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Carbon Dioxide Capture, in Situ Amine Protection and Nanoparticle Synthesis

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Carbon Dioxide Capture, in Situ Amine Protection and Nanoparticle Synthesis APPLICATIONS OF REVERSIBLE AND SUSTAINABLE AMINE-BASED CHEMISTRIES: CARBON DIOXIDE CAPTURE, IN SITU AMINE PROTECTION AND NANOPARTICLE SYNTHESIS A Thesis Presented to The Academic Faculty By Amy Lynn Ethier In Partial Fulfillment Of the Requirements for the Degree Doctor of Philosophy in Chemical Engineering Georgia Institute of Technology December 2013 Copyright © Amy L. Ethier 2013 APPLICATIONS OF REVERSIBLE AND SUSTAINABLE AMINE-BASED CHEMISTRIES: CARBON DIOXIDE CAPTURE, IN SITU AMINE PROTECTION AND NANOPARTICLE SYNTHESIS Approved By: Dr. Charles Eckert Dr. Amyn Teja School of Chemical and Biomolecular School of Chemical and Biomolecular Engineering Engineering Georgia Institute of Technology Georgia Institute of Technology Dr. Charles Liotta Dr. Andrei Fedorov School of Chemistry and Biochemistry School of Mechanical Engineering Georgia Institute of Technology Georgia Institute of Technology Dr. Carson Meredith School of Chemical and Biomolecular Date Approved: 24 July 2013 Engineering Georgia Institute of Technology For Dr. Nikhil Bhiwankar, who helped me to see my potential ACKNOWLEDGEMENTS I would first like to thank my graduate advisors, Dr. Charles Eckert and Dr. Charles Liotta. Dr. Eckert and Dr. Liotta have had such a positive impact on my education; and the lessons I have learned will guide me in the rest of my career. Dr. Eckert encouraged me to explore new ideas and inspired me through his insight and inspiration. Dr. Liotta always showed such enthusiasm for this research and has greatly expanded my knowledge of organic chemistry. Both Dr. Eckert and Dr. Liotta have instilled the importance of thoughtful concise presentations. I also greatly appreciate the input and feedback I’ve received from my committee members; thank you to Dr. Amyn Teja, Dr. Carson Meredith and Dr. Andrei Fedorov. I would also like to thank Dr. Pamela Pollet. She has provided me with mentorship and direction. She has become a friend and a role model to me during my graduate studies. My family and friends were critical to my success in school. I am so appreciative for Lauren, Mandy and Emily who have been such great friends. I have many group members—former and present—to be grateful for including Jackson Switzer, Wilmarie Medina-Ramos and Kyle Flack. Many thanks to my family: my parents Robert and Jeanette and my sister Corey for their love and encouragement. I am fortunate to be part of such a caring family. I am very thankful for my husband, Nathan, who has been my source of support. I appreciate the patience and understanding he showed while I completed this work. iv TABLE OF CONTENTS ACKNOWLEDGEMENTS ............................................................................................ iv LIST OF TABLES ............................................................................................................ x LIST OF FIGURES ......................................................................................................... xi LIST OF ABBREVIATIONS ....................................................................................... xix SUMMARY ................................................................................................................... xxii CHAPTER 1 - INTRODUCTION ................................................................................... 1 1.1 Green Chemistry Principles ................................................................................... 1 1.2 CO2 Capture with Reversible Ionic Liquids ......................................................... 2 1.3 In-situ, Reversible Amine Protection with CO2 ................................................... 4 1.4 Reversible Ionic Liquids as Switchable Surfactants for Gold Nanoparticle Synthesis......................................................................................................................... 5 1.5 References ................................................................................................................ 5 CHAPTER 2 - SILYLAMINES AS REVERSIBLE IONIC LIQUIDS FOR CO2 CAPTURE ......................................................................................................................... 8 2.1 Introduction ............................................................................................................. 8 2.2 Background ........................................................................................................... 12 2.3 Experimental Methods ......................................................................................... 13 2.3.1 Materials .......................................................................................................... 13 2.3.2 Instrumentation ................................................................................................ 14 v 2.3.3 Apparatus and Procedures................................................................................ 16 2.4 Results and Discussion .......................................................................................... 20 2.4.1 CO2 Capture Capacity of Silylamines.............................................................. 20 2.4.2 Viscosity of Reversible Ionic Liquid Systems ................................................. 46 2.4.3 Thermodynamic Properties of the Reversible Ionic Liquid Systems .............. 53 2.4.4 CO2 Capture from High Pressure Streams ....................................................... 61 2.5 Conclusions ............................................................................................................ 68 2.6 References .............................................................................................................. 70 CHAPTER 3 - CARBON DIOXIDE AS A PROTECTING GROUP IN CHEMICAL SYNTHESES............................................................................................ 75 3.1 Introduction ........................................................................................................... 75 3.2 Background ........................................................................................................... 79 3.3 Experimental Section ............................................................................................ 81 3.3.1 Materials .......................................................................................................... 81 3.3.2 Instrumentation ................................................................................................ 85 3.4 Results and Discussion .......................................................................................... 86 3.4.1 Amine Protection through the Formation of an Ammonium-Carbamate Ionic Salt ............................................................................................................................ 86 3.4.2 Amine Protection through the Formation of a Stabilized Carbamic Acid Species ...................................................................................................................... 91 3.4.3 Amine Protection through the Stabilization of the Carbamate Salt with Added Base ........................................................................................................................... 96 3.4.4 Model Reaction: Nucleophilic Acyl Substitution .......................................... 104 vi 3.5 Conclusions .......................................................................................................... 114 3.6 References ............................................................................................................ 115 CHAPTER 4 - REVERSIBLE IONIC LIQUIDS AS SWITCHABLE SURFACTANTS FOR GOLD NANOPARTICLE SYNTHESIS ............................ 120 4.1 Introduction ......................................................................................................... 120 4.2 Experimental ....................................................................................................... 123 4.2.1 Materials ........................................................................................................ 123 4.2.2 Experimental Procedures ............................................................................... 124 4.3 Results and Discussion ........................................................................................ 127 4.3.1 Structure of Reverse Micelles ........................................................................ 127 4.3.2 Gold Nanoparticle Synthesis with Reversible Ionic Liquids ......................... 137 4.4 Conclusions .......................................................................................................... 147 4.5 References ............................................................................................................ 148 CHAPTER 5 - CONCLUSIONS AND RECOMMENDATIONS ............................ 154 5.1 Overall Conclusions ............................................................................................ 154 5.2 Recommendations ............................................................................................... 155 5.3 Reversible Ionic Liquids for CO2 Capture ....................................................... 155 5.3.1 Conclusions .................................................................................................... 155 5.3.2 Recommendations .......................................................................................... 157 5.4 CO2 as a Protecting Group in Chemical Syntheses ......................................... 160 5.4.1 Conclusions ...................................................................................................
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