(浙江工業(yè)大學(xué) 化學(xué)工程與材料學(xué)院，杭州 310014)
摘 要: 在含NH4F 的聚乙二醇(PEG-200)電解液中通過(guò)陽(yáng)極氧化制備高度有序的二氧化鋯納米管陣列(ZrO2-NTs)。考察氧化電壓、氧化時(shí)間以及電解液水含量對(duì)ZrO2-NTs 形貌的影響，并討論其生長(zhǎng)機(jī)制，采用等效電路Rs(QfRf)(QdRc)對(duì)ZrO2-NTs 的電化學(xué)阻抗譜進(jìn)行擬合。結(jié)果表明，在該體系中ZrO2-NTs 的形成包括氧化、水解形核以及膜溶解過(guò)程，氧化電壓、氧化時(shí)間以及電解液水含量是影響ZrO2-NTs 生長(zhǎng)的重要因素，在含1.0% NH4F(質(zhì)量分?jǐn)?shù))和5% H2O(體積分?jǐn)?shù))的PEG-200 電解液中，20 V 電壓下氧化3 h 可制備得到管徑為100~120 nm 的ZrO2-NTs。電化學(xué)阻抗譜分析結(jié)果表明，ZrO2 膜層的界面電荷轉(zhuǎn)移電阻較大。
關(guān)鍵字: ZrO2 納米管陣列；聚乙二醇；陽(yáng)極氧化；生長(zhǎng)機(jī)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
