English

Cu²⁺ Modified g-C₃N₄ Photocatalysts for Visible Light Photocatalytic Properties

• Li Xiaowei ,
• Wang Bin ,
• Yin Wenxuan ,
• Di Jun ,
• Xia Jiexiang ^, ,
• Zhu Wenshuai ^, ,
• Li Huaming

• School of Chemistry and Chemical Engineering, Institute for Energy Research, Jiangsu University, Zhenjiang 212013, Jiangsu Province, P. R. China

Corresponding author: Xia Jiexiang, xjx@ujs.edu.cn Zhu Wenshuai, zhuws@ujs.edu.cn

• Received Date: 01 February 2019
  Accepted Date: 13 May 2019
  Revised Date: 03 May 2019
  Available Online: 15 March 2020
• Fund Project:

  the National Natural Science Foundation of China (21722604, 21576122), Chinese Postdoctoral Science Foundation (2017M611726) and Postgraduate Research & Practice Innovation Program of Jiangsu Province, China (SJKY19_2573)

Abstract: Photocatalytic technology can effectively solve the problem of increasingly serious water pollution, the core of which is the design and synthesis of highly efficient photocatalytic materials. Semiconductor photocatalysts are currently the most widely used photocatalysts. Among these is graphitic carbon nitride (g-C₃N₄), which has great potential in environment management and the development of new energy owing to its low cost, easy availability, unique band structure, and good thermal stability. However, the photocatalytic activity of g-C₃N₄ remains low because of problems such as wide bandgap, weakly absorb visible light, and the high recombination rate of photogenerated carriers. Among various modification strategies, doping modification is an effective and simple method used to improve the photocatalytic performance of materials. In this work, Cu/g-C₃N₄ photocatalysts were successfully prepared by incorporating Cu²⁺ into g-C₃N₄ to further optimize photocatalytic performance. At the same time, the structure, morphology, and optical and photoelectric properties of Cu/g-C₃N₄ photocatalysts were analyzed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy, UV-Vis diffuse reflectance spectroscopy (DRS), and photoelectric tests. XRD and XPS were used to ensure that the prepared photocatalysts were Cu/g-C₃N₄ and the valence state of Cu was in the form of Cu²⁺. Under visible light irradiation, the photocatalytic activity of Cu/g-C₃N₄ and pure g-C₃N₄ photocatalysts were investigated in terms of the degradation of RhB and CIP by comparing the amount of introduced copper ions. The experimental results showed that the degradation ability of Cu/g-C₃N₄ photocatalysts was stronger than that of pure g-C₃N₄. The N₂ adsorption-desorption isotherms of g-C₃N₄ and Cu/g-C₃N₄ demonstrated that the introduction of copper had little effect on the microstructure of g-C₃N₄. The small difference in specific surface area indicates that the enhanced photocatalytic activity may be attributed to the effective separation of photogenerated carriers. Therefore, the enhanced photocatalytic degradation of RhB and CIP over Cu/g-C₃N₄ may be due to the reduction of carrier recombination rate by copper. The photoelectric test showed that the incorporation of Cu²⁺ into g-C₃N₄ could reduce the electron-hole recombination rate of g-C₃N₄ and accelerate the separation of electron-hole pairs, thus enhancing the photocatalytic activity of Cu/g-C₃N₄. Free radical trapping experiments and electron spin resonance indicated that the synergistic effect of superoxide radicals (O₂^•−), hydroxyl radicals (•OH) and holes could increase the photocatalytic activity of Cu/g-C₃N₄ materials.

Key words:
• Cu/g-C₃N₄
•  /  Photocatalytic
•  /  Visible light
•  /  Active species
•  /  RhB
•  /  CIP

• 1. [1]

     Hochbaum, A. I.; Yang, P. Chem. Rev. 2010, 110, 527. doi: 10.1021/cr900075v

  2. [2]

     Zou, Z. G.; Ye, J. H.; Sayama, K.; Arakawa, H. Nature 2001, 414, 625. doi: 10.1038/414625a

  3. [3]

     Shi, R.; Waterhouse, G. I. N.; Zhang, T. Solar Rrl. 2017, 1, 1700126. doi: 10.1002/solr.201700126

  4. [4]

     Cao, S.; Li, H.; Tong, T.; Chen, H.; Yu, A.; Yu, J.; Chen, H. M. Adv. Funct. Mater. 2018, 28, 180216932. doi: 10.1002/adfm.201802169

  5. [5]

     弓程, 向思弯, 张泽阳, 孙岚, 叶陈清, 林昌健.物理化学学报, 2019, 35, 616. doi: 10.3866/PKU.WHXB201805082

  6. [6]

     Guo, X.; Li, X.; Qin, L.; Kang, S.; Li, G. Appl. Catal. B-Environ. 2019, 243, 1. doi: 10.1016/j.apcatb.2018.10.030

  7. [7]

     Casillas, J. E.; Tzompantzi, F.; Castellanos, S. G.; Mendoza-Damian, G.; Perez-Hernandez, R.; Lopez-Gaona, A.; Barrera, A. Appl. Catal. B-Environ. 2017, 208, 161. doi: 10.1016/j.apcatb.2017.02.030

  8. [8]

     Lops, C.; Ancona, A.; Di Cesare, K.; Dumontel, B.; Garino, N.; Canavese, G.; Hernandez, S.; Cauda, V. Appl. Catal. B-Environ. 2019, 243, 629. doi: 10.1016/j.apcatb.2018.10.078

  9. [9]

     Jin, Z.; Zhang, Q.; Hu, L.; Chen, J.; Cheng, X.; Zeng, Y.; Ruan, S.; Ohno, T. Appl. Catal. B-Environ. 2017, 205, 569. doi: 10.1016/j.apcatb.2016.12.069

  10. [10]

      Jelinska, A.; Bienkowski, K.; Jadwiszczak, M.; Pisarek, M.; Strawski, M.; Kurzydlowski, D.; Solarska, R.; Augustynski, J. ACS Catal. 2018, 8, 10573. doi: 10.1021/acscatal.8b03497

  11. [11]

      Chen, Y.; Zhu, G.; Hojamberdiev, M.; Gao, J.; Zhu, R.; Wang, C.; Wei, X.; Liu, P. J. Hazard. Mater. 2018, 344, 42. doi: 10.1016/j.jhazmat.2017.10.015

  12. [12]

      Yamaguchi, Y.; Usuki, S.; Kanai, Y.; Yamatoya, K.; Suzuki, N.; Katsumata, K.; Terashima, C.; Suzuki, T.; Fujishima, A.; Sakai, H.; et al. ACS Appl. Mater. Inter. 2017, 9, 31393. doi: 10.1021/acsami.7b07786

  13. [13]

      Guo, S.; Tang, Y.; Xie, Y.; Tian, C.; Feng, Q.; Zhou, W.; Jiang, B. Appl. Catal. B-Environ. 2017, 218, 664. doi: 10.1016/j.apcatb.2017.07.022

  14. [14]

      Weon, S.; Kim, J.; Choi, W. Appl. Catal. B-Environ. 2018, 220, 1. doi: 10.1016/j.apcatb.2017.08.036

  15. [15]

      Liu, J.; Zhang, C.; Ma, B.; Yang, T.; Gu, X.; Wang, X.; Zhang, J.; Hu, C. Nano Energy. 2017, 38, 271. doi: 10.1016/j.nanoen.2017.05.052

  16. [16]

      Wang, B.; Di, J.; Zhang, P.; Xia, J.; Dai, S.; Li, H. Appl. Catal. B-Environ. 2017, 206, 127. doi: 10.1016/j.apcatb.2016.12.049

  17. [17]

      Wang, B.; Di, J.; Liu, G.; Yin, S.; Xia, J.; Zhang, Q.; Li, H. J. Colloid Interf. Sci. 2017, 507, 310. doi: 10.1016/j.jcis.2017.07.094

  18. [18]

      Teixeira, I. F.; Barbosa, E. C. M.; Tsang, S. C. E.; Camargo, P. H. C. Chem. Soc. Rev. 2018, 47, 7783. doi: 10.1039/c8cs00479j

  19. [19]

      Huang, D.; Yan, X.; Yan, M.; Zeng, G.; Zhou, C.; Wan, J.; Cheng, M.; Xue, W. ACS Appl Mater Inter. 2018, 10, 21035. doi: 10.1021/acsami.8b03620

  20. [20]

      Yu, H.; Shi, R.; Zhao, Y.; Bian, T.; Zhao, Y.; Zhou, C.; Waterhouse, G. I. N.; Wu, L.; Tung, C.; Zhang, T. Adv. Mater. 2017, 29, 160514816. doi: 10.1002/adma.201605148

  21. [21]

      Zhou, C.; Shi, R.; Shang, L.; Wu, L.; Chen-Ho, T.; Tierui, Z. Nano Res. 2018, 11, 3462. doi: 10.1007/s12274-018-2003-2

  22. [22]

      Han, C.; Li, J.; Ma, Z.; Xie, H.; Waterhouse, G. I. N.; Ye, L.; Zhang, T. Sci. China Mater. 2018, 61, 1159. doi: 10.1007/s40843-018-9245-y

  23. [23]

      Zhao, H.; Ding, X.; Zhang, B.; Li, Y.; Wang, C. Sci. Bull. 2017, 62, 602. doi: 10.1016/j.scib.2017.03.005

  24. [24]

      Xia, P.; Antonietti, M.; Zhu, B.; Heil, T.; Yu, J.; Cao, S. Adv. Funct. Mater. 2019, 29, 1900093. doi: 10.1002/adfm.201900093

  25. [25]

      Wu, M.; Zhang, J.; He, B.; Wang, H.; Wang, R.; Gong, Y. Appl. Catal. B-Environ. 2019, 241, 159. doi: 10.1016/j.apcatb.2018.09.037

  26. [26]

      Xu, Y.; Ge, F.; Chen, Z.; Huang, S.; Wei, W.; Xie, M.; Xu, H.; Li, H. Appl. Surf. Sci. 2019, 469, 739. doi: 10.1016/j.apsusc.2018.11.062

  27. [27]

      Cao, S.; Huang, Q.; Zhu, B.; Yu, J. J. Power Sources. 2017, 351, 151. doi: 10.1016/j.jpowsour.2017.03.089

  28. [28]

      Zheng, Y.; Lin, L.; Wang, B.; Wang, X. Angew. Chem. Int. Edit. 2015, 54, 12868. doi: 10.1002/anie.201501788

  29. [29]

      Yang, L.; Li, H.; Yu, Y.; Yu, H.Catal. Commun. 2018, 110, 51. doi: 10.1016/j.catcom.2018.03.014

  30. [30]

      Jiang, L.; Yuan, X.; Pan, Y.; Liang, J.; Zeng, G.; Wu, Z.; Wang, H. Appl. Catal. B-Environ. 2017, 217, 388. doi: 10.1016/j.apcatb.2017.06.003

  31. [31]

      Jiang, J.; Cao, S.; Hu, C.; Chen, C. Chin. J. Catal. 2017, 38, 1981. doi: 10.1016/S1872-2067(17)62936-X

  32. [32]

      Zhang, H.; Guo, L.; Wang, D.; Zhao, L.; Wan, B. ACS Appl. Mater. Inter. 2015, 7, 1816. doi: 10.1021/am507483q

  33. [33]

      Yan, Y.; Yu, Y.; Huang, S.; Yang, Y.; Yang, X.; Yin, S.; Cao, Y. J. Phys. Chem. C 2017, 121, 1089. doi: 10.1021/acs.jpcc.6b07180

  34. [34]

      Mao, Z.; Chen, J.; Yang, Y.; Wang, D.; Bie, L.; Fahlman, B. D. ACS Appl. Mater. Inter. 2017, 9, 12427. doi: 10.1021/acsami.7b00370

  35. [35]

      Wang, X.; Maeda, K.; Thomas, A.; Takanabe, K.; Xin, G.; Carlsson, J. M.; Domen, K.; Antonietti, M. Nat. Mater. 2009, 8, 76. doi: 10.1038/NMAT2317

  36. [36]

      Tian, N.; Zhang, Y.; Li, X.; Xiao, K.; Du, X.; Dong, F.; Waterhouse, G. I. N.; Zhang, T.; Huang, H. Nano Energy 2017, 38, 72. doi: 10.1016/j.nanoen.2017.05.038

  37. [37]

      Sun, Z.; Zhu, M.; Fujitsuka, M.; Wang, A.; Shi, C.; Majima, T. ACS Appl. Mater. Inter. 2017, 9, 30583. doi: 10.1021/acsami.7b06386

  38. [38]

      Kong, C.; Tang, L.; Zhang, X.; Sun, S.; Yang, S.; Song, X.; Yang, Z. J. Mater. Chem. A. 2014, 2, 7306. doi: 10.1039/c4ta00703d

  39. [39]

      Wang, W.; Li, G.; An, T.; Chan, D. K. L.; Yu, J. C.; Wong, P. K. Appl. Catal. B-Environ. 2018, 238, 126. doi: 10.1016/j.apcatb.2018.07.004

  40. [40]

      Zheng, Y.; Liu, J.; Liang, J.; Jaroniec, M.; Qiao, S. Z. Energy Environ Sci. 2012, 5, 6717. doi: 10.1039/C2EE03479D

  41. [41]

      Akbarzadeh, R.; Fung, C. S. L.; Rather, R. A.; Lo, I. M. C. Chem. Eng. J. 2018, 341, 248. doi: 10.1016/j.cej.2018.02.042

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