比起其他儲氫技術（高壓氫，液態氫，吸附劑，奈米碳管，金屬氫化物）化學儲氫具安全、化學穩定性、高重量密度與體積小之優點。硼氫化鈉（NaBH4）是重要的化學儲氫材料之一，因為其儲氫效率與轉化氫效率極高，且可藉由觸媒催化提升其生成氫氣效率，故硼氫化鈉應用於燃料電池化學氫之研究，一直廣為科學家所探討。另一方面，有效的回收它的副產物-偏硼酸鈉（NaBO2）以節省能源、操作成本並降低對環境的衝擊亦成為一個重要的研究課題，本研究將著重於硼氫化鈉溶液產氫與電解回收可行性之研究。
在本研究中，我們利用Ru觸媒(Ru/Al2O3)進行硼氫化鈉鹼性溶液的水(醇)解產氫實驗，探討氫氧化納濃度、硼氫化鈉濃度和反應溫度等變因對產氫的影響。在常溫常壓下進行硼氫化鈉鹼性溶液的水(醇)解反應，產氫速率隨著氫氧化鈉的濃度增加而減慢。在硼氫化鈉的水解產氫實驗部份，濃度為10 wt.%的硼氫化鈉溶液有最佳的產氫速率。然而硼氫化鈉的醇解產氫實驗部份，產氫速率並不隨著硼氫化鈉的濃度增加而增加。另外，硼氫化鈉鹼性溶液的水解和醇解系統的反應活化能分別為41.8和42.1 kJmol-1。另外，我們鑑定了硼氫化鈉經Ru觸媒(Ru/Al2O3)催化下產氫後生成的副產物。在不同反應條件下產生的結晶經過X-ray繞射分析儀的鑑定，判定為硼砂或偏硼酸鈉。以電化學法再生硼氫化鈉並不可行。

Compared with other hydrogen storage technologies (high-pressure gas cylinders, liquid hydrogen, high surface absorbent, carbon nanotube, metal hydride), chemical hydrogen storage has more advantages such as high density of weight and low volume. Sodium borohydride is a strong candidate for hydrogen storage because of its hydrogen storage capacity, chemistry, safety, and functionality. Besides, the ability of recycling the spent fuel (borates) back to borohydride is more and more important.
In this study, the rate of hydrogen generation was measured using Ru/Al2O3 catalyst as a function of the concentrations of NaOH and NaBH4, as well as the reaction temperature, in the hydrolysis and methanolysis of alkaline NaBH4 solution. With increasing NaOH concentration, hydrogen generation rate decreased. The hydrogen generation rate increases for lower NaBH4 concentrations in the hydrolysis of alkaline NaBH4 solution and decreases after reaching a maximum at 10 wt.% of NaBH4. However, the hydrogen generation rate is found to be constant with respect to the concentration of NaBH4 in the methnaolysis of alkaline NaBH4 solution. Activation energy for the hydrolysis and methnaolysis of alkaline NaBH4 solution were found to be 41.8 and 42.1 kJmol-1. We found that the hydrolysis by-product of borohydride through heterogeneous catalyst is borax or sodium metaborate. The electrochemical reduction method is not available.

摘 要 II
ABSTRACT 1
致謝 2
總 目 錄 3
圖 目 錄 6
第一章 緒論 12
1.1 背景 12
1.2 目的 15
第二章 文獻回顧 16
2.1 硼氫化鈉的發現與應用 16
2.2 硼氫化鈉應用於儲氫的瓶頸 24
2.3 硼氫化鈉的再生方法 28
2.3.1 金屬鎂還原法 28
2.3.2 電化學還原法 37
第三章 實驗方法 51
3.1 研究架構 51
3.1.1 魚骨圖 51
3.1.2 實驗架構 52
3.2 實驗藥品與分析方法 53
3.2.1 實驗藥品 53
3.2.2 硼氫化鈉分析方法 54
3.2.3 硼氫化鈉副產物的鑑定 61
3.3 儀器設備和實驗步驟 66
3.3.1 Ru觸媒的製備步驟 66
3.3.2 硼氫化鈉的產氫實驗 67
3.3.3 硼氫化鈉廢液電化學還原法 70
第四章 結果與討論 73
4.1 硼氫化鈉的水解產氫實驗 74
4.1.1產氫效率 74
4.1.2 氫氧化鈉濃度對產氫速率的影響 77
4.1.3 硼氫化鈉濃度對產氫速率的影響 80
4.1.4 溫度對產氫速率的影響 86
4.1.5 觸媒重量對產氫速率的影響 90
4.1.6 觸媒使用次數對產氫速率的影響 93
4.2 硼氫化鈉的醇解產氫實驗 96
4.2.1產氫效率 96
4.2.2 氫氧化鈉濃度對產氫速率的影響 98
4.2.3 硼氫化鈉濃度對產氫速率的影響 101
4.2.4 含水量對產氫速率的影響 104
4.2.5 溫度對產氫速率的影響 107
4.3 硼氫化鈉的副產物鑑定 112
4.3.1 Ru觸媒表面形態觀察(SEM)與成分分析(EDS) 112
4.3.2 XRD結晶晶相分析 118
4.3.3超導核磁共振(NMR)分析 124
4.4 硼氫化鈉廢液電化學還原法 133
4.4.1 水溶液系統中硼氫化鈉的檢量線 133
4.4.2 水溶液系統中的電化學還原 136
第五章 結論與建議 139
5.1 結論 139
5.2 建議 140
參考文獻 141

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