光催化剂TiO2改性的研究进展

doi:10.16085/j.issn.1000-6613.2016.08.22

摘要/Abstract

摘要： TiO₂具有光催化性能好、化学性质稳定、毒性低、价格低廉等优点，但由于禁带较宽，只对紫外光有响应，且电子和空穴容易复合，导致光催化活性和效率降低。本文介绍了TiO₂的几种主要改性方法的最新研究进展。表面沉积贵金属、半导体复合、染料敏化可以降低TiO₂的禁带宽度，增加其响应波长，提高太阳光的利用率。离子掺杂可使得TiO₂晶体表面产生缺陷，抑制光生电子和空穴的复合，增加表面活性中心的数量。碳纳米管和石墨烯掺杂则能够提高TiO₂对可见光的吸收率，扩大光响应范围，同时加快电子传输，减少载流子复合，提高催化效率。指出石墨烯作为新型掺杂材料具有很大的发展潜力，TiO₂基多组分复合型光催化剂可获得比单种组分表面改性或者掺杂TiO₂更好的效果。最后介绍了TiO₂表面的亲/疏水改性研究进展。

关键词: 催化剂, 二氧化钛, 活性, 表面改性, 掺杂

Abstract: TiO₂ has such advantages as excellent photocatalytic performance,high chemical stability,low toxicity and price. However,it only responds to UV light due to its wide forbidden band,and the electrons and holes are prone to recombination,leading to a decrease of catalytic activity and efficiency. This paper introduced the latest research progress on several main modification methods of TiO₂. Surface deposition of noble metal,semiconductor composite and dye sensitization can reduce the width of the forbidden band,increase the response wavelength and make full use of the sunlight. Ion doping can make TiO₂ crystal surface generate the defects,restrain the recombination of photoproduction electrons and holes,and increase the number of surface active centers. Carbon nanotube and graphene modification can improve light absorption of TiO₂to the visible,extend the response range, speed up the electronic transmission,reduce the carrier recombination,and upgrade the catalytic efficiency. As a new doping material graphene has great potentials,and TiO₂-based multi-components composite photocatalysts are promising to achieve better catalytic properties than single-component surface modified or doped TiO₂. Finally,research progress on hydrophilic/hydrophobic surface modification of TiO₂ was reviewed.

Key words: catalyst, titanium oxide, reactivity, surface modification, doping

中图分类号:

刘文芳, 周汝利, 王燕子 . 光催化剂TiO₂改性的研究进展[J]. 化工进展, 2016, 35(08): 2446-2454.

LIU Wenfang, ZHOU Ruli, WANG Yanzi. Research progress on modification of TiO₂ photocatalyst[J]. Chemical Industry and Engineering Progree, 2016, 35(08): 2446-2454.

参考文献

[1] FUJISHIMA A,HONDA K. Electrochemical photolysis of water at a semiconductor electrode[J]. Nature,1972,238:37-38.
[2] ZHANG J,WU W C,YAN S,et al. Enhanced photocatalytic activity for the degradation of rhodamine B by TiO₂ modified with Gd₂O₃ calcined at high temperature[J]. Applied Surface Science,2015,344:249-256.
[3] MICHA T. Scaling properties in photocatalysis[J]. Catalysis Today,2000,58(2/3):151-159.
[4] MELE G,ANNESE C,D'ACCOLTI L,et al. Photoreduction of carbon dioxide to formic acid in aqueous suspension:a comparison between phthalocyanine/TiO₂ and porphyrin/TiO₂ catalysed processes[J]. Molecules,2015,20(1):396-415.
[5] SUBRAMANIAN V,WOLF E E,KAMAT P V. Catalys is with TiO₂/gold nanocomposites,effect of metal particle size on the Fermi level equilibration[J]. Journal of American Chemical Society,2004,126(15):4943-4950.
[6] 张金龙,陈锋,何斌. 光催化[M]. 上海:华东理工大学出版社,2004:35-37,87-89.
[7] ABDELAAL M Y,MOHAMED R M. Novel Pd/TiO₂ nanocomposite prepared by modified sol-gel method for photocatalytic degradation of methylene blue dye under visible light irradiation[J]. Journal of Alloys and Compounds,2013,576:201-207.
[8] ROSSELER O,ULHAQ-BOUILLET C,BONNEFONT A,et al. Structural and electronic effects in bimetallic PdPt nanoparticles on TiO₂ for improved photocatalytic oxidation of CO in the presence of humidity[J]. Applied Catalysis B:Environmental,2015,166:381-392.
[9] TAN L L,ONG W J,CHAI S P,et al. Noble metal modified reduced graphene oxide/TiO₂ ternary nanostructures for efficient visible-light-driven photoreduction of carbon dioxide into methane[J]. Applied Catalysis B:Environmental,2015,166:251-259.
[10] 于濂清,张志萍,周小岩,等. Ag改性TiO₂纳米管阵列的光电化学性能研究[J]. 中国石油大学学报(自然科学版),2015,39(3):183-187.
[11] 徐荣,葛骁,郭海宁,等. 银钛共负载型光催化材料降解甲基橙废水[J]. 环境工程学报. 2014,8(1):150-156.
[12] MIRGHANI M,ALMUBAIYEDH U A,NASSER M S,et al. Experimental study and modeling of photocatalytic reduction of Pb²⁺ by WO₃/TiO₂ nanoparticles[J]. Separation and Purification Technology,2015,141:285-293.
[13] SUN H,DONG B H,SU G,et al. Towards TiO₂ nanotubes modified by WO₃ species:influence of ex situ crystallization of precursor on the photocatalytic activities of WO₃/TiO₂ composites[J]. Journal of Physics D:Applied Physics,2015,48(35):1-9.
[14] ZHANG L Q,GAO Z F,LIU C,et al. Synthesis of TiO₂ decorated Co₃O₄ acicular nanowire arrays and their application as an ethanol sensor[J]. Journal of Materials Chemistry A,2015,3(6):2794-2801.
[15] LI Y P,WANG B W,LIU S H,et al. Synthesis and characterization of Cu₂O/TiO₂ photocatalysts for H₂ evolution from aqueous solution with different scavengers[J]. Applied Surface Science,2015,324:736-744.
[16] LI C Z,TANG J,SUN X L,et al. Synthesis of graphene/Ni/TiO₂/CNTs composites and photocatalytic activities[J]. Journal of Inorganic Materials,2014,29(10):1061-1066.
[17] 李莉,王丽丽,赵月红,等. 3DOM ZnO/ZrO₂-TiO₂(P123)紫外光催化降解甲基橙[J]. 齐齐哈尔大学学报,2013,29(5):17-19.
[18] 赵阳阳. Ag-AgBr/载体复合光催化剂的制备及其在偶氮染料废水降解中的应用[D]. 上海:华东师范大学化学系,2013.
[19] GAO H Z,WANG H E,JIN Y L,et al. Controllable fabrication of immobilized ternary CdS/Pt-TiO₂ heteronanostructures toward high-performance visible-light driven photocatalysis[J]. Physical Chemistry Chemical Physics,2015,17(27):17755-17761.
[20] 王俏,王威,崔福义,等. 二氧化钛纳米管的制备、改性及应用[J]. 化工进展,2015,34(5):1311-1316.
[21] 苗慧,崔玉民,张坤. 二氧化钛光催化活性[M]. 北京:化学工业出版社,2014:56.
[22] RUAN C H,ZHANG L F,YELING Q L,et al. Synthesis of porphyrin sensitized TiO₂/graphene and its photocatalytic property under visible light[J]. Materials Letters,2015,141:362-365.
[23] 王晨. 卟啉和金属卟啉的设计合成及其作为光敏剂敏化TiO₂的研究[D]. 西安:西北大学,2009.
[24] 蔡金华,黄锦汪,叶元坚,等. 卟啉敏化二氧化钛复合微球的制备及其光催化性能[J]. 催化学报,2009,30(5):440-446.
[25] YAMAMOTO A,MIZUNO Y,TERAMURA K,et al. Visible-light-assisted selective catalytic reduction of NO with NH₃ on porphyrin derivative-modified TiO₂ photocatalysts[J]. Catalysis Science & Technology,2015,5(1):556-561.
[26] 吕陈秋. 新型TiO₂光催化剂用于NADH再生的研究[D]. 天津:天津大学,2005.
[27] 杜雪岩,王峭,续京,等. 曙红,叶绿素铜三钠共敏化TiO₂纳米颗粒的光催化性能[J]. 材料导报B:研究篇,2014,28(1):46-50.
[28] 付宁,吕功煊. 杂多蓝在可见光照射下对TiO₂的光敏作用研究[J]. 化学学报,2007,65(14):1325-1332.
[29] SERIANI N,PINILLA C,CRESPO Y. Presence of gap states at Cu/TiO₂ anatase surfaces:consequences for the photocatalytic activity[J]. Journal of Physical Chemistry C,2015,119(12):6696-6702.
[30] 李英柳,李爱莲,吴凤丽. Fe³⁺改性TiO₂光催化降解甲醛废水试验研究[J]. 江苏工业学院学报,2006,18(2):19-21.
[31] ZHANG X L,LI Y C,DI L B,et al. Preparation and properties of co-doped TiO₂ with assistance of ionic liquid[J]. Journal of Inorganic Materials,2014,29(8):801-806.
[32] 段萍,罗玉萍,刘健梅,等. Co掺杂TiO₂光催化剂的研究[J]. 功能材料,2014,45(12):12074-12078.
[33] VARGAS D X M,DE LA ROSA J R,LUCIO-ORTIZ C J,et al. Photocatalytic degradation of trichloroethylene in a continuous annular reactor using Cu-doped TiO₂ catalysts by sol-gel synthesis[J]. Applied Catalysis B-Environmental,2015,179:249-261.
[34] 魏健,沈常宇,代凯. 铒掺杂二氧化钛制备及其光催化性能研究[J]. 中国计量学院学报,2015,26(1):80-86.
[35] VILLABONALEAL E G,LOPEZNEIRA J P,PEDRAZAAVELLA J A,et al. Screening of factors influencing the photocatalytic activity of TiO₂:Ln (Ln = La,Ce,Pr,Nd,Sm,Eu and Gd) in the degradation of dyes[J]. Computational Materials Science,2015,107:48-53.
[36] ZHANG P,GUO J L,ZHAO P,et al. Promoting effects of lanthanum on the catalytic activity of Au/TiO₂ nanotubes for CO oxidation[J]. Rsc Advances,2015,5(16):11989-11995.
[37] ZHANG H,LV A J,LIANG J S,et al. The preparation of TiO₂ composite materials modified with Ce and tourmaline and the study of their photocatalytic activity[J]. RSC Advances,2015,5(69):55704-55712.
[38] JIANG Z Y,LU C Q,WU H. Photoregeneration of NADH using carbon-containing TiO₂[J]. Industrial & Engineering Chemistry Research,2005,44(12):4165-4170.
[39] 刘健梅,朱忠其,张瑾,等. S掺杂改性TiO₂光催化剂的研究[J]. 功能材料,2014,45(1):1006-1010.
[40] SHI Q,YANG D,JIANG Z,et al. Visible-light photocatalytic regeneration of NADH using P-doped TiO₂ nanoparticles[J]. Journal of Molecular Catalysis B:Enzymatic,2006,43(1/2/3/4):44-48.
[41] CHEN D,YANG D,WANG Q,et al. Effects of boron doping on photocatalytic activity and microstructure of titanium dioxide nanoparticles[J]. Industrial & Engineering Chemistry Research,2006,45(12):4110-4116.
[42] 段萍,刘健梅,罗玉萍,等. 硫掺杂TiO₂光催化剂的研究[J]. 功能材料,2014,45(22):22036-22040.
[43] WANG H Q,YANG X F,XIONG W F,et al. Photocatalytic reduction of nitroarenes to azo compounds over N-doped TiO₂:relationship between catalysts and chemical reactivity[J]. Research on Chemical Intermediates,2015,41(6):3981-3997.
[44] 张新亚,宋子健,周府治,等. 氟氮共掺杂二氧化钛/还原氧化-石墨烯复合光催化剂的制备及其可见光催化性能[J]. 硅酸盐学报,2015,43(7):919-925.
[45] WANG X F,YU R,WANG P,et al. Co-modification of F- and Fe(Ⅲ) ions as a facile strategy towards effective separation of photogenerated electrons and holes[J]. Applied Surface Science,2015,351:66-73.
[46] 李张君. N掺杂和N-Fe共掺杂TiO₂薄膜的制备及光催化性能的研究[D]. 太原:太原理工大学,2014.
[47] LIU S Y,TANG W H,FENG Q G,et al. Synthesis of N,Fe Co-doped TiO₂ nanomaterials via solid state reaction and their photodegradation of quinoline irradiated under visible light[J]. Journal of Inorganic Materials,2010,25(9):921-927.
[48] 刘健梅,段萍,肖斌,等. 碳掺杂TiO₂光催化剂的制备与性能研究[J]. 功能材料,2014,45(21):21035-21039.
[49] 谭习有,黎华玲,彭洪亮,等. 石墨烯制备新技术及其在燃料电池催化剂中的应用[J]. 化工进展,2013,32(s1):158-166.
[50] 肖淑娟,于守武,谭小耀. 石墨烯类材料的应用及研究进展[J]. 化工进展,2015,34(5):1345-1348.
[51] MOHAMED R M,MKHALID I A. Visible light photocatalytic degradation of cyanide using Au-TiO₂/multi-walled carbon nanotube nanocomposites[J]. Journal of Industrial and Engineering Chemistry, 2015,22:390-395.
[52] HU J,LI H,WU Q,et al. Synthesis of TiO₂ nanowire/reduced graphene oxide nanocomposites and their photocatalytic performances[J]. Chemical Engineering Journal,2015,263:144-150.
[53] 朱冬韵,廖高祖,唐仲豪,等. 二氧化钛/石墨烯光催化降解草酸的研究[J]. 华南师范大学学报(自然科学版),2015,47(2):67-71.
[54] RONG X S,QIU F X,ZHANG C,et al. Preparation of Ag-AgBr/TiO₂ graphene and its visible light photocatalytic activity enhancement for the degradation of polyacrylamide[J]. Journal of Alloys and Compounds,2015,639:153-161.
[55] 黄伟欣,黄洪. 改性纳米TiO₂薄膜超亲水性的研究进展[J]. 材料开发与应用,2008,23(6):71-75.
[56] BANERJEE S,DIONYSIOU D D,PILLAI S C. Self-cleaning applications of TiO₂ by photo-induced hydrophilicity and photocatalysis[J]. Applied Catalysis B-Environmental,2015,176:396-428.
[57] ZHOU Y,LI M Y,ZHONG X,et al. Hydrophobic composite coatings with photocatalytic self-cleaning properties by micro/nanoparticles mixed with fluorocarbon resin[J]. Ceramics International,2015,41(4):5341-5347.
[58] WU Y P,ZHOU Z H,TUO Y F,et al. A transparent CNTs/TiO₂ composite film with superhydrophobic and photocatalytic functions self-assembled by liquid-phase deposition[J]. Materials Chemistry and Physics,2015,149:522-529.
[59] QI D Y,XING M Y,ZHANG J L. Hydrophobic carbon-doped TiO₂/MCF-F composite as a high performance photocatalyst[J]. Journal of Physical Chemistry C,2014,118(14):7329-7336.

光催化剂TiO₂改性的研究进展

Research progress on modification of TiO₂ photocatalyst

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