宏观尺寸大孔-介孔TiO_2-SiO_2光催化剂的制备及其在染料降解中的应用
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摘要
以柱撑式环氧树脂大孔聚合物为模板,制备宏观尺寸的大孔-介孔SiO_2;以其为载体,通过钛酸四丁酯原位水解和高温焙烧制得大孔-介孔TiO_2纳米晶-SiO_2复合材料。应用SEM、TEM、XRD、FTIR和N_2吸附-脱附法对材料进行表征。以偶氮荧光桃红为模拟污染物,用氙灯模拟日光光源,考察了不同条件下大孔-介孔TiO_2-SiO_2的光催化性能。结果表明,大孔-介孔SiO_2具有三维连续贯通的大孔孔道,孔壁为连续的纳米SiO_2薄膜;TiO_2纳米晶以纳米薄膜的形式均匀地原位生长在SiO_2纳米薄膜的两侧,得到的复合材料孔壁上存在丰富的介孔。当焙烧温度为600℃、TiO_2的负载量为15.7wt%、染料溶液浓度为10mg·L~(-1)且pH为3时,大孔-介孔TiO_2-SiO_2光催化剂对污染物的光催化降解效率最高,而且具有良好的重复使用性。
The macro-sized macro-mesoporous SiO_2 was prepared by using apillared epoxy resin macroporous polymer as the template and it was used as support to prepare macro-mesoporous TiO_2 nanocrystalline-SiO_2 composite through an in situ hydrolysis of tetrabutyl titanate and a subsequent calcination at high temperature.The macro-mesoporous TiO_2-SiO_2 samples were characterized by SEM,TEM,XRD,FTIR and N_2 adsorption-desorption.Using azophloxine as a simulated pollutant,the photocatalytic activity of the macro-mesoporous TiO_2-SiO_2 was studied under the sunlight irradiation simulated by Xenon lamp under different conditions.The results show that the macromesoporous SiO_2 has 3D continuous pass-through macropore structure and its pore wall is continuous SiO_2 nanofilm.TiO_2 nanocrystallines,in the form of nano-film,in situ grow uniformly on both sides of the nano SiO_2 film,and abundant mesopores were observed on the pore wall of the obtained macro-mesoporous TiO_2-SiO_2 composite.The macro-mesoporous TiO2-SiO_2 photocatalyst exhibits the best activity for photocatalytic degradation of pollutant from the macro-mesoporous TiO2-SiO_2 composite containing 15.7 wt% of TiO_2 calcined at 600℃,under the conditions of azophloxine concentration 10 mg·L~(-1) and pH of 3.The macro-mesoporous TiO_2-SiO_2 photocatalyst also has good reusability.
The macro-sized macro-mesoporous SiO_2 was prepared by using apillared epoxy resin macroporous polymer as the template and it was used as support to prepare macro-mesoporous TiO_2 nanocrystalline-SiO_2 composite through an in situ hydrolysis of tetrabutyl titanate and a subsequent calcination at high temperature.The macro-mesoporous TiO_2-SiO_2 samples were characterized by SEM,TEM,XRD,FTIR and N_2 adsorption-desorption.Using azophloxine as a simulated pollutant,the photocatalytic activity of the macro-mesoporous TiO_2-SiO_2 was studied under the sunlight irradiation simulated by Xenon lamp under different conditions.The results show that the macromesoporous SiO_2 has 3D continuous pass-through macropore structure and its pore wall is continuous SiO_2 nanofilm.TiO_2 nanocrystallines,in the form of nano-film,in situ grow uniformly on both sides of the nano SiO_2 film,and abundant mesopores were observed on the pore wall of the obtained macro-mesoporous TiO_2-SiO_2 composite.The macro-mesoporous TiO2-SiO_2 photocatalyst exhibits the best activity for photocatalytic degradation of pollutant from the macro-mesoporous TiO2-SiO_2 composite containing 15.7 wt% of TiO_2 calcined at 600℃,under the conditions of azophloxine concentration 10 mg·L~(-1) and pH of 3.The macro-mesoporous TiO_2-SiO_2 photocatalyst also has good reusability.
引文
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[26]王婷,严孝清,赵士舜,等.三维有序介孔/大孔TiO_2微球的制备、表征及光催化性能[J].分子催化,2014(4):359-366.WANG T,YAN X Q,ZHAO S S,et al.Preparation,Characterization and photocatalytic activity of three-dimensionally ordered mesoporous/macroporous TiO_2 microspheres[J].Journal of Molecular Catalysis(China),2014,28(4):359-366(in Chinese).
[27]ZHANG H,ZHANG L,DENG J,et al.Dual templating preparation and enhanced low temperature reducibility of three-dimensionally ordered macroporous ceria with mesoporous walls[J].Chinese Journal of Catalysis,2011,32(5):842-852.
[28]YU X,LIU S,YU J.Superparamagneticγ-Fe2O3@SiO_2@TiO_2,composite microspheres with superior photocatalytic properties[J].Applied Catalysis B:Environmental,2011,104(1):12-20.
[29]WANG X,SL,REN S,et al.The influence of crystallite size and crystallinity of anatase nanoparticles on the photodegradation of phenol[J].Journal of Catalysis,2014,310(2):100-108.
[30]易筱筠,李新军,古国榜,等.有机染料在TiO_2上的吸附及对光催化降解的影响[J].华南理工大学学报,2002,30(9):23-26.YI X Y,LI X J,GU G B,et al.Adsorption of organic dyes on TiO_2and its effect on photocatalytic degradation[J].Journal of South China University of Technology,2002,30(9):23-26(in Chinese).
[2]ZHOU S,LV J,GUO L K,et al.Preparation and photocatalytic properties of N-doped nano-TiO_2/muscovite composites[J].Applied Surface Science,2012,258(16):6136-6141.
[3]DONG F,WANG H,SEN G,et al.Enhanced visible light photocatalytic activity of novel Pt/C doped TiO_2/PtCl4threecomponent nanojunction system for degradation of toluene in air[J].Journal of Hazardous Materials,2011,187(1-3):509-516.
[4]WANG J,ZHANG P,LI X,et al.Synchronical pollutant degradation and H2,production on a Ti 3+-doped TiO_2,visible photocatalyst with dominant(001)facets[J].Applied Catalysis B:Environmental,2013,134-135(9):198-204.
[5]CHEN Z,LI D,ZHANG W,et al.Photocatalytic degradation of dyes by ZnIn2S4 microspheres under visible light irradiation[J].Journal of Physical Chemistry C,2009,113(11):4433-4440.
[6]胡海霞,朱曜峰,董余兵,等.纳米TiO_2/涤纶海岛丝针刺无纺布光催化复合材料的制备及性能[J].复合材料学报,2018,35(11):3172-3179.HU H X,ZHU Y F,DONG Y B,et al.Preparation and properties of photocatalytic composites of nanoTiO_2/polyester sea-island filament needle punched nonwoven[J].Acta Materiae Compositae Sinica,2018,35(11):3172-3179(in Chinese).
[7]WANG Q,CHEN C,ZHAO D,et al.Change of adsorption modes of dyes on fluorinated TiO_2and its effect on photocatalytic degradation of dyes under visible irradiation.[J].Langmuir the ACS Journal of Surfaces&Colloids,2008,24(14):7338-7345.
[8]姚志强,李惠娟,周徐胜,等.TiO_2/蒙脱土复合材料的制备及光催化降解苯酚性能[J].复合材料学报,2015,32(6):1581-1589.YAO Z Q,LI H J,ZHOU X S,et al.Preparation and photocatalysis degradation performances forphenol of TiO_2/montmorillonite composites[J].Acta Materiae Compositae Sinica,2015,32(6):1581-1589(in Chinese).
[9]郭宇,金玉家,吴红梅,等.负载型二氧化钛光催化材料的制备及其光催化性能研究[J].光谱学与光谱分析,2015,35(6):1677-1681.GUO Y,JIN J Y,WU H M,et al.Preparation and photocatalytic properties of supported TiO_2photocatalytic material[J].Spectroscopy and Spectral Analysis,2015,35(6):1677-1681(in Chinese).
[10]胡小龙,孙青,徐春宏,等.纳米TiO_2/沸石复合材料光催化降解苯酚的性能[J].化工进展,2016,35(5):1519-1523.HU X L,SU Q,XU C H,et al.Photocatalytic degradation of phenol with nano-TiO_2/zeolite composite material[J].Chemical Industry and Engineering Progress 2016,35(5):1519-1523(in Chinese).
[11]ZHANG H,LI K,SUN T,et al.Removal of styene using dielectric barrier discharge plasma combined with solgel prepared TiO_2,coatedγ-Al2O3[J].Chemical Engineering Journal,2014,241:92-102.
[12]SHI J W,CUI H J,CHEN J W,et al.TiO_2/activated carbon fibers photocatalyst:Effects of coating procedures on the microstructure,adhesion property,and photocatalytic ability[J].Journal of Colloid and Interface Science,2012,388(1):201-208.
[13]FARRUSSENG D,TUEL A.Perspectives on zeolite-encapsulated metal nanoparticles and their applications in catalysis[J].Cheminform,2016,40(5):3933-3949.
[14]SILVESTRI S,HENNEMANN B,ZANATTA N,et al.Photocatalytic efficiency of TiO_2,supported on raw red clay disks to discolour reactive red 141[J].Water Air&Soil Pollution,2018,229(2):40.
[15]RESENDE S F,NUNES E H M,HOUMARD M,et al.Simple sol-gel process to obtain silica-coated anatase particles with enhanced TiO_2-SiO_2,interfacial area[J].Journal of Colloid&Interface Science,2014,433(11):211-217.
[16]TANG R,ZHOU S,YUAN Z,et al.Metal-organic framework derived Co3O4/TiO_2/Si heterostructured nanorod array photoanodes for efficient photo-electrochemical water oxidation[J].Advanced Functional Materials,2017,27(37):1701102.
[17]龙能兵,张瑞丰.大尺寸TiO_2/SiO_2大孔材料的制备及光降解性能[J].无机化学学报,2009,25(7):1153-1158.LONG N B,ZHANG R F,Preparation and photo-degradation of large-sized TiO_2/SiO_2macroporous materials[J].Chinese Journal of Inorganic Chemistry,2009,25(7):1153-1158(in Chinese).
[18]KAPRIDAKI C,PINHO L,MOSQUERA M J,et al.Producing photoactive,transparent and hydrophobic SiO_2-crystalline TiO_2,nanocomposites at ambient conditions with application as self-cleaningcoatings[J].Applied Catalysis B:Environmental,2014,s156-157(6):416-427.
[19]CHANG W,YAN L,LIU B,et al.Photocatalyic activity of double pore structure TiO_2/SiO_2 monoliths[J].Ceramics International,2017,43(8):5881-5886.
[20]KAMEGAWA T,ISHIGURO Y,SETO H,et al.Enhanced photocatalytic properties of TiO_2-loadedporous silica with hierarchical macroporous and mesoporous architectures in water purification[J].Journal of Materials Chemistry A,2015,3(5):2323-2330.
[21]LIAO Z H,CHEN J J,YAO K F,et al.Progress of nanometer-TiO_2photocatalyst immobilization[J].Journal of Inorganic Materials,2004,19(1):17-24.
[22]GUO N,IANG Y L,LAN S,et al.Uniform TiO_2-SiO_2hollow nanospheres:Synthesis,characterization and enhanced adsorption photodegradation of azodyes and phenol[J].Applied Surface Science,2014,305:562-574.
[23]DONG W,SUN Y,MA Q,et al.Excellent photocatalytic degradation activities of ordered mesoporous anatase TiO_2-SiO_2nanocomposites to various organic contaminants.[J].Journal of Hazardous Materials,2012,229-230:307-320.
[24]李笑迎,白文静,陶凯,等.大孔/介孔多级孔SiO_2的制备及其在固定化脂肪酶中的应用[J].材料导报,2018,32(10):1695-1700+1715.LI X Y,BAI W J,TAO K,et al.Preparation of hierarchical macroporous silica and its application in lipase immobilization[J].Materials Review,2018,32(10):1695-1700+1715(in Chinese).
[25]郭兴忠,李文彦,朱阳,等.溶胶-凝胶伴随相分离制SiO_2多孔块体[J].物理化学学报,2013,29(3):646-652.GUO X Z,LING W Y,ZHU Y,et al.Macroporous SiO_2monoliths prepared via sol-gel process accompanied by phase separatioo[J].Acta Physico-Chimica Sinica,2013,29(3):646-652(in Chinese).
[26]王婷,严孝清,赵士舜,等.三维有序介孔/大孔TiO_2微球的制备、表征及光催化性能[J].分子催化,2014(4):359-366.WANG T,YAN X Q,ZHAO S S,et al.Preparation,Characterization and photocatalytic activity of three-dimensionally ordered mesoporous/macroporous TiO_2 microspheres[J].Journal of Molecular Catalysis(China),2014,28(4):359-366(in Chinese).
[27]ZHANG H,ZHANG L,DENG J,et al.Dual templating preparation and enhanced low temperature reducibility of three-dimensionally ordered macroporous ceria with mesoporous walls[J].Chinese Journal of Catalysis,2011,32(5):842-852.
[28]YU X,LIU S,YU J.Superparamagneticγ-Fe2O3@SiO_2@TiO_2,composite microspheres with superior photocatalytic properties[J].Applied Catalysis B:Environmental,2011,104(1):12-20.
[29]WANG X,SL,REN S,et al.The influence of crystallite size and crystallinity of anatase nanoparticles on the photodegradation of phenol[J].Journal of Catalysis,2014,310(2):100-108.
[30]易筱筠,李新军,古国榜,等.有机染料在TiO_2上的吸附及对光催化降解的影响[J].华南理工大学学报,2002,30(9):23-26.YI X Y,LI X J,GU G B,et al.Adsorption of organic dyes on TiO_2and its effect on photocatalytic degradation[J].Journal of South China University of Technology,2002,30(9):23-26(in Chinese).