Acid and Base Gas Exposure and Solvent Effects on Metal-Organic
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Acid and Base Gas Exposure and Solvent Effects on Metal-Organic Framework Structure and Gas Adsorption Properties A Dissertation Presented to The Academic Faculty By William Pratt Mounfield, III In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in Chemical Engineering Georgia Institute of Technology December 2016 COPYRIGHT © 2016 WILLIAM PRATT MOUNFIELD, III Acid and Base Gas Exposure and Solvent Effects on Metal-Organic Framework Structure and Gas Adsorption Properties Approved by: Dr. Krista S. Walton, Advisor Dr. Michael A. Filler School of Chemical & Biomolecular School of Chemical & Biomolecular Engineering Engineering Georgia Institute of Technology Georgia Institute of Technology Dr. Ryan P. Lively Dr. David S. Sholl School of Chemical & Biomolecular School of Chemical & Biomolecular Engineering Engineering Georgia Institute of Technology Georgia Institute of Technology Dr. Angus P. Wilkinson School of Chemistry and Biochemistry Georgia Institute of Technology Date Approved: October, 27, 2016 ACKNOWLEDGEMENTS I express my deepest thanks to my advisor, Dr. Krista S. Walton. Your technical and personal guidance throughout my Ph.D. journey has been invaluable. You challenged me to find my passion and to not allow setbacks to cause me to lose focus. I appreciate and value your trust in allowing me to serve as the group safety officer. Your example of working hard and having fun is something I continually strive to achieve. I am deeply appreciative of the valuable guidance provided by my committee members, Dr. Michael A. Filler, Dr. Ryan P. Lively, Dr. David S. Sholl, and Dr. Angus P. Wilkinson. Thank you for pushing me to refine my proposal and deepen my research work. I thank my collaborators at Oak Ridge National Lab, Dr. Uma Tumuluri and Dr. Zili Wu. It was a pleasure working alongside you in the UNCAGE-ME EFRC. Thank you, Chu Han, for supporting and making my ideas come to life with your computational simulations. I am grateful to the Army Research Office for support of Chapters 3 and 6 under PECASE Award W911NF-10-0079 and ARO Contract W911NF-10-0076. I am also grateful to the Center for Understanding and Control of Acid Gas-Induced Evolution of Materials for Energy (UNCAGE-ME), an Energy Frontier Research Center funded by U.S. Department of Energy, Office of Science, Basic Energy Sciences for support of Chapters 4 and 5 under Award #DE-SC0012577. I thank the Walton Group members, Dr. Katrina Stults, Dr. Yang Cai, Ken Onubogu, Dr. Greg Cmarik, Dr. Chris Murdock, Dr. Tim Duerinck, Erika Garcia-Gutierrez, Dr. Sudhir Sharma, Yutao Gong, Jake Deneff, Lalit Darunte, Julian Hungerford, Jay Joshi, and Colton Moran for valuable discussions throughout my Ph.D. I iii express my gratitude to Dr. Nicholas Burtch, Dr. Himanshu Jasuja, Dr. Yi Huang, Dr. Michael Mangarella, Dr. Karen Tulig, Dr. Cody Morelock, Dr. Ian Walton, Rod Sefton, Eli Carter, Yang Jiao, and Michael Dutzer for discussions both serious and not. I offer my sincere thanks to my office mate, Dr. Bogna Grabicka, for our many discussions and all of the lovely puppies that have brightened my days in the office. Finally, I thank my mother, Dr. Luegina C. Mounfield, and my father, Dr. Wm. Pratt Mounfield, Jr., for encouraging me to follow my dreams, and Dr. Micaela Taborga Claure, who has been by my side these past four years-an example of grace, perseverance, and determination. William Pratt Mounfield, III, 10/15/2016 iv TABLE OF CONTENTS ACKNOWLEDGEMENTS ................................................................................................. iii LIST OF TABLES ............................................................................................................. vii LIST OF FIGURES .......................................................................................................... viii LIST OF SYMBOLS AND ABBREVIATIONS .................................................................. xiv SUMMARY ...................................................................................................................... xv CHAPTER 1 INTRODUCTION ........................................................................................ 1 1.1 Synthesis Modification for Modified Gas Adsorption Properties ........................... 2 1.2 Effects of Acid Gas Adsorption on Stability and Gas Adsorption Properties ........ 3 1.3 Developing Mechanistic Understanding of MOF Degradation Processes ............ 5 1.4 Investigation of Complementary Binding Materials for Toxic Gas Adsorption ...... 7 1.5 Dissertation Scope ............................................................................................... 8 1.6 References ......................................................................................................... 10 CHAPTER 2 MATERIALS AND METHODS .................................................................. 18 2.1 Materials for Investigation of Synthesis Solvent Effects ..................................... 18 2.2 Materials for Investigation of Acid Gas Effects ................................................... 19 2.3 Materials for Investigation of Beneficial Binding Materials.................................. 21 2.4 Conclusions ........................................................................................................ 22 2.5 References ......................................................................................................... 24 CHAPTER 3 EFFECT OF SYNTHESIS SOLVENT ON MIL-53(Al) ............................... 30 3.1 Experimental Section .......................................................................................... 31 3.2 Results and Discussion ...................................................................................... 33 3.3 Conclusions ........................................................................................................ 46 3.3 References ......................................................................................................... 47 APPENDIX 3.A MIL-53(Al) CHARACTERIZATION ...................................................... 49 CHAPTER 4 ROLE OF DEFECTS AND METAL COORDINATION ON ADSORPTION OF ACID GASES IN MOFS AND METAL OXIDES ........................................................ 57 4.1 Experimental Section .......................................................................................... 58 4.2 Results and Discussion ...................................................................................... 62 4.2.1 Characterization of pristine materials ...................................................... 62 4.2.2 Structure of SOx species from SO2 adsorption ...................................... 64 4.2.3 Effect of SO2 exposure on adsorbed species during CO2 adsorption . 70 4.2.4 Material stability after SO2 adsorption ..................................................... 73 4.2.5 Effect of water adsorption on material stability ...................................... 79 4.3 Conclusions ........................................................................................................ 81 4.4 References ......................................................................................................... 82 APPENDIX 4.A Ce AND Ti MATERIAL CHARACTERIZATION ................................... 85 v CHAPTER 5 SYNERGISTIC EFFECTS OF WATER AND SO2 ON DEGRADATION OF MIL-125 IN THE PRESENCE OF ACID GASES........................................................... 100 5.1 Experimental Procedure ................................................................................... 101 5.2 Results and Discussion .................................................................................... 106 5.2.1 Material characterization and acid gas exposure ....................................... 106 5.2.2 Elucidation of acid gas degradation mechanism ........................................ 111 5.2.2.1 Structural investigation ............................................................................ 111 5.2.2.2 Surface chemistry investigation ............................................................... 113 5.2.2.3 Simulation of reaction mechanisms ......................................................... 115 5.2.2.4 Adsorbed species investigation ............................................................... 119 5.4. Conclusions ..................................................................................................... 122 5.5. References ...................................................................................................... 124 APPENDIX 5.A MIL-125 COMPUTATIONAL SIMULATIONS AND CHARACTERIZATION .................................................................................................. 127 CHAPTER 6 SYNERGISTIC EFFECT OF MIXED OXIDE ON THE ADSORPTION OF AMMONIA WITH METAL-ORGANIC FRAMEWORKS ................................................. 143 6.1 Experimental Procedure ................................................................................... 144 6.2 Results and Discussion .................................................................................... 148 6.2.1 Material characterization ............................................................................ 148 6.2.2 Ammonia breakthrough adsorption experiments ........................................ 150 6.2.3 Characterization of materials after ammonia adsorption ............................ 153 6.2.4 Synergistic effect of MMO .......................................................................... 155 6.3 Conclusions