Citation: Liu Shengwei, Zhao Jianjun, Xu Yiming. Larger Adsorption Effect of Fluoride than Phosphate on Phenol Degradation over the Irradiated Anatase TiO₂ and Pt/TiO₂[J]. Acta Chimica Sinica, ;2019, 77(4): 351-357. doi: 10.6023/A19010009 shu

Larger Adsorption Effect of Fluoride than Phosphate on Phenol Degradation over the Irradiated Anatase TiO₂ and Pt/TiO₂

Department of Chemistry and State Key Laboratory of Silicon Materials, Zhejiang University, Hangzhou 310027

Corresponding author: Xu Yiming, xuym@zju.edu.cn
Received Date: 4 January 2019
Available Online: 5 April 2019
Fund Project: the Funds for Creative Research Group of NSFC 21621005Project supported by the Funds for Creative Research Group of NSFC (No. 21621005)

Figures(6)

It is known that fluoride and phosphate in aqueous solution can accelerate the photocatalytic degradation of phenol over anatase or P25 TiO₂. But the mechanism still remains under debate. In this work, an anion-free anatase TiO₂ is prepared, followed by deposition with 0.52 wt% Pt (Pt/TiO₂). Reaction was performed in aqueous solution at initial pH 5.2, where 99% of anions were in the form of F^- or H₂PO₄^-. On the addition of 0.1~30 mmol/L anions, the rate constants of phenol degradation (k_obs) were all increased, confirming the positive effect of fluoride and phosphate, respectively. Interestingly, there was a linear relationship between the increase of k_obs and the amounts of anion adsorption, the slope of which became larger in the order of fluoride>phosphate, and Pt/TiO₂>TiO₂. These observations indicate that the positive effect of anions originates from the adsorbed anions on solid, and that fluoride was more active than phosphate. A (photo)electrochemical measurement showed that fluoride and phosphate were negative and positive, respectively, to O₂ reduction, but they were all beneficial to phenol oxidation. Furthermore, in the presence of fluoride and phosphate, the flat band potentials of TiO₂ were shifted by -159 and 89 mV, respectively. The former favors orbital overlapping of phenol with TiO₂ valence band, and the latter favors orbital overlapping of O₂ with TiO₂ conduction band, all of which promotes the interfacial charge transfers. Since inorganic anions are widely present, this result would benefit the mechanism study of a semiconductor photocatalyis and its application. As a reference, pure anatase was prepared from the hydrolysis of tetrabutyl titanate, followed by calcination in air at 400℃ for 2 h. The solid was then deposited with Pt, produced in situ from the photocatalytic reduction of H₂PtCl₆ in the presence of methanol. Solid was characterized with X-ray diffraction, N₂ adsorption, Raman, and X-ray photoelectron spectroscopy. After Pt deposition, anatase phase remained unchanged, but the solid pores were blocked by a mixture of Pt and PtO₂. Photoreactions were performed at room temperature under UV light at wavelengths equal to and longer than 320 nm. Organic compounds and inorganic anions were quantitatively analyzed with a high performance liquid and ionic chromatography, respectively. (Photo)electrochemical measurement was performed in a three-electrode compartment, where a Pt gauze was used as counter electrode, and a AgCl/Ag as reference electrode.
- anatase TiO₂,
- fluoride,
- phosphate,
- adsorption,
- photoelectrocatalysis,
- charge transfer
1. [1]
  Wu, J. J.; Ji, Z. Y.; Shen, X. P.; Miao, X. L.; Xu, K. Q. Acta Chim. Sinica 2017, 75, 1207.
2. [2]
  Du, P. J.; Su, T. M.; Luo, X.; Zhou, X. T.; Qin, Z. Z.; Ji, H. B.; Chen, J. H. Chin. J. Chem. 2018, 36, 538. doi: 10.1002/cjoc.v36.6
3. [3]
  Chai, Y. Y.; Liu, Q. Q.; Zhang, L.; Ren, J.; Dai, W. L. Chin. J. Chem. 2017, 35, 173. doi: 10.1002/cjoc.v35.2
4. [4]
  Zhang, F. L.; Duan, F.; Ding, Z. G.; Chen, M. Q. Chin. J. Chem. 2017, 35, 226. doi: 10.1002/cjoc.v35.2
5. [5]
  Hoffmann, M.; Martin, S.; Choi, W.; W. Bahnemann, D. W. Chem. Rev. 1995, 95, 69. doi: 10.1021/cr00033a004
6. [6]
  Tachikawa, T.; Fujitsuka, M.; Majima, T. J. Phys. Chem. C 2007, 111, 5259.
7. [7]
  Zielińska-Jurek, A.; Zaleska, A. Catal. Today 2014, 230, 104. doi: 10.1016/j.cattod.2013.11.044
8. [8]
  Chen, K. T.; Lu, C. S.; Chang, T. H.; Lai, Y. Y.; Chang, T. H.; Wu, C. W.; Chen, C. C. J. Hazard. Mater. 2010, 174, 598. doi: 10.1016/j.jhazmat.2009.09.094
9. [9]
  Chiang, K.; Amal, R.; Tran, T. J. Mol. Catal. A:Chem. 2003, 193, 285. doi: 10.1016/S1381-1169(02)00512-5
10. [10]
  Kumar, A.; Mathur, N. J. Colloid Interf. Sci. 2006, 300, 244. doi: 10.1016/j.jcis.2006.03.046
11. [11]
  Lv, K. L.; Li, X. F.; Deng, K. J.; Sun, J.; Li, X. H.; Li, M. Appl.Catal. B:Environ 2010, 95, 383. doi: 10.1016/j.apcatb.2010.01.017
12. [12]
  Minero, C.; Mariella, G.; Maurino, V.; Pelizzetti, E. Langmuir 2000, 16, 2632. doi: 10.1021/la9903301
13. [13]
  Minero, C.; Mariella, G.; Maurino, V.; Vione, D.; Pelizzetti, E. Langmuir 2000, 16, 8964. doi: 10.1021/la0005863
14. [14]
  Vohra, M. S.; Kim, S.; Choi, W. J. Photochem. Photobiol., A:Chem. 2003, 160, 55. doi: 10.1016/S1010-6030(03)00221-1
15. [15]
  Park, H.; Choi, W. J. Phys. Chem. B 2004, 108, 4086. doi: 10.1021/jp036735i
16. [16]
  Yu, J. C.; Zhang, L. Z.; Zheng, Z.; Zhao, J. C. Chem. Mater. 2003, 15, 2280. doi: 10.1021/cm0340781
17. [17]
  Zhao, D.; Chen, C. C.; Wang, Y. F.; Ji, H. W.; Ma, W. H.; Zang, L.; Zhao, J. C. J. Phys. Chem. C 2008, 112, 5993. doi: 10.1021/jp712049c
18. [18]
  Zhang, X.; Xiong, X. Q.; Xu, Y. M. RSC Adv. 2016, 6, 61830. doi: 10.1039/C6RA10291C
19. [19]
  Xiong, X. Q.; Xu, Y. M. J. Phys. Chem. C 2016, 120, 3906.
20. [20]
  Xiong, X. Q.; Zhang, X.; Xu, Y. M. J. Phys. Chem. C 2016, 120, 25689. doi: 10.1021/acs.jpcc.6b07951
21. [21]
  Mathpal, M. C.; Tripathi, A. K.; Singh, M. K; Gairola, S. P.; Pandey, S. N.; Agarwal, A. Chem. Phys. Lett. 2013, 555, 182. doi: 10.1016/j.cplett.2012.10.082
22. [22]
  Choi, H. C.; Jung, Y. M.; Kim, S. B. Vib. Spectrosc. 2005, 37, 33. doi: 10.1016/j.vibspec.2004.05.006
23. [23]
  Li, F. B.; Li, X. Z. Chemosphere 2002, 48, 1103. doi: 10.1016/S0045-6535(02)00201-1
24. [24]
  Nie, L. H.; Yu, J. G.; Li, X. Y.; Cheng, B.; Liu, G.; Jaroniec, M. Environ. Sci. Technol. 2013, 47, 2777. doi: 10.1021/es3045949
25. [25]
  Yu, J. G.; Qi, L. F.; Jaroniec, M. J. Phys. Chem. C 2010, 114, 13118. doi: 10.1021/jp104488b
26. [26]
  Vorontsov, A. V.; Savinov, E. N.; Zhensheng, J. J. Photochem. Photobiol., A:Chem. 1999, 125, 113. doi: 10.1016/S1010-6030(99)00073-8
27. [27]
  Cao, Y.; Jing, L.; Shi, X.; Luan, Y.; Durrant, J. R.; Tang, J.; Fu, H. Phys. Chem. Chem. Phys. 2012, 14, 8530. doi: 10.1039/c2cp41167a
28. [28]
  Minella, M.; Maurino, V.; Minero, C.; Pelizzetti, E. J. Nanosci. Nanotechnol. 2015, 15, 3348. doi: 10.1166/jnn.2015.10206
29. [29]
  Nelson, B. P.; Candal, R.; Corn, R. M.; Anderson, M. A. Langmuir 2000, 16, 6094. doi: 10.1021/la9911584
30. [30]
  Li, S. F.; Ye, G. L.; Chen, G. Q. J. Phys. Chem. C 2009, 113, 4031.
31. [31]
  Kim, J.; Lee, C. W.; Choi, W. Environ. Sci. Technol. 2010, 44, 6849. doi: 10.1021/es101981r
32. [32]
  Barbé, C. J.; Arendse, F.; Comte, P.; Jirousek, M.; Lenzmann, F.; Shklover, V.; Grätzel, M. J. Am. Ceram. Soc. 2005, 80, 3157. doi: 10.1111/j.1151-2916.1997.tb03245.x
33. [33]
  Topoglidis, E.; Lutz, T.; Willis, R. L.; Barnett, C. J.; Cass, A. E. G.; Durrant, J. R. Faraday Discuss. 2000, 116, 35. doi: 10.1039/b003313h
34. [34]
  Willis, R. L.; Olson, C.; O'Regan, B.; Lutz, T.; Nelson, J.; Durrant, J. R. J. Phys. Chem. B 2002, 106, 7605. doi: 10.1021/jp020231n
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通讯作者: 陈斌, bchen63@163.com

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沈阳化工大学材料科学与工程学院沈阳 110142

Larger Adsorption Effect of Fluoride than Phosphate on Phenol Degradation over the Irradiated Anatase TiO2 and Pt/TiO2

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通讯作者: 陈斌, bchen63@163.com

Larger Adsorption Effect of Fluoride than Phosphate on Phenol Degradation over the Irradiated Anatase TiO₂ and Pt/TiO₂