| | Table of Contents | |
| | | |
| |
| | Preface | XI |
| 1 | Hybrid Materials, Functional Applications. An Introduction
Pedro Gómez-Romero and Clément Sanchez | 1 |
| 1.1 | From Ancient Tradition to 21st Century Materials | 1 |
| 1.2 | Hybrid Materials. Types and Classifications | 4 |
| 1.3 | General Strategies for the Design of Functional Hybrids | 6 |
| 1.4 | The Road Ahead | 10 |
| 2 | Organic-Inorganic Materials: From Intercalation Chemistry to Devices
Eduardo Ruiz-Hitzky | 15 |
| 2.1 | Introduction | 15 |
| 2.2 | Types of Hybrid Organic-Inorganic Materials | 18 |
| 2.2.1 | Intercalation Compounds | 18 |
| 2.2.1.1 | Intercalation of Ionic Species | 20 |
| 2.2.1.2 | Intercalation of Neutral Species | 23 |
| 2.2.1.3 | Polymer Intercalations: Nanocomposites | 25 |
| 2.2.2 | Organic Derivatives of Inorganic Solids | 27 |
| 2.2.3 | Sol-Gel Hybrid Materials | 30 |
| 2.3 | Functions & Devices Based on Organic-Inorganic Solids | 33 |
| 2.3.1 | Selective Sorbents, Complexing Agents & Membranes | 33 |
| 2.3.2 | Heterogeneous Catalysts & Supported Reagents | 36 |
| 2.3.3 | Photoactive, Optical and Opto-Electronic Materials & Devices | 38 |
| 2.3.4 | Electrical Behaviors: Ionic & Electronic Conductors | 41 |
| 2.3.5 | Electroactivity & Electrochemical Devices | 42 |
| 2.4 | Conclusions | 44 |
| 3 | Bridged Polysilsesquioxanes. Molecular-Engineering Nanostructured Hybrid Organic-Inorganic Materials
K. J. Shea, J. Moreau, D. A. Loy, R. J. P. Corriu, B. Boury | 50 |
| 3.1 | Introduction | 50 |
| 3.2 | Historical Background | 53 |
| 3.3 | Monomer Synthesis | 53 |
| 3.3.1 | Metallation | 54 |
| 3.3.2 | Hydrosilylation | 54 |
| 3.3.3 | Functionalization of an Organotrialkoxysilane | 55 |
| 3.3.4 | Other Approaches | 56 |
| 3.4 | Sol-Gel Processing of Bridged Polysilsesquioxanes | 58 |
| 3.4.1 | Hydrolysis and Condensation | 58 |
| 3.4.2 | Gelation | 59 |
| 3.4.3 | Aging and Drying | 62 |
| 3.5 | Characterization of Bridged Polysilsesquioxanes | 62 |
| 3.5.1 | Porosity in Bridged Polysilsesquioxanes | 64 |
| 3.5.2 | Pore Size Control | 65 |
| 3.5.3 | Pore Templating | 66 |
| 3.6 | Influence of Bridging Group on Nanostructures | 68 |
| 3.6.1 | Surfactant Templated Mesoporous Materials | 68 |
| 3.6.2 | Mesogenic Bridging Groups | 68 |
| 3.6.3 | Supramolecular Organization | 70 |
| 3.6.4 | Metal Templating | 71 |
| 3.7 | Thermal Stability and Mechanical Properties | 71 |
| 3.8 | Chemical Properties | 72 |
| 3.9 | Applications | 73 |
| 3.9.1 | Optics and Electronics | 74 |
| 3.9.1.1 | Dyes | 74 |
| 3.9.1.2 | Nano- and Quantum Dots in Bridged Polysilsesquioxanes | 75 |
| 3.9.2 | Separations Media | 75 |
| 3.9.3 | Catalyst Supports and Catalysts | 76 |
| 3.9.4 | Metal and Organic Adsorbents | 77 |
| 3.10 | Summary | 78 |
| 4 | Porous Inorganic-Organic Hybrid Materials
Nicola Hüsing and Ulrich Schubert | 86 |
| 4.1 | Introduction | 86 |
| 4.2 | Inorganic-Network Formation | 87 |
| 4.3 | Preparation and Properties | 89 |
| 4.3.1 | Aerogels | 89 |
| 4.3.2 | M41S materials | 93 |
| 4.4 | Methods for Introducing Organic Groups into Inorganic Materials | 96 |
| 4.5 | Porous Inorganic-Organic Hybrid Materials | 97 |
| 4.5.1 | Functionalization of Porous Inorganic Materials by Organic Groups | 97 |
| 4.5.1.1 | Post-synthesis Modification | 97 |
| 4.5.1.2 | Liquid-Phase Modification in the Wet Gel Stage or Prior to Surfactant Removal | 100 |
| 4.5.1.3 | Addition of Non-Reactive Compounds to the Precursor Solution | 101 |
| 4.5.1.4 | Use of Organically Substituted Co-precursors | 102 |
| 4.5.2 | Bridged Silsequioxanes | 105 |
| 4.5.3 | Incorporation of Metal Complexes for Catalysis | 107 |
| 4.5.4 | Incorporation of Biomolecules | 110 |
| 4.5.5 | Incorporation of Polymers | 111 |
| 4.5.6 | Creation of Carbon Structures | 115 |
| 5 | Optical Properties of Functional Hybrid Organic-Inorganic Nanocomposites
Clément Sanchez, Bénédicte Lebeau, Frédéric Chaput and Jean-Pierre Boilot | 122 |
| 5.1 | Introduction | 122 |
| 5.2 | Hybrids with Emission Properties | 126 |
| 5.2.1 | Solid-State Dye-Laser Hybrid Materials | 126 |
| 5.2.2 | Electroluminescent Hybrid Materials | 129 |
| 5.2.3 | Optical Properties of Lanthanide Doped Hybrid Materials | 132 |
| 5.2.3.1 | Encapsulation of Nano-Phosphors inside Hybrid Matrices | 134 |
| 5.2.3.2 | One-pot Synthesis of Rare-Earth Doped Hybrid Matrices | 134 |
| 5.2.3.3 | Rare-earth Doped Hybrids made via Non-hydrolytic Processes | 137 |
| 5.2.3.4 | Energy Transfer Processes between Lanthanides and Organic Dyes | 137 |
| 5.3 | Hybrid with Absorption Properties : Photochromic Hybrid Materials | 138 |
| 5.3.1 | Photochromic Hybrids for Optical Data Storage | 138 |
| 5.3.2 | Photochromic Hybrids for Fast Optical Switches | 141 |
| 5.3.3 | Non-Siloxane-Based Hosts for the Design of New Photochromic Hybrid Materials | 144 |
| 5.4 | Nonlinear Optics | 146 |
| 5.4.1 | Second-Order Nonlinear Optics in Hybrid Materials | 146 |
| 5.4.2 | Hybrid Photorefractive Materials | 149 |
| 5.4.3 | Photochemical Hole Burning in Hybrid Materials | 149 |
| 5.4.4 | Optical Limiters | 151 |
| 5.5 | Hybrid Optical Sensors | 153 |
| 5.6 | Integrated Optics Based on Hybrid Material | 155 |
| 5.7 | Hierarchically Organized Hybrid Materials for Optical Applications | 158 |
| 5.8 | Conclusions and Perspectives | 168 |
| 6 | Electrochemistry of Sol-Gel Derived Hybrid Materials
Pierre Audebert and Alain Walcarius | 172 |
| 6.1 | Introduction | 172 |
| 6.2 | Fundamental Electrochemical Studies in Sol-Gel Systems | 174 |
| 6.2.1 | Electrochemistry into Wet Oxide Gels | 175 |
| 6.2.1.1 | Electrochemistry as a Tool for the Investigation of Sol-gel Polymerization | 175 |
| 6.2.1.2 | Conducting Polymers - Sol-gel Composites | 177 |
| 6.2.2 | Electrochemical Behavior of Xerogels and Sol-gel-prepared Oxide Layers | 178 |
| 6.2.2.1 | Fundamental Studies | 179 |
| 6.2.2.2 | Composite Syntheses and Applications | 180 |
| 6.2.3 | Solid Polymer Electrolytes | 183 |
| 6.2.3.1 | Power Sources | 183 |
| 6.2.3.2 | Electrochromic Devices | 183 |
| 6.3 | Electroanalysis with Sol-gel Derived Hybrid Materials | 184 |
| 6.3.1 | Design of Modified Electrodes | 184 |
| 6.3.1.1 | Bulk Ceramic-carbon Composite Electrodes (CCEs) | 184 |
| 6.3.1.2 | Film-based Sol-gel Electrodes | 187 |
| 6.3.1.3 | Other Electrode Systems | 189 |
| 6.3.2 | Analytical Applications | 190 |
| 6.3.2.1 | Analysis of Chemicals | 190 |
| 6.3.2.2 | Biosensors | 198 |
| 6.4 | Conclusions | 200 |
| 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 | 210 |
| 7.1 | Introduction | 210 |
| 7.2 | Conducting Organic Polymers (COPs): from Discovery to Commercialization | 213 |
| 7.3 | Organics and Inorganics in Hybrid Materials | 214 |
| 7.3.1 | Classifications | 219 |
| 7.4 | Synergy at the Molecular Level: Organic-Inorganic (OI) Hybrid Materials | 220 |
| 7.5 | COPs Intercalated into Inorganic Hosts: Inorganic-Organic (IO) Materials | 226 |
| 7.5.1 | Mesoporous Host or Zeolitic-type Materials (silicates inclusive) | 230 |
| 7.6 | Emerging Nanotechnology: Toward Hybrid Nanocomposite Materials (NC) | 232 |
| 7.7 | Current Applications and Future Trends | 237 |
| 7.7.1 | Electronic and Opto-electronic Applications | 237 |
| 7.7.2 | Photovoltaic Solar Cells | 241 |
| 7.7.2.1 | Nanocomposite and Hybrid Solar Cells | 243 |
| 7.7.3 | Energy Storage and Conversion Devices: Batteries, Fuel Cells and Supercapacitors | 247 |
| 7.7.3.1 | Rechargeable Batteries | 247 |
| 7.7.3.2 | Fuel Cells and Electrocatalysis | 250 |
| 7.7.4 | Sensors | 251 |
| 7.7.5 | Catalysis | 252 |
| 7.7.6 | Membranes | 253 |
| 7.7.7 | Biomaterials | 255 |
| 7.8 | Conclusions and Prospects | 255 |
| 8 | Layered Organic-Inorganic Materials: A Way Towards Controllable Magnetism
Pierre Rabu and Marc Drillon | 270 |
| 8.1 | Introduction | 270 |
| 8.2 | Molecule-based Materials with Extended Networks | 271 |
| 8.2.1 | Transition Metal layered Perovskites | 271 |
| 8.2.2 | Bimetallic Oxalate-bridge Magnets | 272 |
| 8.2.2.1 | Magnetism and Conductivity | 276 |
| 8.2.2.2 | Magnetism and Non-linear Optics | 278 |
| | Table of Contents VIII | |
| 8.3 | The Intercalation Compounds MPS3 | 279 |
| 8.3.1 | Ion-exchange Intercalation in MPS3 | 279 |
| 8.3.2 | Properties of the MnPS3 Intercalates | 280 |
| 8.3.3 | Properties of the FePS3 Intercalates | 284 |
| 8.3.4 | Magnetism and Non-linear Optics | 286 |
| 8.4 | Covalently Bound Organic-inorganic Networks | 287 |
| 8.4.1 | Divalent Metal Phosphonates | 287 |
| 8.4.2 | Hydroxide-based Layered Compounds | 290 |
| 8.4.2.1 | Anion-exchange Reactions | 291 |
| 8.4.2.2 | Influence of Organic Spacers | 292 |
| 8.4.2.3 | Origin of the Phase Transition | 297 |
| 8.4.2.4 | Interlayer Interaction Mechanism | 299 |
| 8.4.2.5 | Difunctional Organic Anions | 301 |
| 8.4.2.6 | Metal-radical Based Magnets | 308 |
| 8.4.2.7 | Solvent-mediated Magnetism | 310 |
| 8.5 | Concluding Remarks | 313 |
| 9 | Building Multifunctionality in Hybrid Materials
Eugenio Coronado, José R. Calán-Mascarós, and Francisco Romero | 317 |
| 9.1 | Introduction | 317 |
| 9.2 | Combination of Ferromagnetism with Paramagnetism | 318 |
| 9.2.1 | Magnetic multilayers | 318 |
| 9.2.2 | Host-guest 3D Structures | 322 |
| 9.3 | Hybrid Molecular Materials with Photophysical Properties | 325 |
| 9.3.1 | Photo-active Magnets | 325 |
| 9.3.2 | Photo-active Conductors | 327 |
| 9.4 | Combination of Magnetism with Electric Conductivity | 328 |
| 9.4.1 | Paramagnetic Conductors from Small Inorganic Anions | 329 |
| 9.4.2 | Paramagnetic Conductors from Polyoxometalates | 334 |
| 9.4.3 | Coexistence of Electrical Conductivity and Magnetic Ordering | 338 |
| 9.5 | Conclusions | 342 |
| 10 | Hybrid Organic-Inorganic Electronics
David B. Mitzi | 347 |
| 10.1 | Introduction | 347 |
| 10.2 | Organic-Inorganic Perovskites | 350 |
| 10.2.1 | Structures | 350 |
| 10.2.2 | Properties | 355 |
| 10.2.2.1 | Optical Properties | 356 |
| 10.2.2.2 | Electrical Transport Properties | 361 |
| 10.2.3 | Film Deposition | 362 |
| 10.2.3.1 | Thermal Evaporation | 362 |
| 10.2.3.2 | Solution Processing | 364 |
| 10.2.3.3 | Melt Processing | 369 |
| 10.3 | Hybrid Perovskite Devices | 372 |
| 10.3.1 | Optical Devices | 372 |
| 10.3.2 | Electronic Devices | 378 |
| 10.4 | Conclusions | 383 |
| 11 | Bioactive Sol-Gel Hybrids
Jacques Livage, Thibaud Coradin and Cécile Roux | 387 |
| 11.1 | Introduction | 387 |
| 11.2 | Sol-gel Encapsulation | 389 |
| 11.2.1 | The Alkoxide Route | 389 |
| 11.2.2 | The Aqueous Route | 391 |
| 11.3 | Enzymes | 392 |
| 11.3.1 | Glucose Biosensors | 392 |
| 11.3.2 | Bioreactors, Lipases | 395 |
| 11.4 | Antibody-based Affinity Biosensors | 396 |
| 11.5 | Whole Cells | 398 |
| 11.5.1 | Yeast and Plant Cells | 398 |
| 11.5.2 | Bacteria | 398 |
| 11.5.3 | Biomedical Applications | 400 |
| 11.5.3.1 | Immunoassays in Sol-gel Matrices | 400 |
| 11.5.3.2 | Cell Transplantation | 400 |
| 11.6 | The Future of Sol-gel Bioencapsulation | 401 |
| | Index | 405 |
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