Title Page
Contents
Abstract 13
1. Introduction 14
1-1. Background 14
1-2. Research trends 15
1-3. Research Object 17
2. Theory 20
2-1. Facilitated transport 20
2-2. Dual-sorption theory 25
2-3. Hopping model 27
2-3-1. Noble's model 27
2-3-2. Cussler's model 29
2-4. Concentration fluctuation model 32
3. Experimental 34
3-1. Materials 34
3-2. Preparation of polymer electrolytes 34
3-3. Characterization 34
3-3-1. Gas permeance 34
3-3-2. Propylene Solubility 35
3-3-3. Spectroscopy 36
3-3-4. Differential scanning calorimetry (DSC) 36
3-3-5. Wide angle X-ray Diffraction (WAXS) 36
3-4. Ab initio method 37
4. Results and discussion 38
4-1. Transient crosslinks of polymer electrolytes 38
4-2. Olefin coordination to silver ions 60
4-2-1. Propylene solubility 61
4-2-2. Interaction of silver cation with carbonyl oxygen 62
4-2-3. Interaction of silver cation with anions 67
4-2-4. Comparison of spectroscopical with theoretical results 74
4-2-5. Interaction of silver cation with propylene 76
4-3. Complexation mechanism of olefin with silver ions 81
4-3-1. Ionic constituents 83
4-3-2. Gas transport properties 83
4-3-3. Redissolution of silver salts into free anions 85
4-3-4. Partial recovery of complexed carbonyl bond strength 90
4-3-5. Complexation mechanism of propylene with silver salts 94
4-4. Coordination mode of silver ions in polymer electrolytes 96
4-4-1. Structure of the silver polymer electrolytes 98
4-4-2. Olefin coordination to silver ions 105
4-4-3. Coordination behavior of silver ions 112
5. Conclusions 120
References 124
Summary in Korean 132
Table 1. Main features of liquid and solid state facilitated transport membranes 24
Table 2. Gas permeance and selectivity through polymer electrolyte films of 50:50 (vol%) ethylene:ethane mixture gas at 25 ℃. The mole ratio of carbonyl oxygen to silver ion was fixed at 1:1 41
Table 3. Complexation energy and heterolytic bond dissociation energy at B3LYP level for POZ/Ag salt complexes at 298K 75
Table 4. Parameters used in correlation of propylene solubility in POZ/AgCF₃SO₃ with varying mole ratio of [C=O]:[Ag] 108
Table 5. Dissociation enthalpy (ΔH) at B3LYP level for POZ-Ag-X and C₂H₄- Ag-X at 298K (㎉/mol) 117
Figure 1. Relationship between oxygen permeability and oxygen/nitrogen selectivity for conventional polymer membranes. 22
Figure 2. Mechanism of facilitated transport through solid membrane with a fixed carrier. 23
Figure 3. FT-IR spectra of pure POZ and POZ/AgClO₄ complexes of various [C=O]:[Ag] mole ratios. 44
Figure 4. Deconvoluted carbonyl stretching modes for POZ/AgClO₄ complexes with varying salt... 45
Figure 5. FT-IR spectra of POZ complexes with AgClO₄ and AgBF₄ at 1:1 [C=O]:[Ag] mole ratio. 47
Figure 6. FT-Raman spectra of POZ complexes with AgClO₄ and AgBF₄ at 1:1 [C=O]:[Ag] mole ratio. 48
Figure 7. FT-Raman spectra for BF4- stretching mode of POZ and POZ/AgBF₄ complexes with [C=O]:[Ag] mole ratio.(이미지참조) 49
Figure 8. FT-Raman spectra for ClO4- stretching mode of POZ and POZ/AgClO₄ complexes with [C=O]:[Ag] mole ratio.(이미지참조) 50
Figure 9. Glass transition temperature with increasing salt concentration in POZ electrolytes containing AgClO₄ and AgBF₄. The lines are calculated from Equation (13). 52
Figure 10. Structure of complexes of N-methyl-N-ethyl-propionamide with (a) AgClO₄ and (b) with AgBF₄, where N-methyl-N-ethyl-propionamide is model... 56
Figure 11. d-spacing of POZ electrolytes containing AgClO₄ and AgBF₄ with increasing silver concentration. 57
Figure 12. Propylene solubility vs propylene pressure in silver polymer electrolytes at 25℃. 63
Figure 13. FT-IR spectra of pure POZ and POZ/AgNO₃ complexes with varying [C=O]:[Ag] mole ratios. 64
Figure 14. FT-IR spectra of pure POZ and POZ complexes with AgBF₄, AgCF₃SO₃ and AgNO₃ ([C=O]:[Ag]=1:1 mole ratio) for a range of 1750-1500 ㎝-1.(이미지참조) 65
Figure 15. FT-Raman spectra of pure POZ and POZ complexes with AgBF₄, AgCF₃SO₃ and AgNO₃ ([C=O]:[Ag]=1:1 mole ratio) for a range of 1750... 66
Figure 16. FT-Raman spectra for BF4- stretching mode of POZ and POZ/AgBF₄ complexes with varying [C=O]:[Ag] mole ratios.(이미지참조) 69
Figure 17. FT-Raman spectra for SO3- stretching mode of POZ and POZ/AgCF₃SO₃ complexes with varying [C=O]:[Ag] mole ratios.(이미지참조) 70
Figure 18. FT-Raman spectra for NO3- stretching mode of POZ and POZ/AgNO₃ complexes with varying [C=O]:[Ag] mole ratios.(이미지참조) 71
Figure 19. The deconvoluted curves for the free ion and ion pair in POZ complexes with AgCF₃SO₃ and AgNO₃ (1:1 mole ratio) from Figures 17 and 18. 73
Figure 20. FT-IR spectra of PVP/Ag salt complexes with and without propylene sorption ([C=O]:[Ag]=1:1 mole ratio) for a range of 1800 - 1500 ㎝-1....(이미지참조) 78
Figure 21. The deconvoluted curves for the coordinated carbonyl bond of PVP with silver ion and the complexed double bond of propylene with silver ion from Figure 20. 79
Figure 22. The vs(SO3-) modes in FT-Raman spectra of pure PVP and PVP/AgCF₃SO₃ complexes with various [C=O]:[Ag] mole ratios.(이미지참조) 84
Figure 23. Permeance of propylene and propane in PVP/AgCF₃SO₃ as a function of silver concentration. 87
Figure 24. Time evolution Raman spectra for vs (SO3-) mode in 1:3 PVP/AgCF₃SO₃ absorbing propylene (40 psig).(이미지참조) 88
Figure 25. FT-IR spectra of PVP/AgCF₃SO₃ electrolytes with and without propylene sorption for a various mole ratio of [C=O]:[Ag].... 92
Figure 26. The deconvoluted curves of PVP/AgCF₃SO₃ electrolytes absorbing propylene in the range of 1750 - 1550 ㎝-1 from Figure 25....(이미지참조) 93
Figure 27. Bragg d-spacings calculated from the positions of both peaks in POZ/Ag salt complexes with various silver concentration. 100
Figure 28. Glass transition temperatures of pure POZ and POZ/Ag salt complexes as a function of silver concentration.... 101
Figure 29. Permeance of propane through polymer electrolyte membranes containing AgCF₃SO₃ as a function of silver concentration. 102
Figure 30. Solubility of propylene in pure POZ and POZ/AgCF₃SO₃ complexes against propylene pressure. 107
Figure 31. Solubility of propylene in pure POZ and POZ/AgCF₃SO₃ complexes against silver concentration. 110
Figure 32. Permeance of propylene through polymer electrolyte membranes containing AgCF₃SO₃ as a function of silver concentration. 111
Figure 33. Coordination number of silver for carbonyl oxygen or propylene in POZ/AgCF₃SO₃ as a function of silver concentration. 115