臺灣博碩士論文加值系統

本論文主要分為三個部份，第一個主題，Ta-MCM-41觸媒的結構特徵與反應性質。第二個主題，Ni-MCM-41為觸媒來製備奈米碳管的反應機制。第三個主題，化學氣相沈積法以CoMgO觸媒催化裂解乙炔製備奈米碳管於儲氫方面的應用。

第一部分：Ta-MCM-41於丙烷氧化脫氫及甲醇氧化的反應
以表面積與孔洞分析儀(BET)、小角度X光繞射儀(XRD)、紫外可見近紅外光擴散反射光譜儀(UV–vis–NIR DRS)和拉曼光譜儀(Raman)分析Ta-MCM-41觸媒的結構特性。三種氧化鉭的物種會存在於MCM-41：Isolated TaO4的物種在MCM-41的結構中，Isolated TaO4物種在MCM-41的表面和Bulk Ta2O5，而這三種氧化鉭物種的含量則會與鉭的濃度有關。鉭原子會進入Ta-MCM-41產生Isolated TaO4活性基位，Ta-O-Si的鍵結會存在MCM-41的表面或是結構中。Ta-MCM-41對丙烷氧化脫氫和甲醇氧化反應的催化性質，主要是取決於觸媒上不同的表面活性基位。分散良好的活性基位有較佳的氧化催化性質來生產甲醛(HCHO)和甲酸甲酯(MF)，bulk Ta2O5只具有酸性基位去生成二甲醚(DME)。Ta–O–Si鍵結的存在對氧化反應具有高活性和選擇性。

第二部份：Ni-MCM-41為觸媒製備奈米碳管
Ni-MCM-41為觸媒催化裂解甲烷製備多壁奈米碳管，甲烷通入石英管反應器內經觸媒表面藉由脫氫反應產生碳原子，表面碳原子遷移和重新排列行程奈米碳管。以穿透式電子顯微鏡與掃描式電子顯微鏡來觀察碳管結構與表面型態，以拉曼光譜中多壁奈米碳管的特徵峰Disorder-band和Graphite-band來分析奈米碳管的石墨化程度。藉由改變Ni-MCM-41的濃度比例、甲烷流量及反應溫度，找出最佳的實驗條件。由TEM與SEM的結果可知，隨著Ni含量的增加，奈米碳管的量也會增加，最佳的反應溫度為640~670℃。在低甲烷流量所製備的奈米碳管管徑較為均一，在高甲烷流量下管徑不均一且較多不定形碳，其結果與拉曼分析結果相符。拉曼分析中可知隨著甲烷流量的增加，ID/IG的值會增加。以Ni-MCM-41為觸媒所製備的奈米碳管其成長機制為頂端成長模式，可由TEM的結果看到金屬觸媒包覆於碳管的頂端與中段。

第三部份：CoMgO為觸媒製備奈米碳管於儲氫方面的應用
化學氣相沈積法，以CoMgO為觸媒催化裂解乙炔製備奈米碳管在溫度範圍由400~700℃。將奈米碳管藉由空氣氧化產生缺陷及開蓋，再利用鹽酸酸洗移除奈米碳管上的觸媒。為了增加奈米碳管的儲氫量，將白金粒子於化學還原法擔持於純化後的奈米碳管，白金粒子具有”hydrogen spillover”的能力可以將氫分子解離成氫原子。以BET來測量其表面積及以體積法在適當壓力及室溫下，來量測其儲氫量。以高解析度穿透式電子顯微鏡(HRTEM)來觀察不同反應溫度的奈米碳管，顯示出不同反應溫度下奈米碳管的結構皆不相同。而奈米碳管的儲氫量與表面積似乎有相關。儲氫應用方面，當反應溫度為500℃所製備的奈米碳管其以重量量測法(Sieverts)儲氫量為1.35wt%，純化後的奈米碳管其儲氫量可達1.5%，Pt擔持於純化後的奈米碳管上，所得的儲氫量可達1.9wt%。

In this thesis, there are three major research parts: 1. Structural characteristics and reactivity properties of the tantalum modified mesoporous silicalite catalysts. 2. The formation mechanisms of multi-wall carbon nanotubes over the Ni modified MCM-41 catalysts. 3. Multi-walled carbon nanotubes (MWCNTs) were synthesized by the thermal chemical vapor deposition method (Thermal CVD) using acetylene as carbon source over the CoMgO catalyst for hydrogen storage.

Part I: Ta-MCM-41 catalysts were performed with the methanol oxidation and propane ODH reactions
The structural characteristics of the Ta–MCM-41 catalyst have been investigated by BET measurement, small angle X-ray diffraction, UV–vis–NIR diffuse reflectance spectroscopy (DRS) and Raman spectroscopy techniques. Three types of tantalum oxide species: an isolated TaO4 species in the MCM-41 framework, an isolated surface TaO4 species on the MCM-41 surface, and bulk Ta2O5, can be present individually or coexist on the Ta–MCM-41 catalysts, and its relatively intensity is dependent on the Ta concentration. The local structure of the Ta atoms in the Ta–MCM-41 catalyst forms an isolated active site with the bridging Ta–O–Si bonds on the surface and in the frame structure of MCM-41. The catalytic properties of the Ta–MCM-41 catalysts were chemically probed with propane oxidative dehydrogenation(ODH) and methanol oxidation reactions in order to distinguish the different surface active sites present on the catalyst. Consequently, the well-dispersed isolated active sites exhibit high redox catalytic properties to produce formaldehyde (HCHO) and methyl formate (MF), and bulk Ta2O5 only possesses acid sites to form dimethyl ether (DME). The presence of Ta–O–Si bonds in the catalyst is responsible for the high reactivity/selectivity of the oxidation reactions.

Part II: Growth multi-wall carbon nanotubes over Ni-MCM-41 catalysts
Multi-wall carbon nanotubes (MWCNTs) were grown by thermal chemical vapor deposition (thermal CVD) of CH4 by using Ni-MCM-41 as the catalyst. Methane pyrolysis has been performed in a quartz tube reactor over the catalyst surface to form carbon atoms via dehydrogenation process. The migration and rearrangement of the surface carbon atoms result in the formation of MWCNTs. Transmission electron microscope (TEM) and scanning electron microscope (SEM) were used to determine the morphologies and structures of CNTs, and Raman spectroscopy was exploited to analyze their purity with the relative intensity between the D-band (Disorder band) in the vicinity of 1350 cm–1 which is characteristic of the sp3 structure and G-band (Graphitic band) in vicinity of 1580 cm–1 which is characteristic of the sp2 structure. In addition, the controlling factors of methane pyrolysis such as the catalyst composition; the reaction temperature, and the methane flow rate on the formation of MWCNTs were investigated to optimize the structure and yield of MWCNTs. SEM/TEM results indicate that the yield of the CNTs increases with increasing Ni concentration in the catalyst. The optimized reaction temperature to grow CNT is located between 640 and 670℃. The uniform and narrow diameter MWCNTs form at lower flow rate of methane (~30 sccm), and non-uniform in diameter and disorder structure of MWCNTs are observed at higher flow rate of methane. This is consistent with Raman analysis that the relative intensity of ID/IG increases with increasing methane flow rate. The formation mechanisms of the MWCNTs on the Ni-MCM-41 catalyst have been determined to be a Tip- Growth mode with a nanoscale catalyst particle capsulated in the tip of the CNT.

Part III: Growth carbon nanotubes by CVD over CoMgO catalysts for hydrogen storage
Multi-walled carbon nanotubes (MWCNTs) were synthesized by the thermal chemical vapor deposition method (Thermal CVD) using acetylene as carbon source over the CoMgO catalyst at different temperatures from 400 to 700℃. The raw CNTs were air oxidized to generate the defects and open the end, and were purified using hydrochloride to remove catalyst. For increasing the hydrogen uptake capacity, we were supported the Platinum nanoparticles on the carbon anotube after purification, which is used to dissociate the hydrogen molecules into atomic hydrogen, onto the surface of CNTs. The specific surface area was estimated from the nitrogen Brunauer- Emmett- Teller (BET) method and the hydrogen uptake capacity of MWCNTs was measured by the volumetric Sieverts method under modestly hydrogen pressure (~1000psi) at ambient temperature. The HRTEM images of growth CNTs under different reaction temperaure. It appears that the CNTs can growth at each temperature with different structure of layers. It seems to be a correlation between the specific surface area and hydrogen uptake for the MWCNTs. For hydrogen storage applications, the highest hydrogen uptake in raw MWCNTs is about 1.35 wt% and in purified CNTs is about 1.5%. The hydrogen uptake in Pt/CNTs is reached to 1.9 wt% at room temperature with 1000 psi pressure.

中文摘要 i
Abstract iii
第一章 前言 1
第二章 文獻回顧 3
2-1 MCM-41的特性 3
2-2 MCM-41形成機制 3
2-3 MCM-41的應用 7
2-3-1 催化應用 7
2-3-2 奈米碳管的生成 10
2-4 奈米碳管的結構特性 11
2-5 奈米碳管的製備方法 14
2-6奈米金屬觸媒的製備 16
2-6-1 奈米微粒的性質及應用 16
2-6-2 水熱法合成奈米金屬觸媒 17
2-6-3 奈米Co/MgO的製備 19
2-7 奈米碳管的成長機制 20
2-8 奈米碳管的成長動力學 22
2-9 奈米碳管的純化 23
2-10 奈米碳管儲氫 24
2-10-1 氫能源 24
2-10-2 氫氣生產的方法 25
2-10-3 現有氫氣儲存的方法 27
2-10-4 奈米碳管儲氫 28
2-10-5 奈米碳管儲氫量的量測 29
2-11 氫氣在奈米碳管中吸附儲存過程的理論研究 30
2-12 奈米碳管儲氫研究進展 31
第三章 實驗設備與研究方法 35
3-1實驗藥品 35
3-2觸媒製備 36
3-2-1 MCM41觸媒之製備 36
3-2-2 [M]-MCM41觸媒之製備 36
3-2-3 Co/MgO觸媒之製備 36
3-3 氧化反應實驗 40
3-4奈米碳管之成長 42
3-4-1奈米碳管之純化 43
3-4-2奈米碳管擔持鉑金屬的製備 44
3-5分析儀器 44
3-5-1穿透式電子顯微鏡及電子繞射分析 45
3-5-2場發射掃描式電子顯微鏡 46
3-5-3 粉末X光繞射分析 46
3-5-4 BET表面積分析 47
3-5-5 熱重分析 52
3-5-6拉曼光譜儀Raman 52
3-5-7紫外可見近紅外光擴散式反射光譜儀 53
3-5-8 氣相層析儀 54
3-5-9 Sievert-type儲氫量測系統 55
第四章 MCM-41的應用 58
4-1 Ta-MCM-41於氧化及氧化脫氫反應的應用 58
4-2 Ni-MCM-41觸媒於奈米碳管的應用 65
第五章 CoMgO觸媒製備奈米碳管 75
5-1 不同比例觸媒對成長碳管的影響 75
5-2 乙炔濃度對奈米碳管成長的影響 79
5-3 溫度效應對奈米碳管成長的影響 83
5-4 奈米碳管的純化 95
5-6 奈米碳管儲氫量的結果 104
5-7 奈米碳管的反應機制 107
第六章 結論 111
參考文獻 113

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