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| 研究生： |
譚家彥 Tan, Chia-Yen |
|---|---|
| 論文名稱： |
添加經表面修飾之多壁奈米碳管觸媒對複合金屬氫化物放氫行為的影響研究 Effects of Surface Decorated MWCNTs on the Dehydrogenation Behavior of Complex Metal Hydride |
| 指導教授： |
蔡文達
Tsai, Wen-Ta |
| 學位類別： |
博士 Doctor |
| 系所名稱： |
工學院 - 材料科學及工程學系 Department of Materials Science and Engineering |
| 論文出版年： | 2015 |
| 畢業學年度： | 103 |
| 語文別： | 英文 |
| 論文頁數： | 170 |
| 中文關鍵詞： | 複合金屬氫化物 、鋁氫化鋰 、鋁氫化鈉 、多壁奈米碳管 、化學還原法 、共沉積法 、熱重分析 、臨場同步X光繞射分析 、第一原理模擬分析 |
| 外文關鍵詞： | complex metal hydrides, LiAlH4, NaAlH4, multi-walled carbon nano tubes, chemical reduction process, impregnation process, in-situ XRD analysis, first principle simulation |
| 相關次數： | 點閱：138 下載：1 |
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複合金屬氫化物如鋁氫化鋰(LiAlH4)與鋁氫化鈉(NaAlH4)具有高理論重量氫儲存密度，釋出氫氣純度高，具有作為車載燃料電池氫氣來源使用的潛力，然而因為其分解放氫溫度仍高達170-300 oC，不方便正常操作。故本研究致力於開發奈米過渡金屬顆粒與三氯化鈦批覆修飾之多壁奈米碳管，作為催化複合金屬氫化物放氫反應的觸媒，並探討觸媒對複合金屬氫化物如鋁氫化鋰與鋁氫化鈉的放氫反應影響。研究首先透過化學還原法使過渡金屬顆粒如鎳、鈷、銅、釩、鉑、鈀能夠批覆於多壁奈米碳管上，以及共沉積法製備三氯化鈦混合多壁奈米碳管的複合觸媒。觸媒製備完成後，以掃描式電子顯微鏡、電子能譜分析儀與穿透式電子顯微鏡觀察觸媒附著於多壁奈米碳管上的表面形貌。製備好的過渡金屬披覆多壁奈米碳管觸媒以球磨法混合不同比例添加於鋁氫化鋰與鋁氫化鈉中。混合的粉體以穿透式X光顯微術對金屬披覆多壁奈米碳管觸媒混合於鋁氫化鋰中的粉體進行微觀觀察。而在放氫性質部分使用熱重分析儀分析其放氫性質，並配合臨場同步X光繞射法，了解觸媒在複合金屬氫化物放氫過程中是否參與反應。
實驗結果顯示，多壁奈米碳管本身即具有催化鋁氫化鋰放氫反應的效果。經過添加20 wt%的多壁奈米碳管後，鋁氫化鋰的初始放氫溫度由170 oC降低至140 oC。而若以不同金屬修飾多壁奈米碳管，可有不同程度的提升或抑制多壁奈米碳管催化能力的效果。其中，三氯化鈦以及鎳金屬披覆之多壁奈米碳管，其催化效果提升最為顯著。添加20 wt%的三氯化鈦披覆多壁奈米碳管，以及鎳金屬披覆多壁奈米碳管，可有效降低鋁氫化鋰的初始放氫溫度至70 oC，並大幅提高在恆溫100 oC下的放氫速率。而同步輻射X光繞射結果顯示，三氯化鈦披覆多壁奈米碳管以及鎳金屬披覆多壁奈米碳管雖然可以有效降低鋁氫化鋰的放氫溫度，但卻不會影響其放氫反應路徑。X光繞射結果亦顯示，三氯化鈦與鎳批覆之多壁奈米碳管觸媒以球磨法添加於鋁氫化鋰後，其混合粉體在室溫下即會有緩步分解釋氫的現象，同樣驗證了三氯化鈦與鎳批覆之多壁奈米碳管觸媒對鋁氫化鋰優異的催化效果。
而在鉑或鈀金屬披覆之多壁奈米碳管觸媒部分，熱重分析結果顯示添加鉑或鈀金屬披覆之多壁奈米碳管觸媒於鋁氫化鋰中，同時具有催化與抑制鋁氫化鋰放氫反應的效果。熱重分析與傅立葉紅外光譜顯示，由於鉑或鈀金屬披覆之多壁奈米碳管觸媒具有優異的吸附氫氣能力，添加於鋁氫化鋰中會將其所釋放的氫氣暫時吸附於觸媒上，造成氫氣釋放的延遲狀況。而同步輻射X光繞射結果顯示，鉑與鈀金屬觸媒在高溫下會與第一階段放氫後的產物產生反應，導致其反應路徑改變而放氫量有所不同。詳細的數據解釋會在本文中討論。
在鋁氫化鈉部分，過渡金屬披覆之多壁奈米碳管觸媒亦有類似於添加在鋁氫化鋰中的催化效果。熱重分析結果顯示，三氯化鈦與鎳金屬披覆之多壁奈米碳管觸媒同樣對鋁氫化鈉擁有較佳的催化效果，添加20 wt% 三氯化鈦與鎳金屬披覆之多壁奈米碳管觸媒可分別將鋁氫化鈉的起始放氫溫度由210 oC 降低至150 oC與170 oC，並提高鋁氫化鈉在160 oC下的放氫速率。而鉑與鈀披覆之多壁奈米碳管觸媒添加則同樣對鋁氫化鈉有抑制其釋氫的效果，導致熱重分析結果中鋁氫化鈉的起始放氫溫度些微增加至220 oC。
除了以熱重分析與同步輻射X光繞射實驗了解過渡金屬披覆多壁奈米碳管觸媒對複合金屬氫化物放氫反應影響以外，本研究亦嘗試以第一原理模擬的方式來解釋不同過渡金屬摻雜對鋁氫化鋰晶體以及其放氫行為的影響。先前文獻指出，摻雜之過渡金屬元素容易佔據於鋁氫化鋰中的空乏區，形成間隙摻雜。而摻雜之過渡金屬元素如鈦、鎳、鈷、銅、釩其d軌域電子會與鋁原子電子軌域產生交互作用，因而弱化鋁-氫四面的鍵結強度，以及鋰離子與鋁氫四面體的鍵結強度。導致氫原子脫付能下降。第一原理模擬的結果可間接與熱重分析實驗結果相互呼應，由於附著於多壁奈米碳管上的過渡金屬顆粒對複合金屬氫化物晶體如鋁氫化鋰有不同程度的交互作用，因而解釋了不同過渡金屬元素顆粒修飾多壁奈米碳管對複合金屬氫化物會有不同程度的催化效果。
Complex metal hydride such as LiAlH4 or NaAlH4 is a promising solid hydrogen storage material that possess high volumetric hydrogen storage density up to 10.5 wt%. In addition, the purity of the released hydrogen from complex metal hydrides is high enough which makes it suitable for fuel cell in light duty vehicles. However, the onset dehydrogenation temperature of complex metal hydrides is still at the temperature around 170 to 300 oC, which is unsatisfactory for fuel cell application. Therefore, this study is dedicated on developing nano scale transition metal particles or titanium chloride (Ⅲ) decorated multi-walled carbon nanotubes (MWCNTs) as novel catalysts for improving the dehydrogenation properties of complex metal hydrides and discussing its effect on dehydrogenation reaction of complex metal hydrides.
First, by chemical reduction and impregnation process, the transition metal particles such as Ni, Co, Cu, and V, noble metal such as Pt, Pd and TiCl3 compounds were able to decorate on the surface of MWCNTs. The morphology and chemical composition of the surface decorated MWCNTs was examined by using scanning electron microscope (SEM), transmission electron microscope (TEM) and energy dispersive spectroscopy (EDS). The different percentage of the as prepared surface decorated MWCNTs were admixed with complex metal hydrides such as LiAlH4 or NaAlH4 by ball milling process. The morphology of the admixed powders was examined by transmission X-ray microscopy (TXM). The dehydrogenation properties of the surface decorated MWCNTs admixed LiAlH4 or NaAlH4 was investigated by using thermo-gravimetric analysis (TGA) and the in-situ X-ray diffraction (in-situ XRD) in order to understand whether the catalysts would alter the dehydrogenation reaction.
For LiAlH4, the TGA results showed that the addition of 20 wt% pure MWCNTs could lower the onset dehydrogenation temperature of LiAlH4 from 170 oC to 140 oC. In addition, by decorating different transition metal particles, the catalytic power of MWCNTs could be improved or deteriorated accorded to the decorated transition metal element. Among all the tested catalysts, the TiCl3 or Ni decorated MWCNTs have superior catalytic power in catalyzing the dehydrogenation of LiAlH4. By addition of 20 wt% TiCl3 or Ni decorated MWCNTs, the onset dehydrogenation temperature of LiAlH4 could be reduced to as low as 70 oC. Meanwhile, the hydrogen desorption kinetic of LiAlH4 at 100 oC was significantly improved. Although the TiCl3 or Ni decorated MWCNTs could effectively lower the dehydrogenation temperature of LiAlH4, the in-situ XRD analysis showed that the TiCl3 or Ni decorated MWCNTs catalysts would not alter the dehydrogenation reaction pathways of LiAlH4. Meanwhile, the XRD results implied that the TiCl3 or Ni decorated MWCNTs admixed LiAlH4 would gradually decompose at room temperature, which also verified the superior catalytic power of TiCl3 or Ni decorated MWCNTs.
On the other hand, the Pt or Pd decorated MWCNTs exhibited both catalytic and inhibitive effect on the dehydrogenation of LiAlH4. The TGA and FTIR results revealed the superior capability of Pt or Pd decorated MWCNTs to absorb hydrogen under hydrogen atmosphere. Addition of Pt or Pd decorated MWCNTs could absorb the hydrogen released from the LiAlH4, therefore delaying the hydrogen desorption rate during the TGA tests. Meanwhile, the in-situ XRD analysis showed that Pt and Pd particles would react with the residue of dehydrogenation reaction of LiAlH4 and therefore altering its dehydrogenation reaction pathways. The detailed data would be discussed later in this thesis.
For NaAlH4, the effect of surface decorated MWCNTs on NaAlH4 is similar to that on LiAlH4. The TGA results showed that addition of TiCl3 and Ni decorated MWCNTs could lower the onset dehydrogenation temperature from 210 oC to 150 and 170 oC. At the same time, the hydrogen desorption kinetic of NaAlH4 at 160 oC was significantly improved by addition of TiCl3 and Ni decorated MWCNTs addition. On the other hand, the Pt and Pd decorated MWCNTs also exhibited the inhibitive effect on hydrogen desorption of NaAlH4, where the onset dehydrogenation temperature of NaAlH4 increased slightly from 210 oC to 220 oC. The detailed discussion of TGA and in-situ XRD resulted was be presented later in this thesis.
Other than TGA and in-situ XRD analysis on the effect of surface decorated MWCNTs on the dehydrogenation behavior of complex metal hydrides, the first principle simulation was also adopted in order to better understand the effect of the doping of transition metal elements on the crystal stability and the dehydrogenation behavior of LiAlH4. Previous reports implied that the doped transition metal elements such as Ti, Ni, Co, Cu, V would tend to occupy the interstitial site of LiAlH4, forming the interstitial doping. The d orbitals of doped transition metal elements would interact with the electronic orbital of Al and weaken the bonding between Aland H as well as Li+ and [AlH4]- tetrahedral. The hydrogen removal energy of transition metal doped LiAlH4 is therefore lower than the undoped LiAlH4. The simulation results could indirectly support the experiment results, where the interaction between the decorated transition metal particles on MWCNTs and the LiAlH4 is the reason to explain the different catalytic power of surface decorated MWCNTs.
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