WO_3/TiOF_2复合催化剂的制备及其光催化性能研究
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摘要
采用酞酸丁酯、氢氟酸、无水乙醇、钨酸钠和十六烷基三甲基溴化铵为原料,通过水热法制备了WO_3/TiOF_2复合光催化剂,用X-射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、固体紫外漫反射(UV-vis DRS)、荧光光谱(PL)等分析手段对WO_3/TiOF_2复合催化剂进行了表征;利用罗丹明B的脱色降解研究了WO_3/TiOF_2复合催化剂的光催化性能;通过罗丹明B溶液的紫外可见吸收光谱(UV-Vis)变化研究了催化剂作用下罗丹明B的脱色机理。在加入0.1 g复合催化剂和模拟太阳光源照射下,初始质量浓度为10 mg/L的罗丹明B溶液在2.5 h内降解了95.8%,光催化的性能优异,说明制备的WO_3/TiOF_2复合光催化剂有良好的太阳光催化应用前景。
WO_3/TiOF_2 composite photocatalysts have been prepared by a hydrothermal route using butyl titanate, hydrofluoric acid, absolute ethanol, sodium tungstate and cetyltrimethylammonium bromide as raw materials. The structures of the composite photocatalysts were characterized by XRD, SEM, TEM, UV-Vis and PL techniques. The photocatalytic performance of the TiOF_2/WO_3 composite catalyst was investigated using the decolorization and degradation of rhodamine B as a probe reaction. The mechanism of decolorization of rhodamine B was investigated by monitoring its UV-Vis absorption spectrum. The results showed that doping with WO_3 affects the crystal morphology of TiOF_2 and increases its specific surface area. It thus provides a contact point and space for the degradation of rhodamine B at different levels, and reduces the band gap and the recombination probability of the electron holes. As a result, the photocatalytic activity is enhanced. When a composite catalyst(0.1 g) was dispersed in a rhodamine B solution with an initial concentration of 10 mg/L under solar light irradiation, the degradation of rhodamine B reached 96% after 2.5 h, confirming the excellent performance of the composite catalyst. This work shows that the TiOF_2/WO_3 composite photocatalyst has good prospects for application in solar photocatalysis.
WO_3/TiOF_2 composite photocatalysts have been prepared by a hydrothermal route using butyl titanate, hydrofluoric acid, absolute ethanol, sodium tungstate and cetyltrimethylammonium bromide as raw materials. The structures of the composite photocatalysts were characterized by XRD, SEM, TEM, UV-Vis and PL techniques. The photocatalytic performance of the TiOF_2/WO_3 composite catalyst was investigated using the decolorization and degradation of rhodamine B as a probe reaction. The mechanism of decolorization of rhodamine B was investigated by monitoring its UV-Vis absorption spectrum. The results showed that doping with WO_3 affects the crystal morphology of TiOF_2 and increases its specific surface area. It thus provides a contact point and space for the degradation of rhodamine B at different levels, and reduces the band gap and the recombination probability of the electron holes. As a result, the photocatalytic activity is enhanced. When a composite catalyst(0.1 g) was dispersed in a rhodamine B solution with an initial concentration of 10 mg/L under solar light irradiation, the degradation of rhodamine B reached 96% after 2.5 h, confirming the excellent performance of the composite catalyst. This work shows that the TiOF_2/WO_3 composite photocatalyst has good prospects for application in solar photocatalysis.
引文
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[18] HU Y, LI D Z, ZHENG Y, et al. BiVO4/TiO2 nanocrystalline heterostructure: a wide spectrum responsive photocatalyst towards the highly efficient decomposition of gaseous benzene[J]. Applied Catalysis B: Environmental, 2011, 104(1): 30- 36.
[19] KOWALSKA E, REMITA H, COLBEAU-JUSTIN C, et al. Modification of titanium dioxide with platinum ions and clusters: application in photocatalysis[J]. The Journal of Physical Chemistry C, 2008, 112(4): 1124- 1131.
[20] PARK H, CHOI W. Photocatalytic reactivities of nafion-coated TiO2 for the degradation of charged organic compounds under UV or visible light[J]. The Journal of Physical Chemistry B, 2005, 109(23): 11667- 11674.
[2] 徐斌斌, 傅深渊, 刘丽娜. 掺杂型TiO2光催化研究的最新进展[J]. 化工新型材料, 2017, 45(1): 38- 40. XU B B, FU S Y, LIU L N. Latest progress in the research of doped TiO2 photocatalysis [J]. New Chemical Materials, 2017, 45(1): 38- 40. (in Chinese)
[3] 常刚, 吴小丽. 降解环境污染物的二氧化钛光催化剂制备方法研究进展[J]. 山东化工, 2015, 44(19): 43- 44. CHANG G, WU X L. Research progress in preparation methods of TiO2 photocatalyst for degradation of environmental pollutants[J]. Shandong Chemical Industry, 2015, 44(19): 43- 44. (in Chinese)
[4] PUMA G L, BONO A, KRISHNAIAH D, et al. Preparation of titanium dioxide photocatalyst loaded onto activated carbon support using chemical vapor deposition: a review paper[J]. Journal of Hazardous Materials, 2008, 157(2): 209- 219.
[5] FU X Z, CLARK L A, YANG Q, et al. Enhanced photocatalytic performance of titania-based binary metal oxides: TiO2/SiO2 and TiO2/ZrO2[J]. Environmental Science & Technology, 1996, 30(2): 647- 653.
[6] SONG K Y, PARK M K, KWON Y T, et al. Preparation of transparent particulate MoO3/TiO2 and WO3/TiO2 films and their photocatalytic properties[J]. Chemistry of Materials, 2001, 13(7): 2349- 2355.
[7] ROCQUEFELTE X, GOUBIN F, MONTARDI Y, et al. Analysis of the refractive indices of TiO2, TiOF2 and TiF4: concept of optical channel as a guide to understand and design optical materials[J]. Inorganic Chemistry, 2005, 44(10): 3589- 3593.
[8] PERIYAT P, MCCORMACK D E, HINDER S J, et al. One-pot synthesis of anionic (nitrogen) and cationic (sulfur) codoped high-temperature stable, visible light active, anatase photocatalysts[J]. The Journal of Physical Chemistry C, 2009, 113(8): 3246- 3253.
[9] SHIAN S, SANDHAGE K H. Hexagonal and cubic TiOF2[J]. Journal of Applied Crystallography, 2010, 43(4): 757- 761.
[10] WANG J, CAO F, BIAN Z, et al. Ultrafine single-crystal TiOF2 nanocubes with mesoporous structure, high activity and durability in visible light driven photocatalysis[J]. Nanoscale, 2014, 6(2): 897- 902.
[11] DONG P Y, CUI E T, HOU G H, et al. Synthesis and photocatalytic activity of Ag3PO4/TiOF2 composites with enhanced stability[J]. Materials Letters, 2015, 143: 20- 23.
[12] HOU C T, LIU W L, ZHU J M. Synthesis of NaOH-modified TiOF2 and its enhanced visible light photocatalytic performance on RhB[J]. Catalysts, 2017, 7(8): 243.
[13] 侯晨涛, 柳文莉. 一种新型TiOF2光催化剂及其可见光催化性能研究[J]. 化工新型材料, 2018, 46(3): 130- 133. HOU C T, LIU W L. A novel TiOF2 photocatalyst and its enhanced photocatalytic activity under visible light[J]. New Chemical Materials, 2018, 46(3): 130- 133. (in Chinese)
[14] 闫俊萍, 张中太, 唐子龙, 等. 半导体基纳米复合材料光催化研究进展[J]. 无机材料学报, 2003, 18(5): 980- 988. YAN J P, ZHANG Z T, TANG Z L, et al. Progress in photocatalysis of semiconductor matrix nanocomposites [J]. Journal of Inorganic Materials, 2003, 18(5): 980- 988. (in Chinese)
[15] TONG H X, CHEN Q Y, YIN Z L, et al. Preparation, characterization and photo-catalytic behavior of WO3-TiO2 catalysts with oxygen vacancies[J]. Transactions of Nonferrous Metals Society of China, 2009, 19: 1483- 1488.
[16] 张丹, 张学俊. TiO2光催化剂掺杂改性的研究进展[J]. 化工中间体, 2010(7): 18- 22. ZHANG D, ZHANG X J. Research progress on doping modification of TiO2 photocatalyst [J]. Chemical Intermediate, 2010(7): 18- 22. (in Chinese)
[17] LI D, HANEDA H, HISHITA S, et al. Visible-light-driven N-F-codoped TiO2 photocatalysts. 2. optical characterization, photocatalysis, and potential application to air purification[J]. Chemistry of Materials, 2005, 17(10): 2596- 2602.
[18] HU Y, LI D Z, ZHENG Y, et al. BiVO4/TiO2 nanocrystalline heterostructure: a wide spectrum responsive photocatalyst towards the highly efficient decomposition of gaseous benzene[J]. Applied Catalysis B: Environmental, 2011, 104(1): 30- 36.
[19] KOWALSKA E, REMITA H, COLBEAU-JUSTIN C, et al. Modification of titanium dioxide with platinum ions and clusters: application in photocatalysis[J]. The Journal of Physical Chemistry C, 2008, 112(4): 1124- 1131.
[20] PARK H, CHOI W. Photocatalytic reactivities of nafion-coated TiO2 for the degradation of charged organic compounds under UV or visible light[J]. The Journal of Physical Chemistry B, 2005, 109(23): 11667- 11674.