TiO_2与金属氧化物复合气凝胶能带结构和光催化性质的研究
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摘要
本文采用溶胶法制备TiO_2以及PdO、NiO、SnO_2和SiO_2分别与TiO_2复合的溶胶,利用浸渍提拉法制备TiO_2、PdO/TiO_2、SnO_2/TiO_2、NiO/TiO_2和SnO_2/SiO_2/TiO_2复合气凝胶,并通过薄膜对亚甲基蓝的光降解效率研究添加不同能带结构类型的金属氧化物(MO_x)对TiO_2光催化性能的影响,探索金属氧化物与TiO_2的能带结构.实验结果表明:TiO_2复合气凝胶中金属氧化物的价带和导带电位都应高于TiO_2的价带和导带电位,使TiO_2的价带电子易被激发迁移到金属氧化物的导带上,空穴则留在TiO_2的价带上,这样的能带结构匹配才能够实现电子和空穴的更有效分离,降低复合几率,从而能够较大程度地提高复合气凝胶的光催化效率.
The TiO_2,PdO/TiO_2,SnO_2/TiO_2,NiO/TiO_2 and SnO_2/SiO_2/TiO_2 were prepared using sols in the paper. The MOx/TiO_2 composite aerogels were prepared using sol-gel preceding and dip-drawing method.Based on the photocatalytic degradation of methylene blue by MOx/TiO_2 composite films,the photocatalytic mechanisms of MOx/TiO_2 composite aerogels were explored. The results demonstrated that the potentials of both valence band and conduction band of metallic oxides are higher than those of TiO_2,which leads to the efficient separation of photo-generated holes and electrons and the lower recombination rate of electrons and holes. Thus,the photocatalytic efficiency of metallic oxide doped TiO_2 aerogels would be higher.
The TiO_2,PdO/TiO_2,SnO_2/TiO_2,NiO/TiO_2 and SnO_2/SiO_2/TiO_2 were prepared using sols in the paper. The MOx/TiO_2 composite aerogels were prepared using sol-gel preceding and dip-drawing method.Based on the photocatalytic degradation of methylene blue by MOx/TiO_2 composite films,the photocatalytic mechanisms of MOx/TiO_2 composite aerogels were explored. The results demonstrated that the potentials of both valence band and conduction band of metallic oxides are higher than those of TiO_2,which leads to the efficient separation of photo-generated holes and electrons and the lower recombination rate of electrons and holes. Thus,the photocatalytic efficiency of metallic oxide doped TiO_2 aerogels would be higher.
引文
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[2]Wei W.Synthesis of novel inorganic aerogels for adsorption/photocatalytic performance application[D].Jiangsu:Jiangsu University,2014(in Chinese)[魏巍.新型无机气凝胶的制备及其吸附/光催化性能研究[D].江苏:江苏大学,2014]
[3]Zhao Z Q.Prepatation,structure and characterization of transition metal aerogels[D].Jinan:Shan dong University,2008(in Chinese)[赵忠强.氧化物气凝胶的制备、结构和性质的研究[D].济南:山东大学,2008]
[4]Shao X.Preparation of Ti O2/C nano-composite aerogels and their performance as photocatalysts[D].Shanghai:Shanghai University,2013(in Chinese)[邵霞.Ti O2/C纳米复合气凝胶的制备及光催化性能研究[D].上海大学,2013]
[5]Yu J G,Xiong J F,Cheng B.Low-temperature hydrothermal synthesis of Ti O2photocatalyst with high activity[J].Chinese J.Catals,2005,26:74(in Chinese)[余家国,熊建锋,程蓓.高活性二氧化钛光催化剂的低温水热合成[J].催化学报,2005,26:745]
[6]Sun L,Zhai J,Li H,et al.Study of homologous elements:Fe,Co,and Ni dopant effects on the photoreactivity of Ti O2nanosheets[J].Chem Cat Chem,2014,6:339.
[7]Wang Z,Chen C,Wu F,et al.Photodegradation of rhodamine B under visible light by bimetal codoped Ti O2nanocrystals[J].J.Hazard.Maters.,2009,164:615.
[8]Chen L,Weng D,Si Z,et al.Synergistic effect between ceria and tungsten oxide on WO3-Ce O2-Ti O2catalysts for NH3-SCR reaction[J].Prog.Nat.Sci.:Mater.Int.,2012,22:265.
[9]Yun L Z.Study on preparation and performance of iron doped Bi2WO6visible photocatalyst[J].New Chem.Mater.,2016,2:178(in Chinese)[苑丽质.掺铁Bi_2WO_6可见光催化剂的制备及性能研究[J].化工新型材料,2016,2:178]
[10]Wu N.Preparation and photocatalytic performance of polyaniline/titanium/mica multilayer-coated materials[D].Fuzhou:Fujian Normal University,2015(in Chinese)[吴楠.聚苯胺/Ti O2/云母多层包覆材料的制备及其光催化性能[D].福州:福建师范大学,2015]
[11]Huang J,Tang H,Fang R P,et al.Research status of polymer adsorption materials[J].New Chem.Mater.,2014,4:1(in Chinese)[黄剑,唐辉,方瑞萍,等.高分子吸附材料的研究进展[J].化工新型材料,2014,4:1]
[12]Xiao J D,Xie Y B,Nawaz F,et al.Dramatic coupling of visible light with ozone on honeycomb-like porous g-C3N4towards superior oxidation of water pollutants[J].Applied Catalysis B:Environmental.2016,183:417.
[13]Murugan C,Subramanian E,Pathinettam P D.Enhanced sensor functionality of in situ synthesized polyaniline–Sn O2hybrids toward benzene and toluene vapors[J].Sensors&Actuators:B,2014,205:74.
[14]Ma X L,Ning G Q,Sun Y Z,et al.High capacity Li storage in sulfur and nitrogen dual-doped graphene networks[J].Carbon,2014,79:310.
[15]Jing T.The intrinsic defect and doping properties of several photocatalytic from theoretical studies[D].Jinan:Shandong University,2016(in Chinese)[荆涛.几种光催化材料本征缺陷和掺杂性质的理论研究[D].济南:山东大学,2016]
[16]Chen S R.In situ Carbon-decorated Ti02 Photocatalyst:Design,Synthesis,and Catalytic Properties[D].Jiangsu:Jiangsu University,2016(in Chinese)[陈娟荣.原位碳改性Ti O2光催化剂的设计、合成及其催化性能研究[D].江苏:江苏大学,2016]
[17]Ma X Q.The study of the preparation and photocatalytic activity of series Ti O2/PANI photocatalysts[D].Lanzhou:Lanzhou Jiaotong University,2013(in Chinese)[马学琴.Ti O2/PANI系列光催化剂的制备及催化活性研究[D].兰州:兰州交通大学,2013]
[18]Lu D.Preparation of Ti O2@PANI@ferrite magnetic fluid and its photocatalytic activity and magnetic recovery.[D].Lanzhou:Lanzhou Jiaotong University,2015(in Chinese)[卢迪.Ti O2铁氧体光催化磁流体的制备及其光催化与磁回收性能研究[D].兰州:兰州交通大学,2015]
[19]Zhang Y J.Prearation and catalytic performance of metal oxides with porous structures or regular morphologies[D].Beijing:Beijing University of Technology,2016(in Chinese)[张玉娟.多孔或规整形貌金属氧化物制备及其催化性能研究[D].北京:北京工业大学,2016]
[20]Huang H.Preparation modification and photocatalytic activity of ordered mesoporous metal oxide[D].Suzhou:Suzhou University,2014(in Chinese)[黄徽.有序介孔金属氧化物的制备、改性及其光催化性能研究[D].苏州:苏州大学,2014]