水热法合成二氧化钛纳米管的晶型与形貌控制的研究
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摘要
晶型与形貌的控制对于二氧化钛纳米管的应用具有重要的影响。采用水热法合成了内径约为5~6nm,外径约为9~10 nm,管长为200~300 nm的纳米管。通过XRD、TEM进行表征,研究了TiO_2纳米管在不同焙烧温度的形貌和晶型组成的转化,同时探讨不同粒径和晶相的二氧化钛粉末原料对合成TiO_2纳米管的形貌和晶型的的影响。结果表明:二氧化钛在水热阶段形成无定型结构纳米管,经高温焙烧后结晶度增强,转变成金红石和锐钛矿混合型。当焙烧温度为400℃时,纳米管能维持稳定的管状结构,焙烧温度升高将会导致TiO_2纳米管转变成不同尺寸的纳米棒。不同晶型和粒径的TiO_2合成原料对纳米管形貌和晶型的影响显著,金红石晶型和粒径大的原料有利于纳米管的合成。
The control of crystal type and morphology has important effect on the application of titanium dioxide nanotubes. In this paper,nanotubes with 5~6 nm inner diameter and 9~10 nm outer diameter and 200~300 nm tube length were synthesized by hydrothermal method. The conversion of morphology and crystal structure of titanium dioxide nanotubes at different calcination temperature was studied by using XRD and TEM.And the influence of different particle size and crystal phase of TiO_2 powder on morphology and crystal structure of synthesized TiO_2 nanotubes was investigated. The results showed that amorphous TiO_2 nanotubes were formed in the hydrothermal stage, its crystallinity increased after high-temperature calcination to transform rutile and anatase.The nanotubes maintained stable tubular structure at 400 ℃. The increase of calcination temperature resulted in the conversion of titanium dioxide nanotubes into nanorods of different sizes. The crystal shape and size of titanium dioxide had significant influence on the morphology and crystal form of nanotubes. The rutile crystal and large particle size were good for the synthesis of nanotubes.
The control of crystal type and morphology has important effect on the application of titanium dioxide nanotubes. In this paper,nanotubes with 5~6 nm inner diameter and 9~10 nm outer diameter and 200~300 nm tube length were synthesized by hydrothermal method. The conversion of morphology and crystal structure of titanium dioxide nanotubes at different calcination temperature was studied by using XRD and TEM.And the influence of different particle size and crystal phase of TiO_2 powder on morphology and crystal structure of synthesized TiO_2 nanotubes was investigated. The results showed that amorphous TiO_2 nanotubes were formed in the hydrothermal stage, its crystallinity increased after high-temperature calcination to transform rutile and anatase.The nanotubes maintained stable tubular structure at 400 ℃. The increase of calcination temperature resulted in the conversion of titanium dioxide nanotubes into nanorods of different sizes. The crystal shape and size of titanium dioxide had significant influence on the morphology and crystal form of nanotubes. The rutile crystal and large particle size were good for the synthesis of nanotubes.
引文
[1]谢卫.二氧化钛纳米材料在烟草减害中的应用[M].武汉:华中科技大学出版社,2016-06.
[2]梁建,马淑芳,韩培德,等.二氧化钛纳米管的合成及其表征[J].稀有金属材料与工程,2005,34(2):287-290.
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[6]李雪飞,赵芸,矫庆泽,等.不同Ti O2原料制备一维钛酸盐纳米材料[J].物理化学,2011,27(8):1996-2000.
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[8]黄琮,张开坚,党志,等.钛酸纳米管的制备及TEM表征[J].无机材料学报,2006,21(3):547-552.
[9]孟瑞晋,侯宏英,刘显茜,等.煅烧温度对二氧化钛纳米管阵列的微观结构及锂电性能的影响[J].硅酸盐学报,2015,43(6):817-822.
[10]Spurr R A,Myers H.Quantitative Analysis of Anatase-Rutile Mixtures with an X-ray Diffractometer[J].Anal.Chem,1957,29:760-762.
[11]张青红,高濂,郑珊,等.制备均一形貌的长二氧化钛纳米管[J].化学学报,2002,60(8):1439-1444.
[12]汪静茹,李文尧,姚宝殿,等.水热法制备二氧化钛纳米管:形成机理、影响因素及应用[J].材料导报(综述篇),2016,30(3):144-152.
[13]王鑫,郭翠梨,胡彤宇,等.水热温度和酸洗浓度对水热合成纳米盐纳米管的影响[J].化工新型材料,2013,41(2):123-125.
[14]Lee K,Mazare A,Schmuki P.One-dimensional titanium dioxide nanomaterials:Nanotubes[J].Chemical Reviews,2014,114:9385-9454.
[15]蔡斌,王婷.钛酸纳米管形成过程中不同水热反应阶段产物表征及其对Cd(II)吸附的特性研究[J].北京大学学报(自然科学版),2016,52(6):1141-1147.
[16]滕洪辉,徐淑坤,王继库.超声辅助水热制备超长二氧化钛纳米管[J].稀有金属材料与工程,2014,43(10):2326-2329
[2]梁建,马淑芳,韩培德,等.二氧化钛纳米管的合成及其表征[J].稀有金属材料与工程,2005,34(2):287-290.
[3]Hoyer P.Formation of titanium dioxide nanotube array[J].Langmuir,1996,12:1411-1413.
[4]Bribda B Lakshmi,Charles Patrissi,Charles R Martin.Sol-gel template synthesis of semiconductor oxide micro-and nanostructures[J].J Chem Mater,1997,9(11).
[5]Kasuga T,Hirama Lsu M,Hoson,etal.Titania nanotube prepared by chemical processing[J].Adv Mater,1999,11(15):1307-1311.
[6]李雪飞,赵芸,矫庆泽,等.不同Ti O2原料制备一维钛酸盐纳米材料[J].物理化学,2011,27(8):1996-2000.
[7]Yu J G,Yu H G,Cheng B,et al.Effects of calcination temperature on the microstructures and photocatalytic activity of titanate nanotubes[J].Journal of Molecular Catalysis a-Chemical,2006,249(1-2):135-142.
[8]黄琮,张开坚,党志,等.钛酸纳米管的制备及TEM表征[J].无机材料学报,2006,21(3):547-552.
[9]孟瑞晋,侯宏英,刘显茜,等.煅烧温度对二氧化钛纳米管阵列的微观结构及锂电性能的影响[J].硅酸盐学报,2015,43(6):817-822.
[10]Spurr R A,Myers H.Quantitative Analysis of Anatase-Rutile Mixtures with an X-ray Diffractometer[J].Anal.Chem,1957,29:760-762.
[11]张青红,高濂,郑珊,等.制备均一形貌的长二氧化钛纳米管[J].化学学报,2002,60(8):1439-1444.
[12]汪静茹,李文尧,姚宝殿,等.水热法制备二氧化钛纳米管:形成机理、影响因素及应用[J].材料导报(综述篇),2016,30(3):144-152.
[13]王鑫,郭翠梨,胡彤宇,等.水热温度和酸洗浓度对水热合成纳米盐纳米管的影响[J].化工新型材料,2013,41(2):123-125.
[14]Lee K,Mazare A,Schmuki P.One-dimensional titanium dioxide nanomaterials:Nanotubes[J].Chemical Reviews,2014,114:9385-9454.
[15]蔡斌,王婷.钛酸纳米管形成过程中不同水热反应阶段产物表征及其对Cd(II)吸附的特性研究[J].北京大学学报(自然科学版),2016,52(6):1141-1147.
[16]滕洪辉,徐淑坤,王继库.超声辅助水热制备超长二氧化钛纳米管[J].稀有金属材料与工程,2014,43(10):2326-2329