Functional Hybrid Materials

Pedro Gómez-Romero is a senior research scientist at the materials Science Institute of Barcelona (CSIC), Spain, where he leads a research group working on nanocomposites hybrid materials combining conducting polymers and oxides, clusters and active molecular species, developing energy storage and conversion applications such as duel cells, lithium batteries and supercapacitors. He obtained his B.S. and M.S. from the University of Valencia and his Ph.D. in Chemistry at Georgetown University, USA. He was a visiting scientist at the National Renewable Energy Laboratory at Golden (Co, USA) during 1998 and 1999 as a NATO senior fellow. Popularizing science is Dr. Gómez-Romero’s favorite creative activity outside the lab and, aside from his more than one hundred scientific publications, he has authored an award-winning book and many popular science articles.He is a member of the American Association for the Advancement of Science, the American Chemical Society, the materials Research Society, and the Electrochemical Society. Clément Sanchez is Director of Research at the CNRS, heads the laboratory for condensed matter chemistry at University of Paris VI, and furthermore holds a professional teaching position at École Polytechnique. He studied chemistry at ENSC Paris, received his Ph.D. from the University Pierre et Marie Curie, Paris, and held a post-doctoral position at UC Berkeley, USA.His main scientific interest focus on the study of the relationship between the optical and mechanical properties and the structures of molecularly designed hybrid materials, and on self-assembly processes to build hybrid and inorganic materials organized and textured at different length scales ranging from nano to macro sizes. He is recipient of several awards from IBM, the Société Chimique de France and the French Academy of Science as well as the CNRD Silver Medal. He is editor-in-chief of the New journal of Chemistry and co-author of over 250 scientific publications. He has also given over 50 invited lectures at international meetings.

"... the topics chosen for this book were well selected, presenting a quality overview of the types, properties and applications of hybrid organic-inorganic materials. ... Each chapter provides a wealth of information on the particular subject, and through referencing for readers interested in greater detail or additional coverage of the topic. The combination of a strong review of the fundamentals and an extensive collection of the up-to-date research accounts makes this book a valuable instructional test for students and a good reference for the experienced researcher." (Rick C. Schroden, The Dow Chemical Company, Midland, Advanced Materials, September3, 2004)

• Preface. 1 Hybrid Materials, Functional Applications. An Introduction (Pedro Gómez-Romero and Clément Sanchez).1.1 From Ancient Tradition to 21st Century Materials.1.2 Hybrid Materials. Types and Classifications.1.3 General Strategies for the Design of Functional Hybrids.1.4 The Road Ahead.2 Organic-Inorganic Materials: From Intercalation Chemistry to Devices (Eduardo Ruiz-Hitzky).2.1 Introduction.2.2 Types of Hybrid Organic-Inorganic Materials.2.2.1 Intercalation Compounds.2.2.1.1 Intercalation of Ionic Species.2.2.1.2 Intercalation of Neutral Species.2.2.1.3 Polymer Intercalations: Nanocomposites.2.2.2 Organic Derivatives of Inorganic Solids.2.2.3 Sol-Gel Hybrid Materials.2.3 Functions & Devices Based on Organic-Inorganic Solids.2.3.1 Selective Sorbents, Complexing Agents & Membranes.2.3.2 Heterogeneous Catalysts & Supported Reagents.2.3.3 Photoactive, Opt ical and Opto-Electronic Materials & Devices.2.3.4 Electrical Behaviors: Ionic & Electronic Conductors.2.3.5 Electroactivity & Electrochemical Devices.2.4 Conclusions.3 Bridged Polysilsesquioxanes. Molecular-Engineering Nanostructured Hybrid Organic-Inorganic Materials (K. J. Shea, J. Moreau, D. A. Loy, R. J. P. Corriu, B. Boury).3.1 Introduction.3.2 Historical Background.3.3 Monomer Synthesis.3.3.1 Metallation.3.3.2 Hydrosilylation.3.3.3 Functionalization of an Organotrialkoxysilane.3.3.4 Other Approaches.3.4 Sol-Gel Processing of Bridged Polysilsesquioxanes.3.4.1 Hydrolysis and Condensation.3.4.2 Gelation.3.4.3 Aging and Drying.3.5 Characterization of Bridged Polysilsesquioxanes.3.5.1 Porosity in Bridged Polysilsesquioxanes.3.5.2 Pore Size Control.3.5.3 Pore Templating.3.6 Influence of Bridging Group on Nanostructures.3.6.1 Surfactant Templated Mesoporous Materials.3.6.2 Mesogenic Bridging Groups.3.6.3 Supramolecular Organization.3.6.4 Metal Templating.3.7 Thermal Stability and Mechanical Properties.3.8 Chemical Properties.3.9 Applications.3.9.1 Optics and Electronics.3.9.1.1 Dyes.3.9.1.2 Nano- and Quantum Dots in Bridged Polysilsesquioxanes.3.9.2 Separations Media.3.9.3 Catalyst Supports and Catalysts.3.9.4 Metal and Organic Adsorbents.3.10 Summary.4 Porous Inorganic-Organic Hybrid Materials (Nicola Hüsing and Ulrich Schubert).4.1 Introduction.4.2 Inorganic-Network Formation.4.3 Preparation and Properties.4.3.1 Aerogels.4.3.2 M41S materials.4.4 Methods for Introducing Organic Groups into Inorganic Materials.4.5 Porous Inorganic-Organic Hybrid Materials.4.5.1 Functionalization of Porous Inorganic Materials by Organic Groups.4.5.1.1 Post-synthesis Modification.4.5.1.2 Liquid-Phase Modification in the Wet Gel Stage or Prior to Surfactant Removal.4.5.1.3 Addition of Non-Reactive Compounds to the Precursor Solution.4.5.1.4 Use of Organically Substituted Co-precursors.4.5.2 Bridged Silsequioxanes.4.5.3 Incorporation of Metal Complexes for Catalysis.4.5.4 Incorporation of Biomolecules.4.5.5 Incorporation of Polymers.4.5.6 Creation of Carbon Structures.5 Optical Properties of Functional Hybrid Organic-Inorganic Nanocomposites (Clément Sanchez, Bénédicte Lebeau, Frédéric Chaput and Jean-Pierre Boilot).5.1 Introduction.5.2 Hybrids with Emission Properties.5.2.1 Solid-State Dye-Laser Hybrid Materials.5.2.2 Electroluminescent Hybrid Materials.5.2.3 Optical Properties of Lanthanide Doped Hybrid Materials.5.2.3.1 Encapsulation of Nano-Phosphors inside Hybrid Matrices.5.2.3.2 One-pot Synthesis of Rare-Earth Doped Hybrid Matrices.5.2.3.3 Rare-earth Doped Hybrids made via Non-hydrolytic Processes.5.2.3.4 Energy Transfer Processes between Lanthanides and Organic Dyes.5.3 Hybrid with Absorption Properties : Photochromic Hybrid Materials.5.3.1 Photochromic Hybrids for Optical Data Storage.5.3.2 Photochromic Hybrids for Fast Optical Switches.5.3.3 Non-Siloxane-Based Hosts for the Design of New Photochromic Hybrid Materials.5.4 Nonlinear Optics.5.4.1 Second-Order Nonlinear Optics in Hybrid Materials.5.4.2 Hybrid Photorefractive Materials.5.4.3 Photochemical Hole Burning in Hybrid Materials.5.4.4 Optical Limiters.5.5 Hybrid Optical Sensors.5.6 Integrated Optics Based on Hybrid Material.5.7 Hierarchically Organized Hybrid Materials for Optical Applications.5.8 Conclusions and Perspectives.6 Electrochemistry of Sol-Gel Derived Hybrid Materials (Pierre Audebert and Alain Walcarius).6.1 Introduction.6.2 Fundamental Electrochemical Studies in Sol-Gel Systems.6.2.1 Electrochemistry into Wet Oxide Gels.6.2.1.1 Electrochemistry as a Tool for the Investigation of Sol-gel Polymerization.6.2.1.2 Conducting Polymers – Sol-gel Composites.6.2.2 Electrochemical Behavior of Xerogels and Sol-gel-prepared Oxide Layers.6.2.2.1 Fundamental Studies.6.2.2.2 Composite Syntheses and Applications.6.2.3 Solid Polymer Electrolytes.6.2.3.1 Power Sources.6.2.3.2 Electrochromic Devices.6.3 Electroanalysis with Sol-gel Derived Hybrid Materials.6.3.1 Design of Modified Electrodes.6.3.1.1 Bulk Ceramic-carbon Composite Electrodes (CCEs).6.3.1.2 Film-based Sol-gel Electrodes.6.3.1.3 Other Electrode Systems.6.3.2 Analytical Applications.6.3.2.1 Analysis of Chemicals.6.3.2.2 Biosensors.6.4 Conclusions.7 Multifunctional Hybrid Materials Based on Conducting Organic Polymers. Nanocomposite Systems with Photo-Electro-Ionic Properties and Applications (Monica Lira-Cantú and Pedro Gómez-Romero).7.1 Introduction.7.2 Conducting Organic Polymers (COPs): from Discovery to Commercialization.7.3 Organics and Inorganics in Hybrid Materials.7.3.1 Classifications.7.4 Synergy at the Molecular Level: Organic-Inorganic (OI) Hybrid Materials.7.5 COPs Intercalated into Inorganic Hosts: Inorganic-Organic (IO) Materials.7.5.1 Mesoporous Host or Zeolitic-type Materials (silicates inclusive).7.6 Emerging Nanotechnology: Toward Hybrid Nanocomposite Materials (NC).7.7 Current Applications and Future Trends.7.7.1 Electronic and Opto-electronic Applications.7.7.2 Photovoltaic Solar Cells.7.7.2.1 Nanocomposite and Hybrid Solar Cells.7.7.3 Energy Storage and Conversion Devices: Batteries, Fuel Cells and Supercapacitors.7.7.3.1 Rechargeable Batteries.7.7.3.2 Fuel Cells and Electrocatalysis.7.7.4 Sensors.7.7.5 Catalysis.7.7.6 Membranes.7.7.7 Biomaterials.7.8 Conclusions and Prospects.8 Layered Organic-Inorganic Materials: A Way Towards Controllable Magnetism (Pierre Rabu and Marc Drillon).8.1 Introduction.8.2 Molecule-based Materials with Extended Networks.8.2.1 Transition Metal layered Perovskites.8.2.2 Bimetallic Oxalate-bridge Magnets.8.2.2.1 Magnetism and Conductivity.8.2.2.2 Magnetism and Non-linear Optics.8.3 The Intercalation Compounds MPS3.8.3.1 Ion-exchange Intercalation in MPS3.8.3.2 Properties of the MnPS3 Intercalates.8.3.3 Properties of the FePS3 Intercalates.8.3.4 Magnetism and Non-linear Optics.8.4 Covalently Bound Organic-inorganic Networks.8.4.1 Divalent Metal Phosphonates.8.4.2 Hydroxide-based Layered Compounds.8.4.2.1 Anion-exchange Reactions.8.4.2.2 Influence of Organic Spacers.8.4.2.3 Origin of the Phase Transition.8.4.2.4 Interlayer Interaction Mechanism.8.4.2.5 Difunctional Organic Anions.8.4.2.6 Metal-radical Based Magnets.8.4.2.7 Solvent-mediated Magnetism.8.5 Concluding Remarks.9 Building Multifunctionality in Hybrid Materials (Eugenio Coronado, José R. Calán-Mascarós, and Francisco Romero).9.1 Introduction.9.2 Combination of Ferromagnetism with Paramagnetism.9.2.1 Magnetic multilayers.9.2.2 Host-guest 3D Structures.9.3 Hybrid Molecular Materials with Photophysical Properties.9.3.1 Photo-active Magnets.9.3.2 Photo-active Conductors.9.4 Combination of Magnetism with Electric Conductivity.9.4.1 Paramagnetic Conductors from Small Inorganic Anions.9.4.2 Paramagnetic Conductors from Polyoxometalates.9.4.3 Coexistence of Electrical Conductivity and Magnetic Ordering.9.5 Conclusions.10 Hybrid Organic-Inorganic Electronics (David B. Mitzi).10.1 Introduction.10.2 Organic-Inorganic Perovskites.10.2.1 Structures.10.2.2 Properties.10.2.2.1 Optical Properties.10.2.2.2 Electrical Transport Properties.10.2.3 Film Deposition.10.2.3.1 Thermal Evaporation.10.2.3.2 Solution Processing.10.2.3.3 Melt Processing.10.3 Hybrid Perovskite Devices.10.3.1 Optical Devices.10.3.2 Electronic Devices.10.4 Conclusions.11 Bioactive Sol-Gel Hybrids (Jacques Livage, Thibaud Coradin and Cécile Roux).11.1 Introduction.11.2 Sol-gel Encapsulation.11.2.1 The Alkoxide Route.11.2.2 The Aqueous Route.11.3 Enzymes.11.3.1 Glucose Biosensors.11.3.2 Bioreactors, Lipases.11.4 Antibody-based Affinity Biosensors.11.5 Whole Cells.11.5.1 Yeast and Plant Cells.11.5.2 Bacteria.11.5.3 Biomedical Applications.11.5.3.1 Immunoassays in Sol-gel Matrices.11.5.3.2 Cell Transplantation.11.6 The Future of Sol-gel Bioencapsulation.Index.