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Hydrothermal Organic Reduction and Deoxygenation Hydrothermal Organic Reduction and Deoxygenation by Christiana Bockisch A Dissertation Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy Approved April 2018 by the Graduate Supervisory Committee: Ian Gould, Chair Hilairy Hartnett Everett Shock ARIZONA STATE UNIVERSITY May 2018 ABSTRACT Organic reactions in natural hydrothermal settings have relevance toward the deep carbon cycle, petroleum formation, the ecology of deep microbial communities, and potentially the origin of life. Many reaction pathways involving organic compounds under geochemically relevant hydrothermal conditions have now been characterized, but their mechanisms, in particular those involving mineral surface catalysis, are largely unknown. The overall goal of this work is to describe these mechanisms so that predictive models of reactivity can be developed and so that applications of these reactions beyond geochemistry can be explored. The focus of this dissertation is the mechanisms of hydrothermal dehydration and catalytic hydrogenation reactions. Kinetic and structure/activity relationships show that elimination occurs mainly by the E1 mechanism for simple alcohols via homogeneous catalysis. Stereochemical probes show that hydrogenation on nickel occurs on the metal surface. By combining dehydration with and catalytic reduction, effective deoxygenation of organic structures with various functional groups such as alkenes, polyols, ketones, and carboxylic acids can be accomplished under hydrothermal conditions, using either nickel or copper-zinc alloy. These geomimetic reactions can potentially be used in biomass reduction to generate useful fuels and other high value chemicals. Through the use of earth-abundant metal catalysts, and water as the solvent, the reactions presented in this dissertation are a green alternative to current biomass deoxygenation/reduction methods, which often use exotic, rare-metal catalysts, and organic solvents. i To all the teachers I had throughout my life. Without your support and encouragement, I would have never come this far. ii ACKNOWLEDGMENTS There are many people who helped me get to this point in my career; more than can be listed here. First and most importantly, I thank Dr. Ian Gould for his support, expertise, and direction as my advisor. I am eternally grateful for his dedication to helping me with difficult research problems, in the lab and in the computer, and challenges I encountered as a teaching assistant. I also acknowledge the Hydrothermal Organic Geochemistry group – Dr. Everett Shock, Dr. Hilairy Harnett, Dr. Lynda Williams, Dr. Ziming Yang, Dr. Kristopher Fecteau, Dr. Charlene Estrada, Dr. Kirtland Robinson, Dr. Kristin Johnson, and Joshua Nye. The stimulating discussions we had in HOG meetings were infinitely valuable to my progress. Each of you helped me in so many ways, and I thank each of you for your support. I also thank Dr. Ted Lorance for his remote support as a collaborator from Vanguard University, his expertise as a theoretician, and for running many of my samples on his GC/MS. I thank NSF and NASA for funding so much of this work. There were many others who helped me with my projects in the laboratory, and on a professional level. I thank Dr. Natasha Zolatova for help with GC/MS early on in my graduate career. Dr. Brian Cherry helped me with the numerous challenges I encountered with NMR. I also acknowledge David Wright, Karl Weiss, and Shreya Bhattacharyya for their support on the surface science side of my project. I also am deeply indebted to Dr. Chelsea Brown and Dr. Iolanda Klein for helping me with my job search. iii On a more personal note, I thank my parents, David and Joni Bockisch, for their love and support. Without you, I would not be where I am today. Graduate school had more downs than ups sometimes, and you were there for me. My grandparents, Sharon and Robert Bockisch, also had an important role in my life. Sharon encouraged me to be curious about the world around me, from a young age. I am sure this helped me become a scientist today. The support from my friends, both in and outside of the graduate program was infinitely beneficial. I thank all my graduate student friends, and the happy hour crew for all the good times we’ve had together. I thank Josh for being a good, drama-free roommate. Finally, I thank all my soccer friends; A.S.H. and the staff of Brewers Connection who helped me with a hobby that kept me sane all this time; and my dog friends, Bear, Tig, and Jemma. iv TABLE OF CONTENTS Page LIST OF TABLES...........................................................................................................viii LIST OF FIGURES...........................................................................................................xii CHAPTER 1. INTRODUCTION ........................................................................................................ 1 Overview ................................................................................................................. 1 Introduction to Hydrothermal Conditions ............................................................... 2 Hydrothermal Organic Geochemistry ..................................................................... 5 Geomimicry ............................................................................................................ 9 Mechanisms of Hydrogenation on Metal Surfaces ............................................... 10 Biomass Reduction ............................................................................................... 12 2. METHODS .................................................................................................................. 14 Hydrothermal Reaction Vessel Preparation .......................................................... 14 Hydrothermal Reaction Heating ........................................................................... 15 Reaction Work-up – Water Only .......................................................................... 16 Reaction Work-up – with Metal Powders ............................................................. 17 Gas Chromatography Analysis ............................................................................. 17 Metal Powder Characterization ............................................................................. 19 v CHAPTER Page 3. KINETICS AND MECHANISMS OF DEHYDRATION OF SECONDARY ALCOHOLS UNDER HYDROTHERMAL CONDITIONS .......................................... 20 Introduction ........................................................................................................... 20 Methods................................................................................................................. 25 Results and Discussion ......................................................................................... 26 Implications for Hydrothermal Dehydration Under Laboratory and Geologic Conditions ............................................................................................................. 49 Summary ............................................................................................................... 52 4. SELECTIVE, GREEN, NICKEL-CATALYZED HYDROTHERMAL REDUCTIONS ................................................................................................................. 53 Introduction ........................................................................................................... 53 Methods................................................................................................................. 55 Results and Discussion ......................................................................................... 57 Conclusion ............................................................................................................ 69 5. HYDROTHERMAL REDUCTION AND DEOXYGENATION OF CARBONYLS ........................................................................................................................................... 70 Introduction ........................................................................................................... 70 Methods................................................................................................................. 76 vi CHAPTER Page Results and Discussion ......................................................................................... 77 Conclusion ............................................................................................................ 95 6. HYDROTHERMAL DEHYDRATION AND HYDROGENOLYSIS OF POLYOLS ........................................................................................................................................... 97 Introduction ........................................................................................................... 97 Methods............................................................................................................... 100 Results and Discussion ....................................................................................... 101 Summary and Future Work ................................................................................. 123 7. CONCLUSION ......................................................................................................... 125 REFERENCES ............................................................................................................... 129 APPENDIX A. METAL SURFACE CHARACTERIZATION. ..........................................
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