離子液體中電沉積具催化性之鐵鉑，鈀鎳合金及金屬鈀並應用於氧氣還原，乙醇氧化及葡萄糖氧化催化性之研究

本研究探討在BMP-DCA (N-butyl-N-methylpyrrolidinium dicyanamide)和BMP-TFSI (N-butyl-N-methylpyrrolidinium bis((trifluoromethyl)sulfonyl)imide)及以上兩種離子液體的混合溶液中之Pt(II)、Fe(II)及Pt(II)/Fe(II)混合溶液的電化學行為，並以鎢絲為基材電沉積鉑、鐵及鐵鉑合金，利用電子顯微鏡(SEM)觀察鍍層表面組成型態。在BMP-DCA離子液體中，Pt(II)的來源為PtCl2。Fe(II)則以添加FeCl2或陽極電解鐵絲的方式產生;因為PtCl2無法溶於BMP-TFSI離子液體中，因此必須加入2當量的BMPCl使它和鉑進行配位以幫助溶解;Fe(II)則以添加FeCl2和2當量BMPCl或電解鐵絲的方式得到。以Pt、GC和W三種電極探討Pt(II)及Fe(II)在離子液體中的循環伏安圖。並以不同掃描速率、不同電位折返、於不同轉折電位停留不同時間的方式仔細探討兩者的電化學行為。此外，本研究亦探討Pt(II)及Fe(II)還原成金屬時的成核機制，並探討提升溫度後電化學行為的改變。最後以電沉積所得之FePt合金在0.1 M HClO4溶液中對氧氣還原反應進行催化測試，實驗結果顯示在Fe:Pt原子比約1:1時，相較於純Pt有最大催化效果。在鹼性溶液中，FePt對乙醇氧化也顯現催化效果。電沉積PdNi合金則在BMP-DCA離子液體中完成，並探討各條件下的電化學行為(單圈循環伏安圖、不同掃描速率、不同電位折返、不同轉折電位停留不同時間之循環伏安圖及成核機制等)。電沉積PdNi時選擇鐵絲當作基材可具有最佳的附著性且在鹼性溶液中不會有氧化及腐蝕現象生成。以PdNi合金在1 M NaOH溶液中對乙醇及甲醇氧化反應之電催化進行研究，並以i-t curve針對不同原子比例的PdNi合金對甲醇及乙醇氧化催化的穩定性做了研究。PdNi合金並用於偵測乙醇，其乙醇檢量線利用循環伏安法及i-t curve 2種方式建立，實驗發現PdNi合金對不同濃度乙醇及所得電流之間有良好的線性關係。電沉積Pd電極催化葡萄糖氧化實驗是以拋棄式碳印刷電極做為基材，在含有50 mM PdCl2的BMP-DCA離子液體中電沉積100 mC電量，以此電極做為工作電極在0.1 M NaOH溶液中進行葡萄糖氧化測試，並以SWV、CV及i-t三種方式對高濃度及低濃度葡萄糖進行回收率測試。

關鍵字

離子液體；電沉積；鐵鉑合金；鈀鎳合金；氧氣還原；乙醇氧化；葡萄糖氧化

並列摘要

In this thesis, the electrochemical behaviors of Pt(II), Fe(II) and the mixtures of Pt(II) and Fe(II) were investigated using platinum, glassy carbon and tungsten electrodes in N-butyl-N-methylpyrrolidinium dicyanamide ionic liquid (BMP-DCA IL), N-butyl-N-methyl pyrrolidinium bis((trifluoromethyl)sulfonyl)imide ionic liquid (BMP-TFSI IL) and a mixture of BMP-DCA and BMP-TFSI. In BMP-DCA, the Pt(II) species were attained by adding PtCl2 and the Fe(II) species were attained by adding FeCl2 or anodic dissolution of Fe wire. In BMP-TFSI, PtCl2 was not soluble; additional two equivalents of BMP-Cl were introduced to assist PtCl2 to dissolve. The Fe(II) ions were introduced into BMP-TFSI by adding FeCl2 and two equivalents of BMP-Cl or by anodic dissolution of Fe electrode. The nucleation process of electrochemical reduction of Fe(II) was investigated by using chronoamperometry (CA) and the 3D instantaneous nucleation was involved in the electrodeposition of Fe. The effect of temperature on the electrochemical behavior was also studied. Electrodeposition of Pt, Fe and FePt alloys was achived by potentiostatic electrolysis and the effect of the applied potentials were carefully studied. The surface morphology and composition of all the electrodeposition samples were characterized by scanning electron microscope (SEM) and energy dispersive spectrometry (EDS), respectively. The electrocatalytic activity towards oxygen reduction reaction (ORR) was studied at the FePt alloy-coated electrodes with various atomic ratios of Pt/Fe. The experimental results revealed that the FePt alloy with an atomic ratio of Pt/Fe ~ 0.5/0.5 had the best catalytic activity to ORR in 0.1 M HClO4 in terms of the reduction overpotential and current density. The FePt alloy electrode also revealed catalytic activity toward ethanol oxidation reaction (EOR). On the other hand, Pd(II), Ni(II) and the mixtures of Pd(II) and Ni(II) were introduced into BMP-DCA IL by adding PdCl2 and NiCl2, respectively. The voltammetric behavior of Pd(II) and Ni(II) were studied and electrodeposition of Pd, Ni, and PdNi alloys was achieved by potentiostatic electrolysis. The PdNi alloy with an atomic ratio of Pd/Ni ~ 80/20 showed the best catalytic activity and stability toward ethanol oxidation compare with other PdNi alloys with different atomic ratios in 1 M NaOH. By using cyclic voltammetry, the dependence of the anodic peak current of ethanol oxidation on the concentration of ethanol was linear from 4.92 μM to 962 μM (R2 = 0.9975). A linearity was observed from 4.92 μM to 988 μM (R2 = 0.998) by using hydrodynamic amperometry. The Pd-electrodeposited electrode prepared from BMP-DCA IL displayed good catalytic activity to glucose oxidation in 0.1 M NaOH. The calibration curve of glucose showed two linear ranges; one occurred at low concentration range and the other one at high concentration range. Therefore, CV, SWV and i-t curve were employed to study the dependence of glucose oxidation current on concentration of glucose in the two concentration ranges.