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Selective C-O Hydrogenolysis and Decarboxylation of Biomass-Derived Heterocyclic Compounds Over Heterogeneous Catalysts

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Selective C-O Hydrogenolysis and Decarboxylation of Biomass-Derived Heterocyclic Compounds Over Heterogeneous Catalysts Selective C-O Hydrogenolysis and Decarboxylation of Biomass-Derived Heterocyclic Compounds over Heterogeneous Catalysts By Mei Chia A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy (Chemical Engineering) At the UNIVERSITY OF WISCONSIN-MADISON 2013 Date of final oral examination: 11th July 2013 The dissertation is approved by the following members of the Final Oral Committee: James A. Dumesic, Professor, Chemical and Biological Engineering Thomas F. Kuech, Professor, Chemical and Biological Engineering Manos Mavrikakis, Professor, Chemical and Biological Engineering Brian F. Pfleger, Assistant Professor, Chemical and Biological Engineering Dane Morgan, Associate Professor, Materials Science and Engineering i Selective C-O Hydrogenolysis and Decarboxylation of Biomass-Derived Heterocyclic Compounds over Heterogeneous Catalysts Mei Chia Under the supervision of Professor James A. Dumesic At the University of Wisconsin-Madison The catalytic deoxygenation of biomass-derived compounds through selective C-O hydrogenolysis, catalytic transfer hydrogenation and lactonization, and decarboxylation to value- added chemicals over heterogeneous catalysts was examined under liquid phase reaction conditions. The reactions studied involve the conversion or production of heterocyclic compounds, specifically, cyclic ethers, lactones, and 2-pyrones. A bimetallic RhRe/C catalyst was found to be selective for the hydrogenolysis of secondary C-O bonds for a broad range cyclic ethers and polyols. Results from experimentally- observed reactivity trends, NH3 temperature-programmed desorption, fructose dehydration reaction studies, and first-principles density functional theory (DFT) calculations are consistent with the hypothesis of a bifunctional catalyst which facilitates acid-catalyzed ring-opening and dehydration coupled with metal-catalyzed hydrogenation. C-O hydrogenolysis and fructose dehydration activities were observed to decrease with an increase in reduction temperature and a decrease in the number of surface metallic Re atoms measured by in situ X-ray absorption spectroscopy. No C-O hydrogenolysis activity was detected over RhRe/C under water-free ii conditions. The activation of water molecules by Re atoms on the surface of metallic Rh is suggested to result in the formation of Brønsted acidity over RhRe/C. The catalytic transfer hydrogenation and lactonization of levulinic acid and its esters to γ- valerolactone was accomplished through the Meerwein-Ponndorf-Verley reaction over metal oxide catalysts using secondary alcohols as the hydrogen donor. ZrO2 was a highly active material for CTH under batch and continuous flow reaction conditions; the initial activity of the catalyst was repeatedly regenerable by calcination in air, with no observable loss in catalytic activity. Lastly, the 2-pyrone, triacetic acid lactone, is shown to be a promising biorenewable platform chemical from which a wide range of chemical intermediates and end products can be obtained using heterogeneous catalysts or by thermal decomposition. Mechanistic insights from experimentally-observed reactivity trends and results from DFT calculations indicate that 2- pyrones undergo reactions unique to their structure such as keto-enol tautomerization, retro Diels-Alder, and nucleophilic attack by water. Ring-opening and decarboxylation reactions were found to be governed by key structural features such as the degree of saturation in the ring (e.g., C4=C5 bond), nature of the solvent, and presence of an acid catalyst. Approved by _________________________ Professor James A. Dumesic Date _________________________ iii Acknowledgements This thesis would not have been possible without the generous contributions of many people that I have had the privilege to work with and learn from. I would first like to thank my thesis advisor, Professor James Dumesic, for giving me the opportunity to be part of a legendary research group; his guidance, (contagious) wry humor, and unfailing enthusiasm for science have played a central role in shaping this thesis and my PhD experience. I am very grateful to my labmates, both past and present Dumesic group members, for their help and friendship. I especially would like to thank Mark and Yomaira for showing me the ropes when I first joined the group, and for mentoring me and giving valuable advice over the years. I would also like to thank the many individuals who have contributed to this thesis in so many ways, specifically, Drew, Christian, Ryan, David, Elif, Jesse, Stephanie, Jean, Max, Eric, Gretchen, Ronald, Ana, and Carrie for sharing their knowledge and for technical assistance in the lab, and especially Ricky, Tom S., and Brandon, with whom I have had the opportunity to collaborate on projects with. Many long afternoons in the lab have been made enjoyable through the numerous scientific (and non-scientific/ philosophical) discussions I have had with all of you. I would like to express my gratitude to the many administrators and staff at the Chemical Engineering department, especially Donna Bell, Kathy Heinzen, John Cannon, John Ames, Joel Lord, Eric Codner, and Todd Ninman for their administrative, mechanical, instrumental, and technical support, respectively. Special thanks to Judy Lewison, whose assistance with administrative matters, baked treats, and chats in the hallways have brightened many slow mornings. iv A large part of the work here was only possible through the contributions of many external collaborators. Specifically, the computational work herein was performed by our collaborators at the University of Virginia; I would especially like to thank Professor Matthew Neurock for sharing valuable knowledge and ideas during our project discussions, and through whom I, as an experimentalist, have been able to gain some insight into computational chemistry. I would also like to acknowledge Dr. M. Ali Haider, David Hibbitts and Qiaohua Tan, all of whose contributions are instrumental to the fruition of much of the work here. I am grateful for generous help from Professor George Kraus and Gerald Pollock (Iowa State University) who synthesized organic compounds for reaction studies that enabled us to tell a complete “story” for the pyrone chemistry. The microscopy work presented in this thesis was performed by collaborators at the University of New Mexico, Professor Abhaya Datye and Dr. Hien Pham. I would also like to thank Dr. Jeffery Miller (Argonne National Laboratory) who was invaluable in obtaining and interpreting XAS data, and Professor Fabio Riberio and Paul Dietrich (Purdue University) for access to and assistance with equipment for performing XAS experiments. I would also like to acknowledge funding from the NSF Engineering Research Centre for Biorenewable Chemicals (CBiRC), and Professor Brent H. Shanks for sharing his perspective of the CBiRC vision which has influenced the work here. Also, I am especially grateful to the late Dr PK Wong, who gave me invaluable professional advice over the years. Finally, I would like to thank my family and friends for their unwavering support over the years. In particular, I would like to thank my parents, who have always encouraged me to pursue my aspirations and interests, and my aunt, April, who has been so supportive of my pursuits. Lastly, I would like to thank my brother, who inspired me to take the road less travelled. v To my family vi There is a pleasure in the pathless woods vii Table of Contents Abstract i Acknowledgements iii Dedication v List of Figures xi List of Tables xviii 1. Introduction 1 1.1 Current production and consumption of fuel and chemicals 1 1.2 Future outlook for fossil-based resources 4 1.3 Biomass as feedstock for the production of fuel and chemicals 6 1.4 Catalytic strategies for the production of chemicals from biomass-based feedstocks 13 1.4.1 5-hydroxymethylfurfural as a platform chemical 13 1.4.2 Bimetallic catalysts and applications for biomass conversion 16 1.4.3 Catalytic upgrading of biologically-produced compounds 21 1.5 Research overview and strategy 24 1.6 References 25 2. Experimental techniques 30 2.1 Catalyst preparation and synthesis methods 30 2.1.1 Supported metal catalysts 30 2.1.2 Metal oxide catalysts 31 2.1.3 Ion-exchange resins and zeolites 31 2.2 Reaction studies 31 2.2.1 Batch reactions 31 2.2.2 Continuous flow reactions 32 2.3 Analytical methods 33 2.3.1 High performance liquid chromatography 33 2.3.2 Gas chromatography 33 2.3.3 Nuclear magnetic resonance spectroscopy 34 2.4 Catalyst characterization 34 viii 2.4.1 Temperature-programmed methods 36 2.4.2 CO adsorption 36 2.4.3 Electron microscopy 36 2.4.4 In situ and operando X-ray absorption spectroscopy 36 2.5 References 38 3. Selective C-O hydrogenolysis over bimetallic catalysts 39 3.1 Introduction 39 3.1.1 Importance of C-O hydrogenolysis as a deoxygenation strategy 39 3.1.2 Current state of the art 41 3.2 Catalyst development 46 3.2.1 Highly reducible metals 46 3.2.2 Effect of varying catalyst composition 47 3.2.3 Precursor effects for Mo-promoted catalysts 48 3.2.4 Support effects 49 3.2.5 Initial reactivity studies 50 3.3 Characterization studies of RhRe/C 52 3.3.1 Temperature-programmed reduction 52 3.3.2 HAADF-STEM and EDS 53 3.3.3 CO adsorption 55 3.3.4 NH3 temperature-programmed desorption 56 3.4 Catalyst pretreatment and stability 57 3.5 Reactivity trends and Density Functional Theory calculations 59 3.5.1 Cyclic ethers 59 3.5.2 Diols and polyols 69 3.5.3 Governing principles of substrate reactivity and selectivity
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