applications of reversible and sustainable amine-based chemistries

280 Pages·2013·6.86 MB·English

by  Amy L. Ethier

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.
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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 CO Capture with Reversible Ionic Liquids ......................................................... 2
2
1.3 In-situ, Reversible Amine Protection with CO ................................................... 4
2
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 CO
2
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
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2.3.3 Apparatus and Procedures................................................................................ 16
2.4 Results and Discussion .......................................................................................... 20
2.4.1 CO Capture Capacity of Silylamines.............................................................. 20
2
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 CO Capture from High Pressure Streams ....................................................... 61
2
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
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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 CO Capture ....................................................... 155
2
5.3.1 Conclusions .................................................................................................... 155
5.3.2 Recommendations .......................................................................................... 157
5.4 CO as a Protecting Group in Chemical Syntheses ......................................... 160
2
5.4.1 Conclusions .................................................................................................... 160
5.4.2 Recommendations .......................................................................................... 161
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5.5 Reversible Ionic Liquids as Switchable Surfactants for Gold Nanoparticle
Synthesis..................................................................................................................... 163
5.5.1 Conclusions .................................................................................................... 163
5.5.2 Recommendations .......................................................................................... 163
5.6 References ............................................................................................................ 165
APPENDIX A - ADDITIONAL INFORMATION ON SILYLAMINES AS
REVERSIBLE IONIC LIQUIDS FOR CARBON DIOXIDE CAPTURE ............. 167
A.1 Introduction ........................................................................................................ 167
A.2 Synthesis of Silylamines ..................................................................................... 167
APPENDIX B - QUANTITATIVE REFLECTANCE SPECTROSCOPY: THEORY
AND APPLICATION ................................................................................................... 187
B.1 Introduction ........................................................................................................ 187
B.2 Background ......................................................................................................... 187
B.3 Attenuated Total Reflectance Spectroscopy .................................................... 189
B.4 Conclusions ......................................................................................................... 202
B.5 References ........................................................................................................... 203
APPENDIX C - SAFE ASSEMBLY AND OPERATING PROCEDURE FOR THE
HIGH PRESSURE SAPPHIRE CELL APPARATUS ............................................. 204
C.1 Introduction ........................................................................................................ 204
C.2 Apparatus ........................................................................................................... 204
C.3 Safe Handling of the Sapphire Cell .................................................................. 206
C.4 Assembly of the Sapphire Cell .......................................................................... 206
C.5 Operation of the Sapphire Cell Apparatus ...................................................... 208
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C.6 Cleaning the Sapphire Cell................................................................................ 209
C.7 Disassembling the Sapphire Cell ...................................................................... 209
APPENDIX D - INTEGRATING REVERSIBLE IONIC LIQUIDS WITH
ATOMIZER TECHNOLOGY FOR EFFICIENT CO CAPTURE ....................... 211
2
D.1 Introduction ........................................................................................................ 211
D.2 Abstract ............................................................................................................... 211
D.3 MRC 1: Scientific and Technical Merit ........................................................... 212
D.4 MRC2. Technical Approach and Understanding ........................................... 236
D.5 References ........................................................................................................... 250
APPENDIX E - ADDITIONAL INFORMATION ON CO AS A PROTECTING
2
AGENT .......................................................................................................................... 253
E.1 Standard NMRs .................................................................................................. 253

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LIST OF TABLES

Table 2.1. Gravimetrically determined CO capacities .................................................... 25
2
Table 2.2. Henry's Law constants of select RevILs at 25°C and 35°C ............................. 35
Table 2.3. Quantitative 13C NMR areas of TPSA RevIL .................................................. 40
Table 2.4. Gravimetric CO capture capacities at 25°C and 1 bar CO pressure ............. 43
2 2
Table 2.5. Optimal CO capture solvents based on maximum CO capacity ................... 46
2 2
Table 2.6. RevIL viscosities at 25°C ................................................................................ 47
Table 2.7. RevIL viscosities at 40°C ................................................................................ 51
Table 2.8. Reversal temperatures of RevILs as determined by DSC................................ 55
Table 2.9. Enthalpy of regeneration of RevILs................................................................. 58
Table 2.10. CO uptake capacity at 40°C for a select group of silylamines ..................... 60
2
Table 2.11. Equilibrium conversions of TPSA RevIL system at 1 bar CO pressure ...... 61
2
Table 2.12. Structures and properties of TEtSMA and trans-TEtSA ............................... 70
Table 3.1. Quantitative 13C NMR integrations for protected species ............................. 101
Table 4.1. Experimental and literature values for the hydrodynamic radius (r ) for AOT-
h
water-isooctane system ................................................................................................... 132
Table 4.2. Solubility of ACN in isooctane in the presence of TPSA RevIL .................. 134
Table 4.3. Optimal conditions for nanoparticle synthesis............................................... 141
Table B.1 IR absorption regions calculated using Hookes's law and observed values ...189
Table B.2. Refractive index of select silylamine and RevILs at 25°C ............................193
Table B.3. Silylamine and RevIL density at 25°C for three select systems ....................198
Table D.1. Three silylamine solvents proposed in this project ........................................213
Table D.2. State-point data table......................................................................................215
Table D.3. Comparison of pure RevILs post CO capture with MEA .............................231
2

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