本研究以改變離子交換法及化學還原法之條件製備鈷硼觸媒，探討負載量、表面結構、表面積、金屬比例、分散性以及結晶態與硼氫化鈉水解產氫動力學參數之關係，並將結果應用至硼氫化鈉產氫系統。在離子交換部分，以TP-207樹脂為載體，改變前驅物、pH值、溫度，結果顯示使用CoCl2在pH值3.93還原溫度25℃時，擁有最佳之鈷離子交換量；在觸媒還原階段中，改變還原劑種類、濃度、分散劑濃度、還原溫度、還原劑添加速率。藉由調整個還原變數，能夠改變金屬比例、表面積以及特地之結晶態。當Co/B接近2、表面積提升、能提升40℃及80℃下之活性。從結晶態結果得知，不同之晶型結果會影響水解產氫在40及80℃之活性。由還原階段之合成條件結果顯示: 以0.5 wt.% 之KBH4、10 wt.% 乙二醇、75℃的還原溫度、5 ml/min的還原劑添加速率，可以得到最佳之Co-B觸媒活性。經由L-H動力學模式進行實驗數據回歸，並與觸媒表面結構與組成做比較，選用KBH4還原劑並降低其還原劑濃度、還原溫度、添加速率可以提升觸媒活性。降低還原劑濃度、提升還原溫度、降低還原劑添加速率則能改善釋氫之拖尾現象。

In this work, the ion exchange and chemical reduction method were used to synthesize Co-B catalyst. Catalyst loading, surface structure, surface area, metal composition, and crystal structure of Co-B catalyst were investigated in order to understand the connection between surface morphology/composition and the kinetic parameters of NaBH4 hydrolysis reaction. In the ion exchange step, the maximum Co ion exchange amount over TP-207 resin was operated at the synthesis condition: CoCl2 precursor, 3.93 pH, 25 oC ion exchange temperature. In the reduction step, types and concentrations of reduction agents, the concentration of dispersion agent, the reduction temperatures, and injection rates were investigated. The metal composition, surface area, and crystal structure were adjusted by the synthesis variable. The 40 and 80oC activities of Co-B catalyst were improved by adjusting the ratio of Co and B to 2, increasing surface area, and synthesing the certain Co-B crystal type. The results show that the 40 and 80 oC activity of Co-B catalyst was improved while different crystal structure was formation. The optimal result shows the best Co-B catalyst activity was located on following synthesis condition: 0.5 wt.% KBH4, 10 wt.% Ethylene glycol, 75 oC reduction temperature and 5 ml/min injection rate. After regressing kinetic parameters by using L-H model, the catalyst activity can be improved by decreasing KBH4 concentration, reduction temperature and injection rate; the tail of hydrogen generation curve can be improved by decreasing KBH4 concentration and injection rate.

目錄
目錄	III
圖目錄	VIII
表目錄	XIV
第一章、緒論	1
1.1背景	1
1.2文獻回顧	5
1.2.1硼氫化鈉應用	5
1.2.2硼氫化鈉觸媒反應	6
1.2.3 硼氫化鈉水解觸媒之速率表現	11
1.2.4 觸媒製備方法	12
1.2.4.1離子交換	12
1.2.4.2鈷硼觸媒還原	13
1.3 研究動機	14
1.4 論文組織	15
第二章、實驗藥品與裝置介紹	16
2.1 實驗材料	16
2.1.1 觸媒合成及硼氫化鈉水溶液產氫實驗藥品	16
2.1.2 觸媒合成及硼氫化鈉產氫實驗設備	18
2.2 實驗裝置	18
2.2.1硼氫化鈉水溶液產氫實驗裝置	19
2.3觸媒分析鑑定	21
2.4實驗步驟	23
2.4.1 鈷硼觸媒製備步驟	23
2.4.1.1離子交換	24
2.4.1.2鈷硼觸媒還原	25
2.4.2硼氫化鈉水解產氫實驗步驟	26
2.5實驗數據測量	27
2.6觸媒負載量量測	30
2.7實驗數據處理	30
第三章、鈷硼觸媒製備及其製備條件分析	31
3.1　離子交換法製備鈷錋觸媒之介紹	31
3.1.1 離子交換變數	31
3.1.2 鈷硼觸媒還原	34
3.2鈷錋觸媒製備變數分析	35
3.2.1離子交換	35
3.2.1.1離子交換與前驅物關係	36
3.2.1.2離子交換與pH值關係	37
3.2.1.3離子交換與溫度關係	40
3.2.2鈷硼觸媒還原	42
3.2.2.1還原劑種類與最佳濃度	47
3.2.2.1.1還原劑種類與產氫活性	47
3.2.2.1.2還原劑種類與觸媒結構/組成分析	48
3.2.2.1.3還原劑濃度與產氫活性	50
3.2.2.1.4還原劑濃度與表面結構/組成分析	51
3.2.2.2分散劑添加及濃度改變	56
3.2.2.2.1分散劑添加及濃度改變與產氫活性	56
3.2.2.2.2分散劑添加及濃度改變對觸媒負載量與pH值影響	59
3.2.2.2.3分散劑添加及濃度改變與結構/組成分析	60
3.2.2.3還原溫度	65
3.2.2.3.1還原溫度與產氫活性	65
3.2.2.3.2還原溫度與結構/組成分析	68
3.2.2.4還原劑添加速率	73
3.2.2.4.1還原劑添加速率與產氫活性	74
3.2.2.4.2還原劑添加速率與結構分析	77
3.2.2.5  NaBH4與KBH4兩還原劑所製備之觸媒活性與結構比較	81
3.4總結	82
第四章、觸媒動力學參數迴歸	84
4.1 系統描述	84
4.2 觸媒動力式	85
4.3 反應速率常數及吸附常數迴歸	87
4.4觸媒動力學參數迴歸	90
4.4.1 頻率因子與活化能迴歸	90
4.4.2 L-H動力式之吸附常數	92
4.4.3 迴歸結果	94
4.4.3.1 還原劑種類	94
4.4.3.2 KBH4還原劑濃度	95
4.4.3.3 分散劑濃度	95
4.4.3.4 還原溫度	96
4.4.3.7還原劑添加速率	97
第五章、鈷硼觸媒綜合性分析	120
5.1 動力學參數與觸媒結構	120
5.1.1 還原劑最適化條件對觸媒活性綜合分析	122
5.1.2分散劑對觸媒活性綜合分析	126
5.1.3 還原溫度對觸媒活性綜合分析	129
5.1.4添加速率對觸媒綜合影響	132
5.1.5 總結	135
5.2 觸媒耐久性測試	137
第六章、結論	138
參考文獻	141
 
圖目錄
圖1-1、燃料電池運作方式	2
圖1-2、硼氫酸根與酸催化反應機制圖	7
圖1-3、硼氫酸根與金屬觸媒催化反應機制圖	8
圖1-4、非貴金屬與貴金屬活性比較圖	9
圖1-5、硼氫化納水解觸媒速率圖	11
圖2-1、硼氫化鈉水解產氫實驗與量測裝置圖	19
圖2-2、硼氫化鈉水解產氫實驗與量測裝置圖	20
圖2-3、觸媒製備示意圖	24
圖2-4、溫度紀錄程式圖示	27
圖2-5、溫度紀錄程式操作介面	28
圖2-6、電子天秤紀錄程式圖示	28
圖2-7、電子天秤紀錄程式操作介面	29
圖2-8、平滑化處理前後比較圖	30
圖3-1 IR-120與TP-207樹脂載體之耐久性測試後SEM圖 30000x(a)IR-120 (b)TP-207	33
圖3-2、Co-B觸媒使用不同前驅物pH值與負載量關係圖	36
圖3-3、pH值與離子交換量	38
圖3-4、Co-B觸媒使用不同NaOH wt.%之與負載量	38
圖3-5、Co-B觸媒使用不同NaOH wt.%之前後pH值	39
圖3-6、改變離子交換溫度之負載量關係圖	40
圖3-7、Co-B觸媒SEM圖 200000X 還原劑種類為	48
(a)NaBH4, (b)KBH4	48
圖3-8、改變還原劑濃度與最佳條件在40℃下產氫測試	50
圖3-9、改變還原劑濃度與最佳條件在80℃下產氫測試	51
圖3-10、Co-B觸媒SEM圖 200000x 還原劑KBH4濃度為 0.5 wt.%	52
圖3-11、X光光電子能譜圖(a) Co能譜圖、(b)B能譜圖	54
圖3-12、X光繞射分析圖 (K-01)	55
圖3-13、添加乙二醇對BH4-分散性之示意圖	56
圖3-14、KBH4改變還原劑濃度在40℃產氫測試圖	57
圖3-15、KBH4改變還原劑濃度在80℃產氫測試圖	58
圖3-16、NaBH4改變還原劑濃度在40℃產氫測試圖	58
圖3-17、NaBH4改變還原劑濃度在40℃產氫測試圖	59
圖3-18、觸媒負載量與pH值隨乙二醇濃度變化圖(a)KBH4 0.5 wt.%, (b)NaBH4 10wt.%	60
圖3-19、Co-B觸媒使用NaBH4及KBH4還原劑添加乙二醇之SEM圖	62
(a)KBH4 EG 0wt.% x10000, (b)KBH4 10 wt.% EG x10000, (c)KBH4 0wt.% EG x200000, (d)KBH4 10 wt.% EG x200000, (e)NaBH4 0 wt.% EG x10000, (f)NaBH4 10 wt.% EG x10000, (g)NaBH4 0 wt.% EG x200000, (h)NaBH4 10 wt.% EG x200000	62
圖3-20、K-07之EDS元素比例分析圖	63 64
圖3-21、X光繞射分析圖 (K-07)	65
圖3-22、KBH4改變還原溫度在40℃產氫測試	66
圖3-23、KBH4改變還原溫度在80℃產氫測試	67
圖3-24、NaBH4改變還原溫度在40℃產氫測試	67
圖3-25、NaBH4改變還原溫度在80℃產氫測試	67
圖3-26、Co-B觸媒使用NaBH4及KBH4還原劑改變還原溫度之SEM圖200000x (a)KBH4 0℃ , (b)KBH4 75℃, (c)NaBH4 25℃, (d)NaBH4 75℃	69
圖3-27、X光繞射分析圖 (K-09)	72
圖3-28、X光繞射分析圖 (K-11)	72
圖3-29、KBH4改變添加速率在40℃產氫測試	75
圖3-30、KBH4改變添加速率在80℃產氫測試	75
圖3-31、NaBH4改變添加速率在40℃產氫測試	76
圖3-32、NaBH4改變添加速率在80℃產氫測試	76
圖3-33、Co-B觸媒使用NaBH4及KBH4還原劑改變添加速率之SEM 圖x100000 (a)KBH4 50 ml(once), (b) KBH4 5 ml/min, (c)NaBH4 50ml(once), (d)NaBH4 5ml/min	78
圖3-34、X光繞射分析圖 (K-13)	80
圖4-1、K-01觸媒反應溫度40、60、80℃氫氣累積圖	85
圖4-2、K-01觸媒反應溫度40、60、80℃L-H動力參數迴歸	89
圖4-3、反應速率常數中頻率因子及活化能之線性迴歸圖	91
圖4-4、吸附常數中焓變化(ΔH0)及熵變化(ΔS0)之線性迴歸圖	93
圖4-5、改變還原劑種類之產氫實驗氫氣累積圖操作溫度(a)40℃(b)60℃(c)80℃	98
圖4-6、改變還原劑種類之動力學參數迴歸圖操作溫度(a)40℃(b)60℃(c)80℃	99
圖4-7、改變還原劑種類之速率常數迴歸(a)K-01 (b)Chen and Pan. (2014)	100
圖4-8、改變還原劑種類之吸附常數迴歸(a)K-01 (b)Chen and Pan. (2014)	101
圖4-9、改變KBH4還原劑濃度之產氫實驗氫氣累積圖操作溫度(a)40℃(b)60℃(c)80℃	102
圖4-10、改變還原劑濃度之動力學參數迴歸圖操作溫度(a)40℃(b)60℃(c)80℃	103
圖4-11、改變還原劑濃度之速率常數迴歸(a)K-01(b)K-02(c)K-03(d)K-04(e)K-05	104
圖4-12、改變還原劑濃度之吸附常數迴歸(a)K-01(b)K-02(c)K-03(d)K-04(e)K-05	105
圖4-13、不同還原劑改變分散劑濃度之產氫實驗氫氣累積圖操作溫度(a)KBH4 40℃(b) KBH4 60℃(c) KBH4 80℃ (d)NaBH4 40℃ (e) NaBH4 60℃ (f) NaBH4 80℃	106
圖4-14、不同還原劑改變分散劑濃度之動力學參數迴歸圖操作溫度(a)KBH4 40℃(b) KBH4 60℃(c) KBH4 80℃ (d)NaBH4 40℃ (e) NaBH4 60℃ (f) NaBH4 80℃	107
圖4-15、不同還原劑改變分散劑濃度之速率常數迴歸	108
(a)K-01(b)K-06(c)K-07(d)K-08(e)Chen and Pan.(2014)(f)N-02(g)N-03 (h)N-04	108
圖4-16、不同還原劑改變分散劑濃度之吸附常數迴歸	109
(a)K-01(b)K-06(c)K-07(d)K-08(e)Chen and Pan.(2014)(f)N-02(g)N-03 (h)N-04	109
圖4-17、不同還原劑改變還原溫度之產氫實驗氫氣累積圖操作溫度(a)KBH4 40℃(b) KBH4 60℃(c) KBH4 80℃ (d)NaBH4 40℃ (e) NaBH4 60℃ (f) NaBH4 80℃	110
圖4-18、不同還原劑改變還原溫度之動力學參數迴歸圖操作溫度(a)KBH4 40℃(b) KBH4 60℃(c) KBH4 80℃ (d)NaBH4 40℃ (e) NaBH4 60℃ (f) NaBH4 80℃	111
圖4-19、不同還原劑改變還原溫度之速率常數迴歸	112
(a)K-09(b)K-07(c)K-10(d)K-11(e)N-05(f)N-03(g)N-06(h)N-07	112
圖4-20、不同還原劑改變還原溫度之吸附常數迴歸	113
(a)K-09(b)K-07(c)K-10(d)K-11(e)N-05(f)N-03(g)N-06(h)N-07	113
圖4-21、不同還原劑改變添加速率之產氫實驗氫氣累積圖操作溫度	114
(a)KBH4 40℃(b) KBH4 60℃(c) KBH4 80℃ (d)NaBH4 40℃ (e) NaBH4 60℃ (f) NaBH4 80	114
圖4-22、不同還原劑改變添加速率之動力學參數迴歸圖操作溫度(a)KBH4 40℃(b) KBH4 60℃(c) KBH4 80℃ (d)NaBH4 40℃ (e) NaBH4 60℃ (f) NaBH4 80℃	115
圖4-23、不同還原劑改變添加速率之速率常數迴歸	116
(a)K-11(b)K-12(c)K-13(d)N-03(e)N-08(f)N-09	116
圖4-24、不同還原劑改變添加速率之吸附常數迴歸	117
(a)K-11(b)K-12(c)K-13(d)N-03(e)N-08(f)N-09	117
圖5-1、觸媒微結構到巨觀產氫結果示意圖	121
圖5-2、還原劑最適化條件速率圖操作溫度(a)40℃(b)60℃	124
圖5-3、分散劑濃度之速率圖操作溫度(a)40℃(b)60℃	127
圖5-4、還原溫度之速率圖操作溫度(a)40℃(b)60℃	130
圖5-5、添加速率之速率圖操作溫度(a)40℃(b)60℃	133
 
表目錄
表1-1、各類燃料電池分類及應用	3
表1-2、單位體積下所能達到儲存之能量密度	4
表1-3、儲氫物儲氫量比較表	5
表1-4、貴金屬觸媒文獻研究資料彙	9
表1-5、非貴金屬載體觸媒文獻研究資料彙整	10
表2-1、實驗設備與儀器	18
表3-1、離子交換樹脂物性比較表	33
表3-2、還原變數分析	44
表3-3、觸媒各條件比較總表-1	45
表3-4、觸媒各條件比較總表-2	46
表3-5、還原劑NaBH4及KBH4之表面積分析及脫附直徑	49
表3-6、最佳還原劑條件之NaBH4及KBH4之BET分析	52
表3-7、ICP-MS檢測之Co與B含量	53
表3-8、K-01之X光光電子能譜檢測之Co與Co-B比例分析	54
表3-9、K-01之X光光電子能譜檢測之B與Co-B比例分析	55
表3-10、EDS元素比例分析	63
表3-11、KBH4最佳分散劑條件之表面積分析及脫附直徑	61
表3-12、改變分散劑濃度ICP-MS檢測之Co與B含量	64
表3-13、觸媒合成之還原溫度對觸媒表面積及脫附直徑分析表	69
表3-14、改變還原溫度0℃及75℃ICP-MS檢測之Co與B含量	70
表3-15、不同還原溫度其結晶型及種類與產氫活性比較	73
表3-16、改變添加速率50 ml(once)及5 ml/min表面積及脫附直徑分析	79
表3-17、改變添加速率50 ml(once)及5 ml/min ICP-MS檢測之Co與B含量	79
表4-1、K-01觸媒操作溫度對反應速率常數及吸附常數迴歸表	89
表4-2、使用KBH4充當還原劑各條件動力學參數	118
表4-3、使用NaBH4充當還原劑各條件動力學參數	119
表5-1、各效應對於產氫實驗以及動力學上影響	122
表5-2、還原劑最適化條件動力學參數表	125
表5-3、分散劑條件動力學參數表	128
表5-4、還原溫度條件動力學參數表	131
表5-5、添加速率條件動力學參數表	134
表5-6、觸媒設計方向	136

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