Zn-Ti-O/FTO 复合薄膜的选择降解

doi:10.12066/j.issn.1007-2861.2063

摘要/Abstract

摘要：

采用溶胶-凝胶法在氟掺杂氧化锡(fluorine-doped tin oxide, FTO) 导电玻璃上制备 Zn-Ti-O/FTO 复合薄膜, 并通过 X 射线衍射 (X-ray diffraction, XRD)分析样品的物相结构, 利用紫外可见 (ultra-violet and visible, UV-Vis) 分光光度计测试样品的吸收光谱, 使用扫描电子显微镜(scanning electron microscope, SEM)表征样品的微观形貌. 分别研究了 Zn-Ti-O/FTO 对甲基橙 (methyl orange, MO)、亚甲基蓝 (methylene blue, MB) 以及罗丹明 B (rhodamine B, RhB) 的光催化降解作用. 结果表明: 所得到的 Zn-Ti-O/FTO 结构表现出明显的有机物降解的优选性, 对于 MB 具有光催化降解效率为 90.3%/(6 h) 的最优降解效果. 这种优选性可能与薄膜、衬底的导带底/价带顶以及有机降解物的最低未占分子轨道能级和最高占据分子轨道能级的相对位置相关.

关键词: Zn-Ti-O/FTO, 光催化, 优选性, 溶胶-凝胶

Abstract:

The Zn-Ti-O composite film prepared from fluorine-doped tin oxide (FTO) conducting glass with sol-gel technology has been investigated, whose phase structures analyzed by X-ray diffraction (XRD), absorption spectra measured by UV-Vis spectrophotometer, and morphologies characterized by scanning electron microscope (SEM). The photocatalytic reaction of Zn-Ti-O/FTO has been tested by ultraviolet light with wavelength of 255 nm as light source to methyl orange (MO), methylene blue (MB) and rhodamine B (RhB), respectively. Results indicate that the Zn-Ti-O film prepared on FTO substrate shows obvious preference for degradation of organic compounds---the optimal degradation of MB is 90.3%/(6 h). This preference may be related to the relative positions of the bottom of conduction band/the top of valence band of film and substrate, and the lowest unoccupied molecular orbital/highest occupied molecular orbital of the organic degradation.

Key words: Zn-Ti-O/FTO, photocatalysis, preference, sol-gel

中图分类号:

TB383

石基, 赵加栋, 俞圣雯. Zn-Ti-O/FTO 复合薄膜的选择降解[J]. 上海大学学报(自然科学版), 2021, 27(1): 133-143.

SHI Ji, ZHAO Jiadong, YU Shengwen. Selective degradation of Zn-Ti-O/FTO composite film[J]. Journal of Shanghai University（Natural Science Edition）, 2021, 27(1): 133-143.

图/表 9

表1

图1

图2

图3

图4

图5

表2

表3

图6

参考文献 36

[1]	Ghosh A, Mondal A. Fabrication of stable, efficient and recyclable p-CuO/n-ZnO thin film heterojunction for visible light driven photocatalytic degradation of organic dyes[J]. Materials Letters, 2016,164:221-224.
[2]	Lachheb H, Puzenat E, Houas A, et al. Photocatalytic degradation of various types of dyes (Alizarin S, Crocein Orange G, Methyl Red, Congo Red, Methylene Blue) in water by UV-irradiated titania[J]. Applied Catalysis B: Environmental, 2002,39(1):75-90.
[3]	Konstantinou I K, Albanis T A. TiO$_{2}$-assisted photocatalytic degradation of azo dyes in aqueous solution: kinetic and mechanistic investigations: a review[J]. Applied Catalysis B-Environmental, 2004,49(1):1-14. doi: 10.1016/j.apcatb.2003.11.010
[4]	Yildirim O A, Arslan H, Sönmezo$\check{\rm g}$u S, et al. Facile synjournal of cobalt-doped zinc oxide thin films for highly efficient visible light photocatalysts[J]. Applied Surface Science, 2016,390:111-121.
[5]	Li X, Yu J G, Jaroniec M. Hierarchical photocatalysts[J]. Chemical Society Reviews, 2016,45:2603-2636. doi: 10.1039/c5cs00838g pmid: 26963902
[6]	Zhang W, Song N, Guan L X, et al. Photocatalytic degradation of formaldehyde by nanostructured TiO$_{2}$ composite films[J]. Journal of Experimental Nanoscience, 2016,11(3):185-196.
[7]	Rokhsat E, Akhavan O. Improving the photocatalytic activity of graphene oxide/ZnO nanorod films by UV irradiation[J]. Applied Surface Science, 2016,371:590-595.
[8]	Li X Z, Li F B, Yang C L, et al. Photocatalytic activity of WO$x$-TiO$_{2}$ under visible light irradiation[J]. Journal of Photochemistry and Photobiology A: Chemistry, 2001,141(2/3):209-217.
[9]	Hazem R, Izerrouken M, Trari M, et al. Reactor neutrons irradiation effect on the photocatalytic activity of SnO$_{2}$ thin films[J]. High Energy Chemistry, 2016,50(4):240-244.
[10]	Malik R, Tomer V K, Chaudhary V, et al. Facile synjournal of hybridized mesoporous Au@TiO$_{2}$/SnO$_{2}$ as efficient photocatalyst and selective VOC sensor[J]. ChemistrySelect, 2016,1:3247-3258.
[11]	Moghaddam S, Zerafat M M, Sabbaghi S. Response surface methodology for optimization of phenol photocatalytic degradation using carbon-doped TiO$_{2}$ nano-photocatalyst[J]. International Journal of Nano Dimension, 2018,9(1):89-103.
[12]	Channei D, Inceesungvorn B, Wetchakun N, et al. Photocatalytic degradation of methyl orange by CeO$_{2 }$and Fe-doped CeO$_{2}$ films under visible light irradiation[J]. Scientific Reports, 2014,4(5757):1-7.
[13]	Tian J T, Chen L J, Yin Y S, et al. Photocatalyst of TiO$_{2}$/ZnO nano composite film: preparation, characterization, and photodegradation activity of methyl orange[J]. Surface & Coatings Technology, 2009,204(1/2):205-214.
[14]	Chen L, Zheng K, Liu Y. Geopolymer-supported photocatalytic TiO$_{2}$ film: preparation and Characterization[J]. Construction and Building Materials, 2017,151:63-70.
[15]	Rokhsat E, Akhavan O. Improving the photocatalytic activity of graphene oxide/ZnO nanorod films by UV irradiation[J]. Applied Surface Science, 2016,371:590-595.
[16]	Zhang F, Zhang W J, Luo X L, et al. Electrodeposition of ZnO film with enhanced photocatalytic activity towards methylene blue degradation[J]. Internation Journal Electrochemical Science, 2017,12(5):3756-3764.
[17]	Carneiro J O, Teixeira V, Portinha A, et al. Iron-doped photocatalytic TiO$_{2}$ sputtered coatings on plastics for self-cleaning applications[J]. Materials Science and Engineering B: Solid State Materials for Advanced Technology, 2007,138(2):144-150. doi: 10.1016/j.mseb.2005.08.130
[18]	Liu J, Jin J, Li Y, et al. Tracing the slow photon effect in a ZnO inverse opal film for photocatalytic activity enhancement[J]. Journal of Materials Chemistry A, 2014,2(14):5051-5059. doi: 10.1039/c3ta15044e
[19]	Xiao F X. Construction of highly ordered ZnO-TiO$_{2}$ nanotube arrays (ZnO/TNTs) heterostructure for photocatalytic application[J]. ACS Applied Materials & Interfaces, 2012,4(12):7055-7062. doi: 10.1021/am302462d pmid: 23186082
[20]	Issarapanacheewin S, Wetchakun K, Phanichphant S, et al. Efficient photocatalytic degradation of Rhodamine B by a novel CeO$_{2}$/Bi$_{2}$WO$_{6 }$ composite film[J]. Catalysis Today, 2016,278:280-290.
[21]	Haya S, Brahmia O, Halimi O, et al. Sol-gel synjournal of Sr-doped SnO$_{2}$ thin films and their photocatalytic properties[J]. Materials Research Express, 2017,4(10):106406.
[22]	Wang T, Tang J, Wu S C, et al. Preparation of ordered mesoporous WO$_{3}$-TiO$_{2}$ films and their performance as functional Pt supports for synergistic photoelectrocatalytic methanol oxidation[J]. Journal of Power Sources, 2014,248:510-516.
[23]	Wu R F, Shen S Y, Xia G F, et al. Soft-templated self-assembly of mesoporous anatase TiO$_{2}$/Carbon composite nanospheres for high-performance lithium ion batteries[J]. ACS Applied Material Interfaces, 2016,8(31):19968-19978.
[24]	陈思. TiO$_{2}$ 光催化剂在废水处理中应用的研究进展[J]. 辽宁化工, 2017,46(5):479-481.
	Chen S. Research progress application of TiO$_{2}$ photocatalysts in wastewater trratment [J]. Liaoning Chemical Industry, 2017,46(5):479-481.
[25]	Ângelo J, Andrade L, Medeira L M, et al. An overview of photocatalysis phenomena applied to NO$_x$ abatement[J]. Journal of Environmental Management, 2013,129:522-539. doi: 10.1016/j.jenvman.2013.08.006 pmid: 24018117
[26]	Padoin N, Soares C. An explicit correlation for optimal TiO$_{2}$ film thickness in immobilized photocatalytic reaction systems[J]. Chemical Engineering Journal, 2017,310:381-388. doi: 10.1016/j.cej.2016.06.013
[27]	Chang X F, Gondal M A Al-Saadi A A, et al. Photodegradation of Rhodamine B over unexcited semiconductor compounds of BiOCl and BiOBr[J]. Journal of Colloid and Interface Science, 2012,377:291-298. doi: 10.1016/j.jcis.2012.03.021 pmid: 22537655
[28]	Zhao H P, Zhang Y F, Li G F, et al. Rhodamine B-sensitized BiOCl hierarchical nanostructure for methyl orange photodegradation[J]. RSC Advance, 2016,6(10):7772-7779.
[29]	Shen J S, Yu T, Xie J W, et al. Photoluminescence of CdTe nanocrystals modulated by methylene blue and DNA. A label-free luminescent signaling nanohybrid platform[J]. Physical Chemistry Chemical Physics, 2009,11(25):5062-5069. doi: 10.1039/b900053d pmid: 19562136
[30]	Basu K, Benetti D, Zhao H G, et al. Enhanced photovoltaic properties in dye sensitized solar cells by surface treatment of SnO$_{2}$ photoanodes[J]. Scientific Reports, 2016,6:1-10. doi: 10.1038/s41598-016-0001-8 pmid: 28442746
[31]	Bak T, Nowotny J, Rekas M, et al. Photo-electrochemical hydrogen generation from water using solar energy. Materials-related aspects[J]. International Journal of Hydrogen Energy, 2002,27(10):991-1022.
[32]	Dorenbos P. The electronic structure of lanthanide impurities in TiO$_{2}$, ZnO, SnO$_{2}$ and related compounds[J]. ECS Journal of Solid State Science and Technology, 2014,3:19-24.
[33]	Cheng C, Amini A, Zhu C, et al. Enhanced photocatalytic performance of TiO$_{2}$-ZnO hybrid nanostructures[J]. Scientific Reports, 2014,4:1-5.
[34]	Hoye R L Z, Ehrler B, Böhm M, et al. Improved open-circuit voltage in ZnO-PbSe quantum dot solar cells by understanding and reducing losses arising from the ZnO conduction band tail[J]. Advanced Energy Materials, 2014,4:1-6. doi: 10.1002/aenm.201400054 pmid: 26190956
[35]	Quemener V, Alnes M, Vines L, et al. The work function of $n$-ZnO deduced from heterojunctions with Si prepared by ALD[J]. Journal Physical D: Applied Physics, 2012,45(31):1-5.
[36]	Surendar T, Kumar S, Shanker V. Influence of La-doping on phase transformation and photocatalytic properties of ZnTiO$_{3}$ nanoparticles synthesized via modified sol-gel method[J]. Physical Chemistry Chemical Physsics, 2014,16(2):728-735.