Functional Hybrid Materials: Functional Hybrid Materials.jpg

The Editors of this Volume
Pedro Gómez-Romero
Materials Science Institute of Barcelona
(ICMAB)
Campus della UAB, 08193, Bellaterra
Barcelona
Spain
Clément Sanchez
Laboratoire de Chimie de la
Matière Condensée (CMC)
4, place Jussieu
75252 Paris cedex 05
France
This book was carefully produced. Nevertheless,
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warrant the information contained therein to
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in mind that statements, data, illustrations,
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be inaccurate.
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&copy; 2004 WILEY-VCH Verlag GmbH
& Co. KGaA, Weinheim
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Druckhaus &raquo;Thomas Müntzer&laquo;,
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Printed in the Federal Republic of Germany.
ISBN 3-527-30484-3

Table of Contents
Preface XI
1 Hybrid Materials, Functional Applications. An Introduction 1
Pedro Gómez-Romero and Clément Sanchez
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 15
Eduardo Ruiz-Hitzky
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 50
K. J. Shea, J. Moreau, D. A. Loy, R. J. P. Corriu, B. Boury
3.1 Introduction 50
3.2 Historical Background 53
3.3 Monomer Synthesis 53
V
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 86
Nicola Hüsing and Ulrich Schubert
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
VI Table of Contents
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 122
Clément Sanchez, Bénédicte Lebeau, Frédéric Chaput and Jean-Pierre Boilot
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 172
Pierre Audebert and Alain Walcarius
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
Table of Contents VII
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 210
Monica Lira-Cantú and Pedro Gómez-Romero
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 270
Pierre Rabu and Marc Drillon
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
VIII Table of Contents
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 317
Eugenio Coronado, José R. Calán-Mascarós, and Francisco Romero
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 347
David B. Mitzi
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
Table of Contents IX
10.3.1 Optical Devices 372
10.3.2 Electronic Devices 378
10.4 Conclusions 383
11 Bioactive Sol-Gel Hybrids 387
Jacques Livage, Thibaud Coradin and Cécile Roux
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

Preface
The book you have in your hands is the result of a thrilling struggle. A struggle to
depict, in a bit more than a handful of chapters, the blooming and multifaceted
world of hybrid materials with functional properties and applications.
Hybrid organic-inorganic materials constitute indeed a remarkable and growing
category within the world of Materials Science. A realm where engineering the
combination of dissimilar components at the nanometric and molecular level leads
both to new challenges and opportunities for the development of novel and improved
materials. This is a field where the boundaries between molecular and extended
materials blur out, a field where ceramics and polymers meet at the chemical
dimension to yield new materials that go well beyond conventional composites, a
domain in which nanocomposites push forward the frontier of discovery. In this
exciting field, remarkable structural materials, halfway between glass and polymers
have been developed. Yet, the hybrid approach also offers great opportunities for
the development of functional materials, a fertile ground to harness the chemical,
physical, electrochemical or biological activity of a myriad organic and inorganic
components and put them to work in the materials of tomorrow.
Collecting a thorough taxonomic list of contents that could fairly represent this
fascinating family of materials would be impossible. Instead, we have strived to
select a few topics that would criss-cross the field revealing in some detail both a
variety of materials and a variety of functional properties and applications. Thus,
beginning with some historical perspective – if that is possible at all in a field that
has developed in the last two or three decades-the book goes from mineral intercalates,
sol-gel hybrids and polysiloxanes, to other radically different types of
hybrids and approaches, such as hybrids based on conducting polymers. Also very
varied are the functional properties and multifunctional combinations and applications
you will find in these chapters, ranging from optical or magnetic properties,
to energy storage and conversion or from the wealth of electroactive materials used
in sensors, batteries or solar cells, to the fascinating bioactive materials discussed
in the final chapter.
We hope this impressionistic portrait of a very dynamic field will contribute to
give the reader a feeling of the great potential, the multiple possibilities and the
many promising trends behind the development of functional hybrid materials.
August 2003 Pedro Gómez-Romero Clément Sanchez

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