Title Page
Contents
ABSTRACT 11
Chapter Ⅰ. Introduction 13
Chapter Ⅱ. Theoretical background 16
1. Catalyst 16
1-1. Active phase 16
1-2. Supporting material 17
1-3. Catalytic promoter 18
2. Metal-organic frameworks (MOFs) 19
3. Metal-organic polyhedra (MOP) 21
Chapter Ⅲ. Experimental methods 23
1. External catalytic promoter 23
1-1. Materials 23
1-2. Synthesis 23
1-3. Characterization 24
2. Catalytic promoter within the supporting material 26
2-1. Materials 26
2-2. Synthesis 26
2-3. Characterization 30
Chapter Ⅳ. Results and discussion 32
1. External catalytic promoter 32
1-1. Synthesis of Re-MOF, Re-MOP 32
1-2. Structural characterization 37
1-3. Analysis for light absorption ability 43
1-4. Photocatalytic measurement of Re-MOF, Re-MOF with Ru ligand, Re-MOP and Re-MOP with Ru ligand 45
2. Catalytic promoter within the supporting material 49
2-1. Synthesis of Re-MOF, Re-MOF-(NH₂)₂, Re₃-MOP, Re-MOP-(NH₂)₂ 49
2-2. Structural characterization 52
2-3. Analysis for light absorption ability 60
2-4. Photocatalytic measurement of Re-MOF, Re-MOF-(NH₂)₂, Re₃-MOP, Re-MOP-(NH₂)₂ 62
Chapter Ⅴ. Conclusion 68
Chapter Ⅵ. Reference 70
ABSTRACT IN KOREAN 75
Figure 1. A schematic diagram of the photocatalytic CO₂ conversion within Ru linker and Re-MOP. Ru linker is externally added as catalytic promoter to enhance... 15
Figure 2. A schematic diagram of the photocatalytic CO₂ conversion within Re-MOP-(NH₂)₂-NH₂ multi-functionalized linker is introduced directly with the MOP... 15
Figure 3. A schematic diagram for synthesis of metal-organic frameworks (MOFs). Atom labelling scheme: C, black; O, red; Zr, blue polyhedra; H atoms are omitted... 20
Figure 4. Diagram for application of MOFs. 20
Figure 5. A schematic diagram for synthesis of metal-organic polyhedra (MOP). Atom labelling scheme: C, black; O, red; Zr, blue polyhedra; H atoms are omitted... 22
Figure 6. Schematic images for MOP in crystal and MOP in discrete cage. (a) The weak hydrogen bonding between metal clusters results in the arrangement of discrete... 22
Figure 7. A synthesis of -NH₂ multi-functionalized complex. (a) A schematic diagram for synthesis of -NH₂ multi-functionalized complex, (b) Chemical analysis... 28
Figure 8. A schematic diagram for synthesis of Re ligand (H₂ ReTC). 34
Figure 9. A schematic diagram for synthesis of Ru ligand [Ru(bpy)₂(bpdc)]. 34
Figure 10. A schematic diagram for synthesis of Re-MOF. Atom labelling scheme: C, black; O, red; Zr, blue polyhedra; Re, yellow; Cl, green; H atoms are omitted for clarity. 35
Figure 11. A schematic diagram for synthesis of Re-MOP. Atom labelling scheme: C, black; O, red; Zr, blue polyhedra; Re, yellow; Cl, green; H atoms are omitted for clarity. 36
Figure 12. Schematic images for Re-MOP in crystal and Re-MOP in discrete cage. (a) The weak hydrogen bonding between metal clusters results in the arrangement of... 36
Figure 13. SEM images of (a) Re-MOF (b) Re-MOP in crystal (left) and Re-MOP in discrete cage (right). 40
Figure 14. SEM-EDS mapping images of Re-MOP in crystal. Zirconium is mapped in red, chloride is mapped in orange and rhenium is mapped in green. 40
Figure 15. PXRD patterns of BPDC-MOF, Re-MOF, BPDC-MOP and Re-MOP in crystal. 41
Figure 16. N₂ adsorption isotherms of Re-MOF and Re-MOP. 41
Figure 17. Digested ¹H-NMR spectra of H₂ ReTC ligand, BPDC ligand, Re-MOF and Re-MOP. 42
Figure 18. UV-vis spectrums of Re linker, Ru linker, Re-MOF and Re-MOP 44
Figure 19. Schematic image of photocatalytic system for Re linker, Ru linker, Re linker + Ru linker, Re-MOF, Re-MOF + Ru linker, Re-MOP and Re-MOP+ Ru linker. 47
Figure 20. Photocatalytic activity of Re linker, Ru linker, Re linker + Ru linker, Re-MOF, Re-MOF + Ru linker, Re-MOP and Re-MOP+ Ru linker. 48
Figure 21. SEM images of (a) Re-MOF, (b) Re-MOF-(NH₂)₂, (c) Re₃-MOP in crystal (left) and Re₃-MOP in discrete cage (right), (d) Re-MOF-(NH₂)₂ in crystal(left) and... 56
Figure 22. SEM-EDS mapping images of (a) Re₃-MOP in crystal and (b) Re-MOF-(NH₂)₂ in crystal. Zirconium is mapped in red, chloride is mapped in orange and... 57
Figure 23. PXRD patterns of Re-MOF, Re-MOF-(NH₂)₂, Re₃-MOP and Re-MOP-(NH₂)₂ in crystal. 58
Figure 24. N₂ adsorption isotherms of Re-MOF, Re-MOF-(NH₂)₂, Re₃-MOP and Re-MOP-(NH₂)₂. 58
Figure 25. Digested ¹H-NMR spectra of H₂ BPDC ligand, H₂ ReTC ligand, H₂ BPDC-(NH₂)₂ ligand, Re-MOF, Re-MOF-(NH₂)₂, Re₃-MOP and Re-MOP-(NH₂)₂. 59
Figure 26. UV-vis spectrums of Re-MOF, Re-MOF-(NH₂)₂, Re₃-MOP and Re-MOP-(NH₂)₂. 61
Figure 27. Schematic image of photocatalytic system for Re-MOF, Re-MOF-(NH₂)₂, Re₃-MOP and Re-MOP-(NH₂)₂. 64
Figure 28. Photocatalytic activity of Re₃-MOP and Re-MOP-(NH₂)₂. Each sample was prepared 24h, 72h, 96h before the photocatalytic experiments. 65
Figure 29. Photocatalytic activity of Re-MOF, Re-MOF-(NH₂)₂, Re₃-MOP and Re-MOP-(NH₂)₂. All samples were prepared 96h before the photocatalytic experiments. 66
Figure 30. A schematic diagram for accessibility of CO₂ to-NH₂ multi-functionalized linkers within Re-MOF-(NH₂)₂ and Re-MOP-(NH₂)₂ . Atom labelling... 67