New class of mesoporous silica supports for heterogeneous catalysts
New class of mesoporous silica supports for heterogeneous catalysts
- 주제(키워드) Meso-porous silica particle , Heterogeneous catalyst
- 발행기관 고려대학교 대학원
- 지도교수 이석중
- 발행년도 2019
- 학위수여년월 2019. 2
- 학위구분 석사
- 학과 대학원 화학과
- 세부전공 유기 화학
- 원문페이지 95 p
- 실제URI http://www.dcollection.net/handler/korea/000000083223
- UCI I804:11009-000000083223
- DOI 10.23186/korea.000000083223.11009.0000825
- 본문언어 영어
- 제출원본 000045978784
초록/요약
Many porous materials such as metal-organic frameworks (MOFs), porous organic polymers (POPs), and covalent organic frameworks (COFs), zeolites, meso-porous silica particles (MPSMs) have been studied in both academic and the industrial communities. Their specific properties are good enough to using various application such as gas adsorption, catalysis, gas storage, and separation of molecules. In catalytic system especially, porous materials can play important role in heterogeneous catalyst. It present a much poor catalytic activity and selectivity than homogeneous catalyst but their advantages such as recyclability for several times and easy to separation from products have enough to attractive in industrial process. In this thesis, SBA-15 among meso-porous silica particles (MPSMs) was used for heterogeneous supports having embedded metal complex catalyst because it is useful to control various pore size. Second chapter is described various olefins oxidation using SBA-15 and pSBA-15. SBA-15 having uni-dimensional pore structure was prepared by the stöber method and the pSBA-15 which had been prepared by surfactant-assistant pseudomorphic transformation from mother SBA-15 material have a two different pore size having interconnect respectively. After introducing Mn(III)-porphyrin into silica surface respectively, catalytic performance of pSBA-15 in olefin epoxidation shown a much faster rate of reaction than SBA-15 for various olefins. Also both catalysts could be recyclable without losing their catalytic activity. In third chapter, ethylene dimerization was performed using SBA-15 (4 nm of pore size) grafted with different concentration of Ni(II)-bpy (bispyridine) to selectively produce to 1-butene. Using HD-Ni-SBA-15 (high density of Ni(II) contents) and LD-Ni-SBA-15 (low density of Ni(II) contents), liquid phase ethylene dimerization was carried out at 150 °C and under 30 bar of ethylene pressure in 8 mL heptane with Et2AlCl as co-catalyst. LD-Ni-SBA-15 have shown a dramatically increased intrinsic activity toward 1-butene than HD-Ni-SBA-15. And LD-Ni-SBA-15 could be recyclable for several times because it hardly produced high molecular weight side products and polyethylene (PE) which can block to catalytic active site.
more목차
CHPTER 1 : General Introduction 1
INTRODUCTION 2
1.1. Meso-porous silica materials (MPSMs) 4
1.1.1. Pseudomorphic transformation 9
1.2. Olefins epoxidation 10
1.3. Ethylene oligomerization 11
1.3.1. Mechanism 12
1.4. References 15
CHAPTER 2 : Immobilization of Porphyrinic Mn(III) Catalyst on a New Class of Silica Support Based on Two Different Sizes of Three-Dimensionally Interconnected Pores 18
2.1. Experimental Section 19
2.1.1. Instruments 19
2.1.2. Materials 20
2.1.3. Synthesis of starting materials 21
2.1.4. Catalysis 28
2.2. Characterization and Measurements 29
2.3. Results and Discussion 44
2.3.1. Olefins oxidation 44
2.4. Conclusion 49
2.5. References 50
CHAPTER 3 : Dramatic change in catalytic activity for ethylene dimerization with Ni(II)bpy catalyst loading density on SBA-15 support 52
3.1. Experimental Section 53
3.1.1. Instruments 53
3.1.2. Materials 54
3.1.3. Synthesis of starting materials 55
3.1.4. Catalysis 62
3.2. Characterization and Measurements 63
3.3. Results and Discussion 73
3.3.1. Dimerization Reaction 73
3.4. Conclusion 81
3.5. References 82
