. 2021, 536, 147784. doi: 10.1016/j.apsusc.2020.147784 doi: 10.1016/j.apsusc.2020.147784
41. [41]
  Zhao, Y.; Zhang, P.; Yang, Z.; Li, L.; Gao, J.; Chen, S.; Xie, T.; Diao, C.; Xi, S.; Xiao, B.; et al. Nat. Commun. 2021, 12, 3701. doi: 10.1038/s41467-021-24048-1 doi: 10.1038/s41467-021-24048-1
42. [42]
  Chen, L.; Chen, C.; Yang, Z.; Li, S.; Chu, C.; Chen, B. Adv. Funct. Mater. 2021, 31, 2105731. doi: 10.1002/adfm.202105731 doi: 10.1002/adfm.202105731
43. [43]
  Sun, P.; Chen, Z.; Zhang, J.; Wu, G.; Song, Y.; Miao, Z.; Zhong, K.; Huang, L.; Mo, Z.; Xu, H. Appl. Catal. B-Environ. 2023, 123337. doi: 10.1016/j.apcatb.2023.123337 doi: 10.1016/j.apcatb.2023.123337
44. [44]
  Xia, L.; Sun, Z.; Wu, Y.; Yu, X.; Cheng, J.; Zhang, K.; Sarina, S.; Zhu, H.; Weerathunga, H.; Zhang, L.; et al. Chem. Eng. J. 2022, 439, 135668. doi: 10.1016/j.cej.2022.135668 doi: 10.1016/j.cej.2022.135668
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Built-in Electric Fields Enhancing Photocarrier Separation and H2 Evolution

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Built-in Electric Fields Enhancing Photocarrier Separation and H₂ Evolution