水热法制备p-CoFe2O4/n-CdS及其光催化制氢性能

引用本文: 胡海龙, 王晟, 侯美顺, 刘福生, 王田珍, 李天龙, 董乾乾, 张鑫. 水热法制备p-CoFe₂O₄/n-CdS及其光催化制氢性能[J]. 物理化学学报, 2017, 33(3): 590-601. doi: 10.3866/PKU.WHXB201611241 shu

Citation: HU Hai-Long, WANG Sheng, HOU Mei-Shun, LIU Fu-Sheng, WANG Tian-Zhen, LI Tian-Long, DONG Qian-Qian, ZHANG Xin. Preparation of p-CoFe₂O₄/n-CdS by Hydrothermal Method and Its Photocatalytic Hydrogen Production Activity[J]. Acta Physico-Chimica Sinica, 2017, 33(3): 590-601. doi: 10.3866/PKU.WHXB201611241 shu

水热法制备p-CoFe₂O₄/n-CdS及其光催化制氢性能

胡海龙 ^1, ,
王晟 ^1, ,
侯美顺 ^1, ,
刘福生 ^2, ,
王田珍 ^1, ,
李天龙 ^1, ,
董乾乾 ^1, ,
张鑫 ^1,

1.
南京工业大学化工学院, 南京 210009;
2.
南京林业大学理学院化学与材料科学系, 南京 210037
基金项目:
国家自然科学基金（50876047）；江苏高校品牌专业建设工程项目（TAPP，PPZY2015A044）和江苏省普通高校研究生科研创新计划项目（SJLX15-0346）资助

摘要: 水热法制备了系列p-n复合半导体p-CoFe₂O₄/n-CdS。采用X射线衍射（XRD）、冷场发射扫描电子显微镜（SEM）、紫外-可见漫反射光谱（UV-Vis DRS）、透射电镜（TEM）和电化学工作站等对制得的光催化剂进行了结构和性能表征。研究了p-CoFe₂O₄/n-CdS复合光催化剂的可见光催化制氢性能及光腐蚀性能，并对光催化活性的提高、反应条件的影响及光腐蚀行为的抑制机理进行了分析。结果表明：由于CoFe₂O₄和CdS两种窄带隙半导体复合增加了光吸收率；CdS独特的树形结构以及CoFe₂O₄和CdS二者复合所产生的能带交迭和内建电场的三重作用，促进了电子从CoFe₂O₄向CdS的迁移，减少电子-空穴对复合的概率，增强了光催化活性。光生电子-空穴对的分离效率以及光催化剂表面吸附性能都对产氢速率有重要影响。CH₃OH水溶液的pH对光催化剂中光生电子-空穴对的分离效率以及光催化剂表面吸附性能都有影响。牺牲剂CH₃OH的加入以及CoFe₂O₄和CdS二者复合所产生的能带交迭和内建电场的作用都对CdS的光腐蚀起了抑制作用，后者的抑制效果更好。

关键词:

CoFe₂O₄
/ CdS
/ 光催化
/ 制氢
/ 光腐蚀

English

Preparation of p-CoFe₂O₄/n-CdS by Hydrothermal Method and Its Photocatalytic Hydrogen Production Activity

1.
College of Chemical Engineering, Nanjing Tech University, Nanjing 210009, P. R. China;
2.
Department of Chemistry and Materials Science, College of Science, Nanjing Forestry University, Nanjing 210037, P. R. China
Received Date: 01 August 2016
Revised Date: 23 November 2016
Fund Project:
The project was supported by the National Natural Science Foundation of China (50876047)

Abstract: A series of p-n coupled p-CoFe₂O₄/n-CdS photocatalysts were prepared by a hydrothermal method. The structure and properties of p-CoFe₂O₄/n-CdS were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS), transmission electron microscopy (TEM) and the electrochemical workstation. The photocatalytic activities of p-CoFe₂O₄/nCdS were evaluated by photocatalytic hydrogen production under visible light irradiation. The effects of photocorrosion of CdS in p-CoFe₂O₄/n-CdS were investigated by analyzing the cadmium concentration of the supernatant collected after the photocatalytic reactions. The mechanism of the catalytic activity enhancement, effects of reaction conditions on the photocatalytic hydrogen evolution rate, and cadmium leakage resistance are discussed. The results show that p-CoFe₂O₄/n-CdS exhibits higher photocatalytic activity attributed to stronger light absorption by the two types of narrow band gap semiconductor CoFe₂O₄ and CdS, the formation of a "forest-like" structure of CdS and rapid electron transfer from CoFe₂O₄ to CdS, resulting from band overlap and an inner electric field in p-CoFe₂O₄/n-CdS, to reduce the probability of electron/hole pair recombination. Both the separation efficiency of photo-generated electron-hole pairs and the adsorption performance of photocatalysts had an important influence on the hydrogen production rate. The pH of the CH₃OH aqueous solution influenced the separation efficiency of photogenerated electron-hole pairs and the adsorption properties of the photocatalyst. p-CoFe₂O₄/n-CdS also exhibited resistance against cadmium leakage under light irradiation owing to the presence of methanol in the reaction solution, the band overlap of the semiconductors and the inner electric field in p-CoFe₂O₄/n-CdS. The band overlap and inner electric field had the most influence on the cadmium leakage resistance.

Key words:

1. [1]
  Guo, X. Y.; Chen, C. F.; Song, W. Y.; Wang, X.; Di, W. H.; Qin, W. P. J. Mol. Catal. A-Chem.2014, 387, 1. doi: 10.1016/j.molcata.2014.02.020
2. [2]
  Yan, J. J.; Wang, K.; Xu, H.; Qian, J.; Liu, W.; Yang, X.W.; Li, H. M. Chin. J. Catal.2013, 34 (10), 1876. doi: 10.1016/S1872-2067(12)60677-9
3. [3]
  Wang, C.; Wang, L.; Jin, J.; Liu, J.; Li, Y.; Wu, M.; Chen, L. H.; Wang, B. J.; Yang, X. Y.; Su, B. L. Appl. Catal. B 2016, 188, 351. doi: 10.1016/j.apcatb.2016.02.017
4. [4]
  Wang, Y. J.; Sun, J. Y.; Feng, R. J.; Zhang, J. Acta Phys.-Chim.Sin.2016, 32 (3), 128.[王彦娟, 孙佳瑶, 封瑞江, 张健. 物理化学学报, 2016, 32 (3), 128.] doi: 10.3866/PKU.WHXB201511303
5. [5]
  Xing, W. N.; Ni, L.; Liu, X. L.; Luo, Y. Y.; Lu, Z. Y.; Yan, Y. S.; Huo, P.W. Desalin. Water Treat.2015, 53 (3), 794. doi: 10.1080/19443994.2013.844082
6. [6]
  Yang, J. H.; Yan, H. J.; Wang, X. L.; Wen, F. Y.; Wang, Z. J.; Fan, D. Y.; Shi, J. Y.; Li, C. J. Catal.2012, 290, 151. doi: 10.1016/j.jcat.2012.03.008
7. [7]
  Sasikala, R.; Shirole, A. R.; Sudarsan, V.; Girija, K. G.; Rao, R.; Sudakar, C.; Bharadwaj, S. R. J. Mater. Chem.2011, 21 (41), 16566. doi: 10.1039/c1jm12531a
8. [8]
  Xing, W. N.; Ni, L; Yan, X. S.; Liu, X. L.; Luo, Y. Y.; Lu, Z. Y.; Yan, Y. S.; Huo, P.W. Acta Phys.-Chim. Sin.2014, 30 (1), 141.[邢伟男, 倪良, 颜学升, 刘馨琳, 罗莹莹, 逯子扬, 闫永胜, 霍鹏伟. 物理化学学报, 2014, 30 (1), 141.] doi: 10.3866/PKU.WHXB201311211
9. [9]
  Du, H.; Wang, S.; Liu, L. L.; Liu, Z. X.; Li, Z.; Lu, N.; Liu, F. S.Acta Phys.-Chim. Sin.2010, 26 (10), 2726.[杜欢, 王晟, 刘恋恋, 刘忠祥, 李振, 卢南, 刘福生. 物理化学学报, 2010, 26 (10), 2726.] doi: 10.3866/PKU.WHXB20101023
10. [10]
  Liu, F. S.; Wang, S.; Liu, L. L.; Du, H. Adv. Mater. Res.2012, 512, 1677. doi: 10.4028/www.scientific.net/AMR.512-515.1677
11. [11]
  An, L.; Wang, G. H.; Cheng, Y.; Zhao, L.; Gao, F.; Cheng, Y.Russ. J. Phys. Chem. A 2015, 89 (10), 1878. doi: 10.1134/S0036024415100180
12. [12]
  Shen, J. F.; Huang, W. S.; Li, N.; Ye, M. X. Ceram. Int.2014, 41(1), 761. doi: 10.1016/j.ceramint.2014.08.135
13. [13]
  Zhang, D.; Liu, F. S.; Wang, S.; Li, Z.; Qian, Q. Q.; Wang, X.Q.; Si, G. L. Mater. Sci. Semicond. Process.2015, 40, 602. doi: 10.1016/j.mssp.2015.06.043
14. [14]
  Ye, L. J.; Jiang, Y. J.; Yan, C.; An, X. Y.; Li, N. Appl. Chem.Industry.2015, 44 (11), 1992.[叶林静, 姜韵婕, 闫超, 安小英, 李娜. 应用化工, 2015, 44 (11), 1992.] doi: 10.16581/j.cnki.issn1671-3206.2015.11.006
15. [15]
  Singh, S.; Khare, N. RSC Adv.2015, 5 (117), 96562. doi: 10.1039/c5ra14889h
16. [16]
  Shi, Y. Q.; Zhou, K. Q.; Wang, B. B.; Jiang, S. H.; Qian, X. D.; Gui, Z.; Yuen, R. K. K.; Hu, Y. J. Mater. Chem. A 2014, 2 (2), 535. doi: 10.1039/c3ta13409a
17. [17]
  Singh, S.; Khare, N. Mater. Lett.2015, 161, 64. doi: 10.1016/j.matlet.2015.07.035
18. [18]
  Ao, Y. H.; Wang, K. D.; Wang, P. F.; Wang, C.; Hou, J. Appl.Catal. B 2016, 194, 157. doi: 10.1016/j.apcatb.2016.04.050
19. [19]
  Ao, Y. H.; Bao, J. Q.; Wang, P. F.; Wang, C.; Hou, J. J. Colloid Interface Sci.2016, 476, 71. doi: 10.1016/j.jcis.2016.05.021
20. [20]
  Zhao, W.; Liu, Y.; Wei, Z. B.; Yang, S. G.; He, H.; Sun, C. Appl.Catal. B 2016, 185, 242. doi: 10.1016/j.apcatb.2015.12.023
21. [21]
  Peng, T. Y.; Ke, D. N.; Zeng, P.; Zhang, X. H.; Fan, K. Acta Phys.-Chim. Sin.2011, 27 (9), 2160.[彭天右, 柯丁宁, 曾鹏, 张晓虎, 范科. 物理化学学报, 2011, 27 (9), 2160.] doi: 10.3866/PKU.WHXB20110913
22. [22]
  Min, S. X.; Lü, G. X. Acta Phys.-Chim. Sin.2011, 27 (9), 2178.[敏世雄, 吕功煊. 物理化学学报, 2011, 27 (9), 2178.] doi: 10.3866/PKU.WHXB20110904
23. [23]
  Guo, X. Y.; Chen, C. F.; Song, W. Y.; Wang, X.; Di, W. H.; Qin, W. P. J. Mol. Catal. A:Chem.2014, 387, 1. doi: 10.1016/j.molcata.2014.02.020
24. [24]
  Sathishkumar, P.; Mangalaraja, R.V.; Anandan, S.; Ashokkumar, M. Chem. Eng. J.2013, 220, 302. doi: 10.1016/j.cej.2013.01.036
25. [25]
  Li, W. J.; Li, D. Z.; Zhang, W. J.; Hu, Y.; He, Y. H.; Fu, X. Z.J. Phys. Chem. C 2010, 14 (5), 2154. doi: 10.1021/jp9066247
26. [26]
  Jia, Y. S.; Yang, J. X.; Zhao, D.; Han, H. X.; Li, C. J. Energy Chem.2014, 23 (4), 420. doi: 10.1016/S2095-4956(14)60167-4
27. [27]
  Panda, R.; Rathore, V.; Rathore, M.; Shelke, V.; Badera, N.; Chandra, L. S. S.; Jain, D.; Gangrade, M.; Shripati, T.; Ganesan, V. Appl. Surf. Sci.2012, 258 (12), 5086. doi: 10.1016/j.apsusc.2012.01.131
28. [28]
  Dong, X.; Tao, J.; Li, Y. Y.; Wang, T.; Zhu, H. Acta Phys.-Chim.Sin.2009, 25 (9), 1874.[董祥, 陶杰, 李莹滢, 汪涛, 朱宏. 物理化学学报, 2009, 25 (9), 1874.] doi: 10.3866/PKU.WHXB20090913
29. [29]
  Qi, Q.; Wang, Y. Q.; Wang, S. S.; Qi, H. N.; Wei, T.; Sun, Y. M.Acta Phys.-Chim. Sin.2015, 31 (12), 2332.[齐齐, 王育乔, 王莎莎, 祁昊楠, 卫涛, 孙岳明. 物理化学学报, 2015, 31 (12), 2332.] doi: 10.3866/PKU.WHXB201510202
30. [30]
  Zhang, J.; Nosaka, Y. Appl. Catal. B 2015, 166, 32. doi: 10.1016/j.apcatb.2014.11.006
31. [31]
  Chai, B.; Zhou, H.; Zhang, F.; Liao, X.; Ren, M. X. Mater. Sci.Semicond. Process.2014, 23, 151. doi: 10.1016/j.mssp.2014.02.021
32. [32]
  Lam, S. M.; Sin, J. C.; Abdullah, A. Z.; Mohamed, A. R. Sep.Purif. Technol.2014, 132, 378. doi: 10.1016/j.seppur.2014.05.043
33. [33]
  Jia, H. M.; He, W.W.; Wamer, W. G.; Han, X. N.; Zhang, B. B.; Zhang, S.; Zheng, Z.; Xiang, Y.; Yin, J. J. J. Phys. Chem. C 2014, 118, 21447. doi: 10.1021/jp505783y
34. [34]
  Li, R. G.; Wang, X. L.; Jin, S. Q.; Zhou, X.; Feng, Z. C.; Li, Z.; Shi, J. Y.; Zhang, Q.; Li, C. Sci. Rep.2015, 5, 13475. doi: 10.1038/srep13475
35. [35]
  Zheng, X. J.; Wei, Y. J.; Wei, L. F.; Xie, B.; Wei, M. B. Int. J.Hydrog. Energy 2010, 35 (21), 11709. doi: 10.1016/j.ijhydene.2010.08.090
36. [36]
  Catano, F. A.; Valencia, S. H.; Hincapie, E. A.; Restrepo, G. M.; Marin, J. M. Lat. Am. Appl. Res.2012, 42 (1), 33.

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

水热法制备p-CoFe₂O₄/n-CdS及其光催化制氢性能

English

Preparation of p-CoFe₂O₄/n-CdS by Hydrothermal Method and Its Photocatalytic Hydrogen Production Activity

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