混價金屬氧化鎳/鎳赤血鹽與鎳赤血鹽/磷鉬酸鹽混合薄膜的製備、特性及其電催化性質研究

Preparation and Characterization of Mixed-valent Nickel Oxide/Nickel Hexacyanoferrate and Nickel Hexacyanoferrate/Phosphomolybdate Hybrid Films and Their Electrocatalytic Properties

劉慶勇(ching-young Liou)

指導教授 ： 陳生明

國立臺北科技大學/工程學院/化學工程研究所/碩士(2007年)

https://doi.org/10.6841/NTUT.2007.00077

摘要

本研究主要分為兩部份來討論:第一部份為利用循環伏安法製備混價金屬氧化鎳/鎳赤鹽混合薄膜，氧化鎳和鎳赤鹽混合薄膜是在酸性溶液或pH 9.0的緩衝液中混合 Ni2+和Fe(CN)63- 離子，在循環伏安法中鎳赤血薄膜會產生一對氧化還原對而氧化鎳/鎳赤鹽混合薄膜會具有二對氧化還原對，在許多基本的緩衝溶液中循環伏安法顯示鎳赤血薄膜會逐漸轉變成氧化鎳薄膜。利用電化學石英晶體微天平法與循環伏安法可用來研究氧化鎳和鎳赤鹽混合薄膜生長的情形。由氧化鎳和鎳赤鹽混合薄膜可以得到二對的氧化還原對，我們可使用氧化鎳和鎳赤鹽混合薄膜修飾電極來對抗壞血酸 (ascorbic acid)、聯胺(N2H4)、羥胺(NH2OH)作電催化氧化反應。
第二部份為利用循環伏安法製備混價金屬鎳赤鹽和磷鉬酸鹽混合薄膜，鎳赤鹽/磷鉬酸鹽混合薄膜是在酸性水溶液中混合 Ni2+、Fe(CN)6-3和PMo12O403-離子，在混價金屬鎳赤鹽/磷鉬酸鹽混合薄膜會產生四對氧化還原對。利用電化學石英晶體微天平法、循環伏安法與電子顯微掃描可用來研究混價金屬鎳赤鹽/磷鉬酸鹽混合薄膜和鎳磷鉬酸鹽(Ni3(PMo12O40)2合成薄膜成長情形。利用電化學石英晶體微天平和循環伏安法產生混價金屬鎳赤鹽/磷鉬酸鹽混合薄膜和鎳磷化鉬混合薄膜顯示其製程中的氧化還原反應，我們可藉由混價金屬鎳赤鹽/磷鉬酸鹽混合薄膜和鎳磷鉬酸鹽薄膜修飾電極來對S2O82-和抗壞血酸作電催化氧化反應。

關鍵字

鎳赤血鹽 ； 氧化鎳 ； 薄膜修飾電極 ； 電催化 ； 混價金屬 ； 磷鉬酸鹽 ； 聯胺

並列摘要

Part Ⅰ：Polynuclear mixed-valent of nickel oxide and nickel hexacyanoferrate hybrid films have been prepared using repetitive cyclic voltammetry. Two types film of nickel hexacyanoferrate film, nickel oxide and nickel hexacyanoferrate hybrid films have been prepared directly from the mixing of Ni2+ and Fe(CN)63- ions from the acidic solutions and pH 9.0 aqueous solutions. The cyclic voltammogram of the nickel hexacyanoferrate film is characterized by one redox couple and the nickel oxide and nickel hexacyanoferrate hybrid film exhibits two redox couples and both films were confined to the immobilized film. In stronger basic aqueous solution, he cyclic voltammograms show the nickel hexacyanoferrate films were transferred to nickel oxide films gradually. The electrochemical quartz crystal microbalance, and cyclic voltammetry were used to study the growth mechanism of nickel oxide and nickel hexacyanoferrate hybrid films. The nickel oxide and nickel hexacyanoferrate hybrid films exhibited two redox couples with formal potentials that demonstrated a proton effect. Electrocatalytic reactions of N2H4, NH2OH, and ascorbic acid were carried out by the nickel oxide and nickel hexacyanoferrate films, respectively.
Part II：Polynuclear mixed-valent films of nickel hexacyanoferrate/
phosphomolybdate (NiFe(CN)6/PMo12O403-) have been prepared using repetitive cyclic
voltammetry. The nickel phosphomolybdate(Ni3(PMo12O40)2 films have also been
prepared using repetitive cyclic voltammetry. The cyclic voltammograms recorded the
deposition of the mixed-valent nickel hexacyanoferrate/ phosphomolybdate hybrid films
directly from the mixing of Ni2+, Fe(CN)63– and PMo12O403- ions from the acidic
aqueous solutions. The polynuclear mixed-valent films nickel hexacyanoferrate /
phosphomolybdate films exhibited four obviously redox couples. The electrochemical
quartz crystal microbalance, cyclic voltammetry, and scanning electron microscopy
were used to study the growth mechanism of the polynuclear mixed-valent nickel
hexacyanoferrate/ phosphomolybdate films and nickel phosphomolybdate
(Ni3(PMo12O40)2 films. The electrochemical quartz crystal microbalance and cyclic
voltammetry results indicated that the redox process was confined to the immobilized
mixed-valent nickel hexacyanoferrate/phosphomolybdate films and nickel
phosphomolybdate films. Electrocatalytic reactions of S2O82- and ascorbic acid were carried out by the mixed-valent nickel hexacyanoferrate/phosphomolybdate films and nickel phosphomolybdate films.

並列關鍵字

nickel hexacyanoferrate ； nickel oxide ； film modified electrodes ； electrocatalysis ； phosphomolybdate ； mixed valent ； hydrazine.

參考文獻

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