在本文研究，我們製備了多孔性的硫酸化二氧化鋯並且應用其特性在質子交換膜燃料電池中質子傳導膜的基材。除了檢測其材料的多孔結構性質及表面酸度外，並加以討論此兩者的相互關係及兩者對質子導度的單方及相互的影響。製備多孔結構的硫酸化二氧化鋯，是利用不同長碳鏈的介面活性劑當作模板以共沉澱法或水熱法合成。中孔洞硫酸化二氧化鋯隨著界面活性劑的增加，其比表面積從78增加至128 m2/g，相對的質子導度也從1.2×10-2提升至2.0 ×10-2 S/cm。微孔洞硫酸化二氧化鋯有較高的質子導度約2.6×10-2 S/cm。推測其微孔的小孔徑及其高的表面酸度使得質子易在表面傳遞。而利用中孔洞硫酸化二氧化鋯(C16TAB/Zr= 0.5, average pore size= 2.8, surface area= 128 m2/g)的樣品用0.9M的硫酸溶液做再披覆後發現，質子導度提升為原本2.0 ×10-2 S/cm至9.5 ×10-2 S/cm，且此數值比現今商業質子交換膜(Nafion, 5.2×10-2 S/cm)之效益高約兩倍。孔徑大小與表面酸性皆影響著水含量並且控制著質子傳導的能力。即便微孔洞的硫酸化二氧化鋯有著最高的水分吸附能力，但其質子導度卻並沒有如經過再披覆硫酸的樣品來的高，推測小於0.6 nm的微孔洞材料，水分會因為太緊密的吸附在表面而導致質子不易傳導，因此適當的孔徑大小和表面酸性結合可使材料具有高的質子導度特性。

In this study, porous sulfated ZrO2 (S-ZrO2) powders were prepared as a promising alternative proton-conducting material for fuel cells. The porous structure, surface acidity and proton conductivity were examined and their relationships were investigated. The S-ZO2 samples were prepared through templating precipitation and hydrothermal method. The mesoporous S-ZrO2 samples exhibited the proton conductivities of 1.2-2.0×10-2 S/cm, and the conductivities were highly dependent on their specific surface areas (78-128 m2/g). The microporous S-ZrO2 sample templated with octyltrimethylammonium bromide (C8TAB) had a higher proton conductivity of 2.6 ×10-2 S/cm. Small pore sizes assist protons hopping between bulk water and surface acidic sites to promote conductive efficiency. Post impregnation of the mesoporous S-ZrO2 sample (C16TAB/Zr= 0.5, average pore size= 2.8, surface area= 128 m2/g) with a 0.9 M H2SO4 solution remarkably improved its proton conductivity from 2.0 ×10-2 to 9.5 ×10-2 S/cm. This value is twice higher than that of the commercial Nafion (5.2×10-2 S/cm). Both the pore size and surface acidity determine the water content and control the proton conductivity. Even though the microporous S-ZrO2 samples showed the highest capability for keeping water molecules, their proton conductivity were not higher than the post sulfation powders. Microporous channels with the pore size smaller than 0.6 nm block water tightly and retard proton diffusion. Therefore, the optimal pore size (0.6-2.8nm) and surface acidity can contribute to high proton conductivity.

中文摘要 i
Abstract ii
謝誌 iii
Content Index iv
Figure Index vi
Table Index viii
Chapter 1. Introduction - 1 -
1-1. Motivation - 1 -
1-2. Objectives - 3 -
Chapter 2. Literature Review - 4 -
2-1. Proton exchange membranes (PEMs) - 4 -
2-1-1. Proton exchange membrane fuel cell (PEMFCs) - 4 -
2-1-2. Function of the PEM 7
2-1-3. Nafion 8
2-2. Proton Conductivity 10
2-2-1. Proton transfer mechanism in aqueous solution 10
2-2-2. Proton transfer mechanism in hydrated acidic polymer 13
2-2-3. Conductivity measurement 15
2-3. Different kind of proton-conducting materials 19
2-4. Key factors to high proton conductivity 27
2-4-1. Water content 27
2-4-2. Surface acidity 28
2-4-3. Microstructures 30
2-5. Sulfated zirconia 31
2-5-1. Properties of sulfated zirconia 31
2-6. Porous structure material 33
2-6-1. Templates 33
Chapter 3. Materials and Methods 36
3-1. Chemicals 36
3-2. Preparation of porous sulfated zirconium 36
3-2-1. Precipitation process 36
3-2-2. Hydrothermal process 37
3-3. Characterization 37
3-3-1. Nitrogen adsorption and desorption isothermal 37
3-3-2. Fourier Transform Infrared Spectrometer (FTIR) 37
3-3-3. X-ray photoelectron Spectroscopy (XPS) 38
3-3-4. Thermo Gravimetric Analysis (TGA) 39
3-3-5. Water content measurement 39
3-3-6. Proton conductivity measurement 39
3-3-7. Temperature programmed desorption (TPD) 40
3-3-8. High Resolution Transmission Electron Microscope (TEM) 41
3-3-9. Inductively Coupled Plasma- Mass Spectrometry (ICP-MS) 41
Chapter 4. Result and Discussion 42
4-1. Thermal Analysis 42
4-2. Surface functional group 45
4-3. Chemical compositions 47
4-4. NH3 adsorption and desorption 54
4-5. Textures and proton conductivities of the sulfated zirconia 55
4-6. Post sulfation 62
4-7 Water content 67
Chapter 5. Summary 70
5-1. Conclusions 70
References 71
Appendix A. XPS patterns of S-ZrO2 77
Appendix B. N2 adsorption and desorption isotherm and BJH pore size distribution of S-ZrO2. 80
Appendix C. SEM images of sulfatd ZrO2 82
Appendix D. Water content of C16S-ZrO2 series samples 85
Appendix F. TEM images of sulfated ZrO2 87

Figure Index
Figure 2 1 A diagram of a fuel cell - 5 -
Figure 2 2 Total Number of PEM Units Installed Globally by Application [20] 7
Figure 2 3 These two models were the microphases of swollen Nafion membranes. A, B and C represented the hydrophobic polymer, the solvent bridges and the hydrophilic regions, respectively.[5] 9
Figure 2 4 Klaus’smodel is called Parallel water-channel (inverted-micelle cylinder) of Nafion[23]. 10
Figure 2 5 Showed Proton conduction in water.[2] 11
Figure 2 6 The hydrodynamic model of Grotthuss diffusion mechanism.[3] 12
Figure 2 7 Two-dimensional illustration of some microstructural features of Nafion for an intermediate water content.[2] 13
Figure 2 8 Proton transfer in the Nafion in a fully hydrated condition.[3] 14
Figure 2 9 Sample arrangements of (a) 2-probe (b) 4-probe measurement in the direction of thickness 16
Figure 2 10 The Nyquist plot 18
Figure 2 11 The equivalent circuit for the complex impedance of the Nafion membranes and the electrode structure.[25] 19
Figure 2 12 Acid strength of various liquid and solid acids.[50] 32
Figure 2 13 Sulfated Zirconia Structure Proposed by (a) Jin et al. and (b) Ward and Ko.[50] 33
Figure 2 14 Different kinds of members of the M41S family.[60] 34
Figure 2 15 Illustration of the synthesis procedure of mesoporous metal oxides possessing a 2D hexagonal pore structure by self-assembly method. [61] 34
Figure 2 16 The two-step mechanism of the formation of the zirconia/CTAB mesophase.[63] 35
Figure 4 1 The TGA curve of Zr(SO4)2 • 4H2O, and as-prepared C16S-ZrO2, C16S-ZrO2, C8S-ZrO2, C8S-ZrO2 (EtOH) and C8S-ZrO2 (IEE). 43
Figure 4 2 The TGA curves of C16S-ZrO2, C16SS-ZrO2, C8S-ZrO2(IEE), C8S-ZrO2(EtOH), and S-ZrO2 samples. 44
Figure 4 3 FTIR spectra of the S-ZrO2, C16S- S-ZrO2, C16SS- S-ZrO2, C8S- S-ZrO2 (IEE), and C8S-ZrO2 (EtOH) samples. (a) the original spectra, and (b) the zoom-in spectra in the 700-2200 cm-1. 46
Figure 4 4 The S (2p) XPS of the S-ZrO2, C16S-ZrO2, C16SS-ZrO2, C8S-ZrO2 (EtOH), and C8S-ZrO2 (IEE) samples. 48
Figure 4 5 The O (1s) XPS of the S-ZrO2, C16S-ZrO2, C16SS-ZrO2, C8S-ZrO2 (EtOH), and C8S-ZrO2 (IEE) samples. 51
Figure 4 6 The chemical structures of the sulfated groups on the different ZrO2 samples. (a) the S-ZrO2 powder, (b) the C16S-ZrO2, C16SS-ZrO2, and C8S-ZrO2 (EtOH) samples, (c) the C8S-ZrO2 (IEE) sample. 52
Figure 4 7 Formation of C8S-ZrO2 (IEE). 53
Figure 4 8 NH3 TPD patterns of the S-ZrO2, C16S-ZrO2, C16SS-ZrO2, C8S-ZrO2 (EtOH), and C8-S-ZrO2 (IEE) samples. 54
Figure 4 9 Nitrogen adsorption-desorption isotherms of the C16S-ZrO2 samples synthesized with different CTAB/Zr molar ratios. 56
Figure 4 10 Pore size distributions of the C16S-ZrO2 samples synthesized with different CTAB/Zr molar ratios. 56
Figure 4 11 N2 adsorption and desorption isotherm and BJH pore size distribution of the C16SS-ZrO2 sample. 59
Figure 4 12 N2 adsorption and desorption isotherm and BJH pore size distribution of C8S-ZrO2 (IEE) 60
Figure 4 13 N2 adsorption and desorption isotherm and BJH pore size distribution of C8S-ZrO2 (EOH) samples. 60
Figure 4 14 NH3 TPD patterns for C16S-ZrO2 (CTAB/Zr= 0.5) and which impregnated with different concentrations of H2SO4. 64


Table Index
Table 2 1 Different kind of FCs [20] 6
Table 2 2-2. The references regarding organic membranes. 24
Table 2 3 The references regarding organic-inorganic complex membranes. 25
Table 2 4 The references regarding inorganic membranes. 26
Table 4 1 Sulfur-to-zirconium atomic ratios in the different sulfated ZrO2 samples. 49
Table 4 2 The surface O-S/S, O-Zr/Zr, and O-H/Zr atomic ratios 50
Table 4 3 Summaries of the BET properties and the proton conductivities of the C16S-ZrO2 synthesized with different CTAB/Zr molar ratios. 57
Table 4 4 The textural results and proton conductivities of S-ZrO2, C16SS-ZrO2, C8S-ZrO2 (IEE) and C8S-ZrO2 (EtOH) samples. 61
Table 4 5 The total and surface S/Zr ratios of the C16S-ZrO2 sample post treated with sulfuric acid at different concentrations. 63
Table 4 6 The O-S/S, O-Zr/Zr, and O-H/Zr ratios of the C16S-ZrO2 sample impregnated with sulfuric acid at different concentrations. 63
Table 4 7 The textural properties and the proton conductivities of the C16S-ZrO2 powders after post sulfation. 66
Table 4 8 The water content, proton conductivity and pore size of all sulfated ZrO2 samples. 69

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