S掺杂无定形TiO_2的制备及可见光催化活性
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摘要
以硫脲为硫源,采用溶胶-凝胶法和低温煅烧法制备S掺杂二氧化钛(S-TiO_2),用XRD、TEM、XPS、FTIR和UV-vis DRS等方法对其进行表征,以水溶液中甲基橙(MO)为目标污染物,评价了其在可见光(λ>400 nm)下的催化性能。结果表明,300℃条件下制备的S-TiO_2为无定型态,呈不规则表面粗糙的类片状结构;S-TiO~(4+)_2中Ti以Ti~(4+)和Ti~(3+)存在,S分别以S~(6+)和S的氧化态存在并取代TiO_2晶格中部分Ti,形成Ti-O-S结构,缩小了TiO_2的带隙,增强了其在可见光下的光催化活性。S掺杂量对催化活性有一定的影响,S掺杂量为3%的无定形S-TiO_2(300)催化剂对甲基橙有较好的催化降解效果,光生空穴在降解有机物中起重要作用。
Using thiourea as sulfur source,S doped titanium dioxide(S-TiO_2) was synthesized by sol-gel method and low temperature calcination method. The characteristics of photocatalysts were investigated by X-ray diffraction, Transmission electron microscope, X-ray photoelectron spectrometer, Fourier transform infrared and UV-vis diffuse reflection spectroscopy. With Methyl Orange(MO) as target pollutant, the catalytic activity of S-TiO_2 under visible light(λ>400 nm) was evaluated. The results indicate that S-TiO_2 prepared at 300 ℃ is amorphous and has a sheet-like structure in irregular rough surface.Ti exists in S-TiO_2 with Ti~(4+) and Ti~(3+), S exists in the oxidation state of S~(6+) and S~(4+) and replaces part of Ti in the TiO_2 lattice to form Ti-O-S structure, which reduces the band gap of TiO_2 and enhances its photocatalytic activity under visible light. The amount of S doping has a certain effect on the catalytic activity. The amorphous S-TiO_2(300) catalyst with S content of 3% has great catalytic degradation effect on methyl orange. Photogenerated holes play an important role in the degradation of organic matter.
Using thiourea as sulfur source,S doped titanium dioxide(S-TiO_2) was synthesized by sol-gel method and low temperature calcination method. The characteristics of photocatalysts were investigated by X-ray diffraction, Transmission electron microscope, X-ray photoelectron spectrometer, Fourier transform infrared and UV-vis diffuse reflection spectroscopy. With Methyl Orange(MO) as target pollutant, the catalytic activity of S-TiO_2 under visible light(λ>400 nm) was evaluated. The results indicate that S-TiO_2 prepared at 300 ℃ is amorphous and has a sheet-like structure in irregular rough surface.Ti exists in S-TiO_2 with Ti~(4+) and Ti~(3+), S exists in the oxidation state of S~(6+) and S~(4+) and replaces part of Ti in the TiO_2 lattice to form Ti-O-S structure, which reduces the band gap of TiO_2 and enhances its photocatalytic activity under visible light. The amount of S doping has a certain effect on the catalytic activity. The amorphous S-TiO_2(300) catalyst with S content of 3% has great catalytic degradation effect on methyl orange. Photogenerated holes play an important role in the degradation of organic matter.
引文
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[2]Lyu K,Fang S,Si L,et al.Fabrication of TiO2nanorod assembly grafted rGO(rGO@TiO2-NR)hybridized flakelike photocatalyst[J].Applied Surface Science,2017,391:218-227.
[3]Wang D,Xu Y,Sun F,et al.Enhanced photocatalytic activity of TiO2under sunlight by MoS2nanodots modification[J].Applied Surface Science,2016,377:221-227.
[4]Zhang L,Jing D,She X,et al.Heterojunctions in gC3N4/TiO2(B)nanofibres with exposed(001)plane and enhanced visible-light photoactivity[J].Journal of Materials Chemistry A,2014,2(7):2071-2078.
[5]Liang J,Wang N,Zhang Q,et al.Exploring the mechanism of a pure and amorphous black-blue TiO2:H thin film as a photoanode in water splitting[J].Nano Energy,2017,42:151-156.
[6]Shao P,Tian J,Zhao Z,et al.Amorphous TiO2doped with carbon for visible light photodegradation of Rhodamine Band 4-chlorophenol[J].Applied Surface Science,2015,324:35-43.
[7]Di Valentin C,Pacchioni G.Trends in non-metal doping of anatase TiO2:B,C,N and F[J].Catalysis Today,2013,206:12-18.
[8]Zhu M,Zhai C,Qiu L,et al.New method to synthesize S-doped TiO2with stable and highly efficient photocatalytic performance under indoor sunlight irradiation[J].ACSSustainable Chemistry&Engineering,2015,3(12):3123-3129.
[9]Chen Z,Ma J,Yang K,et al.Preparation of S-doped TiO2-three dimensional graphene aerogels as a highly efficient photocatalyst[J].Synthetic Metals,2017,231:51-57.
[10]Huang Z,Gao Z,Gao S,et al.Facile synthesis of S-doped reduced TiO2-xwith enhanced visible-light photocatalytic performance[J].Chinese Journal of Catalysis,2017,38(5):821-830.
[11]Li M,Xing Z,Jiang J,et al.Surface plasmon resonance-enhanced visible-light-driven phocatalysis by Ag nanoparticles decorated S-TiO2-xnanorods[J].Journal of the Taiwan Institute of Chemical Engineers,2018,82:198-204.
[12]陈俊,严非男.S掺杂锐钛矿TiO2电子结构的第一性原理研究[J].上海理工大学学报,2010,32(4):340-344.Chen Jun,Yan Feinan.First-principles study on the electronic structure of S-doped anatase TiO2crystal[J].Journal of University of Shanghai for Science and Technology,2010,32(4):340-344.
[13]Hannula M,Ali-L?ytty H,Lahtonen K,et al.Improved stability of atomic layer deposited amorphous TiO2photoelectrode coatings by thermally induced oxygen defects[J].Chemistry of Materials,2018,30(4):1199-1208.
[14]Liu S,Chen X.A visible light response TiO2photocatalyst realized by cationic S-doping and its application for phenol degradation[J].Journal of Hazardous Materials,2008,152(1):48-55.
[15]Boningari T,Inturi S N R,Suidan M,et al.Novel one-step synthesis of sulfur doped-TiO2by flame spray pyrolysis for visible light photocatalytic degradation of acetaldehyde[J].Chemical Engineering Journal,2018.doi:10.1016/j.cej.2018.01.063.
[16]Chen X,Kuo D H,Lu D.Visible light response and superior dispersed S-doped TiO2nanoparticles synthesized via ionic liquid[J].Advanced Powder Technology,2017,28(4):1213-1220.
[17]Devi L G,Kavitha R.Enhanced photocatalytic activity of sulfur doped TiO2for the decomposition of phenol:a new insight into the bulk and surface modification[J].Materials Chemistry and Physics,2014,143(3):1300-1308.
[18]Han C,Pelaez M,Likodimos V,et al.Innovative visible light-activated sulfur doped TiO2films for water treatment[J].Applied Catalysis B:Environmental,2011,107(1/2):77-87.
[19]Nam S H,Kim T K,Boo J H.Physical property and photocatalytic activity of sulfur doped TiO2catalysts responding tovisiblelight[J].CatalysisToday,2012,185(1):259-262.
[20]Yu J C,Ho W,Yu J,et al.Efficient visible-light-induced photocatalytic disinfection on sulfur-doped nanocrystalline titania[J].Environmental Science and Technology,2005,39(4):1175-1179.
[21]Hassan M S,Amna T,Yang O B,et al.TiO2nanofibers doped with rare earth elements and their photocatalytic activity[J].Ceramics International,2012,38(7):5925-5930.
[22]Zhu M,Zhai C,Qiu L,et al.New method to synthesize S-doped TiO2with stable and highly efficient photocatalytic performance under indoor sunlight irradiation[J].ACSSustainable Chemistry&Engineering,2015,3(12):3123-3129.
[23]Etacheri V,Michlits G,Seery M K,et al.A highly efficient TiO2-xCxnano-heterojunction photocatalyst for visible light induced antibacterial applications[J].ACS Applied Materials&Interfaces,2013,5(5):1663-1672.
[24]McManamon C,O'Connell J,Delaney P,et al.A facile route to synthesis of S-doped TiO2nanoparticles for photocatalytic activity[J].Journal of Molecular Catalysis A:Chemical,2015,406:51-57.
[25]Li F,Zhao Y,Hao Y,et al.N-doped P25 TiO2-amorphous Al2O3composites:one-step solution combustion preparation and enhanced visible-light photocatalytic activity[J].Journal of Hazardous Materials,2012,239:118-127.
[26]Chen Y,Yang S,Wang K,et al.Role of primary active species and TiO2surface characteristic in UV-illuminated photodegradation of Acid Orange 7[J].Journal of Photochemistry and Photobiology A:Chemistry,2005,172(1):47-54.
[27]Li W,Li D,Lin Y,et al.Evidence for the active species involved in the photodegradation process of Methyl Orange on TiO2[J].The Journal of Physical Chemistry C,2012,116(5):3552-3560.
[28]Lyu K,Xu Y.Effects of polyoxometalate and fluoride on adsorption and photocatalytic degradation of Organic Dye X3Bon TiO2:the difference in the production of reactive species[J].The Journal of Physical Chemistry B,2006,110(12):6204-6212.