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研究生： 謝景軒
Hsieh, Ching-Hsuan
論文名稱： 以無電鍍方法製備磁性Co-Ni/r-GO觸媒應用於硼氫化鈉水解產氫之研究
Hydrogen generation from catalyzed hydrolysis of sodium borohydride in presence of Co-Ni/r-GO catalyst prepared with electroless plating process
指導教授： 陳炳宏
Chen, Bing-Hung
學位類別： 碩士
Master
系所名稱： 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年： 2013
畢業學年度： 101
語文別： 中文
論文頁數： 97
中文關鍵詞： 質子交換膜燃料電池 、硼氫化鈉 、無電鍍 、氧化石墨烯 、水解反應
外文關鍵詞： PEMFC, graphene oxide, electroless plating, sodium borohydride, hydrolysis reaction
相關次數： 點閱：121  下載：5 
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    • 　　目前，在再生能源的發展中，質子交換膜燃料電池 (PEMFC)是一種極具潛力並且值得深入研究的對象。PEMFC具有較高的能源轉換效率，而且其主要產物為水，並不會對環境造成汙染，不僅可以減緩溫室效應日益嚴重的趨勢，也可以降低人類對於化石燃料的依賴，是人類在追求永續發展的過程中一樣相當重要的能源。
    　　在PEMFC中，氫氣的供應以及儲存方法是一個很重要的議題。相較於物理儲氫與金屬氫化物，化學氫化物被認為是最有效率的儲氫方法，因為化學氫化物的儲氫量高，產氫純度高且不需要消耗額外的能源就能到達到儲氫的目的。
    　　其中，硼氫化鈉在化學氫化物中有較高的氫氣儲存量，大約為10.6 %，是一個備受矚目的儲氫材料；除了含氫量高之外，在一般環境下將硼氫化鈉儲存在鹼性溶液中有很好的穩定性及安全性，只要利用適當的觸媒即可催化其水解反應，釋放氫氣。
    　　本研究中，我們致力於硼氫化鈉水解反應觸媒的研究，利用無電鍍的方法將Co金屬與Ni金屬析鍍在氧化石墨烯上，製備出質量輕且催化活性佳的Co-Ni/r-GO觸媒，並將其應用於硼氫化鈉的液相水解反應中。我們也嘗試改變實驗條件去觀察對於水解反應的影響，包括：硼氫化鈉濃度、氫氧化鈉濃度、觸媒添加量與溫度，並且從中了解到Co-Ni/r-GO觸媒催化硼氫化鈉水解反應的最佳操作條件以及動力學常數，之後進行觸媒回收實驗，測試Co-Ni/r-GO觸媒是否能夠重複的循環利用，降低製造成本。最後，利用SEM/EDS、TEM、XRD、ICP-OES進行觸媒鑑定，了解觸媒的表面型態與特殊性質，另一方面則利用11B-NMR鑑定水解反應後的產物。

    　　Proton exchange membrane fuel cells (PEMFCs) using hydrogen as fuel are attracting much attention because of their higher energy efficiency and regarded as one of the emerging technologies in green energy. Methods of supplying hydrogen to PEMFC need to be considered. Chemical hydrides have been regarded as the most potential materials for hydrogen supply and have larger hydrogen storage capacity. Hydrogen evolution via hydrolysis reaction from NaBH4 is a promising technique, and catalysts play an important role in the hydrolysis reaction.
    　　In this work, hydrolysis of sodium borohydride using Co-Ni/r-GO catalysts was studied. The electroless plating method was used to deposit Co-Ni nanoparticles on graphene oxide. Various instruments including SEM/EDS, TEM, OM, XRD, ICP-AES and SQUID were utilized to characterize Co-Ni/r-GO catalysts. Magnetic property of the cobalt-based catalyst makes it convenient for being recycled from spent NaBH4 solution. Also, 11B-NMR was utilized to characterize the by-product, NaBO2.
    　　Furthermore, the rate of hydrogen generation from catalyzed hydrolysis of alkaline NaBH4 solution was determined as a function of temperature, NaBH4 concentration, NaOH concentration, and catalyst loading in the presence of as-prepared Co-Ni/r-GO catalyst. The activation energy of NaBH4 hydrolysis reaction was found at 55.12 kJ mol-1, which was comparable with others reported in the open literatures.

    摘要 I ABSTRACT III 誌謝 V 目錄 VII 表目錄 XI 圖目錄 XII 第一章 緒論 1 1.1　前言 1 1.2　研究動機與目的 3 第二章　文獻回顧 8 2.1　燃料電池　(Fuel cell, FC) 8 2.1.1　運作原理 8 2.1.2　燃料電池分類 9 2.1.3　應用 15 2.2　氫能　(Hydrogen energy) 18 2.2.1　產氫製程 18 2.2.1.1　熱化學法 18 2.2.1.2　電化學法 20 2.2.1.3　光電化學法(Haryanto et al., 2005) 21 2.2.1.4　生物產氫法 21 2.2.2　儲氫系統 24 2.2.2.1　物理儲氫系統 24 2.2.2.2　金屬氫化物 29 2.2.2.3　化學氫化物 29 2.3　硼氫化鈉 (Sodium borohydride, SB) 31 2.3.1　硼氫化鈉的合成 32 2.3.2　硼氫化鈉水解產氫 34 2.3.3　副產物－NaBO2回收 39 2.4　氧化石墨烯 (Graphene oxide, GO) 42 2.4.1　氧化石墨烯製備 42 2.4.2　氧化石墨烯結構 43 2.4.3　應用領域 45 2.5　電鍍 (Electroplating) 及無電鍍 (Electroless deposition) 46 2.5.1　電鍍 (Electroplating) 46 2.5.2　氣相沉積 (Vapor deposition, VD) 47 2.5.3　無電鍍 (Electroless deposition) 48 第三章　實驗 52 3.1　實驗藥品 52 3.2　實驗儀器 53 3.3　實驗步驟 57 3.3.1　氧化石墨烯的製備 57 3.3.2　Co-Ni/r-GO金屬觸媒的製備 57 3.3.2.1 氧化石墨烯的前處理 58 3.3.2.2 鍍浴配製 58 3.3.3　硼氫化鈉的水解反應 59 第四章　結果與討論 62 4.1　Co-Ni/r-GO觸媒 62 4.1.1　觸媒活性及再現性 63 4.1.2　空白實驗 64 4.1.3　Co-Ni/r-GO觸媒鑑定 66 4.1.3.1　感應耦合電漿質譜分析儀【ICP-OES】 66 4.1.3.2　掃描式電子顯微鏡與能量散射光譜儀【SEM/EDS】 67 4.1.3.3　X射線繞射分析儀 【XRD】 70 4.1.3.4　光學顯微鏡【OM】 72 4.1.3.5　穿透式電子顯微鏡【TEM】 72 4.1.3.5　超導量子干涉磁量儀【SQUID】 74 4.2　Co-Ni/r-GO觸媒催化硼氫化鈉水解產氫實驗 76 4.2.1　 NaOH(aq.)濃度對於反應的影響 76 4.2.2　 NaBH4(aq.)濃度對於反應的影響 79 4.2.3　觸媒添加量(Catalyst loading)對於反應的影響 85 4.2.4　控制反應溫度探討Co-Ni/r-GO觸媒催化水解反應的活化能 87 4.2.5　觸媒回收與再利用 89 4.2.6　以超導核磁共振儀【11B-NMR】檢驗反應的副產物 90 第五章　結論 92 參考文獻 93

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