本研究以濕式化學沉澱法全程於手套箱內合成氫化鋁(AlH3)，最後成功製備出單一α相、單一γ相、及混雜少許α與γ相的β相氫化鋁。三相皆是以層狀結晶堆積而成的結構。
α與γ相氫化鋁的X光繞射圖譜、IR吸收圖譜及其熱性質都與文獻符合。利用原位紅外線光譜(in situ FTIR)佐以二維紅外線光譜(2D IR)分析法進一步觀察相轉及裂解行為，α相氫化鋁觀察到了裂解，發生時光譜的基線會逐步上升；γ相氫化鋁觀察到了二種裂解途徑，一是先轉為α相、再進行裂解，二是直接以γ相裂解，前者路徑早於後者發生，然而實驗過程中，並沒有觀察到晶相以α相為主的區段。穩定性方面，α相氫化鋁遠比γ相來得穩定。
為了更進一步的提高α相氫化鋁的穩定性，導入了摻雜及表面處理二種穩定化程序。藉由摻雜入鎂，氫化鋁的裂解溫度最高提高至191 °C；藉由鹽酸的酸洗程序，大幅提高了氫化鋁在空氣中的穩定度。

In this research, aluminum hydride (AlH3) was synthesized by wet chemical precipitation method in the glovebox. Single phase α-AlH3, single phase γ-AlH3, and β-AlH3 coexisting with other phases were obtained. All of polymorphs consist of packs of crystalline lamenae.
For α and γ polymorphs, x-ray diffraction pattern, IR absorption spectra and thermal properties all have great agreement with literature. In Situ FTIR was used and analyzed by 2D IR to observe the behaviors of phase transition and decomposition. It turned out that for α-AlH3, decomposition was observed by the form of rising baseline. For γ polymorph, two decomposition routes were observed. It transformed to α polymorph followed by decomposition, or it decomposed directly from γ polymorph. The former rout occurred prior to the latter, whereas no region that α polymorph dominating was observed. Stable wise, α polymorph exhibits better stability than γ polymorph.
Stabilization achieved by doping and surface treatment was introduced to further enhance the stability of α-AlH3. Doped by Mg, Td of AlH3 increased at most to 191 °C. Otherwise, surface treatment via HCl acid wash workshop had a promising effect on enhancing the stability in the air.

論文審定書 i
致謝 ii
Abstract iii
摘要 iv
Contents v
List of Figures vii
List of Tables x
Chapter 1 Introduction 1
1.1 Backgrounds 1
1.2 Motivation and objectives 4
Chapter 2 Literature Review 6
2.1 Complex hydrides for hydrogen storage 6
2.1.1 Alanates 6
2.1.2 Amides 7
2.1.3 Borohydrides 8
2.2 Synthesis of AlH3 9
2.3 Structures and morphologies of AlH3 11
2.4 Thermodynamics of AlH3 14
2.5 Stabilization of AlH3 15
2.6 Two-dimensional infrared spectroscopy 16
Chapter 3 Experimental 22
3.1 Synthesis of AlH3 23
3.1.1 α-/β-AlH3 23
3.1.2 γ-AlH3 24
3.2 Stabilization of AlH3 25
3.3 Chemicals 26
3.4 Instruments 26
3.4.1 Glovebox 27
3.4.2 X-ray diffraction (XRD) 27
3.4.3 Scanning electron microscope (SEM) 27
3.4.4 Fourier transform infrared spectrometer (FTIR) 28
3.4.5 Differential scanning calorimeter (DSC) 29
Chapter 4 Results and Discussion 33
4.1 Characterization 33
4.1.1 X-ray diffractometer 33
4.1.2 Infrared spectrometer 36
4.2 Thermal analysis 38
4.2.1 DSC 38
4.2.2 In situ FTIR 40
4.3 Morphology 44
4.4 Stability 47
4.4.1 Stability of unstabilized AlH3 47
4.4.2 Effect of oxidation 49
4.5 Analysis of stabilization 50
4.5.1 Stabilization via doping 51
4.5.2 Stabilization via surface treatment 52
Chapter 5 Conclusions 78
References 80
Appendix 84
A.1 Vibrational study of β-AlH3 by in situ FTIR 84
A.2 References of tables and figures 88

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