서강대학교

목차

Abstract iv
List of Figures vi
List of Tables xiv
CHAPTER 1 Introduction 1
1.1 Need for Adsorption-Based Separation Processes 2
1.1.1 Carbon Dioxide Capture 4
1.1.2 Acetylene Separation 5
1.2 Research Objectives 8
1.3 Dissertation Overview 9
CHAPTER 2 Background and Theory 13
2.1 Nanoporous Materials 14
2.1.1 Classification of Nanoporous Materials 14
2.1.2 Metal–Organic Frameworks （MOFs） 16
2.1.3 HSAB Theory-Guided Design of Stable MOFs 17
2.2 Evaluation of Adsorption Performance 19
2.2.1 Adsorption Isotherm 19
2.2.2 Brunauer–Emmett–Teller Theory 21
2.2.3 Isosteric Heat of Adsorption （Qst） 22
2.2.4 Ideal Adsorbed Solution Theory 23
2.2.5 Breakthrough Experiment 25
2.2.6 Dynamic Separation Factor 26
CHAPTER 3 Carbon Dioxide Capture in a Carbonate-Pillared Ultramicroporous
Metal–Organic Framework 30
3.1 Introduction 31
3.2 Experimental 33
3.2.1 Materials 33
3.2.2 Synthesis of Zn2（atz）2（CO3） 34
3.2.3 Characterization of Materials 34
3.2.4 Gas Adsorption Measurement 34
3.2.5 Breakthrough Experiment 35
3.2.6 Computational Details 37
3.3 Results and Discussion 38
3.3.1 Structure Characterizations of Zn2（atz）2（CO3） 38
3.3.2 Gas Adsorption Properties and Stability of Zn2（atz）2（CO3） 50
3.3.3 Preferential CO2 Binding Sites in Zn2（atz）2（CO3） 66
3.3.4 CO2/N2 Breakthrough Performance under Humid Conditions 70
3.4 Conclusion 73
CHAPTER 4 Tailoring Nitrogen Functionality in Aluminum-Based Metal–Organic
Frameworks for Selective C2H2/CO2 Separation 82
4.1 Introduction 83
4.2 Experimental 85
4.2.1 Materials 85
4.2.2 Synthesis of Aluminum-based MOF Adsorbents 85
4.2.3 Characterization of Materials 86
4.2.4 Gas Adsorption Measurement 87
4.2.5 Breakthrough Experiment 87
4.2.6 Computational Details 88
4.3 Results and Discussion 90
4.3.1 Synthesis and Characterization 90
4.3.2 C2H2/CO2 Adsorption Performance 98
4.3.3 Dynamic Breakthrough Experiment 108
4.3.4 Molecular-Level Origin of C2H2-Selective Adsorption 113
4.4 Conclusions 119
CHAPTER 5 A green, Scalable, and Flexible Metal–Organic Framework for
Thermodynamically and Kinetically Selective Acetylene Adsorption 127
5.1 Introduction 128
5.2 Experimental 130
5.2.1 Materials 130
5.2.2 Synthesis of MKC-1 130
5.2.3 Gas Adsorption Characterization 131
5.2.4 Supplementary Characterizations 131
5.2.5 Rietveld Refinement 132
5.2.6 Calculation of Diffusion Time Constants and Kinetic Selectivity 133
5.2.7 Computational Details 134
5.2.8 Breakthrough Experiment 135
5.3 Results and Discussion 136
5.3.1 Synthesis, Structure, and Characterization of MKC-1 136
5.3.2 Single-Component Gas Adsorption 163
5.3.3 Binding Site Analysis 181
5.3.4 Mixed Gas Separation 185
5.4 Conclusion 193
CHAPTER 6 Conclusion and Future Perspectives 201
6.1 Summary and Conclusions 202
6.2 Future Perspectives 204
국문 초록 206