纳米二氧化钛热处理过程研究
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摘要
以四氯化钛为原料,采用碱中和法制备水合二氧化钛,然后在不同温度下热处理分别制备锐钛型纳米二氧化钛和金红石型纳米二氧化钛。采用拉曼光谱、XRD和紫外可见光谱等手段分析了热处理过程对样品的晶体结构、比表面积、微孔体积、紫外吸收光谱等性能的影响。试验结果表明,未经热处理的样品存在氧空位缺陷,具有较大的晶格畸变,随着热处理温度的提高,样品晶粒尺寸从6 nm逐渐长大至70 nm,比表面积从186 m~2·g~(-1)减少至5.6 m~2·g~(-1),总孔体积从0.085 cm~3·g~(-1)减小至0.001 3 cm~3·g~(-1),晶型由无定型向锐钛型和金红石相逐步转化,晶格畸变逐渐减小。在600℃以下热处理样品为锐钛型,在600～650℃的温度下处理形成金红石与锐钛的混晶,680～750℃有六钛酸钠生成,800℃以后全部转化为金红石结构。
Titanium tetrachloride was used as raw material to prepare hydrated titanium dioxide by alkali neutralization method,and then anatase nano-TiO_2 and rutile nano-TiO_2 were prepared by heat treatment at different temperatures.The effects of heat treatment on the crystal structure,specific surface area,pore volume and UV absorption spectrum of the sample were analyzed by Raman spectroscopy,XRD and UV-visible spectroscopy,respectively.The experimental results show that the unheated samples have oxygen vacancy defects and have large lattice strain.With increase of the heat treatment temperature,the grain size of the samples grows from 6 nm to 70 nm with the specific surface area decreased from 186 m~2·g~(-1) to 5.6 m~2·g~(-1) and the total pore volume decreased from 0.085 cm~3·g~(-1) to 0.001 3 cm~3·g~(-1),respectively.Meanwhile,the crystal structure gradually transforms from amorphous phase into anatase and rutile phases accompanying gradual decrease of the lattice strain.The samples are composed of anatase phase with heat treatment temperature below 600 ℃,mixture of anatase and rutile phase at 600～650 ℃,and rutile phase with heat treatment temperature higher than 800 ℃.At 680～750 ℃,sodium hexatitanate is formed.
Titanium tetrachloride was used as raw material to prepare hydrated titanium dioxide by alkali neutralization method,and then anatase nano-TiO_2 and rutile nano-TiO_2 were prepared by heat treatment at different temperatures.The effects of heat treatment on the crystal structure,specific surface area,pore volume and UV absorption spectrum of the sample were analyzed by Raman spectroscopy,XRD and UV-visible spectroscopy,respectively.The experimental results show that the unheated samples have oxygen vacancy defects and have large lattice strain.With increase of the heat treatment temperature,the grain size of the samples grows from 6 nm to 70 nm with the specific surface area decreased from 186 m~2·g~(-1) to 5.6 m~2·g~(-1) and the total pore volume decreased from 0.085 cm~3·g~(-1) to 0.001 3 cm~3·g~(-1),respectively.Meanwhile,the crystal structure gradually transforms from amorphous phase into anatase and rutile phases accompanying gradual decrease of the lattice strain.The samples are composed of anatase phase with heat treatment temperature below 600 ℃,mixture of anatase and rutile phase at 600～650 ℃,and rutile phase with heat treatment temperature higher than 800 ℃.At 680～750 ℃,sodium hexatitanate is formed.
引文
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[17] Zhang Zhikun,Cui Zuolin.Nanotechnology and nanomaterials[M].Beijing:Defence Industry Press,2000:69-70.(张志焜,崔作林.纳米技术与纳米材料[M].北京:国防工业出版社,2000:69-70.)
[2] Wu Jianchun,Sun Zuofeng,Huang Wanxia.Research on modifying exterior latex coating with nano-TiO2 and nano-SiO2[J].Iron Steel Vanadium Titanium,2005,26(1):34.(吴健春,孙作凤,黄婉霞.纳米TiO2、SiO2复合改性苯丙外墙乳胶漆的研究[J].钢铁钒钛,2005,26(1):34.)
[3] Zhang Qinghong,Gao Lian.One-step preparation of size-de?ned aggregates of TiO2 nanocrystals with tuning of their phase and composition[J].Journal of the European Ceramic Society ,2006,26 :1535-1545.
[4] Takeshi Morimoto,Hiroyuki Tomonaga,Akemi Mitani.Ultraviolet ray absorbing coatings on glass for automobiles[J].Thin Solid Films,1999,351 :61-65.
[5] Wu Jianchun,Du Jianqiao,Wang Bin,et al.Application of rutile nano-TiO2 in automotive paint[J].Iron Steel Vanadium Titanium,2018,39(6):65-70.(吴健春,杜剑桥,王斌,等.金红石纳米TiO2及其在汽车漆中的应用[J].钢铁钒钛,2018,39(6):65-70.)
[6] Wang Xu,Hu Xiaowen,Liang Jiyu,et al.Preparation of nano-TiO2 and its application in self-cleaning materials[J].China Leather,2018,47(2):28-34,39.)(王旭,胡小稳,梁纪宇,等.纳米二氧化钛的制备及其在自清洁材料的应用[J].中国皮革,2018,47(2):28-34,39.)
[7] Andrew Mills,Richard H Davies,David Worsley1.Water purification by semiconductor photocatalysis[J].Chemical Society Review,1993:417.
[8] Jean-Marie Herrmann,Jean Disdier,Pierre Pichat.Photocatalytic deposition of silver on powder titania:Consequences for the recovery of silver[J].Journal of Catalysis,1988 (113):72-81.
[9] Wei Shaodong,Wang Xing.Research progress of nano-TiO2 preparation by gasphase method[J].China Paint,2005,20(10):29-31.(魏绍东,王杏.气相法制备纳米二氧化钛的研究进展[J].中国涂料,2005,20(10):29-31.)
[10] Wang Lin,Wu Yining,Wang Yan.Study on preparation and characterization of nanometer-sized TiO2 by Sol-Gel method[J].Journal of Harbin University of Commerce (Natural Sciences Edition) ,2006,22(3):76-79.(王琳,吴忆宁,汪炎.溶胶—凝胶法制备纳米二氧化钛及其性能研究[J].哈尔滨商业大学学报(自然科学版),2006,22(3):76-79.)
[11] Niu Xinshu,Xu Yajie,Zhang Xuezhi,et al.Preparation in microemulsion and photocatalytic oxidation properties of nanosized TiO2[J].Journal of Functional Materials,2003,34(5):548-552.(牛新书,许亚杰,张学治,等.微乳液法制备纳米二氧化钛及其光催化活性[J].功能材料,2003,34(5):548-552.)
[12] Qiu Yongliang.Studies on the preparation and modification of photocatalytic activity of titania by hydrothermal method[D].Nanjing:Nanjing University of Technology,2004.(丘永樑.水热法TiO2制备及光活性修饰研究[D].南京:南京工业大学,2004.)
[13] Nam H D,Kim S J,Jung C H,et al.Preparation of ultrafine crystalline TiO2 powders from aqueous TiCl4 solution by precipitation[J].Japanese Journal of Applied Physics,1998,37(8):4603-4608.
[14] Wang Zuyuan,Zhang Fengbao.The study on the preparation of titanium dioxide thin film by liquid phase deposition method[J].Journal of Molecular Catalysis,2003,17(6):421-424.(王祖鹓,张凤宝.二氧化钛薄膜的液相沉积法制备研究[J].分子催化,2003,17(6):421-424.)
[15] Wijn Hoven JEGJ,Vos W L.Preparation of photonic crystals made of air spheres in titania[J].Science,1998,281:802-804.
[16] Brian T H,Christopher F B,Andreas S.Synthesis of macroporous minerals with high lyordered three-dimensional arrays of spheroidal voids[J].Science,1998,281:538-540.
[17] Zhang Zhikun,Cui Zuolin.Nanotechnology and nanomaterials[M].Beijing:Defence Industry Press,2000:69-70.(张志焜,崔作林.纳米技术与纳米材料[M].北京:国防工业出版社,2000:69-70.)