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
1. [1]
  Jianyin He , Liuyun Chen , Xinling Xie , Zuzeng Qin , Hongbing Ji , Tongming Su . ZnCoP/CdLa₂S₄肖特基异质结的构建促进光催化产氢. Acta Physico-Chimica Sinica, 2024, 40(11): 2404030-. doi: 10.3866/PKU.WHXB202404030
2. [2]
  Xiutao Xu , Chunfeng Shao , Jinfeng Zhang , Zhongliao Wang , Kai Dai . Rational Design of S-Scheme CeO₂/Bi₂MoO₆ Microsphere Heterojunction for Efficient Photocatalytic CO₂ Reduction. Acta Physico-Chimica Sinica, 2024, 40(10): 2309031-. doi: 10.3866/PKU.WHXB202309031
3. [3]
  Hui Wang , Abdelkader Labidi , Menghan Ren , Feroz Shaik , Chuanyi Wang . 微观结构调控的g-C₃N₄在光催化NO转化中的最新进展：吸附/活化位点的关键作用. Acta Physico-Chimica Sinica, 2025, 41(5): 100039-. doi: 10.1016/j.actphy.2024.100039
4. [4]
  Benhua Wang , Chaoyi Yao , Yiming Li , Qing Liu , Minhuan Lan , Guipeng Yu , Yiming Luo , Xiangzhi Song . 一种基于香豆素氟离子荧光探针的合成、表征及性能测试——“科研反哺教学”在有机化学综合实验教学中的探索与实践. University Chemistry, 2025, 40(6): 201-209. doi: 10.12461/PKU.DXHX202408070
5. [5]
  Fang Niu , Rong Li , Qiaolan Zhang . Analysis of Gas-Solid Adsorption Behavior in Resistive Gas Sensing Process. University Chemistry, 2024, 39(8): 142-148. doi: 10.3866/PKU.DXHX202311102
6. [6]
  Yan LIU , Jiaxin GUO , Song YANG , Shixian XU , Yanyan YANG , Zhongliang YU , Xiaogang HAO . Exclusionary recovery of phosphate anions with low concentration from wastewater using a CoNi-layered double hydroxide/graphene electronically controlled separation film. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1775-1783. doi: 10.11862/CJIC.20240043
7. [7]
  Fan JIA , Wenbao XU , Fangbin LIU , Haihua ZHANG , Hongbing FU . Synthesis and electroluminescence properties of Mn²⁺ doped quasi-two-dimensional perovskites (PEA)₂Pb_yMn_1-yBr₄. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1114-1122. doi: 10.11862/CJIC.20230473
8. [8]
  Jingzhao Cheng , Shiyu Gao , Bei Cheng , Kai Yang , Wang Wang , Shaowen Cao . 4-氨基-1H-咪唑-5-甲腈修饰供体-受体型氮化碳光催化剂的构建及其高效光催化产氢研究. Acta Physico-Chimica Sinica, 2024, 40(11): 2406026-. doi: 10.3866/PKU.WHXB202406026
9. [9]
  Guang Huang , Lei Li , Dingyi Zhang , Xingze Wang , Yugai Huang , Wenhui Liang , Zhifen Guo , Wenmei Jiao . Cobalt’s Valor, Nickel’s Foe: A Comprehensive Chemical Experiment Utilizing a Cobalt-based Imidazolate Framework for Nickel Ion Removal. University Chemistry, 2024, 39(8): 174-183. doi: 10.3866/PKU.DXHX202311051
10. [10]
  Jingke LIU , Jia CHEN , Yingchao HAN . Nano hydroxyapatite stable suspension system: Preparation and cobalt adsorption performance. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1763-1774. doi: 10.11862/CJIC.20240060
11. [11]
  Peng XU , Shasha WANG , Nannan CHEN , Ao WANG , Dongmei YU . Preparation of three-layer magnetic composite Fe₃O₄@polyacrylic acid@ZiF-8 for efficient removal of malachite green in water. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 544-554. doi: 10.11862/CJIC.20230239
12. [12]
  Zeyu XU , Anlei DANG , Bihua DENG , Xiaoxin ZUO , Yu LU , Ping YANG , Wenzhu YIN . Evaluation of the efficacy of graphene oxide quantum dots as an ovalbumin delivery platform and adjuvant for immune enhancement. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1065-1078. doi: 10.11862/CJIC.20240099
13. [13]
  Jing Wang , Pingping Li , Yuehui Wang , Yifan Xiu , Bingqian Zhang , Shuwen Wang , Hongtao Gao . Treatment and Discharge Evaluation of Phosphorus-Containing Wastewater. University Chemistry, 2024, 39(5): 52-62. doi: 10.3866/PKU.DXHX202309097
14. [14]
  Fugui XI , Du LI , Zhourui YAN , Hui WANG , Junyu XIANG , Zhiyun DONG . Functionalized zirconium metal-organic frameworks for the removal of tetracycline from water. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 683-694. doi: 10.11862/CJIC.20240291
15. [15]
  Wei Li , Jinfan Xu , Yongjun Zhang , Ying Guan . 共价有机框架整体材料的制备及食品安全非靶向筛查应用——推荐一个仪器分析综合化学实验. University Chemistry, 2025, 40(6): 276-285. doi: 10.12461/PKU.DXHX202406013
16. [16]
  You Wu , Chang Cheng , Kezhen Qi , Bei Cheng , Jianjun Zhang , Jiaguo Yu , Liuyang Zhang . ZnO/D-A共轭聚合物S型异质结高效光催化产H₂O₂及其电荷转移动力学研究. Acta Physico-Chimica Sinica, 2024, 40(11): 2406027-. doi: 10.3866/PKU.WHXB202406027
17. [17]
  Peng Li , Yuanying Cui , Zhongliao Wang , Graham Dawson , Chunfeng Shao , Kai Dai . Efficient interfacial charge transfer of CeO₂/Bi₁₉Br₃S₂₇ S-scheme heterojunction for boosted photocatalytic CO₂ reduction. Acta Physico-Chimica Sinica, 2025, 41(6): 100065-0. doi: 10.1016/j.actphy.2025.100065
18. [18]
  Jiajie Cai , Chang Cheng , Bowen Liu , Jianjun Zhang , Chuanjia Jiang , Bei Cheng . CdS/DBTSO-BDTO S-scheme photocatalyst for H₂ production and its charge transfer dynamics. Acta Physico-Chimica Sinica, 2025, 41(8): 100084-0. doi: 10.1016/j.actphy.2025.100084
19. [19]
  Shuanglin TIAN , Tinghong GAO , Yutao LIU , Qian CHEN , Quan XIE , Qingquan XIAO , Yongchao LIANG . First-principles study of adsorption of Cl₂ and CO gas molecules by transition metal-doped g-GaN. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1189-1200. doi: 10.11862/CJIC.20230482
20. [20]
  Weikang Wang , Yadong Wu , Jianjun Zhang , Kai Meng , Jinhe Li , Lele Wang , Qinqin Liu . Green H₂O₂ synthesis via melamine-foam supported S-scheme Cd_0.5Zn_0.5In₂S₄/S-doped carbon nitride heterojunction: synergistic interfacial charge transfer and local photothermal effect. Acta Physico-Chimica Sinica, 2025, 41(8): 100093-0. doi: 10.1016/j.actphy.2025.100093

Get Citation

PDF

XML

Metrics

PDF Downloads(9)
Abstract views(1647)
HTML views(214)

通讯作者: 陈斌, bchen63@163.com

1.
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

Metrics

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