阳极氧化钛纳米管阵列膜可控制备

张贺, 张驰, 宋晔

doi:10.7536/PC151046

化学进展 ›› 2016, Vol. 28 ›› Issue (6) :773-783 DOI: 10.7536/PC151046

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阳极氧化钛纳米管阵列膜可控制备

张贺, 张驰, 宋晔

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Fabrication of Anodic Titania Nanotube Arrays with Tunable Morphologies

Zhang He, Zhang Chi, Song Ye

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摘要

阳极氧化钛纳米管(anodic titania nanotubes,ATNTs)阵列膜具有制备简便、比表面积大和有序度高等优点因而备受人们关注,已广泛应用于太阳能电池、传感器、光催化和超级电容器等领域。但与类似的多孔阳极氧化铝相比,在可控制备即微观形貌控制方面仍相差甚远。迄今,ATNTs的综述文章多侧重于ATNTs的形成机理、改性及应用方面,而本文则聚焦于近十年来ATNTs制备技术成果,试图揭示其在管长、管径和规整度等方面的可控制备规律。首先介绍了在乙二醇(EG)电解液中制备ATNTs的常规阳极氧化条件,以及得到的ATNTs的典型形貌特征。然后评述了非EG电解液体系中,ATNTs的生长规律和形貌特征。在此基础上,综述了如何通过改变阳极氧化工艺参数,如电解液温度、F^-浓度、氧化电压和时间等来实现对ATNTs管径及规整性的调控,并讨论了制备超长纳米管膜的难点和方法,以及获得ATNTs自支撑膜的各种工艺。最后指出了目前ATNTs可控制备存在的不足及今后的发展方向。

Abstract

Anodic titania nanotubes (ATNTs) have recently attracted particular attention due to their ease of preparation, low cost, large surface area, alignment and self-ordering. Especially, ATNTs are of interest for a wide variety of applications, including dye-sensitized solar cells, electrochemical sensors, photocatalysts, supercapacitors, etc. However, compared with analogous porous anodic alumina, the synthesis of ATNTs with regular and controllable microscopic morphologies is still under development. Although a number of excellent reviews on ATNTs have appeared, most of them have generally focused on their formation mechanism, properties, modifications and applications. This review attempts to pay close attention to the controllable fabrication of ATNTs, i.e., length, tube diameter, and self-ordering of nanotubes can be adjusted over large length scales. The preparation techniques of ATNTs in the last decade are summarized and the key factors for synthesis of ATNTs with tunable morphologies are discussed. In this review, we first present the anodization conditions of fabricating conventional ATNTs in ethylene glycol (EG) electrolytes and the typical microscopic morphologies of as-obtained ATNTs. Then, we discuss the growth characteristics and morphological parameters of ATNTs anodized in other electrolyte systems, such as aqueous solution, glycerol, dimethyl sulfoxide. It has been demonstrated that anodization conditions, including the solvent, temperature, anodization voltage, anodization duration and F^- concentration, have profound effects on the morphologies of ATNTs. On the basis of these experimental findings, we overview how to adjust tube diameter, tube length, wall thickness and self-organization of ATNTs by changing anodization parameters. Some fabrication methods for nanotubes with a length of over several hundreds micrometers and the structural features of such thick ATNT films are also given. In addition, the strategies to detach as-formed ATNTs from the metallic substrate and to obtain free-standing ATNT membranes are described. Finally, we emphasize some related issues for fabrication of ATNTs with tunable morphologies and indicate the main challenges and potential future directions of the field.

Contents
1 Introduction
2 Anodization conditions of fabricating the conventional ATNTs
3 ATNTs grown in non-ethylene glycol (EG)-based electrolyte systems
4 Adjustment of tube diameter and ordering of ATNTs
4.1 Adjustment of tube diameter
4.2 Achievement of an improved ordering for ATNTs
5 Methods for fabricating ATNTs with ultralong nanotubes
6 Strategies to obtain free-standing ATNT membranes
7 Conclusion

Graphical abstract

关键词

TiO₂纳米管 / 阳极氧化 / 氟化物 / 电解液 / 可控制备

Key words

TiO₂ nanotubes / anodization / fluorides / electrolytes / controllable preparation

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张贺, 张驰, 宋晔. 阳极氧化钛纳米管阵列膜可控制备[J]. 化学进展, 2016, 28(6): 773-783 DOI:10.7536/PC151046

Zhang He, Zhang Chi, Song Ye. Fabrication of Anodic Titania Nanotube Arrays with Tunable Morphologies[J]. Progress in Chemistry, 2016, 28(6): 773-783 DOI:10.7536/PC151046

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