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Phenolic Resin Aerogels Scholars' Mine Doctoral Dissertations Student Theses and Dissertations Fall 2018 Phenolic resin aerogels: The significance of inserting an oxidative ring-fusion aromatization step at the early stages of pyrolytic carbonization, and the application of these materials in CO₂ storage and separation Hojat Majedi Far Follow this and additional works at: https://scholarsmine.mst.edu/doctoral_dissertations Part of the Chemistry Commons Department: Chemistry Recommended Citation Majedi Far, Hojat, "Phenolic resin aerogels: The significance of inserting an oxidative ring-fusion aromatization step at the early stages of pyrolytic carbonization, and the application of these materials in CO₂ storage and separation" (2018). Doctoral Dissertations. 2725. https://scholarsmine.mst.edu/doctoral_dissertations/2725 This thesis is brought to you by Scholars' Mine, a service of the Missouri S&T Library and Learning Resources. This work is protected by U. S. Copyright Law. Unauthorized use including reproduction for redistribution requires the permission of the copyright holder. For more information, please contact [email protected]. ii PHENOLIC RESIN AEROGELS: THE SIGNIFICANCE OF INSERTING AN OXIDATIVE RING-FUSION AROMATIZATION STEP AT THE EARLY STAGES OF PYROLYTIC CARBONIZATION, AND THE APPLICATION OF THESE MATERIALS IN CO2 STORAGE AND SEPARATION by HOJAT MAJEDI FAR A DISSERTATION Presented to the Faculty of the Graduate School of the MISSOURI UNIVERSITY OF SCIENCE AND TECHNOLOGY In Partial Fulfillment of the Requirements for the Degree DOCTOR OF PHILOSOPHY in CHEMISTRY 2018 Approved by: Dr. Chariklia Sotiriou-Leventis, Advisor Dr. Nicholas Leventis Dr. Jeffrey G. Winiarz Dr. Amitava Choudhury Dr. F. Scott Miller ii © 2018 HOJAT MAJEDI FAR All Rights Reserved iii TO MY PARENTS iv PUBLICATION DISSERTATION OPTION This dissertation consists of the following two articles that have been published for publication: Paper I, pages 32–116, has been published in RSC Advances. Paper II, pages 117–195, has been published in Macromolecular Chemistry and Physics. v ABSTRACT Phenolic aerogels, prepared via polycondensation of phenolic monomers and formaldehyde, were converted to carbon aerogels at 800 °C/Ar followed by reactive etching under flowing CO2. Previously, it was found that a lower-temperature air- oxidation of polybenzoxazine aerogels was necessary in order to obtain highly porous, isomorphic carbon aerogels with high carbonization yields. Using those findings as the point of departure, phenolic aerogels were oxidized at 240 °C/air prior to carbonization. During that air-oxidation step, phenolic aerogels based on phloroglucinol (1,3,5- trihydroxybenzene) undergo fusion of their aromatic rings, yielding 6-membered heteroaromatic pyryliums with pendant phenoxide ions. The resulting carbon aerogels have higher surface areas than other carbon aerogels not subjected to aromatization. Subsequently, carbon aerogels were studied for their CO2 adsorption capacity at 273 K up to 1 bar, relevant to post-combustion separation of CO2 from N2. Carbon aerogels from phenolic resins were compared to carbon aerogels from Ishida’s polybenzoxazine, and from a random copolymer of polyamide, polyurea, and polyimide. The results show that phenolic resin-derived carbons (containing phenoxide) adsorb more CO2 than the latter, which contain N in addition to oxygen. Interestingly, resorcinol-formaldehyde-derived -1 carbon aerogels uptook 14.8 ± 3.9 mmol g CO2, which is much higher than the values reported in the literature for other microporous materials. Opening of closed micropores and enlargement of micropore size, resulted in a multilayer coverage of micropore walls with CO2. The high capacity for CO2 was attributed to an energy-neutral reaction between surface phenoxides and CO2. vi ACKNOWLEDGEMENTS I ought to profoundly thank my advisors, Dr. Chariklia Sotiriou-Leventis and Dr. Nicholas Leventis, who are wonderful sources of ideas and insights. One especially nice aspect of them is their ease of availability and engagement in research with students. Their caring regard for students makes them more than just advisors. I cannot thank them enough for all of their time and energy. I would also like to thank Dr. Jeffrey G. Winiarz, Dr. Amitava Choudhury, and Dr. F. Scott Miller for serving as my committee members and their valuable suggestions. I would like to thank Mr. Shannon D. Roark and Ms. Tina M. Balch, our secretaries, and Mr. Jonathon Sidwell, senior research specialist, for all their help and nice behavior. I especially thank Mr. Joseph A. Counsil, Research Engineer. Not only did he train me on the instruments, but he was also an amazing person to discuss various problems with related to instrumentation. I also thank Dr. Nathan Leigh and Mr. Dave Satterfield for their efforts in fixing some of the instruments. I wish my father was alive to see this moment in my life, but I thank him for teaching me things that have helped me cope with problems in my life. My mother has been a great source of support and patience throughout my life. The rest of my family, my brothers and sisters, have also been very supporting and encouraging. I would also like to thank all my colleagues: Dr. Abhishek Bang, Dr. Adnan Malik Saeed, Dr. Suraj Donthula, Parwani M. Rewatkar, Tahereh Taghvaee, Chandana Mandal, Rushi Soni, Shaheen ud Doulah, and Vaibhav Edlabadkar for their valuable discussions, assistance in the lab, and friendship. vii TABLE OF CONTENTS Page PUBLICATION DISSERTATION OPTION ................................................................... iv ABSTRACT .........................................................................................................................v ACKNOWLEDGEMENTS ............................................................................................... vi LIST OF ILLUSTRATIONS ............................................................................................ xii LIST OF SCHEMES........................................................................................................ xiv LIST OF TABLES .............................................................................................................xv LIST OF ABBREVIATIONS .......................................................................................... xvi SECTION 1. INTRODUCTION ...................................................................................................... 1 1.1. AEROGELS........................................................................................................ 1 1.2. ORGANIC AEROGELS .................................................................................... 3 1.2.1. Other Types of Organic Aerogels. ........................................................... 8 1.2.2. Synthesis of Terephthalaldehyde-Phloroglucinol (TPOL) Aerogels. ...... 9 1.3. POLYMERIC CARBON AEROGELS ............................................................ 10 1.3.1. Background. ........................................................................................... 12 1.3.2. The Importance of Ring Fusion Aromatization Step in the Carbonization of PAN Fibers and PBO Aerogels and Extension to Other Phenolic Resin Aerogels ......................................................... 14 1.3.3. Activation of Carbons. ........................................................................... 25 1.4. CARBON AEROGELS IN CO2 SEQUESTRATION AND GAS PURIFICATION .............................................................................................. 27 1.4.1. Background. ........................................................................................... 28 viii 1.4.2. Solid CO2 Sorbents. ................................................................................ 29 PAPER I. AIR-OXIDATION OF PHENOLIC RESIN AEROGELS: BACKBONE REORGANIZATION, FORMATION OF RING-FUSED PYRYLIUM CATIONS, AND THE EFFECT ON MICROPOROUS CARBONS WITH ENHANCED SURFACE AREAS ........................................................................... 32 ABSTRACT ................................................................................................................. 32 1. INTRODUCTION ............................................................................................... 34 2. RESULTS AND DISCUSSION .......................................................................... 37 2.1. MATERIAL SYNTHESIS. ...................................................................... 37 2.2. PYROLYSIS PRODUCTS AT 240 OC/AIR VERSUS 240 OC/Ar .......... 41 2.3. THE MECHANISM OF RING-FUSION AROMATIZATION .............. 46 2.4. CHEMICAL TRANSFORMATIONS ALONG FURTHER PYROLYSIS OF RES-240(AIR) VERSUS RES ..................................... 48 2.5. THE EVOLUTION OF MATERIAL PROPERTIES ALONG PYROLYTIC CARBONIZATION AND REACTIVE ETCHING ......... 53 2.6. THE PYROLYTIC EVOLUTION OF THE NANOSTRUCTURE AND THE POROUS NETWORK............................................................ 57 3. CONCLUSION .................................................................................................... 62 4. EXPERIMENTAL ............................................................................................... 63 4.1. MATERIALS ........................................................................................... 63 4.2. PREPARATION OF PHENOLIC RESIN AEROGELS (RES) .............. 64 4.3. AIR OXIDATION OF RES AND PREPARATION OF RES-240(AIR) .65 4.4. CONVERSION OF AS-PREPARED RES AEROGELS, OR AIR- OXIDIZED RES-240(AIR) AEROGELS INTO CARBON AEROGELS C-RES-D- AND
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