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研究生：	王耀廷 Wang, Yao-Ting
論文名稱：	應用於二氧化碳、碳氫化合物分離之孔洞材料的結構工程研究 The structural engineering of Porous Materials for CO₂ and Hydrocarbon Separations
指導教授：	柯碧蓮 Kaveevivitchai, Watchareeya
學位類別：	博士 Doctor
系所名稱：	工學院 - 化學工程學系 Department of Chemical Engineering
論文出版年：	2026
畢業學年度：	114
語文別：	英文
論文頁數：	230
中文關鍵詞：	金屬有機骨架、多孔分子晶體、氣體分離、丙烯/丙烷分離、變壓吸附、碳捕集
外文關鍵詞：	Metal–Organic Frameworks, Porous Molecular Crystals, Gas Separation, Carbon Capture, Olefin/Paraffin Separation, Pressure Swing Adsorption
相關次數：	點閱：3 下載：0
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減緩人為二氧化碳排放以緩解全球氣候變遷，並推動碳捕集、利用與封存技術，是達成全球碳中和目標的關鍵課題。與此同時，工業上高純度一氧化碳的純化以及丙烯/丙烷等輕質碳氫化合物的分離，高度依賴深冷蒸餾與化學吸收等高能耗工藝。基於物理吸附的變壓吸附技術具備低能耗與低操作成本的潛力，但傳統吸附劑長期面臨「高吸附親和力」與「低再生能耗」之間的內在權衡，且普遍缺乏嚴苛環境下的穩定性。本論文旨在透過精確的結晶孔道環境設計與結構柔性調控，系統性地開發一系列具備低再生能耗、高耐濕性及高選擇性的結晶多孔材料，構建從剛性框架、超分子結晶到柔性動態結構的完整材料工程故事線。
本論文之核心研究內容分為三個漸進式的主題：
剛性金屬有機框架之微觀孔道與官能基工程：在第三章中，針對結構與尺寸高度接近的丙烯/丙烷混合氣，透過在UiO-66框架的配位基中同步整合氟（−F）與羥基（−OH）雙官能基，成功合成新型框架UiO-66-F₂(OH)₂。質子化羥基與丙烯的 π 鍵形成選擇性[π⋯H-O]鍵結，氟原子則精準調控電負性與空間位阻。在298 K 與 1 bar條件下，UiO-66-F₂(OH)₂對等莫耳C3H6/C3H8混合氣展現出 2.51的IAST選擇性，顯著優於單官能基對照組UiO-66-F₄ (1.13)與UiO-66-(OH)₂ (1.08)。材料在pH 1–11水溶液中浸泡7 天仍維持完整晶像；並在連續5次動態穿透循環中穩定分離 C3H6/C3H8，產出純度高達 98.6%以上的高純度丙烷。
多孔分子晶體（PMC）之剛性大環堆積與極性孔道分離：為打破傳統多孔分子晶體在脫去溶劑後結構易塌陷的瓶頸，第四章與第五章採用具備非共價大環堆積的乙酸環四苯偶姻（Cyclotetrabenzoin Acetate, PMC 1）。PMC 1具備7.1 × 7.1 Å的本徵大環通道，向內延伸的極性酯基羰基（C=O）限制出5.0 × 5.0 Å的有效孔徑窗，在298 K與1 bar 下具備68 cm3 g−1（3.04 mmol g−1）的CO2吸附量與極低的初始吸附熱（Qst = 33.7 kJ mol−1）。在第五章中，更進一步應用於極難分離的CO2/CO體系，在298 K與1 bar條件下，PMC 1成功逆向吸附CO2，在連續30 次（> 900 min）PSA循環中穩定產出純度高達 > 99.99% 的工業級高純度CO。
柔性金屬有機框架之動態閘門效應與低能耗再生：為打破吸附容量與低再生能耗的內在矛盾，第六章開發了具備適度柔性與苯醌（Quinone）配位的陰離子型銅三唑框架NCKU-56。NCKU-56具備獨特的動態閘門響應機制，在298 K與1 bar 下具備24.8 cm3 g−1(1.11 mmol g−1)的CO2吸附量。對模擬煙道氣（CO2/N2 =15/85）展現出高達315 的超高IAST選擇性(在 50:50 混合氣下亦有65的高選擇性)。最關鍵的是，其初始吸附熱維持在溫和區間（Qst = 30.1 kJ mol−1），無須高溫脫附，僅需在298 K進行常溫氣流沖洗即可於數分鐘內完成100%脫附再生，在多循環操作下大幅提升單位時間通量，展現出極具工業價值的超低再生能耗優勢。

Mitigating anthropogenic carbon dioxide (CO2) emissions to combat global climate change and advancing Carbon Capture, Utilization, and Storage (CCUS) platforms represent critical imperatives toward achieving global carbon neutrality. Concurrently, industrial purification of high-purity carbon monoxide and the separation of light hydrocarbons, such as propylene/propane (C3H6/C3H8), remain heavily reliant on energy-intensive operations including cryogenic distillation and chemical scrubbing. While physisorption-based pressure swing adsorption (PSA) offers a promising low-energy alternative, conventional solid adsorbents suffer from an intrinsic trade-off between high adsorption affinity and low regeneration energy penalties, alongside limited moisture/chemical stability under operational conditions. This dissertation establishes a systematic structural engineering framework for crystalline porous solids, spanning from rigid frameworks and supramolecular crystals to flexible dynamic architectures, to deliver minimal regeneration energy, remarkable chemical resilience, and high separation selectivity.
The core research achievements are categorized into three interconnected thematic advances:
Dual-Functionality Integration in Rigid MOFs: In Chapter 3, to address the challenging separation of C3H6/C3H8 mixtures with nearly identical physical dimensions, fluorine (−F) and hydroxyl (−OH) dual-functionalities were simultaneously integrated into the BDC linkers of UiO-66, yielding UiO-66-F₂(OH)₂. Acidic protons of the hydroxyl groups form selective [π⋯H-O] complexes with the electron-rich double bonds of propylene, while electronegative fluorine atoms alter the electrostatic landscape to minimize contact with propane. Consequently, UiO-66-F₂(OH)₂ achieves an enhanced IAST selectivity of 2.51 for equimolar C3H6/C3H8 mixtures at 298 K and 1 bar, outperforming its mono-functionalized counterparts, UiO-66-F₄ (1.13) and UiO-66-(OH)₂ (1.08). The framework preserves its crystalline integrity after 7-day immersion in aqueous solutions across pH 1–11. Dynamic column breakthrough tests across 5 consecutive cycles yield purified C3H8 with a purity exceeding 98.6%.
Polar Channel Engineering in Permanent Porous Molecular Crystals (PMCs): To prevent desolvation-induced structural collapse typical of PMCs, Chapters 4 and 5 utilize cyclotetrabenzoin acetate (PMC 1), a solution-processable macrocyclic supramolecular crystal. PMC 1 features an intrinsic macrocyclic channel of 7.1 × 7.1 Å restricted to an effective 5.0 × 5.0 Å aperture by inward-pointing polar ester carbonyls, delivering a CO2 uptake of 68 cm3 g−1 (3.04 mmol g−1) at 298 K and 1 bar alongside a mild isosteric heat of adsorption (Qst = 33.7 kJ mol−1). Chapter 5 further demonstrates the application of PMC 1 in the challenging CO2/CO separation, selectively capturing CO2 to continuously produce polymer-grade CO with an ultra-high purity exceeding 99.99% across 30 PSA cycles (> 900 min) at 298 K and 1 bar.
Dynamic Gate-Opening and Elastic Flexibility in Quinone-Based MOFs: To break the capacity-regeneration energy deadlock, Chapter 6 introduces NCKU-56, an anionic copper–triazolate framework constructed with quinone linkers and framework flexibility. NCKU-56 exhibits a structural gating behavior, recording a CO2 uptake of 24.8 cm3 g−1 (1.11 mmol g −1) at 298 K and 1 bar. Notably, it exhibits an outstanding IAST CO2/N2 (15:85) selectivity of 315 (and 65 for 50/50 mixture). Crucially, its adsorption heat remains within a mild regime (Qst = 30.1 kJ mol−1), enabling complete desolvation at 298 K within minutes under ambient purge without thermal activation, thereby offering significant throughput and energy-efficiency advantages in multi-cycle post-combustion carbon capture.
In summary, this dissertation quantitatively validates the integration of dual-functionalized rigid pore tuning, supramolecular polar channel confinement, and dynamic gate-opening responsiveness. By overcoming the trade-off between adsorption selectivity and regeneration energy penalties, this work establishes a comprehensive design paradigm for energy-efficient and chemically resilient porous adsorbents for industrial gas purification and carbon capture.

Chapter 1	Introduction	1
1	Industrial Significance and Thermodynamic Challenges of Gas Separations 1
1.1	Carbon Capture, Utilization, and Storage (CCUS) Platforms 2
1.2	High-Purity Light Hydrocarbon Separations 10
1.3	Limitations of Industrial Technologies 15
2	Classification and Architectural Attributes of Advanced Porous Materials 21
2.1	Conventional Inorganic and Carbonaceous Adsorbents 22
2.2	Metal-Organic Frameworks (MOFs) and Porous Coordination Polymers (PCPs) 27
2.3	Covalent Organic Frameworks (COFs) 32
2.4	Porous Organic Cages (POCs) and Porous Molecular Crystals (PMCs) 34
3	Principles of Structural Engineering for Tailoring Pore Environments 38
3.1	Spatial Confinement and Pore Size Customization 39
3.2	Pore Surface Functionalization: A Comprehensive Review of Polar Environments 43
3.3	Framework Dynamics and Stimuli-Responsive Flexibility 47
4	Organization of the Dissertation 49
Chapter 2	Experimental Methods and Characterization Techniques 52
1	Chemicals and Gases	52
2	Instruments 57
2.1	Single Crystal X-ray Diffractometer 57
2.2	Gas Loading Holder for SCXRD 58
2.3	Powder X-ray Diffractometer 59
2.4	Fourier-transform Infrared Spectrometer 60
2.5	Thermogravimetric Analyzer 61
2.6	Critical Point Dryer 62
2.7	Freeze-Dryer 63
2.8	Gas Adsorption Analyzer 64
2.9	Pressure Swing Adsorption Analyzer 65
3	General Methods 66
3.1	Fitting of CO2 Adsorption Isotherm 66
3.2	Isosteric Heat of Adsorption (Qₛₜ) 66
3.3	IAST Selectivity Calculation 67
3.4	Evaluation of Brunauer–Emmett–Teller (BET) Surface Area 67
3.5	Crystallographic Data 68
Chapter 3	Rational Integration of Fluorine and Hydroxyl Functionalities in UiO-66 Metal−Organic Framework for Enhanced Propylene/Propane Separation 71
1	Introduction 72
1.1	Bridging Rigid Frameworks to Sub-Angstrom Hydrocarbon Discrimination 72
1.2	Multivariate Surface Engineering: Orthogonal Synergy of –F and –OH Arrays 73
1.3	Research Objectives and Chapter Scope 74
2	Experimental Section	75
2.1	Synthesis of UiO-66 Derivatives 75
2.2	Instrumental Characterizations 77
3	Results and Discussion 77
3.1	Synthesis and Structural Characterization of UiO-66 Derivatives 77
3.2	Thermal and Chemical Stability, and Porosity Analysis 79
3.3	Single-Component C₃H₆ and C₃H₈ Adsorption Isotherms 82
3.4	Thermodynamic Evaluation and Theoretical Calculations (IAST & DFT) 85
3.5	Dynamic Breakthrough Separation and Recycling Stability 88
4	Conclusion 90
Chapter 4	Porous Molecular Crystals Based on Cyclotetrabenzoin Acetate for High-Performance CO₂ Separation via Cyclic Adsorption 91
1	Introduction	92
1.1	Transitioning from Extended Networks to Solution-Processable Supramolecular Crystals 92
1.2	The Stability Deadlock: Desolvation Collapse and Extrinsic Void Unpredictability 93
1.3	Pore Aperture Engineering in PMC 1 and Chapter Scope 95
2	Experimental Section	96
2.1	Synthesis and Preparation of Cyclotetrabenzoin Acetate (PMC 1) 96
2.2	Materials and General Characterizations 97
2.3	Single-Component Gas Sorption and Thermodynamics (Qst) 98
2.4	In situ Single-Crystal and Synchrotron Powder X-ray Diffraction Analyses 99
2.5	Dynamic Column Breakthrough Experiments 101
2.6	Two-Bed Pressure Swing Adsorption (PSA) Cycling Setup 103
3	Results and Discussion 104
3.1	Characterization and Crystal Packing Diagrams of Compound 1 104
3.2	Gas Adsorption Isotherms, IAST Selectivity, and Vapor Sorption Characterization 105
3.3	Host–Guest Binding Sites Probed by In situ SCXRD Studies 107
3.4	In situ Synchrotron Powder X-ray Diffraction Studies 110
3.5	Column Breakthrough Experiments and Regenerability 112
3.6	Gas Separation Cycles under Pressure Swing Adsorption Conditions 114
4	Conclusion 116
Chapter 5	Efficient CO₂ / CO Separation by Pressure Swing Adsorption Using an Intrinsically Nanoporous Molecular Crystal 118
1	Introduction 119
1.1	Industrial Significance of Carbon Monoxide Purification and CO₂/CO Separation 119
1.2	Limitations of CO Sorbents and Rationale for CO₂ Physisorption 120
1.3	Macrocyclic Porous Molecular Crystals for CO₂/CO Mixtures Separation 121
2	Experimental Section	122
2.1	Material Activation and Volumetric Gas Adsorption Measurements 122
2.2	Setup of Dynamic Column Breakthrough Experiments 123
2.3	Two-Bed Pressure Swing Adsorption (PSA) Operational Logic and Energy Evaluation 125
2.4	Computational Details 127
3	Results and Discussion 128
3.1	Gas Sorption Thermodynamics and Pure-Component Isotherms	128
3.2	Analysis of Isosteric Heat of Adsorption (Qst) 133
3.3	Dynamic Mixed-Gas Breakthrough Separation 135
3.4	Industrial-Scale Simulated PSA Cycling and Material Robustness	137
4	Conclusion 139
Chapter 6	A Moderately Flexible Copper–Triazolate Framework with Quinone-based Linkers: Balancing Effective CO₂ Capture and Low-energy Regeneration 141
1 Introduction 142
1.1	Limitations of Conventional Carbon Capture Systems 142
1.2	MOFs as Advanced Sorbents and Thermodynamic Trade-Offs 143
1.3	Moderate Framework Flexibility in Polar Quinone Environments 145
1.4	Strategic Design and Scope 146
2	Experimental Section	147
2.1	Synthesis of Sorbent Constituents and Core Coordination Framework 147
2.2	Supercritical Carbon Dioxide (scCO₂) Activation Protocol 149
2.3	Instrumental Characterizations and Synchrotron Spectroscopic Analyses 150
2.4	Specialized Crystallographic and Fixed-Bed Dynamic Flow Separations 150
2.5	Computational Details (Made by Anton S. Pozdeev and Alexander S. Ivanov.) 153
3	Results and Discussion 155
3.1	Architectural Analysis of the Pristine Network and Valence Verification 155
3.2	Desolvation-Driven Structural Contraction and Framework Elasticity 158
3.3	Isothermal Gas Sorption Divergence and Thermodynamic Separation Selectivity 160
3.4	Mechanistic Insights from CO2-Loaded Single-Crystal Structures 166
3.5	In Situ PXRD of Single-Phase Elastic Transition 169
3.6	DFT-optimized geometries of NCKU-56 170
3.7	Dynamic Kinetic Profiles and Fixed-Bed Multi-Component Adsorption Separation 173
4	Conclusion 177
Chapter 7	Conclusions and Future Outlook 179
1	General Conclusions 179
2	Future Outlook 181
2.1	Industrial Scaling Up and Shaping Engineering of PMCs 182
2.2	Interdisciplinary Collaboration for Mixed-Matrix Membranes (MMMs) 184
References 187
                                    

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