English

Novel Carboxy-Functionalized PVP-CdS Nanopopcorns with Homojunctions for Enhanced Photocatalytic Hydrogen Evolution

• Na Zhao ^{1, 2,} ,
• Jing Peng ^2, ,
• Jianping Wang ^1, ,
• Maolin Zhai ^{2, ,}

• 1.

  The National Museum of China, Beijing 100006, China

• 2.

  Beijing National Laboratory for Molecular Sciences, Radiochemistry and Radiation Chemistry Key Laboratory of Fundamental Science, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China

Corresponding author: Maolin Zhai, mlzhai@pku.edu.cn

• Received Date: 15 April 2020
  Accepted Date: 06 May 2020
  Revised Date: 01 May 2020
  Available Online: 15 April 2022
• Fund Project:

Abstract: Photocatalytic hydrogen evolution is a scalable pathway to generate hydrogen fuels while mitigating environmental crisis. Strategies based on modification of the host photocatalyst surface are key to improve the adsorption/activation ability of the reaction molecules and the efficiency of charge transport, so that high-efficiency photocatalytic systems can be realized. Cadmium sulfide (CdS), a visible light-responsive semiconductor material, is widely used in photocatalysis because of its simple synthesis, low cost, abundant raw materials, and appropriate bandgap structure. Many researchers have focused on improving the photocatalytic efficiency of CdS because the rapid charge recombination in this material limits its applications. Among the various strategies proposed in this regard, surface modification is an effective and simple method used to improve the photocatalytic performance of materials. In this work, polyvinyl pyrrolidone (PVP)-capped CdS (denoted as P-CdS) nanopopcorns with hexagonal wurtzite (WZ)-cubic zinc blende (ZB) homojunctions were fabricated via one-step gamma-ray radiation-induced reduction under ambient conditions. Subsequent alkaline treatment under ambient conditions led to a dramatic improvement in the activity of the alkalized PVP-capped CdS (MP-CdS) photocatalyst. The structure and properties of the photocatalyst were determined by X-ray diffraction (XRD) analysis, field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) analysis, Brunauer-Emmett-Teller (BET) specific surface area measurements, and photoelectric tests. The photocatalytic performance was evaluated based on the photocatalytic H₂ evolution under visible-light irradiation. The mechanism underlying the enhancement of the photocatalytic activity is also discussed. The results showed that after the alkaline treatment, the crystal structure of CdS with WZ-ZB homojunctions was preserved, but PVP on the surface of CdS hydrolyzed to form PVP hydrolysis product (MPVP) with carboxyl and amino groups. Owing to the increased alkaline solubility, a portion of MPVP dissolved into the solution and was removed from the surface of MP-CdS, exposing a greater number of active sites of the WZ-ZB phase junctions with a larger specific surface area. On the other hand, the carboxyl groups in MPVP coordinated with CdS could affect the bandgap and valence band position of CdS to facilitate the photocatalysis. Because of the synergistic effects of the exposure of WZ-ZB phase junctions and band structure engineering, the alkalized samples at a 1 mol·L^-1 concentration of NaOH showed a H₂ evolution rate of 477 μmol·g^-1·h^-1 under visible-light illumination, which was twice that obtained for the pristine P-CdS photocatalysts. This simple and low-cost post-synthesis strategy can be extended to the preparation of diverse functional photocatalysts. The present work is expected to contribute to the practical application of sulfide photocatalysts.

Key words:
• CdS
•  /  Homojunction
•  /  Alkaline treatment
•  /  Photocatalytic hydrogen evolution

• 1. [1]

     Ning, X.; Lu, G. Nanoscale 2020, 12, 1213. doi: 10.1039/C9NR09183A

  2. [2]

     Zhang, J.; Chen, X.; Bai, Y.; Li, C.; Gao, Y.; Li, R.; Li, C. J. Mater. Chem. A 2019, 7, 10264. doi: 10.1039/C8TA08199A

  3. [3]

     Li, R.; Li, C. Adv. Catal. 2017, 60, 1. doi: 10.1016/bs.acat.2017.09.001

  4. [4]

     曹朋飞, 胡杨, 张有为, 彭静, 翟茂林. 物理化学学报, 2017, 33, 2542. doi: 10.3866/pku.whxb201706151Cao, P. F.; Hu, Y.; Zhang, Y. W.; Peng, J.; Zhai, M. L. Acta Phys. -Chim. Sin. 2017, 33, 2542. doi: 10.3866/pku.whxb201706151

  5. [5]

     Wang, Z.; Wang, L. Chin. J. Catal. 2018, 39, 369. doi: 10.1016/S1872-2067(17)62998-X

  6. [6]

     Chen, J. Z.; Wu, X. J.; Yin, L. S.; Li, B.; Hong, X.; Fan, Z. X.; Chen, B.; Xue, C.; Zhang, H. Angew. Chem. -Int. Edit. 2015, 54, 1210. doi: 10.1002/anie.201410172

  7. [7]

     Jang, J. S.; Joshi, U. A.; Lee, J. S. J. Phys. Chem. C 2007, 111, 13280. doi: 10.1021/jp072683b

  8. [8]

     Jing, D. W.; Guo, L. J. J. Phys. Chem. B 2006, 110, 11139. doi: 10.1021/jp060905k

  9. [9]

     Yuan, Y. J.; Li, Z.; Wu, S.; Chen, D.; Yang, L. X.; Cao, D.; Tu, W. G.; Yu, Z. T.; Zou, Z. G. Chem. Eng. J. 2018, 350, 335. doi: 10.1016/j.cej.2018.05.172

  10. [10]

      Li, L.; Wu, J.; Liu, B.; Liu, X.; Li, C.; Gong, Y.; Huang, Y.; Pan, L. Catal. Today 2018, 315, 110. doi: 10.1016/j.cattod.2018.03.072

  11. [11]

      Low, J.; Dai, B.; Tong, T.; Jiang, C.; Yu, J. Adv. Mater. 2019, 31, 1802981. doi: 10.1002/adma.201802981

  12. [12]

      Wang, P.; Yi, X.; Lu, Y.; Yu, H.; Yu, J. J. Colloid Interface Sci. 2018, 532, 272. doi: 10.1016/j.jcis.2018.07.139

  13. [13]

      Zhao, D.; Chen, C.; Yu, C.; Ma, W.; Zhao, J. J. Phys. Chem. C 2009, 113, 13160. doi: 10.1021/jp9002774

  14. [14]

      Ai, Z. Z.; Zhao, G.; Zhong, Y. Y.; Shao, Y. L.; Huang, B. B.; Wu, Y. Z.; Hao, X. P. Appl. Catal. B-Environ. 2018, 221, 179. doi: 10.1016/j.apcatb.2017.09.002

  15. [15]

      Li, K.; Han, M.; Chen, R.; Li, S. L.; Xie, S. L.; Mao, C.; Bu, X.; Cao, X. L.; Dong, L. Z.; Feng, P.; et al. Adv. Mater. 2016, 28, 8906. doi: 10.1002/adma.201601047

  16. [16]

      Zhao, N.; Peng, J.; Liu, G.; Zhang, Y.; Lei, W.; Yin, Z.; Li, J.; Zhai, M. J. Mater. Chem. A 2018, 6, 18458. doi: 10.1039/C8TA03414A

  17. [17]

      Wang, J.; Cui, W.; Chen, R.; He, Y.; Yuan, C.; Sheng, J.; Li, J.; Zhang, Y.; Dong, F.; Sun, Y. Catal. Sci. Technol. 2020, 10, 529. doi: 10.1039/C9CY02048A

  18. [18]

      Chen, S.; Qi, Y.; Li, C.; Domen, K.; Zhang, F. Joule 2018, 2, 2260. doi: 10.1016/j.joule.2018.07.030

  19. [19]

      Liao, Y.; Cao, S. W.; Yuan, Y.; Gu, Q.; Zhang, Z.; Xue, C. Chem. -A Eur. J. 2014, 20, 10220. doi: 10.1002/chem.201403321

  20. [20]

      Zhong, W.; Wu, X.; Wang, P.; Fan, J.; Yu, H. ACS Sustain. Chem. Eng. 2020, 8, 543. doi: 10.1021/acssuschemeng.9b06046

  21. [21]

      Meng, X.; Ouyang, S.; Kako, T.; Li, P.; Yu, Q.; Wang, T.; Ye, J. Chem. Commun. 2014, 50, 11517. doi: 10.1039/C4CC04848B

  22. [22]

      Zhang, H.; Yang, Z.; Shangguan, L.; Song, X.; Sun, J.; Lei, W. Nanotechnology 2020, 31, 145716. doi: 10.1088/1361-6528/ab6750

  23. [23]

      Zhao, F.; Feng, Y.; Wang, Y.; Zhang, X.; Liang, X.; Li, Z.; Zhang, F.; Wang, T.; Gong, J.; Feng, W. Nat. Commun. 2020, 11, 1443. doi: 10.1038/s41467-020-15262-4

  24. [24]

      Muruganandam, S.; Anbalagan, G.; Murugadoss, G. Optik 2017, 131, 826. doi: 10.1016/j.ijleo.2016.12.001

  25. [25]

      Aisida, S. O.; Ahmad, I.; Ezema, F. I. Phys. B: Conden. Matter 2020, 579, 411907. doi: 10.1016/j.physb.2019.411907

  26. [26]

      Senthil, S.; Srinivasan, S.; Thangeeswari, T.; Ratchagar, V. J. Mater. Sci. -Mater. Electron. 2019, 30, 19841. doi: 10.1007/s10854-019-02351-4

  27. [27]

      Bibi, R.; Huang, H.; Kalulu, M.; Shen, Q.; Wei, L.; Oderinde, O.; Li, N.; Zhou, J. ACS Sustain. Chem. Eng. 2019, 7, 4868. doi: 10.1021/acssuschemeng.8b05352

  28. [28]

      Kour, G.; Gupta, M. Dalton Trans. 2017, 46, 7039. doi: 10.1039/C7DT00822H

  29. [29]

      Huang, P.; Jiang, Q.; Yu, P.; Yang, L.; Mao, L. ACS Appl. Mater. Interfaces 2013, 5, 5239. doi: 10.1021/am401082n

  30. [30]

      Kumar, D. P.; Hong, S.; Reddy, D. A.; Kim, T. K. J. Mater. Chem. A 2016, 4, 18551. doi: 10.1039/C6TA08628D

  31. [31]

      Xiong, J.; Liu, Y.; Wang, D.; Liang, S.; Wu, W.; Wu, L. J. Mater. Chem. A 2015, 3, 12631. doi: 10.1039/C5TA02438B

  32. [32]

      Li, Y. H.; Zhang, F.; Chen, Y.; Li, J. Y.; Xu, Y. J. Green Chem. 2020, 22, 163. doi: 10.1039/C9GC03332G

  33. [33]

      Abdelghany, A. M.; Abdelrazek, E. M.; Rashad, D. S. Spectrochim. Acta A 2014, 130, 302. doi: 10.1016/j.saa.2014.04.049

  34. [34]

      Guo, Y.; Shi, W.; Zhu, Y.; Xu, Y.; Cui, F. Appl. Catal. B-Environ. 2020, 262, 118262. doi: 10.1016/j.apcatb.2019.118262

  35. [35]

      Waehayee, A.; Watthaisong, P.; Wannapaiboon, S.; Chanlek, N.; Nakajima, H.; Wittayakun, J.; Suthirakun, S.; Siritanon, T. Catal. Sci. Technol. 2020, 10, 978. doi: 10.1039/C9CY01782H

  36. [36]

      Buxton, G. V.; Greenstock, C. L.; Helman, W. P.; Ross, A. B. J. Phys. Chem. Ref. Data 1988, 17, 513. doi: 10.1063/1.555805

  37. [37]

      Rossetti, R.; Nakahara, S.; Brus, L. E. J. Chem. Phys. 1983, 79, 1086. doi: 10.1063/1.445834

  38. [38]

      Zhang, L.; Cheng, Z. Q.; Wang, D. F.; Li, J. F. Mater. Lett. 2015, 158, 439. doi: 10.1016/j.matlet.2015.06.042

  39. [39]

      Chava, R. K.; Son, N.; Kim, Y. S.; Kang, M. Nanomaterials 2020, 10, 619. doi: 10.3390/nano10040619

  40. [40]

      Wang, L.; Gao, Z.; Li, Y.; She, H.; Huang, J.; Yu, B.; Wang, Q. Appl. Surf. Sci. 2019, 492, 598. doi: 10.1016/j.apsusc.2019.06.222

  41. [41]

      Jiang, Z.; Zhang, X.; Yang, G.; Yuan, Z.; Ji, X.; Kong, F.; Huang, B.; Dionysiou, D. D.; Chen, J. Chem. Eng. J. 2019, 373, 814. doi: 10.1016/j.cej.2019.05.112

  42. [42]

      Sun, Q.; Wang, N.; Yu, J.; Yu, J. C. Adv. Mater. 2018, 30, 1804368. doi: 10.1002/adma.201804368

  43. [43]

      Wu, Y.; Wang, H.; Tu, W.; Wu, S.; Liu, Y.; Tan, Y. Z.; Luo, H.; Yuan, X.; Chew, J. W. Appl. Catal. B-Environ. 2018, 229, 181. doi: 10.1016/j.apcatb.2018.02.029

  44. [44]

      Ruan, D.; Fujitsuka, M.; Majima, T. Appl. Catal. B-Environ. 2020, 264, 118541. doi: 10.1016/j.apcatb.2019.118541

  45. [45]

      Xing, P.; Chen, Z.; Chen, P.; Lin, H.; Zhao, L.; Wu, Y.; He, Y. J. Colloid Interface Sci. 2019, 552, 622. doi: 10.1016/j.jcis.2019.05.098

  46. [46]

      Qin, Y.; Li, H.; Lu, J.; Meng, F.; Ma, C.; Yan, Y.; Meng, M. Chem. Eng. J. 2020, 384, 123275. doi: 10.1016/j.cej.2019.123275

  47. [47]

      Moniruddin, M.; Oppong, E.; Stewart, D.; McCleese, C.; Roy, A.; Warzywoda, J.; Nuraje, N. Inorg. Chem. 2019, 58, 12325. doi: 10.1021/acs.inorgchem.9b01854

•