本研究為負載於碳黑上鈀-鈷奈米合金氧氣還原反應電催化劑之製備與性質分析，實驗架構主要分為兩部份。
Part 1：使用硼氫化鈉做為還原劑的含浸法製作PdCo奈米合金並負載在碳上，然後在350 oC退火。可以得到四組不同原子比例的催化劑，Pd/C、Pd88Co12/C、Pd76Co24/C、Pd50Co50/C。對製程之電催化劑使用X光繞射分析儀、穿透式電子顯微鏡、化學影像能譜分析儀和動態光散射分析儀測量其表面形態與結構性質分析；並使用旋轉圓盤電極(RDE)進行循環伏安法、線性掃描伏安法，分析電化學活性表面積與ORR效能。PdCo奈米顆粒粒徑為3.9 nm (Pd88Co12/C)到5.5 nm (Pd50Co50/C)之間，PdXCoY/C電催化劑的金屬含量約20 wt%，從電化學測試發現催化活性為Pd88Co12/C > Pd76Co24/C >Pd50Co50/C > Pd/C。
Part 2：別於以往對於PdXCoY/C電催化劑使用熱處理的方式改良其活性，開發新種電化學法氧化處理PdXCoY/C電催化劑並對ORR催化活性進行分析。在鹼性環境下使用定電位氧化PdXCoY/C電催化劑，結果發現電化學法氧化處理PdXCoY/C會造成電催化活性下降，ORR活性也會下降，無法如文獻中熱處理氧化一樣提升ORR活性。

Pd-Co nanoalloy electrocatalysts supported on Vulcan XC-72 carbon black (PdCo/C) for oxygen reduction reaction (ORR) are synthesized and characterization in this study. This study has two part experiments. 
Part 1：PdCo nanoalloys are prepared by impregnation method using sodium borohydride as the reducing agent and then annealed at 350 oC. Electrocatalysts with various Pd:Co atomic ratios of 88:12 (Pd88Co12/C) , 76:24 (Pd76Co24/C) and 50:50 (Pd50Co50/C) are obtained.Pd/C electrocatalyst is also prepared using the same method for comparison.Transmission electron microscope, scanning electron microscopy with energy dispersive spectroscopy and X-ray diffractometer are used to analysis the structure and composition of the electrocatalysts.Electrochemical behaviors and electrocatalytic activity toward ORR of these electrocatalysts are investigated and compared by cyclic voltammetry (CV) and rotating disk electrode (RDE) experiments. The size of the PdCo nanoalloys is ranging from 3.9 nm (Pd88Co12/C) to 5.5 nm (Pd50Co50/C), and the total metal loading of these electrocatalysts is around 20 wt%. Electrochemical active surface area (ECSA) of the electrocatalysts is estimated from CV, and Pd88Co12/C shows a higher ECSA than that of Pd/C. According to the RDE experiments, Pd88Co12/C shows the highest ORR mass activity among all the electrocatalysts prepared in this study, and which is 1.9-fold higher than that of Pd/C. The electron transfer number of ORR on these electrocatalysts is about 4 as estimated by Koutecky-Levich equation. 
Part 2：Develop the new oxidation procedure of PdXCoY / C for different oxidation potentials on ECSA and ORR activity. The PdXCoY / C electrocatalysts are oxidized in alkaline condition by using chronoamperometry. In summuy, electrochemical oxidation of PdXCoY / C are decreased electrocatalytic activity and decreased ORR activity. The ORR activity can not be enhanced as the case of heat treatment oxidation in the literature.

目錄
中文摘要	I
英文摘要	II
目錄	IV
圖目錄	VI
表目錄	VIII
第一章簡介	1
第二章實驗	14
2.1 實驗目的與架構	14
2.2實驗藥品與材料	15
2.3實驗儀器與設備	16
2.4 實驗步驟	16
2.4.1 PdCo電催化劑製備含浸法前置步驟	16
2.4.2 PdCo電催化劑含浸法還原合成步驟	17
2.4.3 PdCo電催化劑燒結合金化步驟	17
2.5 表面性質分析及其樣品製備	19
2.5.1 X光繞射分析儀 (X-ray diffractometer, XRD)	19
2.5.2穿透式電子顯微鏡 (transmission electron microscope, TEM)	19
2.5.3掃描式電子顯微鏡附表面能量散射X光光譜儀 (scanning electron microscope energy dispersive X-ray spectroscopy, SEM-EDS)	20
2.6 電化學分析	20
2.6.1 電化學分析前置準備	20
2.6.2 循環伏安法 (cycle voltammetry, CV)	21
2.6.3 計時安培法 (chronoamperometry, CA)	23
2.6.4線性掃描伏安法 (linear sweep voltammetry, LSV)	24
2.6.4-1 Koutecky-Levich圖譜 (Koutecky-Levich plot, K-L plot)	25
第三章PdXCoY/C電催化劑之比較	26
3.1 SEM-EDS元素分析	26
3.2 XRD晶型結構分析	27
3.3 TEM表面型態與結構之分析	29
3.4 CV分析	31
3.5 ORR效能	32
3.6 ORR轉移電子數	34
第四章PdXCoY/C電催化劑之電化學改質與性質檢測	36
4.1 PdXCoY/C氧化前處理狀態分析	36
4.2 PdXCoY/C氧化前處理後比較	39
4.2.1 ECSA比較	39
4.2.2 ORR比較	40
4.3 Pd50Co50/C氧化前處理在鹼性環境下CV與ORR比較	42
第五章結論	44
參考文獻	45
附錄	48
A. Pt/C與PdXCoY/C電催化劑之ORR轉移電子數	48
B. Pd/C與Pd50Co50/C氧化前處理CV比較	49
C. Pd/C與Pd50Co50/C氧化前處理ORR比較	52
D. Pd75Co25/C-SiO2電化學性質分析	54
D-1 Pd75Co25/C-SiO2製備步驟	54

圖目錄
圖1-1、PEMFC之構造示意圖。	2
圖1-2、不同金屬的氧氣還原活性對氧鍵結能做圖。	3
圖1-3、Pt/C、Pd/C與Pd65Co35/C的Koutecky–Levich圖譜。	4
圖1-4、(A)Pt/C (B)Pd4Co/C-350 在有無甲醇電解液下的CV圖譜。	5
圖1-5、Pt/C與Pd4Co/C在有無甲醇電解液下的ORR圖譜。	6
圖1-6、Pd70Co30/C在不同燒結溫度(e)non (f)300 oC (g)500 oC (h)700 oC下TEM圖。	7
圖1-7、Pd50Co50/C在不同燒結溫度下的HRPD圖。	8
圖1-8、(A)Pd70Co30/C在不同燒結溫度下ORR圖，(B)不同原子比PdXCoY/C的ORR圖。	8
圖1-9、氧化熱處理溫度對ORR活性與Pd DSO影響圖。	9
圖1-10、PdCo奈米合金表面氧化熱處理後提升ORR反應活性模型。	9
圖1-2、Co金屬的pH-電位電化學相圖[19]。	11
圖1-3、Pd金屬的pH-電位電化學[19]。	11
圖2-1、實驗架構及流程圖。	14
圖2-2、含浸法之實驗步驟流程圖。	18
圖2-3、RDE三電極式電化學系統簡示圖。	21
圖2-4、Pd50Co50/C電催化劑在0.5 M H2SO4下的CV圖。	22
圖2-5、	23
圖2-6、Pd50Co50/C電催化劑在0.5 M H2SO4 (O2 saturated)電解液之LSV圖。	24
圖2-7、Pt/C電催化劑的Koutecky-Levich圖譜。	25
圖3-1、PdXCoY/C系列電催化劑之XRD分析圖譜。	28
圖3-2、PdXCoY/C系列電催化劑合金化觀察之XRD圖譜。	28
圖3-3、(A)Pd/C、(B) Pd88Co12/C(C)Pd76Co24/C與(D) Pd50Co50/C電催化劑之TEM影像及粒徑分析。	30
圖3-4、PdXCoY/C系列之電催化劑在0.5 M H2SO4水溶液中之CV圖。	31
圖3-5、PdXCoY/C系列電催化劑之LSV圖。	33
圖3-6、Pt/C與PdXCoY/C系列電催化劑的Koutecky-Levich圖譜。	35
圖4-1、Pd/C的電化學氧化前處理圖譜。	37
圖4-2、Pd50Co50/C的電化學氧化前處理圖譜。	37
圖4-3、Pd/C與Pd50Co50/C在buffer pH10下的CV圖譜。	38
圖4-4、Pd/C與Pd50Co50/C的電化學氧化前處理電流值圖。	38
圖4-5、Pd/C與Pd50Co50/C的電化學氧化前處理ECSA數據比較圖。	39
圖4-6、Pd/C與Pd50Co50/C的電化學氧化前處理半波電位數據比較圖。	40
圖4-7、Pd/C與Pd50Co50/C的電化學氧化前處理Mass Activity數據比較圖。	41
圖4-8、Pd/C與Pd50Co50/C的電化學氧化前處理	41
圖4-9、Pd50Co50/C電催化劑在不同氧化前處理電位下之鹼性環境CV圖。	42
圖A-1、(A)Pt/C (B)Pd/C (C)Pd88Co12/C (D)Pd76Co24/C (E)Pd50Co50/C之不同轉速的ORR反應LSV曲線圖。	49
圖B-1、Pd/C電催化劑在不同氧化前處理電位(A)+0.8 V (B)+0.6 V(C)+0.4 V(D)+0.2 V(E)0.0 V(F)-0.2 V(G)-0.4 V(H)-0.6 V之CV圖。	50
圖B-2、Pd50Co50/C電催化劑在不同氧化前處理電位(A)+0.8 V (B)+0.6 V(C)+0.4 V(D)+0.2 V(E)0.0 V(F)-0.2 V(G)-0.4 V(H)-0.6 V之CV圖。	51
圖C-1、Pd/C電催化劑在不同氧化前處理電位(A)+0.8 V (B)+0.6 V(C)+0.4 V(D)+0.2 V(E)0.0 V(F)-0.2 V(G)-0.4 V(H)-0.6 V之ORR圖。	53
圖C-2、Pd50Co50/C電催化劑在不同氧化前處理電位(A)+0.8 V (B)+0.6 V(C)+0.4 V(D)+0.2 V(E)0.0 V(F)-0.2 V(G)-0.4 V(H)-0.6 V之ORR圖。	54
圖D-1、Pd75Co25/C-SiO2的(A)CV圖譜 (B)ECSA比較 (C)ORR圖譜 (D) Mass Activity比較。	55

表目錄
表1-1、PdCo/C催化劑熱處理改良並應用於ORR的相關文獻。	12
表1-2、PdCo/C催化劑其他改良方式並應用於ORR的相關文獻。	13
表2-1、不同原子比製作的PdXCoY/C系列電催化劑所對應的(NH4)2PdCl4．4H2O與CoCl2．6H2O之實際克數。	18
表3-1、PdXCoY/C系列電催化劑之EDS元素分析表。	26
表3-2、PdXCoY/C系列電催化劑之XRD分析結果。	27
表3-3、PdXCoY/C系列電催化劑中Pt顆粒之平均粒徑。	29
表3-4、PdXCoY/C系列之電催化劑之CV性質參數。	32
表3-5、PdXCoY/C系列電催化劑之ORR效能比較。	33
表3-6、Pt/C與PdXCoY/C系列電催化劑進行ORR反應之轉移電子數(n)。	35

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