本研究主要目的為製備甲醇燃料電池 (Direct Methanol Fuel Cell, DMFC) 的鉑-二氧化鈰/碳電催化劑並對其性質進行分析研究。
  利用多元醇還原法製備鉑-二氧化鈰/碳電催化劑並與商用鉑/碳電催化劑進行分析與比較。電催化劑所使用的碳載體 (XC-72)實驗前先利用氫氧化納水溶液進行鹼修飾或利用硝酸水溶液進行酸修飾，主要目的是為了改變碳載體表面結構而增加電催化劑上金屬或金屬氧化物的分散性。多元醇還原法是利用乙二醇為還原劑將鉑與二氧化鈰還原到碳載體表面而製備成高分散性的鉑-二氧化鈰/碳電催化劑。 
  本研究使用掃描式電子顯微鏡 (scanning electron microscope, SEM) 對電催化劑表面進行元素分析，分析結果顯示電催化劑表面鉑與二氧化鈰的實際值與理論值相當接近。穿透式電子顯微鏡 (transmission electron microscope, TEM) 結果顯示碳載體上的鉑與二氧化鈰分散的非常均勻，沒有任何聚集的情況發生。實驗結果顯示電催化劑上鉑的粒徑大約在3-4 nm 左右，與使用 X 光繞射分析儀 (X-ray diffractometer, XRD) 所計算出的粒徑大小相當吻合。
  碳載體經由硝酸修飾再利用乙二醇還原法所製備的電催化劑 Pt-CeO2/ Ca 利用循環伏安法 (cyclic voltammetry, CV) 進行甲醇氧化反應 (MOR) 效能測試，實驗結果顯示電催化劑的 MOR效能為商用 Pt (E-TEK)/C電催化劑的 2.5 倍。利用計時安培法 (chronoamperometry, CA) 測試電催化劑的穩定性，實驗結果顯示電催化劑 Pt-CeO2/ C 的穩定性也比商用 Pt (E-TEK)/C電催化劑還要佳。
  本研究對於製備電催化劑的方法、碳載體鹼或酸修飾或鉑與鈰在不同莫耳比下所製備出的電催化劑進行分析與比較，並將電催化劑的效能最佳化。

The research are the preparation and characterization of Pt-CeO2/C electrocatalysts for the methanol oxidation reaction (MOR) of a direct methanol fuel cell (DMFC).Pt-CeO2/C electrocatalysts have been synthesized by polyol method and compared with Pt/C (E-TEK) electrocatalysts. Carbon black (Vulcan XC-72) was pretreated with NaOH or HNO3 aqueous solution. A Polyol method is using ethylene glycol as the reducing agent to grows the Pt nanoparticles and CeO2 on the carbon black (CB), then get the Pt-CeO2/C nanocomposite electrocatalysts. Scanning electron microscopic (SEM) images with energy dispersive spectroscopic (EDS) reveal that the Pt and CeO2 contents in the samples are close to the nominal values. Transmission electron microscope (TEM) pictures showed a uniform distribution of platinum on the CB, and observed that the Pt nanoparticles diameter are around 3-4 nm almost close the result of consideration from X-ray diffraction (XRD). The Pt-CeO2/ Ca electrocatalysts by polyol method exhibit 2.5 times higher electrochemical activities for MOR in cyclic voltammetry (CV) experiments, compared with the Pt/C (E-TEK) electrocatalysts. The Pt-CeO2/C electrocatalysts also showed higher stability in chronoamperometry test (CA).In this report,we also compare the property of  Pe/Ce molar ratio and the difference way to pretreat CB effect in the experience.

摘要.......................................................I
目錄.......................................................V
圖目錄...................................................VIII
表目錄....................................................XII
第一章 緒論.................................................1
1.1 前言...................................................1
1.2 燃料電池................................................2
1.3 直接甲醇燃料電池..........................................4
1.3.1 直接甲醇燃料電池工作原理.................................4
1.3.2 甲醇氧化機制...........................................6
1.4 燃料電池催化劑的探討......................................7
1.4.1 多元合金催化劑.........................................7
1.4.2 鉑-金屬氧化物催化劑.....................................8
1.5 研究方向及目標...........................................9
第二章 文獻回顧.............................................10
2.1 利用含浸法製備 Pt-CeO2/C 電催化劑.........................10
2.2 利用多元醇還原法製備 Pt-CeO2/C 電催化劑....................13
2.3 利用微乳化法製備Pt-CeO2/C 電催化劑........................19
第三章 實驗設備與步驟........................................26
3.1 實驗藥品...............................................26
3.2 實驗使用之分析儀器.......................................27
3.3 實驗架構與規劃..........................................28
3.4 Pt-CeO2/C電催化劑之製備.................................29
3.4.1 含浸法 (impregnation method).........................30
3.4.2 微乳化法 (microemulsion method)......................32
3.4.3 多元醇還原法 (polyol method)..........................34
3.4.4 碳載體前處理方法.......................................36
3.5   Pt-CeO2/C 電催化劑的性質與效能分析......................38
3.5.1 表面型態與性質分析.....................................38
3.5.2 電化學方法分析........................................39
第四章 結果與討論............................................47
4.1 電催化劑 Pt-CeO2/C 製備方法選擇..........................47
4.1.1 利用含浸法製備電催化劑..................................48
4.1.2 利用微乳化法製備電催化劑................................51
4.1.3 利用多元醇還原法製備電催化劑.............................54
4.1.4 電催化劑的製備方法比較與選擇.............................57
4.2 鉑與鈰在不同莫耳比對電催化劑的影響..........................59
4.2.1 表面型態與性質分析.....................................59
4.2.2 電化學分析...........................................66
4.3 碳載體鹼處理的影響比較....................................71
4.3.1 表面型態與性質分析.....................................71
4.3.2 電化學分析...........................................76
4.4 碳載體酸處理的影響比較....................................81
4.4.1 表面型態與性質分析.....................................81
4.4.2 電化學分析...........................................86
4.5 電催化劑效能最佳化.......................................90
4.5.1 電催化劑之MOR效能比較..................................90
4.5.2電催化劑之穩定性比較....................................92
第五章 結論................................................93
建議......................................................95
參考文獻...................................................96
圖目錄
圖1 - 1、甲醇燃料電池(DMFC)工作原理[3].........................5
圖2 - 1、Cyclic voltammograms of methanol oxidation in both forward and reverse  sweeps (A) and in forward sweep (B) on Pt–CeO2/carbon black composite anodes (a–c) and a commercially available Pt–Ru/carbon alloy anode (d) at 28℃ in the mixed solution of 0.5M H2SO4 aqueous solution and 0.5M methanol aqueous solution at 50 mV/s. Pt content in anodes (a–d): 3 mg..............................................................11
圖2 - 2、X-ray diffraction patterns of 9% CeO2/C, PC0, PC9 and PC12..................................................12
圖2 - 3、TEM images of CNTs-Pt (a) and CeO2 nanoparticles (b). (c) shows the........................................14
圖2 - 4、XRD patterns of (a) CNTs-Pt and (b) CeO2 nanoparticles.............................................15
圖2 - 5、CV curves for CNTs-Pt and CNTs-Pt + CeO2 in 1M HClO4 +1M.................................................15
圖2 - 6、Chronoamperometry curves for CNTs-Pt and CNTs-Pt + CeO2 in 1M................................................16
圖2 - 7、TEM images of CeO2/C nanocomposite (a) and Pt–CeO2/C catalysts with the molar ratio of Pt and Ce by (b) 1:1, (c) 2:1 and (d) 3:1..................................17
圖2 - 8、The stability of for the electrooxidation of methanol on Pt–CeO2/C catalysts...........................18
圖2 - 9、TEM image of Pt–CeO2/MWNT composites.............19
圖2 - 10、 XRD patterns of Pt–CeO2/MWNT composites........20
圖2 - 11、 Representative scanning TEM images and EDS elemental mapping analysis of (a) PC(6:4)-CBR and (b) PC(6:4)-RME...............................................21
圖2 - 12、(a) Initial mass activity and (b) durability for MOR on commercial Pt/C, commercial PtRu/C, PC(6:4)-CBR, and PC(6:4)-RME. For the durability comparison, the current density values at 0.5 V vs NHE were used from the anodic CV curves cycled between 100 and 1250 mV at a scan rate of 50 mV/s......................................................22
圖3 - 1、實驗流程圖。......................................................................................................................28
圖3 - 2、利用含浸法製備 Pt-CeO2/C-SBH 電催化劑之實驗流程圖。.....31
圖3 - 3、利用微乳化法製備 Pt-CeO2/C-RME 電催化劑之實驗流程圖。...33
圖3 - 4、 利用多元醇還原法製備 Pt-CeO2/C-EGR 電催化劑之實驗流程圖。	.........................................................35
圖3 - 5、碳載體鹼處理實驗流程圖。..............................36
圖3 - 6、碳載體酸處理實驗流程圖。..............................37
圖3 - 7、三極式電化學系統簡示圖。..............................40
圖3 - 8、Pt/C-EGR 電催化劑於 0.5 M 硫酸水溶液的循環伏安圖。......41
圖3 - 9、電催化劑 Pt/C-EGR 於 0.5 M H2SO4 +1.0 M CH3OH水溶液中的MOR      效能圖。..........................................42
圖3 - 10、電催化劑 Pt-CeO2/C-EGR在含飽和一氧化碳的0.5 M硫酸水溶液中的一氧化碳吸/脫附反應圖。.....................................45
圖3 - 11、電催化劑 Pt-CeO2/C-EGR的計時安培法曲線圖,掃描時間1000秒。	..........................................................46
圖4 - 1、電催化劑 Pt-CeO2/C 合成示意圖。........................................................47
圖4 - 2、Pt-CeO2/C-SBH 之 TEM 圖 (a) 25 K (b) 100 K。......49
圖4 - 3、Pt-CeO2/C-SBH (Pt-Ce = 20wt% )與 Pt(E-TEK)/C 於 0.5 M H2SO4 +1.0 M CH3OH 水溶液中之循環伏安圖。...................50
圖4 - 4、Pt-CeO2/C-RME 之 TEM 圖 (a) 40 K，(b) 100K。.......52
圖4 - 5、Pt-CeO2/C-RME (Pt-Ce = 20wt% ) 與Pt (E-TEK)/C 於 0.5 M H2SO4 +1.0 M CH3OH 水溶液中之循環伏安圖。...................53
圖4 - 6、Pt-CeO2/C-EGR 之TEM圖 (a) 40 K，(b) 100 K。........55
圖4 - 7、Pt-CeO2/C-EGR (Pt-Ce = 20wt% ) 與Pt (E-TEK)/C 於 0.5 M H2SO4 +1.0 M CH3OH 水溶液中之循環伏安圖。...................56
圖4 - 8、 利用不同方法製備之 Pt-CeO2/C 電催化劑的 Pt 含量比較圖。	..........................................................57
圖4 - 9、電催化劑Pt-CeO2/C 利用不同方法製備下的MOR 效能比較圖。...58
圖4 - 10、電催化劑Pt-CeO2/C 製備方式選擇圖。...................58
圖4 - 11、Pt-CeO2/C-EGR (Pt-Ce = 20wt%) Pt 與 Ce 在不同莫耳比下的XRD 圖譜；(a)純Pt (b)80:20 (c)60:40 (d)50:50。............61
圖4 - 12、Pt-CeO2/C-EGR之 Pt 與 Ce 不同莫耳比的粒徑比較。......61
圖4 - 13、Pt-CeO2/C-EGR (Pt-Ce = 20wt%, Pt :Ce = 80 : 20 (molar ratio)) 之TEM圖，(a) 100 K、(b) 800 K。.............63
圖4 - 14、Pt-CeO2/C-EGR (Pt-Ce = 20wt%, Pt :Ce = 60 : 40 (molar ratio)) 之TEM圖，(a) 100 K、(b) 800 K。.............64
圖4 - 15、Pt-CeO2/C-EGR (Pt-Ce = 20wt%, Pt :Ce = 50 : 50 (molar ratio)) 之TEM圖，(a) 100 K、(b) 800 K。.............65
圖4 - 16、Pt-CeO2/C-EGR不同莫耳比的EASA 計算比較。............67
圖4 - 17、Pt-CeO2/C-EGR不同莫耳比的MOR 效能比較。.............67
圖4 - 18、Pt-CeO2/C-EGR不同莫耳比的穩定性比較。...............68
圖4 - 19、Pt-CeO2/C-EGR不同莫耳比與商用 Pt(E-TEK)/C的 CO 脫附比較圖。.....................................................70
圖4 - 20、未修飾碳載體 (XC-72) 與鹼處理碳載體 (Cb) 的 FTIR 比較圖。	........................................................72
圖4 - 21、Pt-CeO2/Cb-EGR (Pt-Ce = 20wt%) Pt 與 Ce在不同莫耳比下的XRD 圖譜；(a)純Pt (b)80:20 (c)60:40 (d)50:50。..........74
圖4 - 22、Pt-CeO2/Cb-EGR 中 Pt 與 Ce 不同莫耳比的粒徑比較。....75
圖4 - 23、Pt-CeO2/ Cb -EGR不同莫耳比的MOR 效能比較。..........77
圖4 - 24、Pt-CeO2/Cb-EGR不同莫耳比的穩定性比較。...............78
圖4 - 25、Pt-CeO2/Cb-EGR不同莫耳比與商用 Pt(E-TEK)/C的 CO 脫附比較圖。.....................................................80
圖4 - 26、未修飾碳載體 (XC-72) 與酸處理碳載體 (Ca) 的 FTIR 比較圖。	..........................................................82
圖4 - 27、Pt-CeO2/Ca-EGR (Pt-Ce = 20wt%) Pt 與 Ce 在不同莫耳比下的XRD 圖譜；(a)純Pt (b)80:20 (c)60:40 (d)50:50。..........84
圖4 - 28、Pt-CeO2/Ch-EGR 中 Pt與 Ce 不同莫耳比的粒徑比較。.....85
圖4 - 29、Pt-CeO2/Ca-EGR不同莫耳比的MOR 效能比較。............86
圖4 - 30、Pt-CeO2/Ca-EGR不同莫耳比的穩定性比較。...............87
圖4 - 31、Pt-CeO2/Ca-EGR不同莫耳比與商用 Pt(E-TEK)/C的 CO 脫附比較圖。.....................................................89
圖4 - 32、利用不同碳載體修飾方法Pt-CeO2/C-EGR不同莫耳比的 MOR 效能比較圖。.....................................................91
圖4 - 33、利用不同碳載體製備電催化劑的穩定性比較圖。..............92
表目錄
表4 - 1、Pt-CeO2/C-SBH 的 EDS 表面元素分析結果。..............50
表4 - 2、Pt-CeO2/C-RME 的SEM表面元素分析表。..................53
表4 - 3、電催化劑 Pt-CeO2/C-EGR 的SEM表面元素分析表。..........56
表4 - 4、Pt-CeO2/C-EGR不同莫耳比的SEM表面元素分析。............59
表4 - 5、電催化劑Pt-CeO2/Cb-EGR不同莫耳比的SEM表面元素分析。.....73
表4 - 6、Pt-CeO2/ Cb -EGR不同莫耳比的EASA 計算比較。..........77
表4 - 7、電催化劑Pt-CeO2/Ca-EGR不同莫耳比的SEM表面元素分析。.....83
表4 - 8、電催化劑的 MOR 效能及 Pt 粒徑比較.....................91

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