Title Page
Contents
Abstract 12
요약 16
Ⅰ. Introduction 20
1. Why Need to Produce Alternative Materials? 20
2. Efforts for Carbon Neutrality 22
3. Plastic Pollution Issues and Solutions 25
Ⅱ. Conversion of Biomass Derived 5-Hydroxymethylfurfural into Plastic Monomer 32
1. Biomass Derived Materials Conversion into Valuable Chemicals 32
1.1. Biomass Derived Materials to Substitute Fossil-fuel Based Chemicals 32
1.2. 5-Hydromethylfurfural, Biomass Derived Furan 33
1.3. Oxidation of 5-Hydromethylfrufural 34
2. Aerobic Oxidation of 5-Hydroxymethylfurfural by Heterogeneous Catalyst 36
2.1. Manganese Oxides with Various Oxidation States 36
2.2. Novel Metal Particle (Ru or Pt) on Carbon Support with Tunable Porosity Prepared by Carbonizing Chitosan 52
3. Electro Oxidation of 5-Hydroxymethylfurfural with Electrode 73
3.1. Deep Eutectic Solvent Stabilized Co-P Film 73
4. Experimental 92
4.1. Materials 92
4.2. Characterization of Catalyst 92
4.3. Catalytic Performance for HMF Oxidation 94
Ⅲ. Polyethylene Terephthalate Degradation into Monomer for Upcycling 95
1. Polyethylene Terephthalate Recycling 95
2. Hydrolysis of Polyethylene Terephthalate 98
2.1. Enhance Acidity of MFI-type Zeolite Using Controlled Si/Al Ratio and Kind of Counter Ion 98
3. Experimental 121
3.1. Materials 121
3.2. Characterization of Catalyst 121
Ⅳ. Reference 122
Table Ⅱ.1. Pore Structure Parameters of manganese catalyst 42
Table Ⅱ.2. Species and concentration of basic site on manganese catalyst by CO₂-TPD analysis 43
Table Ⅱ.3. The summary of Mn 3s, Mn 2p, O 1s XPS data of manganese oxide 46
Table Ⅱ.4. Pore parameters of the activated carbon materials 60
Table Ⅱ.5. Results of the O 1s region, values given in % of total intensity 64
Table Ⅱ.6. EDS elemental analysis results of Co and P 81
Table Ⅲ.1. Si/Al ratio of H⁺ form ZSM-5 measured by XRF. 103
Table Ⅲ.2. Total surface area, pore volume and pore diameter of the various types of ZSM-5-based catalysts. 105
Table Ⅲ.3. Species and concentration of acidic site on zeolite-based catalysts by NH₃-TPD analysis; NH₃-TPD curves of the ZSM-5-based catalysts. 116
Figure Ⅰ.1. Diagram of carbon cycle 21
Figure Ⅰ.2. Schematic diagram of achieving carbon neutrality. Carbon generating factors and carbon removal methods. 24
Figure Ⅰ.3. Plastic production process and waste plastic treatment route 27
Figure Ⅰ.4. Trends in Demand and Waste Amount by Plastic Application 28
Figure Ⅰ.5. Schematic diagram of a carbon circular economy approach for the plastic chain compared to a typical linear economic approach 29
Figure Ⅱ.1. SEM images of (a) MnO₂, (b) Mn₂O₃, (c) Mn₃O₄, and (d) MnO. 39
Figure Ⅱ.2. XRD patterns for (a) MnO₂, (b) Mn₂O₃, (c) Mn₃O₄, and (d) MnO. 41
Figure Ⅱ.3. N₂ adsorption–desorption isotherms at 77 K of manganese oxide catalysts. 42
Figure Ⅱ.4. CO₂-TPD profiles of manganese oxide catalysts. 43
Figure Ⅱ.5. High-resolution Mn 3s, Mn 2p, O 1s XPS spectra of manganese oxide catalysts 45
Figure Ⅱ.6. Conversion of HMF and yield of oxidation products with manganese oxide catalyst; (a) without NaHCO₃ and (b) with NaHCO₃. 48
Figure Ⅱ.7. HMF conversion and oxidation product yields with Mn₂O₃ at different reaction conditions; (a) amount of base (equiv. with respect to HMF), (b) temperature,... 50
Figure Ⅱ.8. SEM images of activated chitosan carbon samples (a) CS-800, (b) ACS-600 (1:2), (c) ACS-700 (1:2), (d) ACS-800 (1:0.5), (e) ACS-800 (1:1), (f)... 58
Figure Ⅱ.9. N₂ adsorption-desorption isotherms at 77 K of activated carbon (a) with different activated temperature and (b) with different amount of K₂CO₃. 59
Figure Ⅱ.10. (a) PXRD and (b) Raman spectra of the CS-800 and ACS-t samples prepared at different activation temperatures. 61
Figure Ⅱ.11. O 1s and N 1s XPS spectra of the CS-800 and ACS-t samples. 63
Figure Ⅱ.12. Comparison of catalytic properties for HMF conversion with (a) the presence of activated carbon and (b) the amount of K₂CO₃. 66
Figure Ⅱ.13. Comparison of catalytic properties in base-free HMF conversion using Pt/CS-800 and Pt/ACS-t prepared at different activation temperatures. 68
Figure Ⅱ.14. TEM images and size distribution diagram of (a,b) Pt/ACS-800 and (b,d) Pt-PVP-ACS-800. 69
Figure Ⅱ.15. (a) Comparison of the catalytic properties of Pt/ACS-800 and Pt/PVP ACS-800. (b) Time profiles of HMF oxidation over Pt/PVP-ACS-800. Effect of O₂... 70
Figure Ⅱ.16. (a) Reusability tests of Pt/PVP-ACS 800 (a) and (b) TEM image of the used Pt/PVP-ACS-800 catalyst. 71
Figure Ⅱ.17. Cyclic voltammetry (CV) curves during preparation of (a) Co-P_DES and (b) Co-P_H₂O electrodes. 77
Figure Ⅱ.18. Concentration change of HMF in two electrolytes with different pH conditions over time 80
Figure Ⅱ.19. SEM image of (a) Co–P_DES and (b) Co–P_H₂O electrodes. 82
Figure Ⅱ.20. LSVs of (a) Cu foam, Co metal and Co-P_DES with various concentration of P precursor, and (b) Co-P_DES within different cycles during... 83
Figure Ⅱ.21. LSV curves of Co–P_DES and CoP_H₂O in 0.5 M NaHCO₃ electrolyte. 84
Figure Ⅱ.22. XPS Co 2p spectra of (a) Co–P_DES and (b) Co–P_H₂O, and XPS P 2p spectra of (c) Co–P_DES and (d) CoP_H₂O. 85
Figure Ⅱ.23. HMF conversion and product yield curves vs. charge passed for (a) Co–P_DES and (b) Co–P_H₂O electrodes. 86
Figure Ⅱ.24. ¹H proton NMR spectrum of purified FDCA. 87
Figure Ⅱ.25. SEM images of Co–P_DES (a) before reaction and (b) after reaction, SEM images of Co–P_H₂O (c) before reaction and (d) after reaction. 88
Figure Ⅱ.26. XPS Co 2p spectra of (a) Co–P_DES and (b) Co–P_H₂O after HMF oxidation reaction, and P 2p spectra of (c) Co–P_DES and (d) Co–P_H₂O after the... 89
Figure Ⅱ.27. (a) J–t plot with passed charge of Co–P_DES with repeated reaction cycles, (b) HMF conversion and product yield profile after repeated addition of 5... 90
Figure Ⅲ.1. SEM images of the various types of ZSM-5-based catalysts (a) Na⁺@ZSM-5-25, (b) H⁺@ZSM-5-25, (c) surface H⁺@ZSM-5-25, (d) H⁺@ZSM-... 104
Figure Ⅲ.2. (a) Powder XRD patterns and (b) N₂ adsorption-desorption isotherm curves at 77 K of the various types of ZSM-5-based catalysts. 105
Figure Ⅲ.3. (a) Scheme of the microwave assisted PET hydrolysis system, (b) optical image of microwave assisted PET hydrolysis with a ZSM-5-based catalyst... 107
Figure Ⅲ.4. (a) Reaction temperature-TPA yield curves and (b) detailed reaction temperature-TPA yield curves of the catalyst-free and ZSM-5-based catalyst reactions. 108
Figure Ⅲ.5. PET conversion and TPA yield according to different weight ratio of water and PET with H⁺@ZSM-5-25 catalyst. 109
Figure Ⅲ.6. (a) ¹H NMR and (b) ¹³C NMR spectrum of produced TPA. 110
Figure Ⅲ.7. (a) Reaction time-TPA yield curves, (b) time-ln[A] curves of the catalyst-free and ZSM-5-based catalyst conditions, (c) reaction temperature-TPA... 112
Figure Ⅲ.8. Schematic of the cation exchanged ZSM-5 (H⁺@ZSM-5: fully proton exchanged ZSM-5, Sur-H⁺@ZSM-5: surface proton exchanged ZSM-5,... 113
Figure Ⅲ.9. (a) TPA yield of the different types of zeolite catalysts and (b) TPA yield of the ZSM-5-based catalysts and their acidic site concentration plot. 114
Figure Ⅲ.10. NH₃-TPD curves of (a) ZSM-5-25 based catalysts with various counter ion, and (b) H⁺@ZSM-5 based catalysts with different Si/Al ratio. 116
Figure Ⅲ.11. Recyclability test results for the H⁺@ZSM-5-25 catalyst (catalysts are regenerated after 6 times of reaction). 117
Figure Ⅲ.12. (a) PET hydrolysis mechanism with an acid catalysts. (b) Schematic of the Brønsted acidic site structure in the ZSM-5 zeolite. 119