Molecular simulations for CO2 capture in metal organic frameworks

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Molecular simulations for CO2 capture in metal organic frameworks

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MOLECULAR SIMULATIONS FOR CO2 CAPTURE IN METAL-ORGANIC FRAMEWORKS CHEN YIFEI NATIONAL UNIVERSITY OF SINGAPORE 2012 MOLECULAR SIMULATIONS FOR CO2 CAPTURE IN METAL-ORGANIC FRAMEWORKS CHEN YIFEI (B.Eng., Hebei University of Technology, M. Eng., Tianjin University, Tianjin, China) A THESIS SUBMITTED FOR THE DEGREE OF DOCTOR OF ENGINEERING DEPARTMENT OF CHEMICAL AND BIOMOLECULAR ENGINEERING NATIONAL UNIVERSITY OF SINGAPORE 2012 Acknowledgements First of all, I would like to express my sincere gratitude to my supervisor Professor Jiang Jianwen. His close guidance, suggestions, and discussions have helped me all the time during my study and research at NUS. His patience and encouragement have been of central importance for me to complete my PhD program. His immense knowledge and enthusiasm in research have motivated me and will have substantial impact on my future professional career. I would like to thank my group members: Babarao Ravichandar, Hu Zhongqiao, Anjaiah Nalaparaju, Luo Zhonglin, Fang Weijie, Zhang Liling, Liang Jianchao, Xu Ying, Li Jianguo, Krishan Mohan Gupta, Naresh Thota, Zhang Kang and Huang Zongjun for their interactions during my personal and professional time at NUS. I am grateful for their suggestions, discussions, and comments on my research. I would like to thank my family and friends for their support and encouragement. I am also grateful to NUS for granting me the scholarship. i Table of Contents Acknowledgements . i  Table of Contents .ii  Summary vi  List of Tables ix  List of Figures . x  List of Abbreviations xv  Chapter 1. Introduction . 1  1.1 MOF Structures 3  1.2 MOF Synthesis 6  1.3 MOF Applications 7  1.4 Objective 11  1.5 Thesis Outline 12  Chapter 2. Literature Review . 13  2.1 Experimental Studies . 13  2.1.1 H2, CH4 and CO2 Storage 13  2.1.2 Water Adsorption 18  2.1.3 Gas Separation 19  2.1.4 Adsorption and Separation of Alkanes 22  2.2 Simulation Studies . 23  2.2.1 H2, CH4, CO2 Adsorption 23  ii 2.2.2 Water Adsorption 30  2.2.3 Gas Separation 30  2.2.4 Adsorption and Separation of Alkanes 33  Chapter 3. Models and Methods . 35  3.1 Atomic Models . 35  3.2 Computational Methods . 40  3.2.1 Density Functional Theory . 40  3.2.2 Interaction Potential 41  3.2.2 Molecular Dynamics Simulation 43  3.2.3 Monte Carlo Simulation 43  3.3 Analysis Methods . 45  3.3.1 Radial Distribution Functions . 45  3.3.2 Adsorption Selectivity . 46  3.3.3 Mean-Squared Displacement 46  Chapter 4. Adsorption of CO2 and CH4 in MIL-101 47  4.1 Models and Methods 47  4.2 Results and Discussion 53  4.2.1 Sensitivity of Framework Charges 53  4.2.2 United-Atom and Five-site Models of CH4 54  4.2.3 Adsorption of Pure CO2 and CH4 55  4.2.4 Adsorption of CO2/CH4 Mixture . 63  4.3 Summary 64  iii Chapter 5. Adsorption and Separation in Hydrophobic Zn(BDC)(TED)0.5 . 66  5.1 Models and Methods 66  5.2 Results and Discussion 71  5.2.1 CH3OH/H2O 71  5.2.2 CO2/CH4 75  5.2.3 Hexane 79  5.3 Summary 81  Chapter 6. CO2 Capture in Bio-MOF-11 . 83  6.1 Models and Methods 83  6.2 Results and Discussion 87  6.2.1 Pure Gases . 87  6.2.2 CO2/H2 Mixture 91  6.2.3 CO2/N2 Mixture 94  6.3 Summary 97  Chapter 7. CO2 Adsorption in Cation-Exchanged MOFs 99  7.1 Models 99  7.2 Methods 102  7.3 Results and Discussion 104  7.3.1 Characterization of cations . 105  7.3.2 Isosteric Heat and Henry’s Constant . 107  7.3.3 CO2/H2 Mixture 112  7.4 Conclusions 115  iv Chapter 8. Ionic Liquid/MOF Composite for CO2 Capture 116  8.1 Models and Methods 116  8.1.1 [BMIM][PF6] 116  8.1.2 IRMOF-1 . 118  8.1.3 IL/IRMOF-1 Composite and Adsorption of CO2/N2 Mixture 120  8.2 Results and Discussion 122  8.2.1 Structure and Dynamics of IL in IL/IRMOF-1 . 122  8.2.2 Separation of CO2/N2 Mixture in IL/IRMOF-1 125  8.3 Conclusions 129  Chapter 9. Conclusions and Recommendation . 131  9.1 Conclusions 131  9.2 Recommendation . 135  References . 138  Appendix . 151  Publications 162  v Summary As a special class of hybrid nanoporous materials, metal-organic frameworks (MOFs) have received considerable interest in the past decade. The achievable large surface areas, high porosities, and tunable structures place them at the frontier for a wide range of potential applications such as gas storage, separation, catalysis and drug delivery. Since a vast variety of MOFs with different pore shapes and dimensions have been synthesized and many more are possible, experimental screening of appropriate MOFs for specific application is a formidable task. As an alternative, molecular simulations can provide microscopic insights and quantitative guidelines that otherwise are experimentally inaccessible or difficult to obtain, and thus assist in the rational screening and design of novel MOFs. In this thesis, molecular simulations have been performed primarily for CO2 capture in different MOFs with diverse structures and functionalities. Firstly, CO2 adsorption is investigated in a mesoporous MOF namely MIL-101, which is one of the most porous materials reported to date. The simulation results agree well with experimental data and the terminal water molecules play an interesting role in adsorption. At low pressures, the terminal water molecules act as additional adsorption site and enhance gas adsorption; however, they decrease the available free volume and reduce adsorption at high pressures. The hydrated MIL-101 has a higher adsorption selectivity for CO2/CH4 mixture. Secondly, the adsorption and separation of CO2/CH4, as well as methanol/water, vi in highly hydrophobic Zn(BDC)(TED)0.5 are examined. Good agreement is found between simulation and experimental results and a large separation factor for methanol/water is predicted. This reveals that Zn(BDC)(TED)0.5 could be a good candidate for the purification of liquid fuel. The simulation results also imply that water has a marginal effect on CO2/CH4 separation, thus pre-water treatment is not required prior to separation. Thirdly, CO2 capture is investigated in bio-MOF-11 consisting of biological ligands. The simulation results are in accordance with experimental data. The predicted adsorption selectivities of CO2/H2 and CO2/N2 mixtures in bio-MOF-11 are higher than in many porous materials, which suggests bio-MOF-11 might be interesting for pre- and post-combustion CO2 capture. In addition, water has a negligible effect on the separation of these two CO2-containing mixtures. Fourthly, CO2 adsorption is simulated in rho zeolite-like MOFs (rho-ZMOFs) exchanged with a series of cations (Na+, K+, Rb+, Cs+, Mg2+, Ca2+ and Al3+). The isosteric heat and Henry’s constant at infinite dilution increase monotonically with increasing charge-to-diameter ratio of cation (Cs+ < Rb+ < K+ < Na+ < Ca2+ < Mg2+ < Al3+). The adsorption selectivity of CO2/H2 mixture increases as Cs+ < Rb+ < K+ < Na+ < Ca2+ < Mg2+  Al3+. The simulation study provides microscopic insight into the important role of cations in governing gas adsorption and separation, and suggests that the performance of ionic rho-ZMOFs can be tailored by cations. Finally, a new composite of ionic liquid (IL) [BMIM][PF6] supported on IRMOF-1 is proposed for CO2 capture. The confinement effects of IRMOF-1 on the vii structure and mobility of cation and anion are examined. Ions in the composite interact strongly with CO2, particularly [PF6]anion is the most favorable site for CO2 adsorption. The composite selectively adsorbs CO2 from CO2/N2 mixture, with selectivity significantly higher than polymer-supported ILs. In addition, the selectivity increases with increasing IL ratio in the composite. viii Appendix Table A7. Equilibrium locations of Al3+ ions. Ion index X Y Z 15.490 24.069 9.470 12.431 28.390 31.001 28.544 28.503 11.995 28.059 18.891 0.122 18.804 15.524 27.553 17.685 8.605 8.705 18.967 3.122 30.985 31.013 5.283 22.277 13.169 3.513 17.795 10 17.990 27.601 17.956 11 5.781 23.049 22.649 12 2.987 12.232 0.035 13 2.619 2.632 11.893 14 13.169 15.545 2.724 15 3.478 15.528 12.302 16 27.907 15.547 18.260 161 Publications Publications 1. Y. F. Chen, Z. Q. Hu, K. M. Gupta. J. W. Jiang. Ionic Liquid/Metal-Organic Framework Composite for CO2 Capture: A Computational Investigation. Journal of Physical Chemistry C. 2011, 115, 21736-21742. 2. Y. F. Chen, J. W. Jiang. A Bio-Metal-Organic Framework for Highly Selective CO2 Capture: A Molecular Simulation Study. ChemSusChem. 2010, 3, 982-988. 3. Y. F. Chen, J. Y. Lee, R. Babarao, J. Li, and J. W. Jiang. A Highly Hydrophobic Metal-Organic Framework Zn(BDC)(TED)0.5 for Adsorption and Separation of CH3OH/H2O and CO2/CH4. Journal of Physical Chemistry C. 2010, 114, 6602 6609. 4. Y. F. Chen, R. Babarao, S. I. Sandler, and J. W. Jiang. Metal-Organic Framework MIL-101 for Adsorption and Effect of Terminal Water Molecules: From Quantum Mechanics to Molecular Simulation. Langmuir 2010, 26, 8743-8750. 5. Z. Q. Hu, Y. F. Chen, and J. W. Jiang. Zeolitic Imidazolate Framework-8 as a Reverse Osmosis Membrane for Water Desalination: Insight from Molecular Simulation. Journal of Chemical Physics. 2011, 134, 134705. 6. P. Pachfule, Y. F. Chen, J. W. Jiang, R. Banerjee. Fluorinated Metal Organic Frameworks (F-MOFs): Advantageous for Higher H2 and CO2 Adsorption or not? Chemistry-A European Journal. 2012, 18, 688-694. 7. P. Pachfule, Y. F. Chen, S. C. Sahoo, J. W. Jiang, R. Banerjee. Structural Isomerism and effect of Fluorination of Gas Adsorption in Copper-Tetrazolate Based Metal Organic Frameworks. Chemistry of Materials. 2011, 23, 2908-2916. 8. P. Pachfule, Y. F. Chen, J. W. Jiang, R. Banerjee. Experimental and Computational Approach of Understanding the Gas Adsorption in Amino Functionalized Interpenetrated Metal Organic Frameworks. Journal of Materials Chemistry. 2011, 21, 17737-17745. 162 Publications 9. T. Panda, P. Pachfule, Y. F. Chen, J. W. Jiang. And R. Banerjee. Amino Functionalized Zeolitic Tetrazolate Framework (ZTF) with High Capacity for Storage of Carbon Dioxide. Chemical Communications. 2011, 47, 2011-2013. Presentations 1. Y. F. Chen, A. Nalaparaju, J. W. Jiang, Adsorption and Separation of CO2/H2 in Mono-, Di- and Trivalent Cation-Exchanged th Frameworks: Atomistic Simulation Study, 14 Zeolite-like Metal-Organic Asia Pacific Confederation of Chemical Engineering Congress, Singapore (Feb. 2012). 2. R. Babarao, Y. F. Chen, J. W. Jiang, Effect of Water on Adsorption in Metal-Organic Frameworks: Insight from Molecular Simulations, AIChE Annual Conference, Salt Lake City, Utah, USA (Nov. 2010). 3. Y. F. Chen, J. Lee, J. Li, J. W. Jiang, Adsorption and Separation of CO2/CH4 and CH3OH/H2O in Highly Hydrophobic Zn(BDC)(TED)0.5. 2nd International Conference on Metal-Organic Frameworks and Open Framework Compounds, Marseille, France (Sep. 2010). 4. Y. F. Chen, R. Babarao, J. W. Jiang, Metal-Organic Framework MIL-101 for Adsorption and Effect of Terminal Water Molecules: A Computational Study. 2nd International Conference on Metal-Organic Frameworks and Open Framework Compounds, Marseille, France (Sep. 2010). 163 Rightslink Printable License Page of NATURE PUBLISHING GROUP LICENSE TERMS AND CONDITIONS May 10, 2012 This is a License Agreement between Yifei Chen ("You") and Nature Publishing Group ("Nature Publishing Group") provided by Copyright Clearance Center ("CCC"). The license consists of your order details, the terms and conditions provided by Nature Publishing Group, and the payment terms and conditions. All payments must be made in full to CCC. For payment instructions, please see information listed at the bottom of this form. 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No payment is required. https://s100.copyright.com/App/PrintableLicenseFrame.jsp?publisherID . 5/10/2012 [...]... ever-increasing computational power, molecular simulations have become increasingly important in materials science In particular, microscopic insights gained from simulations are indispensable in quantitatively elucidating the underlying physics and subsequently provide guidelines for the rational design of new materials The objective of this thesis is to investigate CO2 capture using molecular simulations. .. the adsorption of CO2 and CH4 in MIL-101 is examined In Chapter 4, the separation of CH3OH/H2O and CO2/ CH4 in highly hydrophobic MOF Zn(BDC)(TED)0.5 are investigated Chapter 5 describes the CO2 capture in bio-MOF-11 Chapter 6 discusses CO2 adsorption in different cation-exchanged rho-ZMOFs CO2 capture in an ionic liquid /metal- organic framework composite is proposed in Chapter 7 Finally, the conclusions... is studied in a bio -metal organic framework The effect of 11 Chapter 1 Introduction humidity on separation is estimated Fourthly, CO2 adsorption and CO2/ H2 separation in cations exchanged rho-ZMOFs are explored to study the influence of cations Finally, CO2 separation from flue gas in an ionic-liquid/MOF composite is investigated The effect of ionic liquid loading on separation is examined in detail... publications for MOFs (Data from Scopus using metal organic frameworks as the topic on 10 November 2011) In this thesis, CO2 capture by adsorption in different MOFs is investigated The subsequent sections provide an overview for the structures, synthesis and typical applications of MOFs A more detailed literature review for the specific applications in gas adsorption and separation will be presented in Chapter... hybrid materials named as metal- organic frameworks (MOFs)2 or also called porous coordination polymers (PCPs) have attracted a great deal of attention MOFs are crystalline structures assembled from organic linkers and metal oxides Compared with traditional nanoporous materials, almost all cations can participate in MOF frameworks In addition, the wide variety of organic linkers and linker functionalities... to inorganic zeolites.18 However, the difference is oxygen atoms in zeolites are substituted by organic linkers, leading to extra-large cavities and pores in ZMOFs This edge expansion approach offers a great potential towards the design and synthesis of widely open materials In addition, some ZMOFs possess ionic frameworks and contain charge-balancing nonframework ions 5 Chapter 1 Introduction For. .. from Scopus using metal organic frameworks as the topic on 10 November 2011) 2  Figure 1.2 Examples of SBUs from carboxylate MOFs Color scheme: O, red; N, green; C, black In inorganic units, metal- oxygen polyhedra are blue, and the polygon or polyhedron defined by carboxylate carbon atoms (SBUs) are red In organic SBUs, the polygons or polyhedrons to which linkers (all –C6H4– units in these examples)... in these examples) are attached are shown in green.4 3 Chapter 1 Introduction By extending different SBUs with a wide variety of organic linkers, various MOFs can be produced For example, Eddaoudi et al developed a series of MOFs from the prototype MOF-5 by using various functional organic linkers.5 Sixteen highly crystalline isoreticular MOFs (IRMOFs) produced are shown in Figure 1.3 Figure 1.3 Single... and flexible The former have rigid frameworks, largely similar to inorganic counterparts (e.g zeolites) In contrast, the latter can change frameworks at external stimuli like pressure, temperature and accommodating of guest molecules.6-8 The change may include stretching, rotational, breathing and scissoring, and induce various effects 4 Chapter 1 Introduction crystalline structures Based on the framework... and CO2 Storage H2 Storage H2 is regarded as an ideal energy carrier and its storage in MOFs has been extensively studied The first experimental measurement of H2 storage was conducted in IRMOF-1, IRMOF-6, and IRMOF-8.37 In this study, the length of organic link was found to play a dominate role in tuning H2 capacity Therefore, H2 uptake in IRMOF-6 and -8 are much higher than IRMOF-1 Compared with inorganic . MOLECULAR SIMULATIONS FOR CO 2 CAPTURE IN METAL-ORGANIC FRAMEWORKS CHEN YIFEI NATIONAL UNIVERSITY OF SINGAPORE 2012 MOLECULAR SIMULATIONS FOR CO 2 CAPTURE. experimentally inaccessible or difficult to obtain, and thus assist in the rational screening and design of novel MOFs. In this thesis, molecular simulations have been performed primarily for CO 2 capture. Ca 2+ (c) Al 3+ . The initial locations are indicated in pink. 105  Figure 7.4. Porosity  versus the packing fraction of cation  in rho-ZMOFs. The solid line is a linear correlation between

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