Dissertation zur Erlangung des Doktorgrades der Fakultät für Chemie und Pharmazie der Ludwig-Maximilians-Universität München TWO-DIMENSIONAL BUILDING BLOCKS FOR THE SYNTHESIS OF LAYERED HYBRID MATERIALS Stephan Werner aus Wiesbaden, Deutschland 2014 Erklärung Diese Dissertation wurde im Sinne von § 7 der Promotionsordnung vom 28. November 2011 von Frau Prof. Dr. Bettina V. Lotsch betreut. Eidesstattliche Versicherung Diese Dissertation wurde eigenständig und ohne unerlaubte Hilfe erarbeitet. München, 23.06.2014 …………………………………… (Stephan Werner) Dissertation eingereicht am 23.06.2014 1. Gutachter: Prof. Dr. Bettina V. Lotsch 2. Gutachter: Prof. Dr. Christina Scheu Mündliche Prüfung am 14.07.2014 Für Mama und Papa ACKNOWLEDGEMENTS First, I would like to express my gratitude to my supervisor Prof. Dr. Bettina V. Lotsch for giving me the opportunity to do research in her group. Throughout the entire time of work, I appreciated her expertise, the many helpful discussions and help at all times as well as the academic freedom in research. For being the co-referee of my thesis, for many helpful discussions and for help in TEM questions, I thank Prof. Dr. Christina Scheu. I want to thank Prof. Dr. Hans-Christian Böttcher, Prof. Dr. Konstantin Karaghiosoff, Prof. Dr. Dina Fattakhova-Rohlfing and Prof. Dr. Achim Hartschuh for being available as co- examiners in my viva voce. Furthermore, I would like to thank the following colleagues: . Prof. Hauke Clausen-Schaumann for his help and introduction into AFM theory and practice. Vincent Lau for electrochemical measurements and helpful discussions. Viola Duppel, Christian Ziegler and Kulpreet Virdi for TEM measurements and many helpful discussions upon interpretation of the results. Linus Stegbauer for his expertise and tips for improvement of organic syntheses. Claudia Kamella and Roland Eger for many solid state syntheses, helpful support and fun working days in Stuttgart. Hartmut Hartl and Marie-Luise Schreiber for ICP-AES measurements. Marion Sokoll for IR spectroscopy mesurements. Eva Bruecher and Rainer Frankovsky for SQUID measurements. Christine Neumann and Peter Mayer for liquid NMR mesuremnst. Christian Minke for his patience with my samples for SEM and solid-state NMR mesurements. Thomas Bräuniger for many helpful suggestions in terms of interpreting solid state NMR data. Armnin Schulz for Raman measurements. Mitsuharu Konuma for XPS measurements. Sophia Makowski for DTA-TG measurements. Wolfgang Wünschheim for any kind of support concerning computer and other hardware problems. Special thanks go to “my” Bachelor students Katarina Marković, Matthias Wörsching and Philipp Ratza for their work and support in research and for fun evenings after work. Thanks goes to my former and current lab mates of the “24/7 lab” D2.107: Christian Ziegler, Tanja Holzmann, Katharina Schwinghammer, Daniel Weber, Philipp Pust, Sebastian Schmiechen, Martin Mangstl, Sebastian Johansson, Jonas Häusler, Peter Wagatha and Philipp Strobel. Moreover, I would like to thank all members of the Schnick, Johrendt, Hoch, Schmedt auf der Günne and Oeckler groups for a very pleasant working atmosphere, for helping me with any kind of problem I had, for fun group outings and evenings such as SingStar or carnival partys. Big thanks go to the Lotsch group in Stuttgart: Jürgen Köhler, Jeanette Schüller-Knapp, Viola Duppel, Roland Eger, Xiuping Gao, Willi Hölle, Claudia Kamella, Friedrich Kögle, Marie-Luise Schreiber, Alexander Kuhn, Vincent Lau, Olalla Sánchez-Sobrado, Vijay Vyas, Pirmin Ganther, Frederik Haase, Tanja Holzmann, Katharina Schwinghammer, Brian Tuffy, Katalin Szendrei and Daniel Weber. ...and to the group in Munich: Christian Ziegler, Stephan Hug, Annekathrin Ranft, Erik Flügel, Linus Stegbauer, Ida Pavlichenko, Alberto von Mankowski, Claudia Lermer and the alumni Sebastian Junggeburth and Hongji Wang. Thank you to the Skat group for exciting games and amusing breaks: Stebbo, Chris and Erik. Chris, Sepp and Stebbo: Thank you for four unforgettable years. I do not think we did not do any kind of craziness in this time. We had fun evenings and nights in Munich and elsewhere; even though we might not remember all of what happend, it was a great time! I hope we stay in touch after our PhD time. Thank you, Chris! Particularly, I thank my parents, Mama and Papa, and my siblings, Julia and Sebastian. You made my academic career possible with your never ending support, pushing me forward and encouraging me even in the deepest valleys of motivation. Thank you for being the best family I could imagine! Finally, I thank you from the bottom of my heart, Vanessa! You support me in any kind of circumstance and give me the power to overcome all of my problems. Thank you for just being you. Ich mach mein Ding, egal was die anderen sagen. (Udo Lindenberg) TABLE OF CONTENTS 1. INTRODUCTION ...................................................................................... 1 1.1 Two-Dimensional Materials ..................................................................................... 1 1.2 Layered Ionic Solids ................................................................................................ 5 1.2.1 Anionic 2D Materials ....................................................................................... 5 1.2.2 Cationic 2D materials ....................................................................................... 7 1.3 Siloxene .................................................................................................................. 13 1.4 Layer-by-Layer Assembly ..................................................................................... 17 1.5 Objective ................................................................................................................ 20 1.6 Bibliography ........................................................................................................... 22 2. CHARACTERIZATION METHODS.......................................................... 32 2.1 X-ray Diffraction .................................................................................................... 32 2.2 Atomic Force Microscopy ...................................................................................... 33 2.3 Electron Microscopy .............................................................................................. 36 2.3.1 Scanning Electron Microscopy and Energy-dispersive X-ray Spectroscopy . 36 2.3.2 Transmission Electron Microscopy ................................................................ 37 2.4 Vibrational Spectroscopy ....................................................................................... 40 2.4.1 Infrared spectroscopy ..................................................................................... 40 2.4.2 Raman spectroscopy ....................................................................................... 40 2.4.3 UV-Vis spectroscopy ...................................................................................... 41 2.5 Nuclear Magnetic Resonance Spectroscopy .......................................................... 41 2.5.1 Solution-State Nuclear Magnetic Resonance Spectroscopy ........................... 41 2.5.2 Solid-State Nuclear Magnetic Resonance Spectroscopy ................................ 42 2.6 X-ray Photoelectron spectroscopy ......................................................................... 42 2.7 Magnetic measurements ......................................................................................... 43 2.8 Electrochemical Measurements ............................................................................. 43 2.9 Elemental analysis .................................................................................................. 43 2.9.1 Inductively Coupled Plasma Atomic Emission Spectroscopy ....................... 43 2.9.2 CHNS Analysis .............................................................................................. 44 2.10 Light Scattering Experiments ................................................................................. 44 2.11 Photoluminescence Measurements ........................................................................ 44 2.12 Bibliography ........................................................................................................... 45 3. LAYERED DOUBLE HYDROXIDES ........................................................ 46 II III 3.1 Exfoliation of Mn Al Layered Double Hydroxide and Synthesis of LDH/Graphene Oxide Hybrid Material ............................................................................. 47 3.1.1 Introduction .................................................................................................... 47 3.1.2 Experimental ................................................................................................... 50 3.1.3 Results and Discussion ................................................................................... 54 3.1.4 Conclusion ...................................................................................................... 65 3.1.5 Supporting Information .................................................................................. 66 II III 3.2 Layer-By-Layer Assembly of Mn Al LDH and Graphene Oxide ...................... 72 3.2.1 Experimental ................................................................................................... 72 3.2.2 Results and Discussion ..................................................................................