In this paper, TiO2 nanotube arrays were prepared by anodic oxidation method in HF aqueous solution.The influencing of the parameters for the phase composition and miscrostructure of titania nanotube arrays on the titanium surface were systematicdly studied, such as oxidation voltage, oxidation time, electrolyte concentration, pH value and annealing temperature.The main and secondary factors of the preparation of titanium dioxide nanotube arrays with regularity, uniformity and microstructure were discussed.The results show that: the oxidation voltage and pH value are the determining factors for the formation and regularity of TiO2 nanotube arrays.Smaller pH value is beneficial to the preparation of TiO2 nanotube arrays in a short time, but TiO2 nanotubes tend to fall off the surface of the substrate, which affects the integrity and uniformity of the nanotube arrays.When the oxidation voltage is 15~25 V and the pH value is 4~6, the regulation of microstructure of TiO2 nanotube arrays can be realized.The length, diameter and wall thickness of TiO2 nanotube are mainly affected by the oxidation time and electrolyte concentration.If the range is proper, the microstructure can be controlled by tiny changes.The- DOI:10.3969/j.issn.1000-1565.2017.04.008锐钛型TiO2纳米管阵列的制备及微结构调控仇满德,韩庆娇,崔炎龙,牛苗,杨盼(河北大学 化学与环境科学学院,河北 保定 071002)摘 要:采用阳极氧化法,系统考察了HF体系中氧化电压、氧化时间、质量分数、pH值和退火温度等对钛基表面二氧化钛纳米管阵列形成过程中物相和微观形貌的影响,探讨了制备规整性、均一性及微结构可控的二氧化钛纳米管阵列的主要和次要因素.研究结果表明:氧化电压、pH值是决定TiO2纳米管阵列是否形成与规整性的决定因素.较小的pH值虽然有利于在较短的时间内制备TiO2纳米管阵列,但容易导致基体表面TiO2纳米管脱落,影响纳米管阵列的完整性和均一性.氧化电压在15~25 V,pH值为4~6内可以实现TiO2纳米管阵列的微结构调控.氧化时间、电解液浓度主要影响TiO2纳米管的管长、管径、管壁厚度, 只要在合适的范围内可以通过微小的改变,实现微结构的调控.退火温度决定了TiO2的晶相转变,不同的退火温度对TiO2纳米管的管径、管壁、规整性、均一性影响较小,过快的升温和较高的温度不利于锐钛型TiO2纳米管的形成,可以实现在较低温度下的晶相转化.关键词:阳极氧化法;二氧化钛纳米管;制备;微结构调控中图分类号:O614 文献标志码:A 文章编号:1000-1565(2017)04-0378-08Preparation and microstructure control oftitanium dioxide nanotube arraysQIU Mande, HAN Qingjiao, CUI Yanlong, NIU Miao, YANG Pan(College of Chemistry and Environmental Science, Hebei University, Baoding 071002, China)Abstract: In this paper, TiO2 nanotube arrays were prepared by anodic oxidation method in HF aqueous solution.The influencing of the parameters for the phase composition and miscrostructure of titania nanotube arrays on the titanium surface were systematicdly studied, such as oxidation voltage, oxidation time, electrolyte concentration, pH value and annealing temperature.The main and secondary factors of the preparation of titanium dioxide nanotube arrays with regularity, uniformity and microstructure were discussed.The results show that: the oxidation voltage and pH value are the determining factors for the formation and regularity of TiO2 nanotube arrays.Smaller pH value is beneficial to the preparation of TiO2 nanotube arrays in a short time, but TiO2 nanotubes tend to fall off the surface of the substrate, which affects the integrity and uniformity of the nanotube arrays.When the oxidation voltage is 15~25 V and the pH value is 4~6, the regulation of microstructure of TiO2 nanotube arrays can be realized.The length, diameter and wall thickness of TiO2 nanotube are mainly affected by the oxidation time and electrolyte concentration.If the range is proper, the microstructure can be controlled by tiny changes.The- 收稿日期:2016-12-21 基金项目:国家自然科学基金资助项目(21376060);河北省科技厅支撑计划资助项目(10276732) 第一作者:仇满德(1964—),男,河北石家庄人,河北大学副教授,主要从事功能材料的制备及微分析研究.E-mail:hbuqmd@sina.cn第4期仇满德等:锐钛型TiO2纳米管阵列的制备及微结构调控annealing temperature determines the crystal phase transition of TiO2.Different annealing temperature has little effect on the diameter, wall, regularity and uniformity of TiO2 nanotubes.Rapid heatins and high temperature were not beneficial to the formation of anatase TiO2 nanotubes.The transition of crystal phase can be realized at a lower temperature.
[1] KOWALSKI D, KIM D, SCHMUKI P.TiO2, nanotubes, nanochannels and mesosponge: Self-organized formation and applications[J].Nano Today, 2013, 8(3):235-264.DOI:10.1016/j.nantod.2013.04.010.
[2] 肖虹, 步召胜, 孙彬,等.TiO2纳米管的制备及应用研究进展[J].材料导报, 2015, 29(3):30-34.DOI:10.11896/j.issn.1005-023X.2015,03,006. XIAO H, BU Z S, SUN B, et al.Progress on preparation and application of TiO2 nanotubes[J].Materials Review, 2015, 29(3):30-34.DOI:10.11896/j.issn.1005-023X.2015,03,006.
[3] REGONINI D, BOWEN C R, JAROENWORALUCK A, et al.A review of growth mechanism, structure and crystallinity of anodized TiO2, nanotubes[J].Materials Science and Engineering: R: Reports, 2013, 74(12):377-406.DOI: 10.1016/j.mser.2013.10.001.
[4] 李洪义, 王金淑, 陈欣,等.TiO2纳米管阵列薄膜制备及生长机理的研究[J].无机化学学报, 2010, 26(2):217-222. LI H Y, WANG J S, CHEN X, et al.Preparation of TiO2 nanotube array thin films and their growth mechanism[J].Chinese Journal of Inorganic Chemistry, 2010, 26(2):217-222.
[5] 殷广明, 刘大锰, 陈伟, 等.TiO2纳米管阳极氧化制备机理及热处理对其影响[J].无机化学学报, 2012, 28(6):1205-1209. YIN G M, LIU D M, CHEN W, et al.Anodic oxidation mechanism and annealing influence of TiO2 nanotubes arrays[J] , Chinese Journal of Inorganic Chemistry, 2012, 28(6):1205-1209.
[6] KHUDHAIR D, BHATTI A, LI Y, et al.Anodization parameters influencing the morphology and electrical properties of TiO2 nanotubes for living cell interfacing and investigations[J].Mater Sci Eng C Mater Biol Appl,2015, 59:1125-1142.DOI:10.1016/j.msec.2015.10.042.
[7] 郭志君, 周斌, 高琴,等.阳极氧化工艺参数对TiO2纳米管形貌和性能的影响[J].功能材料, 2014(6):111-115.DOI: 10.3969/j.issn.1001-9731.2014.06.024. GUO Z J, ZHOU B, GAO Q, et al.Influences of anodization processing factors on the morphology and property of TiO2 nanotube arrays[J].Journal of Functional Materials, 2014(6):111-115.DOI: 10.3969/j.issn.1001-9731.2014.06.024.
[8] FANG D, CHEN S, JIANG M, et al.Growth mechanisms of multilayered anodic-titanium-oxide nanotube membranes[J].Materials Science in Semiconductor Processing, 2014, 18(2):105-113.DOI:10.1016/j.mssp.2013.10.019.
[9] 龙东平, 晏智鑫, 薛建荣.阳极氧化钛基合金表面TiO2纳米管阵列的研究进展[J].材料导报, 2015, 29(5):8-12. LONG D P, YAN Z X, XUE J R.Research progress of TiO2 nanotube arrays on titanium alloy surface fabricated by anodic oxidation[J].Materials Review, 2015, 29(5):8-12.
[10] GUAN D, HYMEL P J, WANG Y.Growth mechanism and morphology control of double-layer and bamboo-type TiO2, nanotube arrays by anodic oxidation[J].Electrochimica Acta, 2012, 83(12):420-429.DOI:10.1016/j.electacta.2012.08.036.
[11] KIM T H, LEE J W, KIM B S, et al.Morphological investigation of anodized TiO2, nanotubes fabricated using different voltage conditions[J].Microporous and Mesoporous Materials, 2014, 196(13):41-45.DOI:10.1016/j.micromeso.2014.04.056.
[12] 兰瑞家, 李记太, 周秋香,等.TiO2/石墨烯复合材料的合成及其光催化性能[J].河北大学学报(自然科学版), 2013, 33(6):608-613.DOI:10. 3969/j.issn.1000-1565.2013.06.010. LAN R J, LI J T, ZHOU Q X, et al.Preparation and photocatalytic activity of TiO2/graphene composites[J].Journal of Hebei University:Naturnal Science Eition, 2013, 33(6):608-613.DOI: 10.3969/j.issn.1000-1565.2013.06.010.
[13] LIU H, LV T, ZHU Z.Template-assisted synthesis of hollow TiO2@rGO core-shell structural nanospheres with enhanced photocatalytic activity[J].Journal of Molecular Catalysis A: Chemical, 2015, 404:178–185.DOI:10.1016/j.molcata.2015.04.022.
[14] COSTA J D, QUITERIO P, APOLINARIO A, et al.The effect of electrolyte re-utilization in the growth rate and morphology of TiO2, nanotubes[J].Materials Letters, 2016, 171:224-227.DOI:10.1016/j.matlet.2016.02.085.
[15] HU N, GAO N, STARINKTARINK M J.The influence of surface roughness and high pressure torsion on the growth of anodic titania nanotubes on pure titanium[J].Applied Surface Science, 2016, 387:1010-1020.DOI:10.1016/j.apsusc.2016.07.036.
[16] LIU G, DU K, WANG K.Surface wettability of TiO2, nanotube arrays prepared by electrochemical anodization[J].Applied Surface Science, 2016, 388:313-320.DOI:10.1016/j.apsusc.2016.01.010.
[17] 朱绪飞, 韩华, 宋晔,等.阳极氧化物纳米孔道和TiO2纳米管形成机理的研究进展[J].物理化学学报, 2012, 28(6):1291-1305.DOI:10.3866/PKU.WHXB201204093. ZHU G F, HAN H, SONG Y, et al.Research progress in formation mechanism of TiO2 nanotubes and nanopores in porous anodic oxide[J].Acta Physico-Chimica Sinica, 2012, 28(6):1291-1305.DOI:10.3866/PKU.WHXB201204093.
