本論文利用電化學法於深共熔溶劑(deep eutectic solvent, DES)中製備鋅銅鎳以及錫銅鎳三元合金材料。進行合金電鍍之前，先利用循環伏安法探討個別單一金屬離子與分別混合二元及三元金屬離子在Ethaline中的電化學行為。透過調整溶液中金屬離子濃度、控制電位或是脈衝電鍍與時間的改變獲得不同形貌以及成分組成的三元合金鍍層。後續則選擇富含鋅或是錫的三元合金用於電化學去合金實驗。
本研究所製備之鋅銅鎳與三元合金無法在所使用的Ethaline深共熔溶劑中以電化學去合金法選擇性去除鋅金屬以達到製備出孔洞電極的目的，其原因在該三元合金組成金屬於所使用的深共熔溶劑中之氧化電位過於靠近，無法僅去除鋅金屬而獲得明顯的孔洞形貌以及金屬成分變化。故改採兩階段製備的方式，改以在鹼性水溶液中進行電化學去合金實驗。在鹼性水溶液中，鋅銅鎳三元合金透過電化學陽極去合金(anodic dealloying)去除合金中鋅與銅並且獲得表面富含鎳之三元合金孔洞狀的結構。此外，鋅銅鎳三元合金也能藉由在鹼性溶液中還原硝酸根的方式進行陰極去合金(cathodic dealloying)製備出電極表面為富含銅的三元合金孔洞材料。後者可稱為具自增強效應之陰極去合金電極。此研究所發現之獨特的陰極去合金法可應用於其它鋅合金之電化學去合金過程，且兩種不同的去合金法可提供不同的電極表面組成，將可應用於不同表面組成之電催化材料的製備。

The electrodeposition of ZnCuNi and SnCuNi ternary alloys were carried out in Ethaline deep eutectic solvent based on choline chloride and ethylene glycol (in mole ratio 1: 2) at 353K with different electrochemical techniques. The obtained deposits were used as the precursors for the following processes of electrochemical dealloying to prepare porous alloy electrodes. Before the electrodeposition of ternary alloys would be conducted, voltammetry was employed to study the electrochemical behavior of individual metal ions, mixtures of each two of them, and the ternary mixture. The Zn- and Sn-rich alloy deposits can be obtained from constant potential deposition and pulse deposition, respectively. Electrochemical selective dissolution of Zn from ZnCuNi deposits could not be achieved in Ethaline because the oxidation potentials of the three species are too close to each other. A two-step process was developed in which the electrochemical dealloying was performed in aqueous NaOH electrolyte. It was found that Cu was also dealloyed along with Zn from the ZnCuNi alloys during the process of anodic dealloying; porous ZnCuNi alloys with Ni-rich surface were produced. Oppositely, porous ZnCuNi alloys with Cu-rich surface were obtained via cathodic dealloying of Zn during the electrolysis of nitrate reduction in aqueous NaOH. The latter is called “self-enhancing electrode formed by in-situ cathodic dealloying”. Both dealloyed porous electrodes showed improved activities toward nitrate reduction, especially for the cathodically dealloyed one. The reason is due to the porous ZnCuNi prepared by cathodic dealloying exhibited Cu-rich surface. This study demonstrates a new and facile cathodic dealloying that is suitable to dealloy Zn from Zn-based alloys without damage other components. On the other hand, this study indicates that different dealloying approaches formed electrodes with different properties, which will be important for various applications.

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