TiO2纳米环/纳米管分层结构的生长机理及其吸光特性

doi:10.15541/jim20170061

摘要/Abstract

摘要：

由于电解液成分、氧化条件和所制备纳米管尺寸等因素的影响, TiO₂纳米管阵列在阳极氧化过程中容易形成纳米草结构, 而利用两步阳极氧化法可制备出表面整洁的TiO₂纳米环/纳米管分层结构。实验通过控制氧化时间得到了不同生长阶段的TiO₂纳米环/纳米管分层结构, 并对其生长机理及吸光特性展开研究。结果表明, 在第二步阳极氧化过程中, 钛箔表面的周期性六边形纳米洞结构可以使纳米管的生长过程局限于每个纳米洞内部, 从而形成TiO₂纳米环/纳米管分层结构。同时, 存在的纳米环可以为其内部的纳米管提供支撑作用, 防止纳米草结构的形成。TiO₂纳米环/纳米管分层结构的吸收光谱在可见光区域呈现震荡形态, 这是纳米环顶部反射的光与钛基底反射的光相互干涉导致的。根据震荡峰形状与样品厚度的关系, 可以估算出入射光在TiO₂纳米环/纳米管分层结构中的最大穿透深度为2 μm左右。

关键词: TiO₂, 纳米管, 分层结构, 生长机理, 震荡峰

Abstract:

On the top of TiO₂ nanotube arrays, nanograss structure may be generated due to electrolyte composition, the oxidizing condition and the size of nanotube in anodic oxidation process. TiO₂ nanoring/nanotube hierarchical structure with smooth surface was fabricated by two-step anodic oxidation. Growth mechanism and optical absorption properties of the resulting TiO₂ nanoring/nanotube hierarchical structure were investigated by controlling oxidation time of the anodic oxidation. The results show that the growth of nanotubes is limited by regular hexagonal nanocaves on the surface of Ti substrate during the second step of anodization resulting in formation of TiO₂ nanoring/nanotube hierarchical structure. Meanwhile, the nanorings provide the support of their internal nanotubes to avoid formation of nanograss structure. Absorption spectrum of TiO₂ nanoring/nanotube hierarchical structure exhibits oscillating peaks in visible light region, due to the interference between lights reflected from the top of nanorings and the bottom of Ti substrate. Based on the relationship between oscillation peaks shape and film thickness, the maximum optical penetration depth of TiO₂ nanoring/nanotube hierarchical structure is estimated to be ~2 μm.

Key words: TiO₂, nanotube, hierarchical structure, growth mechanism, oscillation peaks

中图分类号:

TK511

赵阳博, 桑丽霞. TiO₂纳米环/纳米管分层结构的生长机理及其吸光特性[J]. 无机材料学报, 2017, 32(12): 1327-1331.

ZHAO Yang-Bo, SANG Li-Xia. TiO₂ Nanoring/Nanotube Hierarchical Structure Growth Mechanism and Optical Absorption Property[J]. Journal of Inorganic Materials, 2017, 32(12): 1327-1331.

图/表 6

图1 不同氧化时间得到的TiO2纳米管阵列的形貌

Fig. 1 Top and cross-sectional (insert) morphologies of TiO2 nanotube arrays grown for different oxidation time(a) 20 V-20 min; (b) 20 V-30 min; (c) 20 V-60 min; (d) 20 V-100 min

图2 纳米草结构(a)及其示意图(b)[10]

Fig. 2 (a) SEM image and (b) schematic diagram of nanograss

图3 去除纳米管后钛箔表面的形貌图

Fig. 3 Morphology of the remaining surface after removal of the TiO2 nanotube array

图4 不同氧化时间下TiO2环/管分层结构的表面和截面形貌图

Fig. 4 Top and cross-sectional (insert) morphologies of TiO2 nanoring/nanotube hierarchical structure grown at different oxidation time in the second step anodization(a) 60 V-1 h/20 V-20 min; (b) 60 V-1 h/20 V-30 min; (c) 60 V-1 h/20 V-60 min; (d) 60 V-1 h/20 V-100 min

图5 TiO2环/管分层结构在第二步阳极氧化过程中的生长机理示意图

Fig. 5 Growth schematic of TiO2 nanoring/nanotube hierarchical structure in the second step anodization

图6 不同氧化时间所得TiO2纳米管阵列(a)和TiO2环/管分层结构(b)的吸收光谱图

Fig. 6 UV-Vis DRS of (a) TiO2 nanotube arrays and (b) TiO2 nanoring/nanotube hierarchical structure grown for different oxidation time

参考文献 21

[1]	SANG L X, ZHAO Y X, BURDA C.TiO2 nanoparticles as functional building blocks.Chemical Reviews, 2014, 114(19): 9283-9318.
[2]	SHANKAR K, MOR G K, FITZGERALD A,et al. Cation effect on the electrochemical formation of very high aspect ratio TiO2 nanotube arrays in formamide-water mixtures. The Journal of Physical Chemistry C, 2007, 111(1): 21-26.
[3]	KIM D, GHICOV A, SCHMUKI P.TiO2 Nanotube arrays: elimination of disordered top layers (“nanograss”) for improved photoconversion efficiency in dye-sensitized solar cells.Electrochemistry Communications, 2008, 10(12): 1835-1838.
[4]	MENG X, LEE T Y, CHEN H,et al Fabrication of free standing anodic titanium oxide membranes with clean surface using recycling process.Journal of Nanoscience and Nanotechnology, 2010, 10(7): 4259-4265.
[5]	SONG Y Y, LYNCH R, KIM D,et al. TiO2 nanotubes: efficient suppression of top etching during anodic growth key to improved high aspect ratio geometries. Electrochemical and Solid-State Letters, 2009, 12(7): C17-C20.
[6]	ZHANG Z, HOSSAIN M F, TAKAHASHI T.Photoelectrochemical water splitting on highly smooth and ordered TiO2 nanotube arrays for hydrogen generation.International Journal of Hydrogen Energy, 2010, 35(16): 8528-8535.
[7]	WANG F, LIU Y, DONG W,et al. Tuning TiO2 photoelectrochemical properties by nanoring/nanotube combined structure. The Journal of Physical Chemistry C, 2011, 115(30): 14635-14640.
[8]	ANITHA V C, BANERJEE A N, JOO S W,et al Fabrication of hierarchical porous anodized titania nano-network with enhanced active surface area: ruthenium-based dye adsorption studies for dye-sensitized solar cell (DSSC) application.Journal of Industrial and Engineering Chemistry, 2015, 29: 227-237.
[9]	ZHANG Z, ZHANG L, HEDHILI M N,et al. Plasmonic gold nanocrystals coupled with photonic crystal seamlessly on TiO2 nanotube photoelectrodes for efficient visible light photoelectrochemical water splitting. Nano Letters, 2012, 13(1): 14-20.
[10]	ROY P, BERGER S, SCHMUKI P.TiO2 nanotubes: synthesis and applications.Angewandte Chemie, 2011, 50(13): 2904-2939.
[11]	BERGER S, KUNZE J, SCHMUKI P,et al. Influence of water content on the growth of anodic TiO2 nanotubes in fluoride- containing ethylene glycol electrolytes. Journal of The Electrochemical Society, 2010, 157(1): C18-C23.
[12]	WANG X, ZHANG S, SUN L.A two-step anodization to grow high-aspect-ratio TiO2 nanotubes.Thin Solid Films, 2011, 519(15): 4694-4698.
[13]	MOR G K, VARGHESE O K, PAULOSE M,et al. A review on highly ordered, vertically oriented TiO2 nanotube arrays: fabrication, material properties, and solar energy applications. Solar Energy Materials and Solar Cells, 2006, 90(14): 2011-2075.
[14]	MACAK J M, TSUCHIYA H, GHICOV A,et al. TiO2 nanotubes: self-organized electrochemical formation, properties and applications. Current Opinion in Solid State and Materials Science, 2007, 11(1): 3-18.
[15]	ZHAO Z, ZHANG X, ZHANG G,et al. Effect of defects on photocatalytic activity of rutile TiO2 nanorods. Nano Research, 2015, 8(12): 4061-4071.
[16]	ZUO F, WANG L, WU T,et al. Self-doped Ti3+ enhanced photocatalyst for hydrogen production under visible light. Journal of the American Chemical Society, 2010, 132(34): 11856-11857.
[17]	WANG H, YOU T, SHI W,et al. Au/TiO2/Au as a plasmonic coupling photocatalyst. The Journal of Physical Chemistry C, 2012, 116(10): 6490-6494.
[18]	CHIARELLO G, TEALDI C, MUSTARELLI P,et al. Fabrication of Pt/Ti/TiO2 photoelectrodes by RF-magnetron sputtering for separate hydrogen and oxygen production. Materials, 2016, 9(4): 279.
[19]	MUTITU J G, SHI S, BARNETT A,et al Hybrid dielectric- metallic back reflector for amorphous silicon solar cells.Energies, 2010, 3(12): 1914-1933.
[20]	SANG L X, ZHANG Z Y, MA C F.Photoelectrical and charge transfer properties of hydrogen-evolving TiO2 nanotube arrays electrodes annealed in different gases.International Journal of Hydrogen Energy, 2011, 36(8): 4732-4738.
[21]	TSUI L K, ZANGARI G.Titania nanotubes by electrochemical anodization for solar energy conversion.Journal of the Electrochemical Society, 2014, 161(7): D3066-D3077.

TiO₂纳米环/纳米管分层结构的生长机理及其吸光特性

TiO₂ Nanoring/Nanotube Hierarchical Structure Growth Mechanism and Optical Absorption Property

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 6

参考文献 21

相关文章 15

编辑推荐

Metrics

本文评价

[1]	马彬彬, 钟婉菱, 韩涧, 陈椋煜, 孙婧婧, 雷彩霞. ZIF-8/TiO₂复合介观晶体的制备及光催化活性[J]. 无机材料学报, 2024, 39(8): 937-944.
[2]	陈海燕, 唐志鹏, 尹良君, 张林博, 徐鑫. CIPs@Mn_0.8Zn_0.2Fe₂O₄-CNTs复合材料低频吸波性能研究[J]. 无机材料学报, 2024, 39(1): 71-80.
[3]	郭春霞, 陈伟东, 闫淑芳, 赵学平, 杨傲, 马文. 埃洛石纳米管负载锆氧化物吸附水中砷的研究[J]. 无机材料学报, 2023, 38(5): 529-536.
[4]	田煜彬, 田超凡, 李森, 赵永鑫, 邢涛, 李智, 陈萧如, 向帅蓉, 代鹏程. 高导电性生物质碳布的制备及其燃料电池气体扩散层性能[J]. 无机材料学报, 2023, 38(11): 1316-1322.
[5]	王梦桃, 索军, 方东, 易健宏, 刘意春, Olim RUZIMURADOV. ITO/TiO₂纳米管阵列复合材料的可见光催化性能[J]. 无机材料学报, 2023, 38(11): 1292-1300.
[6]	贾鑫, 李晋宇, 丁世豪, 申倩倩, 贾虎生, 薛晋波. Pd纳米颗粒协同氧空位增强TiO₂光催化CO₂还原性能[J]. 无机材料学报, 2023, 38(11): 1301-1308.
[7]	安琳, 吴淏, 韩鑫, 李耀刚, 王宏志, 张青红. 非贵金属Co_5.47N/N-rGO助催化剂增强TiO₂光催化制氢性能[J]. 无机材料学报, 2022, 37(5): 534-540.
[8]	吴秋琴, 姚奋发, 金传洪, 郑遗凡. 碳纳米管内填充生长超细一维亚化学计量比氧化钨纳米线[J]. 无机材料学报, 2022, 37(4): 413-419.
[9]	吕庆洋, 张玉亭, 顾学红. 超声辅助溶胶-凝胶法制备中空纤维TiO₂超滤膜[J]. 无机材料学报, 2022, 37(10): 1051-1057.
[10]	刘芳芳, 传秀云, 杨扬, 李爱军. 氮/硫共掺杂对纤水镁石模板碳纳米管电化学性能的影响[J]. 无机材料学报, 2021, 36(7): 711-717.
[11]	肖翔, 郭少柯, 丁成, 张志洁, 黄海瑞, 徐家跃. CsPbBr₃@TiO₂核壳结构纳米复合材料用作水稳高效可见光催化剂[J]. 无机材料学报, 2021, 36(5): 507-512.
[12]	席文, 李海波. TiO₂/Ti₃C₂T_x复合材料的制备及其杂化电容脱盐特性的研究[J]. 无机材料学报, 2021, 36(3): 283-291.
[13]	刘彩, 刘芳, 黄方, 王晓娟. 海藻基CDs-Cu-TiO₂复合材料的制备及其光催化性能[J]. 无机材料学报, 2021, 36(11): 1154-1162.
[14]	李翠霞, 孙会珍, 金海泽, 史晓, 李文生, 孔文慧. 3D多级孔rGO/TiO₂复合材料的构筑及其光催化性能研究[J]. 无机材料学报, 2021, 36(10): 1039-1046.
[15]	王苹,李心宇,时占领,李海涛. Ag与Ag₂O协同增强TiO₂光催化制氢性能的研究[J]. 无机材料学报, 2020, 35(7): 781-788.