Title Page
Contents
국문요약 17
Abstract 20
Chapter 1. Introduction 26
1.1. Synthesis 30
1.2. Characterization 37
1.3. Functionalization 42
1.3.1. Metalation 42
1.3.2. Grafting 43
1.3.3. Metal impregnation 44
1.3.4. Composite 45
1.3.5. Pyrolysis 47
1.4. Adsorption applications 49
1.4.1. Aqueous organic pollutants 49
1.4.2. CO₂, C₂/C₃ and ethanol in gas phase 51
1.4.3. Fluorescence detection of hazardous species in an aqueous system 53
1.5. Catalytic applications (I): Heterogeneous catalysis 56
1.5.1. Epoxidation 56
1.5.2. CO₂ cycloaddition 57
1.5.3. Oxidative carboxylation 58
1.5.4. Oxidation 58
1.5.5. Hydroxylation 60
1.5.6. Dehydrogenation 60
1.5.7. O-H insertion 61
1.5.8. Hetero-Diels-Alder reaction. 61
1.6. Catalytic applications (II): Photocatalysis 62
1.6.1. CO₂ reduction 62
1.6.2. Oxidation 64
1.6.3. H₂ generation 67
1.7. Catalytic applications (III): Electrocatalysis 67
1.7.1. CO₂ reduction 67
1.7.2. Oxidation 68
1.7.3. Oxygen reduction reaction (ORR) 69
1.7.4. Nitrogen reduction reaction (NRR) 69
1.8. Summary 75
Chapter 2. Sonochemical synthesis of Zr-based porphyrinic MOFs 76
2.1. Introduction 76
2.2. Experimental 79
2.2.1. Materials 79
2.2.2. Preparation of H6-TCPP[이미지참조] 79
2.2.3. Sonochemical synthesis of MOF-525 (S-MOF-525) 80
2.2.4. Conventional synthesis of MOF-525 (C-MOF-525) 80
2.2.5. Sonochemical synthesis of MOF-545 (S-MOF-545) 81
2.2.6. Conventional synthesis of MOF-545 (C-MOF-545) 82
2.2.7. Characterization 82
2.2.8. Hydrolysis of dimethyl 4-nitrophenyl phosphate (DMNP) 83
2.2.9. Adsorption of Bisphenol-A (BPA) 84
2.3. Results and discussion 84
2.3.1. Synthesis and characterization of S-MOF-525 84
2.3.2. Synthesis and characterization of S-MOF-545 91
2.3.3. Defect characterization of MOF-525 and MOF-545 99
2.3.4. Catalytic and adsorption properties of SP-MOF-525 and SA-MOF-545 104
2.4. Summary 108
Chapter 3. Adsorption of sulfamethoxazole using Zr-based porphyrinic MOFs 109
3.1. Introduction 109
3.2. Experimental 112
3.2.1. Materials 112
3.2.2. Synthesis of the MOFs 112
3.2.3. Characterizations 117
3.2.4. Adsorption experiment 118
3.3. Results and Discussion 119
3.3.1. Characterization of the adsorbents 119
3.3.2. SMX adsorption by MOF-525 and MOF-545 120
3.4. Summary 142
Chapter 4. One-pot catalytic transformation of olefins into cyclic carbonates over functionalized Zr-based porphyrinic MOF 144
4.1. Introduction 144
4.2. Experimental section 149
4.2.1. Chemicals 149
4.2.2. Catalyst preparation 150
4.2.3. Characterization 154
4.2.4. CO₂/O₂ adsorption 156
4.2.5. Catalytic reactions 156
4.3. Results and discussion 157
4.3.1. Characterization of ImBr-MOF-545(Mn) 157
4.3.2. CO₂/O₂ adsorption 170
4.3.3. Catalytic studies 171
4.4. Summary 214
Conclusions and Perspectives 216
References 223
Table 1. Synthesis and characterization of Zr-based porphyrinic MOFs reported. 36
Table 2. Adsorption and separation studies carried out over Zr-based porphyrinic MOFs. 54
Table 3. Heterogeneous catalysis studies carried out over Zr-based porphyrinic MOFs. 70
Table 4. Textural properties of MOF-525 samples prepared under different... 88
Table 5. Textual properties of S-MOF-545 and SA-MOF-545 obtained under... 97
Table 6. Zr amount of prepared MOF-525 and MOF-545 samples by ICP-MS. 104
Table 7. Kinetic parameters for the adsorption of SMX on MOF-525 and... 126
Table 8. Langmuir parameters for the adsorption of SMX on MOF-525 and... 128
Table 9. Maximum adsorption capacities of adsorbents for the adsorption of... 129
Table 10. Thermodynamic properties for the adsorption of SMX on MOF-525... 134
Table 11. Elemental analyses (C, H, N, Mn, and Br) with the textural properties of the prepared MOF materials. 169
Table 12. Catalytic oxidation of styrene to styrene oxide. 177
Table 13. CO₂ cycloaddition of styrene oxide to styrene carbonate. 187
Table 14. One-pot cascade epoxidation-cycloaddition reaction of styrene and CO₂. 196
Table 15. Comparison of ImBr-MOF-545(Mn) against previous studies reported for the one-pot process of the epoxidation-... 201
Table 16. One-pot cascade epoxidation-CO₂ cycloaddition reaction of various... 202
Fig. 1. MOFs with high hydrothermal stability: UiO-66 and MIL-101. 26
Fig. 2. Representative carboxyphenyl porphyrin ligands for MOFs. 27
Fig. 3. Representative pyridine and other porphyrin ligands for MOFs. 28
Fig. 4. Zr-based porphyrinic MOFs prepared using TCPP. Green, black, red,... 29
Fig. 5. The equilibrium synthesis mechanism of Zr-based porphyrinic MOFs... 32
Fig. 6. PXRD patterns of Zr-based porphyrinic MOFs. 37
Fig. 7. SEM (TEM) images of Zr-based porphyrinic MOFs: (a) MOF-525, (b)... 37
Fig. 8. N₂ adsorption-desorption isotherms of MOF-525 and MOF-545 (inset... 38
Fig. 9. FT-IR spectra of MOF-525 and MOF-545. 38
Fig. 10. Normalized UV-Vis spectra of PCN-222(M). Adapted from Ref.... 39
Fig. 11. ¹H NMR spectra of a digested FA-6000 (PCN-222) in deuterated... 40
Fig. 12. TGA analysis of DFA-600 (PCN-222). Adapted from Ref. with... 41
Fig. 13. Structure of (a) PCN-222(Fe)-Fn and (b) [FeFe]@MOF-545(Zn)....[이미지참조] 44
Fig. 14. TEM images of (a) Pd@UiO-66, (b) Pd@NU-902, and (c) Pd@PCN-... 44
Fig. 15. Synthesis of (a) MOF-525-fiber and (b) core-shell PCN-222... 46
Fig. 16. Schematic illustration of FesA-N-C from SiO₂@PCN-222(Fe).... 48
Fig. 17. Process of photocatalytic CO₂ reduction over Zr-based porphyrinic MOFs. 63
Fig. 18. XRD patterns of MOF-525 samples prepared under different synthesis... 87
Fig. 19. SEM images of the sonochemically synthesized MOF-525 samples... 89
Fig. 20. SEM images of MOF-525 and MOF-545 prepared under different... 90
Fig. 21. N₂ adsorption-desorption isotherms of MOF-525 samples prepared... 91
Fig. 22. SEM images of different synthesis conditions for S-MOF-545: (a) S-... 95
Fig. 23. XRD patterns of S-MOF-545 prepared under different synthesis conditions. 96
Fig. 24. XRD patterns of S-MOF-545 prepared under different synthesis conditions. 96
Fig. 25. N₂ adsorption-desorption isotherms of (a) S-MOF-545 and (b) SA-... 98
Fig. 26. N₂ adsorption-desorption isotherms of S-MOF-545 prepared under... 98
Fig. 27. Pore size distribution of the activated MOF-545. 99
Fig. 28. UV-Vis spectra of (a) TCPP (inset shows the corresponding... 99
Fig. 29. TGA of MOF-525 and MOF-545 samples. 102
Fig. 30. (a) Rate of DMNP hydrolysis and (b) kinetic adsorption of BPA on... 107
Fig. 31. In(Ct/C0) vs. t plot of the catalytic DMNP hydrolysis by MOF-525...[이미지참조] 107
Fig. 32. (a) XRD patterns, (b) N₂ adsorption-desorption isotherms (inset... 120
Fig. 33. The adsorption of SMX over different MOFs after 6 h. The numbers... 121
Fig. 34. (a) XRD patterns and (b) N₂ adsorption isotherms of the MOFs: UiO-... 122
Fig. 35. (a) Effects of time on the adsorption of SMX and (b) the equilibrium... 125
Fig. 36. Kinetic parameters of SMX adsorption: (a) Pseudo First Order and (b)... 126
Fig. 37. (a) Langmuir isotherm linear plots and (b) Freundlich isotherm linear... 128
Fig. 38. (a) Effects of pH on SMX adsorption and (b) Surface charge of MOF-... 131
Fig. 39. (a) Effect of temperature and (b) Linear plot of InKd versus 1/T for...[이미지참조] 134
Fig. 40. FTIR spectra of the adsorbents before and after adsorption. 137
Fig. 41. XPS spectra of (a) MOF-525 and (b) MOF-545. 139
Fig. 42. Deconvoluted XPS spectra of N1s of (a) MOF-525 and (b) MOF-545. 139
Fig. 43. Adsorption of SMX after regeneration of (a) MOF-525 and (b) MOF-... 140
Fig. 44. XRD patterns of (a) MOF-525 and (b) MOF-545: fresh and... 141
Fig. 45. FTIR spectra of the fresh and regenerated MOF-545. 141
Fig. 46. SEM images of (a) MOF-525 and (b) MOF-545 after adsorption. 142
Fig. 47. Adsorption of SMX after regeneration using ethanol as a solvent for... 142
Fig. 48. ¹H NMR spectrum of 1-methyl-3-(2-carboxyethyl)imidazolium bromide. 153
Fig. 49. ¹³C NMR spectrum of 1-methyl-3-(2-carboxyethyl)imidazolium bromide. 153
Fig. 50. Powder XRD pattern of MOF-545, MOF-545(Mn), and fresh/reused... 158
Fig. 51. (a) N₂ adsorption-desorption isotherms and (b) pore size distributions... 159
Fig. 52. FESEM images of (a) MOF-545, (b) MOF-545(Mn), and (c) ImBr-... 160
Fig. 53. FESEM and EDX mapping images of (a-c) MOF-545 and (d-g) MOF-545(Mn). 161
Fig. 54. Energy-dispersive X-ray mapping images for C, N, O, Zr, Mn, and Br... 162
Fig. 55. Infrared spectra of H6-TCPP, MOF-545, MOF-545(Mn), ImBr, and...[이미지참조] 162
Fig. 56. UV-Visible DRS of MOF-545 and MOF-545(Mn). 163
Fig. 57. XPS of (a) C 1s, (b) O 1s, (c) N 1s, (d) Br 3d, (e) Zr 3d & Br 3p, and... 167
Fig. 58. ¹H NMR spectra of MOF-545, MOF-545(Mn), and ImBr-MOF-... 168
Fig. 59. (a) CO₂ and (b) O₂ adsorption isotherms of ImBr-MOF-545(Mn). 170
Fig. 60. (a-b) CO₂ and (c-d) O₂ adsorption isotherms of MOF-545 and MOF-545(Mn). 171
Fig. 61. Powder XRD pattern of the recovered ImBr-MOF-545(Mn) catalyst... 173
Fig. 62. (a) GC analysis for the reaction product mixture of the oxidation of... 175
Fig. 63. (a) GC analysis for the reaction product mixture of the oxidation of... 176
Fig. 64. Effect of (a) O₂ pressure, (b) MOF-545(Mn) loading, (c) reaction... 179
Fig. 65. Progress of the epoxidation reaction under the conditions of styrene... 180
Fig. 66. (a) Kinetics plot at three different amounts of styrene; (b) Double... 180
Fig. 67. Kinetics plot at three different amounts of (a) O₂, (c) MOF-545(Mn)... 182
Fig. 68. (a) GC analysis for the reaction product mixture of the CO₂... 185
Fig. 69. Effect of (a) CO₂ pressure, (b) ImBr-MOF-545(Mn) loading, (c)... 188
Fig. 70. Effect of the reaction time on the CO₂ cycloaddition reaction under... 189
Fig. 71. (a) Kinetics plot at three different amounts of styrene oxide; (b)... 190
Fig. 72. Kinetics plot at three different amounts of (a) CO₂, (c) ImBr-MOF-... 191
Fig. 73. (a) GC analysis for the reaction product mixture of the one-pot process... 194
Fig. 74. Conversion profiles as a function of time under the one-pot reaction... 197
Fig. 75. Recycling of ImBr-MOF-545(Mn) in the one-pot cascade... 199
Fig. 76. ¹H NMR spectrum of 4-phenyl-1,3-dioxolan-2-one(styrene carbonate). 203
Fig. 77. ¹³C NMR spectrum of 4-phenyl-1,3-dioxolan-2-one(styrene carbonate). 204
Fig. 78. ¹H NMR spectrum of 4-(4-bromophenyl)-1,3-dioxolan-2-one. 204
Fig. 79. ¹³C NMR spectrum of 4-(4-bromophenyl)-1,3-dioxolan-2-one. 205
Fig. 80. ¹H NMR spectrum of 4-(phenoxymethyl)-1,3-dioxolan-2-one. 205
Fig. 81. ¹³C NMR spectrum of 4-(phenoxymethyl)-1,3-dioxolan-2-one. 206
Fig. 82. ¹H NMR spectrum of 4-(chloromethyl)-1,3-dioxolan-2-one. 206
Fig. 83. ¹³C NMR spectrum of 4-(chloromethyl)-1,3-dioxolan-2-one. 207
Fig. 84. ¹H NMR spectrum of 4-butyl-1,3-dioxolan-2-one. 207
Fig. 85. ¹³C NMR spectrum of 4-butyl-1,3-dioxolan-2-one. 208
Fig. 86. ¹H NMR spectrum of 4-hexyl-1,3-dioxolan-2-one. 208
Fig. 87. ¹³C NMR spectrum of 4-hexyl-1,3-dioxolan-2-one. 209
Fig. 88. ¹H NMR spectrum of hexahydrobenzo[d][1,3]dioxol-2-one. 209
Fig. 89. ¹³C NMR spectrum of hexahydrobenzo[d][1,3]dioxol-2-one. 210
Fig. 90. Plausible mechanistic pathway for the one-pot cascade reaction of the... 211
Scheme 1. Epoxidation of olefins. 56
Scheme 2. CO₂ cycloaddition of epoxides. 57
Scheme 3. Oxidative carboxylation of olefins. 58
Scheme 4. Oxidation of 1, 2, 3-trihydroxybenzene (THB). 58
Scheme 5. Oxidation of cyclohexane. 59
Scheme 6. Hydroxylation of dimethyl-4-nitrophenyl phosphate (DMNP). 60
Scheme 7. Dehydrogenation of methanol. 60
Scheme 8. Catalytic O-H insertion. 61
Scheme 9. Hetero-Diels-Alder reaction. 61
Scheme 10. Structure of MOF-525 (left) and MOF-545 (right). The green... 78
Scheme 11. Structures of (a) SMX, (b) H2TCPP, (c) MOF-... 112
Scheme 12. Configuration of SMX molecule at different solution pH. 135
Scheme 13. Direct one-pot route for the preparation of cyclic carbonates from olefins. 145
Scheme 14. The synthetic procedure of ImBr-MOF-545(Mn) by post-... 148
Scheme 15. Oxidation of styrene over MOF-545(Mn). 173
Scheme 16. CO₂ cycloaddition reaction with styrene oxide. 184
Scheme 17. One-pot process for the synthesis of styrene carbonate. 193