臺灣博碩士論文加值系統

利用第一族過渡金屬氧化物催化鋁/水系統產氫，經由Arrhenius equation理論求得活化能，證實氧化物皆具有催化活性，純鋁的活化能為164.86 kJ/mol，氧化物催化效果最佳的是Co3O4（70.42 kJ/mol），而最差的是ZnO（140.15 kJ/mol），透過這相對的關係可以印證造成反應速率差異的現象為每個氧化物在鋁/水產氫系統中的催化效果不同。
在氧化物催化鋁/水產氫的重複添加系統，實驗證明為反應後副產物（Al(OH)3）的催化效應，藉由改變Al(OH)3的材料特性（粒徑、結晶、表面積）則會影響其反應速率，結果顯示，當粒徑小，結晶性差，表面積大的材料性質，催化鋁/水產氫系統具有良好的催化活性（31.56 kJ/mol）。
最後以Al：Al(OH)3：H2O＝1：8：50為最佳參數，此反應條件在兩個小時內產氫效率高達94.9%，將此應用於燃料電池上，所產生的氫氣確實能使燈泡發光。從鋁與水的反應中，本研究揭露出一種快速而簡易的產氫方式。

The present study proved that the first family transition metal oxide all facilitated the hydrogen generation from aluminum(Al)/water system by reduction of activation energy. All activation energies were calculated using Arrhenius equation. The activation energies obtained for the pure aluminum is 164.86 kJ/mol. The best catalytic effect is obtained from Co3O4, whose activation energy is only 70.42 kJ/mol. The weakest catalytic effect is obtained from ZnO, whose activation energy is 140.15 kJ/mol. The calculation of activation energy provides an insight of the catalytic effect of transition metal oxide on Al/water system.
It was also found that the consecutive addition of metal Al into water could result in an increasing rapid hydrogen generation rate. Experiments proved that the catalytic effect of reaction by-products (Al(OH)3) exhibited profound effect on the generation rate. The catalytic effect of Al(OH)3 greatly depends on their particle size, crystallinity, surface area. Small particle size, high surface area and poor crystallinity of Al(OH)3 increases the hydrogen generation rate significantly. Al(OH)3 has a strong catalytic effect on aluminum/water system for its hydrogen generation. The activation energy of this system is only 31.56 kJ /mol.
For the best combination of this study, Al: Al(OH)3: H2O = 1:8:50, its hydrogen production efficiency achieves 94.9% within two hours. When the hydrogen generated was applied to a fuel cell as a power source, it indeed turns on the bulb. The present study has discovered a fast and simple way to generate hydrogen gas from Al/water system.

目錄
中文摘要 I
Abstract II
謝誌 III
目錄 V
圖目錄 IX
表目錄 XVI
第一章 緒論 1
1.1 前言 1
1.2 氫氣的簡介 3
1.3 氫氣的製備 4
1.4 氫氣的運輸與儲存 6
1.5 氫氣的應用－燃料電池 7
1.6 研究目的與動機 8
第二章 理論基礎與文獻回顧 10
2.1 鋁的簡介 10
2.2 氫氧化鋁的基本特性 12
2.3 何謂催化 14
2.3.1 歷史背景 14
2.3.2 原理 14
2.3.3 催化劑的性能指標 17
2.3.4 催化反應和催化劑的種類 17
2.4 鋁∕水系統產氫 18
2.4.1 鋁∕水系統產氫－鹼性水溶液 19
2.4.2 鋁∕水系統產氫－氧化物修飾 21
2.4.3 鋁∕水系統產氫－合金 27
2.4.3 鋁∕水系統產氫－無機鹽類 30
第三章 實驗方法與設備 33
3.1 實驗藥品 33
3.2 實驗儀器設備 35
3.3 實驗步驟 36
3.3.1 金屬氧化物對鋁/水產氫系統的影響 36
3.3.2 鋁/水系統的自我催化產氫 39
3.3.3 燃料電池的應用 44
3.4 材料鑑定分析 46
3.4.1 飛行時間二次離子質譜儀（Time-of-Flight Secondary Ion Mass Spectrometer，TOF-SIMS） 46
3.4.2 感應耦合電漿質譜儀（Inductively Coupled Plasma Mass，ICP-MS） 47
3.4.3 粉末X-Ray繞射儀（Powder X-ray diffraction，XRD） 48
3.4.4 場發射掃描式電子顯微鏡（Field Emission Scanning Electron Microscopy，FE-SEM） 50
3.4.5 X光能譜分析儀（Energy Dispersive X-ray Spectrometer，EDS） 50
3.2.6 奈米粒徑分析儀（Dynamic Light Scattering，DLS） 53
3.4.7 比表面積分析儀（Brunauer-Emmett-Teller Apparatus） 54
3.4.8 CEM/Discover聚焦式微波合成反應系統 55
3.4.9 氣體流量計（Gas Flow meter） 56
3.5 實驗裝置 57
3.6 其他實驗器材 58
第四章 結果與討論 59
4.1 實驗參數的影響 59
4.2金屬氧化物對鋁/水產氫系統的影響 65
4.2.1活化能實驗 69
4.2.2結論 119
4.3 鋁/水系統的自我催化產氫 121
4.3.1 氧化物催化效應 124
4.3.2 溶液系統中的效應（pH值） 125
4.3.3 溶液系統中的效應（粉體） 128
4.3.3.1 反應機制 130
4.3.3.2 粒徑 132
4.3.3.3 結晶 136
4.3.3.4 表面積 138
4.3.3.5 產氫 139
4.3.3.6 活化能 141
4.3.4 結論 147
4.4 燃料電池的應用 149
4.4.1結論 155
第五章 總結 156
第六章 未來展望 158
參考文獻 159

圖目錄
圖 1- 1 石油價格十年趨勢 2
圖 1- 2 能源單位能量與質量的比較 3
圖 1- 3 燃料電池示意圖 7
圖 2- 1 三水鋁石、三羥鋁石的層狀堆疊圖樣…...............…..............13
圖 2- 2（a）、（b）催化反應前後活化能與最低限能分子數比較圖 15
圖 2- 3（a）未催化反應與（b）加入催化劑之活化能障礙的比較 15
圖 2- 4 lnk與1/T數據圖（範例） 16
圖 2- 5 孔蝕機制（Point Defect Model for Pitting）示意圖 22
圖 2- 6 均勻腐蝕機制（Uniform Corrosion Modle）示意圖 24
圖 2- 7反應產物（實線）和初始反應物（虛線）的XRD圖譜 24
圖 2- 8 無機鹽類反應機制示意圖 31
圖 2- 9 Al∕C形成核殼結構（core-shell），反應機制示意圖 31
圖 3- 1 燃料電池裝置圖……………………………………………...45
圖 3- 2 SIMS（清華大學） 46
圖 3- 3 ICP-MS（中山大學） 47
圖 3- 4 X射線晶格繞射示意圖 48
圖 3- 5 粉末X-Ray繞射儀（中原大學） 49
圖 3- 6 FE-SEM偵測原理示意圖 51
圖 3- 7 FE-SEM-EDS（中原大學） 52
圖 3- 8 DLS（中原大學） 53
圖 3- 9 BET（中原大學） 54
圖 3- 10 CEM/Discover儀器外觀 55
圖 3- 11 Gas Flow meter 56
圖 3- 12鋁與氧化物利用瑪瑙研缽手磨示意圖 57
圖 3- 13 鋁/水產氫系統裝置圖 57
圖 4- 1 瑪瑙研缽手磨反應機制圖…………………………………...61
圖 4- 2 球磨機球磨反應機制圖 61
圖 4- 3 TOF-SIMS測定水中氧原子含量 63
圖 4- 4 鋁（pure）在去離子水的產氫效率圖 64
圖 4- 5 ICP-MS測定水中鋁離子的含量 64
圖 4- 6 金屬氧化物產氫效率圖（25℃） 67
圖 4- 7 金屬氧化物產氫效率圖（35℃） 67
圖 4- 8 金屬氧化物產氫效率圖（45℃） 68
圖 4- 9 金屬氧化物產氫效率圖（55℃） 68
圖 4- 10 表面形貌與元素分析。（a）Pure Al（EDS掃描區域） 70
圖 4- 11 鋁/水產氫系統（In 35℃反應終止）的表面形貌 71
圖 4- 12 鋁/水系統的材料鑑定（XRD分析圖譜） 71
圖 4- 13 Al與TiO2瑪瑙研缽手磨混合。（a）EDS掃描區域 72
圖 4- 14 TiO2催化鋁/水產氫系統（反應終止）的表面形貌 73
圖 4- 15 TiO2催化鋁/水產氫系統反應前後的物質變化 73
圖 4- 16 Al與Cr2O3瑪瑙研缽手磨混合。（a）EDS掃描區域 74
圖 4- 17 Cr2O3催化鋁/水產氫系統（反應終止）的表面形貌 75
圖 4- 18 Cr2O3催化鋁/水產氫系統反應前後的物質變化 75
圖 4- 19 Al與Mn2O3瑪瑙研缽手磨混合。（a）EDS掃描區域 76
圖 4- 20 Mn2O3催化鋁/水產氫系統（反應終止）的表面形貌 77
圖 4- 21 Mn2O3催化鋁/水產氫系統反應前後的物質變化 77
圖 4- 22 Fe2O3催化鋁/水產氫系統反應前後的物質變化 78
圖 4- 23 Al與Co3O4瑪瑙研缽手磨混合。（a）EDS掃描區域 79
圖 4- 24 Co3O4催化鋁/水產氫系統（反應終止）的表面形貌 80
圖 4- 25 Co3O4催化鋁/水產氫系統反應前後的物質變化 80
圖 4- 26 Al與NiO瑪瑙研缽手磨混合。（a）EDS掃描區域 81
圖 4- 27 NiO催化鋁/水產氫系統（反應終止）的表面形貌 82
圖 4- 28 NiO催化鋁/水產氫系統反應前後的物質變化 82
圖 4- 29 Al與CuO瑪瑙研缽手磨混合。（a）EDS掃描區域 83
圖 4- 30 CuO催化鋁/水產氫系統（反應終止）的表面形貌 84
圖 4- 31 CuO催化鋁/水產氫系統反應前後的物質變化 84
圖 4- 32 Al與ZnO瑪瑙研缽手磨混合。（a）EDS掃描區域 85
圖 4- 33 ZnO催化鋁/水產氫系統（反應終止）的表面形貌 86
圖 4- 34 ZnO催化鋁/水產氫系統反應前後的物質變化 86
圖 4- 35 Al與γ-Al2O3瑪瑙研缽手磨混合。（a）EDS掃描區域 87
圖 4- 36 γ-Al2O3催化鋁/水產氫系統（反應終止）的表面形貌 88
圖 4- 37 γ-Al2O3催化鋁/水產氫系統反應前後的物質變化 88
圖 4- 38 鋁/水產氫系統（產氫數據圖） 99
圖 4- 39 鋁/水產氫系統（ln(k) vs 1000T-1(K)） 99
圖 4- 40 鋁/水產氫系統（Ea示意圖） 100
圖 4- 41 TiO2催化鋁/水產氫系統（產氫數據圖） 101
圖 4- 42 TiO2催化鋁/水產氫系統（ln(k) vs 1000T-1(K)） 101
圖 4- 43 TiO2催化鋁/水產氫系統（Ea示意圖） 102
圖4- 44 Cr2O3催化鋁/水產氫系統（產氫數據圖） 103
圖 4- 45 Cr2O3催化鋁/水產氫系統（ln(k) vs 1000T-1(K)） 103
圖 4- 46 Cr2O3催化鋁/水產氫系統（Ea示意圖） 104
圖 4- 47 Mn2O3催化鋁/水產氫系統（產氫數據圖） 105
圖 4- 48 Mn2O3催化鋁/水產氫系統（ln(k) vs 1000T-1(K)） 105
圖 4- 49 Mn2O3催化鋁/水產氫系統（Ea示意圖） 106
圖 4- 50 Fe2O3催化鋁/水產氫系統（產氫數據圖） 107
圖 4- 51 Fe2O3催化鋁/水產氫系統（ln(k) vs 1000T-1(K)） 107
圖 4- 52 Fe2O3催化鋁/水產氫系統（Ea示意圖） 108
圖 4- 53 Co3O4催化鋁/水產氫系統（產氫數據圖） 109
圖 4- 54 Co3O4催化鋁/水產氫系統（ln(k) vs 1000T-1(K)） 109
圖 4- 55 Co3O4催化鋁/水產氫系統（Ea示意圖） 110
圖 4- 56 NiO催化鋁/水產氫系統（產氫數據圖） 111
圖 4- 57 NiO催化鋁/水產氫系統（ln(k) vs 1000T-1(K)） 111
圖 4- 58 NiO催化鋁/水產氫系統（Ea示意圖） 112
圖 4- 59 CuO催化鋁/水產氫系統（產氫數據圖） 113
圖 4- 60 CuO催化鋁/水產氫系統（ln(k) vs 1000T-1(K)） 113
圖 4- 61 CuO催化鋁/水產氫系統（Ea示意圖） 114
圖 4- 62 ZnO催化鋁/水產氫系統（產氫數據圖） 115
圖 4- 63 ZnO催化鋁/水產氫系統（ln(k) vs 1000T-1(K)） 115
圖 4- 64 ZnO催化鋁/水產氫系統（Ea示意圖） 116
圖 4- 65 γ-Al2O3催化鋁/水產氫系統（產氫數據圖） 117
圖 4- 66 γ-Al2O3催化鋁/水產氫系統（ln(k) vs 1000T-1(K)） 117
圖 4- 67 γ-Al2O3催化鋁/水產氫系統（Ea示意圖） 118
圖 4- 68 TiO2催化鋁/水產氫的重複添加系統 122
圖 4- 69 P90催化鋁/水產氫的重複添加系統 122
圖 4- 70 Cr2O3催化鋁/水產氫的重複添加系統 123
圖 4- 71 Co3O4催化鋁/水產氫的重複添加系統 123
圖 4- 72 TiO2置於水中時間對產氫系統的催化差異 124
圖 4- 73 重複添加次數之產氫速率與pH值關係（TiO2） 126
圖 4- 74 重複添加次數之產氫速率與pH值關係（P90） 126
圖 4- 75 重複添加次數之產氫速率與pH值關係（Cr2O3） 127
圖 4- 76 重複添加次數之產氫速率與pH值關係（Co3O4） 127
圖 4- 77 模擬重複添加之產氫結果 129
圖 4- 78 水溶液系統中氫氧化鋁粉體量的影響 129
圖 4- 79 氫氧化鋁催化鋁/水產氫系統的反應機制示意圖 130
圖 4- 80 微波水熱合成AlO(OH) 131
圖 4- 81 Al(OH)3的表面形態。（A）Al(OH)3（Acros，5μm），（B）Al(OH)3（Acros，5μm）攪拌24hr – TOP（C）Al(OH)3（Acros，5μm）攪拌24hr – Bottom（D）Al(OH)3（NanoAmor，500nm）（E）Al（Alfa Aesar，45μm）after reaction 135
圖 4- 82 Al(OH)3的結晶度。（A）Al(OH)3（Acros，5μm），（B）Al(OH)3（Acros，5μm）攪拌24hr – TOP（C）Al(OH)3（Acros，5μm）攪拌24hr – Bottom（D）Al(OH)3（NanoAmor，0.5μm）（E）Al（Alfa Aesar，45μm）- after reaction（F）Al(OH)3（NanoAmor，0.5μm）+ Al - after reaction 137
圖 4- 83 氫氧化鋁的差異造成產氫速率的影響 140
圖 4- 84 Al與Al(OH)3瑪瑙研缽手磨混合。（a）EDS掃描區域 141
圖 4- 85 Al(OH)3催化鋁/水產氫系統（反應終止）的表面形貌 142
圖 4- 86 Al(OH)3催化鋁/水產氫系統反應前後的物質變化 143
圖 4- 87 Al(OH)3催化鋁/水產氫系統（產氫數據圖） 145
圖 4- 88 Al(OH)3催化鋁/水產氫系統（ln(k) vs 1000T-1(K)） 145
圖 4- 89 Al(OH)3催化鋁/水產氫系統（Ea示意圖） 146
圖 4- 90 鋁與氫氧化鋁不同比例的產氫圖（200 mL D.I. water） 151
圖 4- 91 鋁與氫氧化鋁不同比例的產氫圖（100 mL D.I. water） 151
圖 4- 92 鋁與氫氧化鋁不同比例的產氫圖（50 mL D.I. water） 152
圖 4- 93 不同水量中氫氧化鋁克數對產氫率的影響 152
圖 4- 94 Al：Al(OH)3為1：8時不同水量的產氫差異 153
圖 4- 95 Al(OH)3催化鋁/水產氫系統應用於燃料電池 154

表目錄
表 2- 1 氫氧化鋁不同晶相的熱力學性質比較（T＝298K） 13
表 2- 2 氫氧化鋁不同溫度的熱力學性質比較 18
表 2- 3 鋁∕水系統產氫－鹼性水溶液文獻回顧 20
表 2- 4 鋁∕水系統產氫－氧化物修飾文獻回顧 25
表 2- 5 鋁∕水系統產氫－鋁合金文獻回顧 28
表 2- 6 鋁∕水系統產氫－無機鹽類文獻回顧 32
表 3- 1 實驗藥品清單…………………………………………………33
表 3- 2 實驗儀器名稱與型號 35
表 3- 3 其他實驗器材清單 58
表 4- 1 Pure Al（EDS分析數據）……………………………………….70
表 4- 2 Al與TiO2手磨混合的元素比例 72
表 4- 3 Al與Cr2O3手磨混合的元素比例 74
表 4- 4 Al與Mn2O3手磨混合的元素比例 76
表 4- 5 Al與Co3O4手磨混合的元素比例 79
表 4- 6 Al與NiO手磨混合的元素比例 81
表 4- 7 Al與CuO手磨混合的元素比例 83
表 4- 8 Al與ZnO手磨混合的元素比例 85
表 4- 9 Al與γ-Al2O3手磨混合的元素比例 87
表 4- 10 Al材料的分析結果 89
表 4- 11 TiO2材料的分析結果 90
表 4- 12 Cr2O3材料的分析結果 91
表 4- 13 Mn2O3材料的分析結果 92
表 4- 14 Fe2O3材料的分析結果 93
表 4- 15 Co3O4材料的分析結果 94
表 4- 16 NiO材料的分析結果 95
表 4- 17 CuO材料的分析結果 96
表 4- 18 ZnO材料的分析結果 97
表 4- 19 γ-Al2O3材料的分析結果 98
表 4- 20 氧化物催化鋁/水產氫系統的活化能 120
表 4- 21 重複添加系統反應速率差異統整表 121
表 4- 22 粒徑分析儀數據表 135
表 4- 23 比表面積分析儀數據表 138
表 4- 24 Al與Al(OH)3手磨混合的元素比例 142
表 4- 25 Al(OH)3材料的分析結果 144
表 4- 26 Al(OH)3的材料特性 148
表 4- 27 最佳比例數據整理表（H2 yield/2hr） 155

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