Max-Planck-Institut fu r Kolloid- und Grenzfla chenforschung Functional Nanoporous Carbon-Based Materials derived from Oxocarbon-Metal Coordination Complexes Dissertation zur Erlangung des akademischen Grades Doktor der Naturwissenschaften (Dr. rer. nat.) in der Wissenschaftsdisziplin „Kolloidchemie“ eingereicht an der Mathematisch-Naturwissenschaftlichen Fakultät der Universität Potsdam von Christian Mbaya Mani Geboren am 27.01.1988 in Kinshasa, D.R. Kongo Potsdam-Golm, im September 2017 Dedicated to my family “The important thing in science is not so much to obtain new facts as to discover new ways of thinking about them” Sir William Henry Bragg Acknowledgements I would like to thank Prof. Dr. Markus Antonietti for the opportunity to work in his group and for his support, supervision, and all the contributions to the success of the present thesis. It has been a great honor and inspiration to work with you. My particular thanks go to Dr. Nina Fechler for the excellent supervision, countless support and the many fruitful discussions. I really appreciate that I could always knock on your door and count on your advice. Thank you for the comments, criticism and hard questions which caused me to look at my research from innovative and uncommon perspectives. I thank Prof. Andreas Taubert and Prof. Arne Thomas for agreeing to examine my dissertation. I am grateful to Dr. Valerio Molinari and Dr. Martin Oschatz for the many scientific (and sometimes also very non-scientific) discussions in the hallways, laboratories, offices, Chez Briel and on various balconies of the Max-Planck-Institute. Thanks to Carolin Nuglisch for proofreading my thesis and for the moral support. My sincere thanks also go to my group members Dr. Thomas Jordan and Thomas Berthold as well as to my office mates Dr. Jochen Willersinn and Hui-Chun Lee for the amazing teamwork, the myriad of laughter, and the inspiring discussions we had about work, family and life. Furthermore, I would like to thank Regina Rothe for the constant support in the laboratory and the personal encouragement throughout the whole PhD time. Many thanks to Heike Runge and Rona Pitschke for the introduction into the SEM and TEM devices and for the many images you recorded for me. Thanks to Max Braun for introducing me into the world of the heterogeneous catalysis. A huge thank to all the past as well as present colleagues who have contributed to an excellent and entertaining working environment. I sincerely thank my friends Haddom, Ornella, Mitch, Mario, Kevin, Marcel, Moh, André, Nevena (Olga), Konrad (Jason), and Arno, for being there when I needed you the most. Finalement, je remercie Dieu pour la bonne santé et la force qu’il m’a donné de persister et persévérer dans me buts. Merci à mes parents et à mes sœurs Julia et Odaline; vous êtes la vraie source de ma force et de ma motivation de toujours vouloir atteindre plus. Je vous aime. I Table of Contents 1. Introduction .................................................................................................................................. 1 1.1. Outline ................................................................................................................................... 6 2. Theoretical Fundamentals ............................................................................................................ 9 2.1. Porous Carbon Materials ....................................................................................................... 9 2.1.1. Hierarchically Porous Carbons ..................................................................................... 13 2.1.2. MOF-derived porous carbon materials ......................................................................... 15 2.2. Crystal Engineering ............................................................................................................. 16 2.2.1. Classical Crystallization ................................................................................................ 18 2.2.2. Non-Classical Crystallization ....................................................................................... 20 3. Crystalline superstructures of oxocarbon-based coordination complexes ................................. 24 3.1. Background and State-of-the-Art ........................................................................................ 24 3.2. Characterization of the coordination compounds ................................................................ 29 3.2.1. Squarate-Zinc coordination complexes ......................................................................... 30 3.2.2. Coordination complexes of the squarate ions with various divalent metal ions ........... 42 3.2.3. Croconate-Zinc coordination complexes ...................................................................... 44 4. Functional Porous Carbon-based Materials ............................................................................... 47 4.1. Background and State-of-the-Art ........................................................................................ 47 4.2. Composite and carbon materials derived from squarate-zinc complexes ........................... 50 4.3. Composite and carbon materials derived from coordination complexes of squarate units with various metal ions ............................................................................................................... 56 4.4. Carbon materials derived from croconate-zinc coordination complexes ............................ 62 5. Applications of Composite and Carbon Materials derived from coordination complexes ........ 64 5.1. Background and State-of-the-Art ........................................................................................ 64 II 5.2. Electrochemical capacitors .................................................................................................. 68 5.3. Heterogeneous Catalysis ...................................................................................................... 71 5.3.1. Synthesis of NiC composite catalyst via an impregnation approach ............................ 74 5.3.2. Synthesis of NiC composite catalyst via an one-pot synthesis approach based on nickel-squarate complexes ...................................................................................................... 78 5.3.3. Catalytic performance of the NiC composites .............................................................. 80 6. Summary, Conclusions and Outlook .......................................................................................... 90 7. References .................................................................................................................................. 95 A. Applied Methods ................................................................................................................... 103 B. Experimental part .................................................................................................................. 111 C. Supplementary information .................................................................................................. 115 D. List of abbreviations ............................................................................................................. 129 E. List of publications ............................................................................................................... 131 F. Declaration ............................................................................................................................ 133 III IV 1. Introduction From stone to silicon, materials have fundamentally shaped the history of human civilization and affect how we build, eat, progress, work, and communicate. Each new era has been dominated by a new class of materials which possessed better and more developed properties than the materials of the preceding ages. Each era has brought up a number of innovations which revolutionized the landscape of human civilization from both the social and economic point of view. While the 20th century has been significantly marked by silicon based materials, in the course of the 21st century the spotlight has shifted to another class of materials which is about to dominate a new industrial era referred to as the “new carbon age”.1, 2 Carbon is the fourth most abundant element in the universe and of fundamental importance for life on earth.3 It can possess a range of outstanding properties and is becoming the material of choice in a wide spectrum of applications, ousting silicon and dominating developments in both modern science and industry.2, 4, 5 As a chemical element, carbon possesses at least three stable bonding schemes given by the hybridization states (sp3, sp2 and sp) which can be easily transformed into each other by variation of temperature and pressure or via chemical reactions, thus allowing for the flexible formation of various shapes and geometries. In addition, carbon possesses the exceptional ability to form stable bonds with itself and other elements (e.g. H, O, N, B, metals, etc.) in many different ways, thus giving rise to a variety of compounds and nanostructures.6 These points are important as they allow for the control of structure and chemical functionality with the highest chemical resolution i.e. precision down to the Angstrom level.7 Among the different carbon forms, the sp2 (graphite, nanotube, fullerene) and sp3 (diamond) allotropic configurations (Figure 1.1) attracted much interest as each of them exhibits a list of remarkable properties.8