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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。
Anodic titania nanotubes (ATNTs) array films have attracted people’s attention due to their advantages of simple preparation, large specific surface area and high degree of ordering. They have been widely used in the fields of solar cells, sensors, photocatalysis and supercapacitors. However, there is still a long way to go before controlled porous microstructures can be controlled compared to similar porous anodized aluminum. To date, ATNTs review articles have mostly focused on the formation mechanism, modification and application of ATNTs. However, this article focuses on the results of ATNTs preparation technology in the past decade and attempts to reveal its controllable aspects of tube length, tube diameter and regularity Preparation rules. The typical anodic oxidation conditions for the preparation of ATNTs in ethylene glycol (EG) electrolytes and the typical morphologies of the obtained ATNTs are described. Then, the growth and morphology of ATNTs in non-EG electrolyte system were reviewed. On this basis, how to control the diameter and regularity of ATNTs by changing the anodic oxidation process parameters such as electrolyte temperature, F-concentration, oxidation voltage and time is reviewed. Difficulties and methods, as well as access to ATNTs self-supporting film of various processes. At last, it points out the shortcomings of ATNTs controllable equipment and the future direction of development.