Virginia Commonwealth University VCU Scholars Compass Theses and Dissertations Graduate School 2011 Designed Synthesis of Halogenated Borazine-Linked Polymers and Their Applications in Gas Storage and Separation Thomas Reich Virginia Commonwealth University Follow this and additional works at: https://scholarscompass.vcu.edu/etd Part of the Chemistry Commons © The Author Downloaded from https://scholarscompass.vcu.edu/etd/282 This Dissertation is brought to you for free and open access by the Graduate School at VCU Scholars Compass. It has been accepted for inclusion in Theses and Dissertations by an authorized administrator of VCU Scholars Compass. For more information, please contact [email protected]. © COPYRIGHT BY Thomas E. Reich 2011 All Rights Reserved DESIGNED SYNTHESIS OF HALOGENATED BORAZINE-LINKED POLYMERS AND THEIR APPLICATIONS IN GAS STORAGE AND SEPARATION A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at Virginia Commonwealth University. by Thomas Eugene Reich Bachelor of Science James Madison University, 2003 Director: Hani M. El-Kaderi, Assistant Professor, Department of Chemistry Virginia Commonwealth University Richmond, Virginia December 2011 Acknowledgement I would like to acknowledge the support and guidance of Professor Dr. Hani M. El-Kaderi whose ideas and talents helped to make this work possible. I would also like to acknowledge my committee members Professor Dr. Scott Gronert, Professor Dr. Everett E. Carpenter, and Professor Dr. Purusottam Jena for their input in pursuit of a doctorate. I am very thankful to the members of the El-Kaderi Group who have been a pleasure to work beside. I would also like to thank the Department of Chemistry at Virginia Commonwealth University for giving me the chance to pursue a doctorate as well as for the financial support early in my career. I would also like to acknowledge the selflessness of the many donors who have allowed me to focus my efforts on research more than I ever thought I could have. I would especially like to thank my family for all their love and care. My parents, Richard and Sherry (1952-2006) Reich, have been, and continue to be, a true inspiration for what a good person can be. My brother, Jeremy Reich, serves as an excellent example of what hard work can do for a lifelong goal. I would certainly like to thank my wonderful wife Jessica as well. I could not imagine a better person with whom to share life’s exciting experiences. She is my other half and my better half. Without her by my side, I would not be close to the man that I am today. Most assuredly, I would like to thank F. S. H. for the love, compassion, and guidance that knows no bounds. You are the best. ii Table of Contents List of Tables ................................................................................................................... vi List of Figures ................................................................................................................ viii List of Abbreviations ...................................................................................................... xvi Abstract ........................................................................................................................ xvii Chapter 1—Introduction 1.1 Global Energy Concerns................................................................................ 1 1.2 Hydrogen and Methane Energy ..................................................................... 3 1.3 Purification of Hydrogen and Methane Fuels ................................................. 4 1.4 The Use of Hydrogen in Automotive Applications .......................................... 6 1.5 The Storage of Hydrogen by High Pressure and Liquid Systems .................. 9 1.6 The Storage of Hydrogen by Chemisorption and Physisorption .................. 11 1.6.1 Chemisorption ............................................................................... 14 1.6.2 Physisorption................................................................................. 14 1.7 Borazine ...................................................................................................... 19 1.8 Dissertation Problem ................................................................................... 23 Chapter 2—Reticular Chemistry and the Design of Porous Polymers 2.1 Introduction .................................................................................................. 25 2.2 Design of Borazine-Linked Polymers ........................................................... 27 Chapter 3—Synthesis of Halogenated Borazine-Linked Polymers iii 3.1 Introduction .................................................................................................. 49 3.2 Synthesis of Halogenated Borazine-Linked Polymers ................................. 50 3.3 Characterization of Halogenated Borazine-Linked Polymers....................... 55 Chapter 4—Porosity Measurements and Hydrogen, Carbon Dioxide, and Methane Gas Storage Capabilities of Halogenated Borazine-Linked Polymers 4.1 Introduction .................................................................................................. 89 4.2 Nitrogen Sorption of Halogenated Borazine-Linked Polymers ..................... 97 4.3 Hydrogen, Carbon Dioxide, and Methane Sorption of Halogen-Decorated Borazine-Linked Polymers ......................................................................... 116 Chapter 5—Experimental and Theoretical Calculations for the Isosteric Heat of Adsorption of Hydrogen, Carbon Dioxide, and Methane with Halogenated Borazine- Linked Polymers 5.1 Introduction ................................................................................................ 124 5.2 Experimental Isosteric Heat of Adsorption of Hydrogen, Carbon Dioxide, and Methane with Halogenated Borazine-Linked Polymers ............................. 128 5.3 Theoretical Calculations for the Isosteric Heat of Adsorption of Hydrogen, Carbon Dioxide, and Methane with Halogenated Borazine-Linked Polymers ......................................................................................................................... 133 Chapter 6—Gas Separation and Selectivity Capabilities for Benzimidazole-Linked Polymers and Halogenated Borazine-Linked Polymers 6.1 Introduction ................................................................................................ 139 6.2 IAST Calculations for Benzimidazole-Linked Polymers ............................. 144 iv 6.3 Detailed Methodology for the Calculation of Selectivity by the Ideal Adsorbed Solution Theory ......................................................................................... 172 6.4 IAST Calculations for Halogenated Borazine-Linked Polymers ................. 180 Chapter 7—Concluding Remarks ............................................................................... 191 List of References ....................................................................................................... 196 Vita .............................................................................................................................. 240 v List of Tables Table 1: Typical Composition of Natural Gas ................................................................. 5 Table 2: Nomenclature of Borazine-Linked Polymers .................................................. 28 Table 3: Theoretical Textural Properties of BLPs ......................................................... 34 Table 4: Fractional Atomic Coordinates for the Eclipsed Conformation of BLP-1(Br)... 35 Table 5: Fractional Atomic Coordinates for the Staggered Conformation of BLP-1(Br) ...................................................................................................................................... 36 Table 6: Fractional Atomic Coordinates for the Eclipsed Conformation of BLP-1(Cl) ... 37 Table 7: Fractional Atomic Coordinates for the Staggered Conformation of BLP-1(Cl) ...................................................................................................................................... 38 Table 8: Fractional Atomic Coordinates for the Eclipsed Conformation of BLP-2(Br)... 39 Table 9: Fractional Atomic Coordinates for the Staggered Conformation of BLP-2(Br) ...................................................................................................................................... 40 Table 10: Fractional Atomic Coordinates for the Eclipsed Conformation of BLP-2(Cl) ...................................................................................................................................... 41 Table 11: Fractional Atomic Coordinates for the Staggered Conformation of BLP-2(Cl) ...................................................................................................................................... 42 Table 12: Fractional Atomic Coordinates for the Eclipsed Conformation of BLP-10(Br) ...................................................................................................................................... 43 vi Table 13: Fractional Atomic Coordinates for the Staggered Conformation of BLP-10(Br) ...................................................................................................................................... 44 Table 14: Fractional Atomic Coordinates for the Eclipsed Conformation of BLP-10(Cl) .....................................................................................................................................