(浙江工业大学 化学工程与材料学院，杭州 310014)
摘 要: 在含NH4F 的聚乙二醇(PEG-200)电解液中通过阳极氧化制备高度有序的二氧化锆纳米管阵列(ZrO2-NTs)。考察氧化电压、氧化时间以及电解液水含量对ZrO2-NTs 形貌的影响，并讨论其生长机制，采用等效电路Rs(QfRf)(QdRc)对ZrO2-NTs 的电化学阻抗谱进行拟合。结果表明，在该体系中ZrO2-NTs 的形成包括氧化、水解形核以及膜溶解过程，氧化电压、氧化时间以及电解液水含量是影响ZrO2-NTs 生长的重要因素，在含1.0% NH4F(质量分数)和5% H2O(体积分数)的PEG-200 电解液中，20 V 电压下氧化3 h 可制备得到管径为100~120 nm 的ZrO2-NTs。电化学阻抗谱分析结果表明，ZrO2 膜层的界面电荷转移电阻较大。
关键字: ZrO2 纳米管阵列；聚乙二醇；阳极氧化；生长机制
（College of Chemical Engineering and Materials Science,Zhejiang University of Technology,
Hangzhou 310014,China）
Abstract:Highly ordered ZrO2 nanotube arrays (ZrO2-NTs) were prepared by anodic oxidation in PEG-200 electrolyte containing NH4F. The effects of oxidation voltage,oxidation time and water content of the electrolyte on the morphology and structure of ZrO2-NTs were investigated intensively. Furthermore,the growth mechanism of ZrO2-NTs in PEG-200 electrolyte was discussed. Equivalent circuit model Rs(QfRf)(QdRc) was used to analyze the electrochemical impedance of ZrO2-NTs. The results show that the formation of ZrO2-NTs in this system experiences oxidation,hydrolysis-nucleation and oxide film dissolution processes. The oxidation voltage,oxidation time and water content in the electrolyte are important factors on the growth of ZrO2-NTs. Highly ordered ZrO2-NTs with tube diameters arranging from 100 to 120 nm can be obtained in PEG-200 containing 1.0% NH4F (mass fraction) and 5% H2O (volume fraction) at potential of 20 V for 3 h. The impedance analysis results indicate that the interface charge transfer resistance of the ZrO2 film is large.
Key words: ZrO2 nanotube array; polyethylene glycol; anodic oxidation; growth mechanism
