Preface xi
List of Contributors xiii
1 CARBON CAPTURE IN METAL-ORGANIC FRAMEWORKS 1
Mehrdad Asgari and Wendy L. Queen
1.1 Introduction 1
1.1.1 The Importance of Carbon Dioxide Capture 1
1.1.2 Conventional Industrial Process of Carbon Capture and Limitations: Liquid Amines 3
1.1.3 Metal-Organic Frameworks and Their Synthesis 4
1.1.4 CCS Technologies and MOF Requirements 6
1.1.5 Molecule Specific 10
1.2 Understanding the Adsorption Properties of MOFs 11
1.2.1 Single-Component Isotherms 11
1.2.2 Multicomponent Adsorption 14
1.2.3 Experimental Breakthrough 15
1.2.4 In Situ Characterization 16
1.3 MOFs for Post-combustion Capture 30
1.3.1 Necessary Framework Properties for CO2 Capture 30
1.3.2 Assessing MOFs for CO2/N2 Separations 32
1.3.3 MOFs with Open Metal Coordination Sites (OMCs) 34
1.3.4 MOFs Containing Lewis Basic Sites 37
1.3.5 Stability and Competitive Binding in the Presence of H2O 45
1.4 MOFs for Pre-combustion Capture 48
1.4.1 Advantages of Pre-combustion Capture 48
1.4.2 Necessary Framework Properties for CO2 Capture 49
1.4.3 Potential MOF Candidates for CO2/H2 Separations 50
1.5 MOFs for Oxy-Fuel Combustion Capture 54
1.5.1 Necessary Framework Properties for O2/N2 Separations 54
1.5.2 Biological Inspiration for O2/N2 Separations in MOFs 55
1.5.3 Potential MOF Candidates for O2/N2 Separations 56
1.6 Future Perspectives and Outlook 61
Acknowledgments 63
References 63
2 METAL-ORGANIC FRAMEWORKS MATERIALS FOR POST-COMBUSTION CO2 CAPTURE 79
Anne M. Marti
2.1 Introduction: The Importance of Carbon Capture and Storage Technologies 79
2.1.1 Post-combustion CO2 Capture Technologies 80
2.1.2 Metal-Organic Frameworks: Potential for Post-combustion CCS 82
2.2 Metal-Organic Frameworks as Sorbents 84
2.2.1 Criteria for Choosing the Best CO2 Sorbent 84
2.2.2 Discussion of Defined Sorbent Criteria 87
2.3 Metal-Organic Framework Membranes for CCS 99
2.3.1 Membrane Performance Defined 99
2.3.2 MOF Membrane Fabrication 102
2.4 Summary 104
References 104
3 NEW PROGRESS OF MICROPOROUS METAL-ORGANIC FRAMEWORKS IN CO2 CAPTURE AND SEPARATION 112
Zhangjing Zhang, Jin Tao, Shengchang Xiang, Banglin Chen, and Wei Zhou
3.1 Introduction 112
3.2 Survey of Typical MOF Adsorbents 116
3.2.1 CO2 Capture and Separation at Low Pressure 116
3.2.2 CO2 Capture and Separation at High Pressure 139
3.2.3 Capture CO2 Directly from Air 140
3.2.4 CO2/CH4 Separation 145
3.2.5 CO2/C2H2 Separation 148
3.2.6 Photocatalytic and Electrochemical Reduction of CO2 149
3.2.7 Humidity Effect 152
3.3 Zeolite Adsorbents in Comparison with MOFs 158
3.4 MOFs Membrane for CCS 163
3.5 Summary and Outlook 165
Acknowledgments 166
References 167
4 IN SITU DIFFRACTION STUDIES OF SELECTED METAL-ORGANIC FRAMEWORK MATERIALS FOR GUEST CAPTURE/EXCHANGE APPLICATIONS 180
Winnie Wong-Ng
4.1 Introduction 180
4.1.1 Background 180
4.1.2 In Situ Diffraction Characterization 181
4.2 Apparatus for In Situ Diffraction Studies 182
4.2.1 Single-Crystal Diffraction Applications 182
4.2.2 Powder Diffraction Applications 185
4.3 In Situ Single-Crystal Diffraction Studies of MOFs 186
4.3.1 Thermally Induced Reversible Single Crystal-to-Single Crystal Transformation 187
4.3.2 Structure Transformation Induced by Presence of Guests 188
4.3.3 Dynamic CO2 Adsorption Behavior 190
4.3.4 Unstable Intermediate Stage During Guest Exchange 190
4.3.5 Mechanism of CO2 Adsorption 192
4.4 Powder Diffraction Studies of MOFs 193
4.4.1 Synchrotron/Neutron Diffraction Studies 193
4.4.2 Laboratory X-ray Diffraction Studies 204
4.5 Conclusion 207
References 207
5 ELECTROCHEMICAL CO2 CAPTURE AND CONVERSION 213
Peng Zhang, Jingjing Tong, and Kevin Huang
5.1 Introduction 213
5.2 Current Electrochemical Methods for Carbon Capture and Conversion 214
5.2.1 Ambient-Temperature Approach 215
5.2.2 High-Temperature Approach 218
5.3 Development of High-Temperature Permeation Membranes for Electrochemical CO2 Capture and Conversion 224
5.3.1 Development of MECC Membranes 224
5.3.2 Development of MOCC Membranes 235
5.4 Summary and Outlook 255
Acknowledgments 258
References 258
6 ELECTROCHEMICAL VALORIZATION OF CARBON DIOXIDE IN MOLTEN SALTS 267
Huayi Yin and Dihua Wang
6.1 Introduction 267
6.2 Thermodynamic Analysis of Molten Salt Electrolytes 269
6.2.1 Thermodynamic Analysis of Alkali Metal Carbonates 269
6.2.2 Thermodynamic Analysis of Alkaline-Earth Metal Carbonates 275
6.2.3 Thermodynamic Viewpoint of Variables Affecting Electrolytic Products 277
6.2.4 Thermodynamic Analysis of Mixed Melts 278
6.3 Electrochemistry of Cathode and Anode 282
6.3.1 Electrochemical Reactions at the Cathode 282
6.3.2 Electrochemical Reaction Pathway of CO2 and CO3 (C or CO?) 285
6.3.3 Electrochemical Reaction at the Anode 287
6.4 Applications of Electrolytic Products 289
6.5 Conclusion and Prospects 289
Acknowledgments 292
References 292
7 MICROSTRUCTURAL AND STRUCTURAL CHARACTERIZATION OF MATERIALS FOR CO2 STORAGE USING MULTI-SCALE X-RAY SCATTERING METHODS 296
Greeshma Gadikota and Andrew Allen
7.1 Introduction 296
7.2 Experimental Investigations of Subsurface CO2 Trapping Mechanisms 298
7.3 Comparison of Material Measurements Techniques for Microstructure Characterization 300
7.4 Usaxs/Saxs Instrumentation 302
7.5 Analyses of Ultrasmall- and Small-Angle Scattering Data 304
7.5.1 Determination of the Volume Fractions, Mean Volumes, and Radius of Gyration Using Guinier Approximation and Scattering Invariant 304
7.5.2 Determination of the Surface Area from the Porod Scattering Regime 305
7.5.3 Shapes and Size Distributions 305
7.5.4 Fractal Morphologies 306
7.6 USAXS/SAXS/WAXS Characterization of CO2 Interactions with Na-Montmorillonite 307
7.6.1 Experimental Methods 307
7.6.2 Results and Discussion 310
7.7 Summary 312
Acknowledgments 313
References 313
8 CONTRIBUTION OF DENSITY FUNCTIONAL THEORY TO MICROPOROUS MATERIALS FOR CARBON CAPTURE 319
Eric Cockayne
8.1 Microporous Solids 320
8.2 Overview of DFT 323
8.2.1 Local Density Approximation 324
8.2.2 General Gradient Approximation 325
8.2.3 Meta-GGAs 325
8.2.4 Hybrid Methods 325
8.2.5 DFT+U 326
8.2.6 Van der Waals (Dispersion) Forces 327
8.2.7 Accuracy of DFT 327
8.3 DFT: Applications 328
8.3.1 CO2 Location and Binding Energetics 329
8.3.2 Bandgap 332
8.3.3 Elastic Properties 332
8.3.4 Phonons 333
8.3.5 Thermodynamics 335
8.3.6 NMR 336
8.3.7 Ab Initio Molecular Dynamics 336
8.3.8 CO2 Diffusion 337
8.4 Conclusions and Recommendations 337
References 338
9 COMPUTATIONAL MODELING STUDY OF MNO2 OCTAHEDRAL MOLECULAR SIEVES FOR CARBON DIOXIDE-CAPTURE APPLICATIONS 344
I. Williamson, M. Lawson, E. B. Nelson, and L. Li
9.1 Introduction 344
9.2 Atomic Structure Versus Magnetic Ordering 345
9.3 Pore Size and Dimensionality 346
9.4 CO2 Sorption Behavior 347
9.4.1 Experimental Observations 347
9.4.2 DFT Studies 348
9.5 Comparison of Cation Dopant Types 348
9.5.1 Cation Effects on CO2 Sorption in OMS-2 349
9.6 OMS-5 351
9.7 Summary 353
References 354
Index 357
