<p>Preface XXI</p> <p>List of Contributors XXIII</p> <p>Volume One: Synthesis and Processing</p> <p><b>Part One Sol–Gel Chemistry and Methods 1</b></p> <p><b>1 Chemistry and Fundamentals of the Sol–Gel Process 3</b><br /><i>Ulrich Schubert</i></p> <p>1.1 Introduction 3</p> <p>1.2 Hydrolysis and Condensation Reactions 4</p> <p>1.2.1 Silica-Based Materials 4</p> <p>1.2.1.1 Precursor(s) 9</p> <p>1.2.1.2 Catalyst (pH) 9</p> <p>1.2.1.3 Alkoxo Group/H2O Ratio (Rw) 9</p> <p>1.2.1.4 Solvent 10</p> <p>1.2.1.5 Electrolytes 10</p> <p>1.2.2 Metal Oxide-Based Materials 11</p> <p>1.3 Sol–Gel Transition (Gelation) 17</p> <p>1.3.1 Hydrolytic Sol–Gel Processes 17</p> <p>1.3.2 Nonhydrolytic Sol–Gel Processes 22</p> <p>1.3.3 Inorganic–Organic Hybrid Materials 22</p> <p>1.4 Aging and Drying 24</p> <p>1.5 Postsynthesis Processing 26</p> <p>1.6 Concluding Remarks 26</p> <p>References 27</p> <p><b>2 Nonhydrolytic Sol–Gel Methods 29</b><br /><i>Rupali Deshmukh and Markus Niederberger</i></p> <p>2.1 Introduction 29</p> <p>2.2 Nonaqueous Sol–Gel Routes to Metal Oxide Nanoparticles 31</p> <p>2.2.1 Surfactant-Assisted Synthesis 31</p> <p>2.2.2 Solvent-Controlled Synthesis 33</p> <p>2.2.2.1 Benzyl Alcohol Route 33</p> <p>2.2.2.2 tert-Butyl Alcohol Route 37</p> <p>2.2.2.3 Ether Route 37</p> <p>2.2.2.4 Acetophenone Route 38</p> <p>2.2.2.5 Carboxylic Acid Route 39</p> <p>2.2.2.6 Benzylamine Route 39</p> <p>2.2.3 Microwave-Assisted Synthesis 40</p> <p>2.3 Nonaqueous Sol–Gel Synthesis beyond Metal Oxides 43</p> <p>2.3.1 Composites 43</p> <p>2.3.2 Organic–Inorganic Hybrid Materials 44</p> <p>2.3.3 Metal Sulfides 46</p> <p>2.3.4 Metals 47</p> <p>2.4 Chemical Reaction and Crystallization Mechanisms 48</p> <p>2.4.1 Introduction 48</p> <p>2.4.2 Overview of the Main Chemical Reactions 49</p> <p>2.4.3 Classical and Nonclassical Crystallization Mechanisms 51</p> <p>2.4.4 Selected Examples 51</p> <p>2.5 Assembly and Processing 56</p> <p>2.5.1 Introduction 56</p> <p>2.5.2 Nanoparticle Arrays and Superlattices 57</p> <p>2.5.3 Oriented Attachment and Mesocrystals 59</p> <p>2.5.4 Films 60</p> <p>2.6 Summary and Outlook 63</p> <p>References 63</p> <p><b>3 Integrative Sol–Gel Chemistry 71</b><br /><i>M. Depardieu, N. Kinadjian, D. Portehault, R. Backov, and Clément Sanchez</i></p> <p>3.1 Introduction 71</p> <p>3.2 Design of 0D Structures 72</p> <p>3.2.1 Aerosol Processing 72</p> <p>3.2.2 Capsules 75</p> <p>3.2.2.1 Simple Emulsions Preparation 76</p> <p>3.2.2.2 Mineralization of the Wax Dispersion 76</p> <p>3.2.2.3 Temperature-Triggered Release 77</p> <p>3.2.2.4 Introducing a Hydrophilic Compartment 79</p> <p>3.2.2.5 <a href="mailto:Water@Wax@Water">Water@Wax@Water</a> Emulsion Formulation 80</p> <p>3.2.2.6 <a href="mailto:Water@Wax@Water">Water@Wax@Water</a> Emulsion Mineralization 80</p> <p>3.2.2.7 Temperature-Triggered Release 81</p> <p>3.2.2.8 <a href="mailto:Wax@Water@Oil">Wax@Water@Oil</a> Emulsion Formulation 83</p> <p>3.2.2.9 <a href="mailto:Wax@Water@Oil">Wax@Water@Oil</a> Emulsion Mineralization 84</p> <p>3.2.2.10 Temperature-Triggered Release 85</p> <p>3.3 Design of 1D Macroscopic Structures 88</p> <p>3.3.1 Electrospinning 89</p> <p>3.3.1.1 A First Case: TiO2 Fibers for Dye-Sensitized Solar Cells 89</p> <p>3.3.1.2 Coupling Sol–Gel Reactions and Electrospinning 90</p> <p>3.3.2 Extrusion 93</p> <p>3.3.2.1 V2O5 Fibers as Alcohol Sensor 94</p> <p>3.3.2.2 Composite Fibers Prepared with the Help of Polymer Dehydration/Reticulation 96</p> <p>3.4 Design of Extended 2D Structures 99</p> <p>3.5 Design of Extended 3D Structures 99</p> <p>3.5.1 Foams 99</p> <p>3.5.1.1 Silica Foams: Si-(HIPE) 101</p> <p>3.5.1.2 <a href="mailto:Eu3+@Organo-Si-(HIPE">Eu3+@Organo-Si-(HIPE</a>): Photonic Properties 101</p> <p>3.5.1.3 <a href="mailto:Pd@Organo-Si-(HIPE">Pd@Organo-Si-(HIPE</a>): Cycling Heck Catalysis Reactions 103</p> <p>3.5.1.4 <a href="mailto:Enzyme@Organo-Si-(HIPE">Enzyme@Organo-Si-(HIPE</a>): High Efficiency Biocatalysts 104</p> <p>3.5.1.5 Si-(HIPE) as Hard Template to Carbonaceous Foams and Applications 106</p> <p>3.5.1.6 Carbon-(HIPE) as Li Ion Negative Electrodes 107</p> <p>3.5.1.7 <a href="mailto:LiBH4@Carbon-(HIPE">LiBH4@Carbon-(HIPE</a>) for Hydrogen Storage and Release 107</p> <p>3.5.2 Aerogels 112</p> <p>3.5.3 Dense Nanostructured Monoliths 112</p> <p>3.6 Conclusions 113</p> <p>References 115</p> <p><b>4 Synthetic Self-Assembly Strategies and Methods 121</b><br /><i>Alexandra Zamboulis, Olivier Dautel, and Joël J.E. Moreau</i></p> <p>4.1 Introduction 121</p> <p>4.2 Templated Synthesis of Inorganic Materials 122</p> <p>4.2.1 Self-Assembly of Mesoporous Silicas 123</p> <p>4.2.2 Hydrothermal Rearrangement and Postsynthesis Treatment 125</p> <p>4.2.3 Self-Assembly of Thin Films 126</p> <p>4.2.4 Self-Assembly of Functionalized Mesoporous Silicas 127</p> <p>4.3 Self-Assembled Organosilicas 128</p> <p>4.3.1 Control of the Pore Structure: Templated Synthesis of Mesoporous Bridged Silsesquioxanes 129</p> <p>4.3.2 Self-Organized Organosilicas 132</p> <p>4.3.3 Self-Assembly Synthetic Strategies for Organosilicas with Optical Properties 139</p> <p>4.3.3.1 Toward an H-Aggregation/Card Pack Stacking 141</p> <p>4.3.3.2 From a J- to an H-Aggregation 149</p> <p>4.3.3.3 Transcription of the J-Aggregation from the Precursor to the Material 153</p> <p>4.4 Conclusions 154</p> <p>References 154</p> <p><b>5 Processing of Sol–Gel Films from a Top-Down Route 165</b><br /><i>Plinio Innocenzi and Luca Malfatti</i></p> <p>5.1 Introduction 165</p> <p>5.2 Top-Down Processing by UV Photoirradiation 167</p> <p>5.2.1 UV Curing of Oxides 167</p> <p>5.2.2 UV Curing of Hybrid Sol–Gel Films 169</p> <p>5.2.3 UV Photoirradiation of Mesoporous Films 170</p> <p>5.2.4 Nanocomposite So–Gel Films by UV Photoirradiation 173</p> <p>5.3 Laser Irradiation and Writing 174</p> <p>5.3.1 Thermal-Induced Effects 174</p> <p>5.3.2 Laser-Induced Microfabrication 175</p> <p>5.3.3 Nanofabrication by Two- or Multiphoton Absorption 177</p> <p>5.4 Electron Beam Lithography 178</p> <p>5.5 Top-Down Processing by Hard X-Rays 181</p> <p>5.6 Soft X-Ray Lithography 184</p> <p>References 186</p> <p><b>6 Sol–Gel Precursors 195</b><br /><i>Vadim G. Kessler</i></p> <p>6.1 Introduction 195</p> <p>6.2 Simple Silicon Alkoxides 196</p> <p>6.3 Functional and Mixed Ligand Silicon Alkoxides for More Facile Hydrolysis 197</p> <p>6.4 Functional Silicon Alkoxides: Precursors of Hybrid Materials 198</p> <p>6.5 Simple Metal Alkoxides 200</p> <p>6.5.1 Commercially Available Simple Metal Alkoxide 202</p> <p>6.5.2 Customary Synthesis of Metal Alkoxide Precursors 209</p> <p>6.5.2.1 Interaction of Metals with Alcohols 209</p> <p>6.5.2.2 Alcoholysis of Complexes Derived from Volatile Acids Weaker Than Alcohols 209</p> <p>6.5.2.3 Basic Alcoholysis of Metal Halides: Metathesis Reaction 210</p> <p>6.5.2.4 Alcoholysis of Metal Oxides 210</p> <p>6.5.2.5 Electrochemical Oxidation of Metals in Alcohols 211</p> <p>6.5.2.6 Alcohol Interchange Reaction 211</p> <p>6.6 Functional and Mixed Ligand Metal Alkoxides for More Facile Hydrolysis and Stabilization of Resulting Colloids 212</p> <p>6.7 Precursor and Solvent Choice for Nonhydrolytic Sol–Gel Processes 213</p> <p>6.8 Synthesis of Complex Materials: Single-Source Precursor Approach 214</p> <p>6.9 Sol–Gel Precursors for Special Applications: Biomedical and Luminescent 215</p> <p>Abbreviations 216</p> <p>References 216</p> <p><b>Part Two Sol–Gel Materials 225</b></p> <p><b>7 Nanoparticles and Composites 227</b><br /><i>Guido Kickelbick</i></p> <p>7.1 Introduction 227</p> <p>7.2 Aqueous Sol–Gel Process 228</p> <p>7.2.1 Silica Nanoparticles 228</p> <p>7.2.1.1 Properties of Silica Nanoparticles 230</p> <p>7.2.2 Metal Oxides 231</p> <p>7.3 Nonaqueous Sol–Gel Process 232</p> <p>7.3.1 Metal Oxides 232</p> <p>7.4 Surface Functionalization of Nanoparticles 234</p> <p>7.5 Nanocomposites 236</p> <p>7.5.1 Dispersion of Silica Nanoparticles in Polymer Matrices 237</p> <p>7.5.2 In Situ Production of Silica Particles in a Polymer Matrix 237</p> <p>7.5.3 Melt Production of Silica Particles in a Polymer Matrix 238</p> <p>7.5.4 Properties of Nanoparticle Polymer Nanocomposites 238</p> <p>7.6 Conclusions 239</p> <p>References 239</p> <p><b>8 Oxide Powders and Ceramics 245</b><br /><i>Maria Zaharescu and Luminita Predoana</i></p> <p>8.1 Oxide Powders Obtained by Sol–Gel Methods 245</p> <p>8.2 Ceramics from Sol–Gel Oxide Powders 248</p> <p>8.3 Pure and Doped Single Oxide Ceramics 249</p> <p>8.3.1 Nanocrystalline Yttria 249</p> <p>8.3.2 Gd-Doped Ceria 249</p> <p>8.4 Multicomponent Ceramics 250</p> <p>8.4.1 Zirconium Titanate 250</p> <p>8.4.2 Lead Titanate 251</p> <p>8.4.3 Zr-Doped PbTiO3 251</p> <p>8.4.4 Nb-Doped PZT 252</p> <p>8.4.5 W-Doped PZT 252</p> <p>8.4.6 Ca-Doped PbTiO3 253</p> <p>8.4.7 Barium Titanate 255</p> <p>8.4.8 (Er, Yb)-Doped BaTiO3 256</p> <p>8.4.9 Barium Strontium Titanate 256</p> <p>8.4.10 Co-Doped Barium Strontium Titanate 257</p> <p>8.4.11 Mg-Doped Barium Strontium Titanate 257</p> <p>8.4.12 Magnesium Titanate 257</p> <p>8.4.13 B-Doped MgTiO3 258</p> <p>8.4.14 Calcium Titanate 258</p> <p>8.4.15 CaTiO3–(Sm, Nd)AlO3 Solid Solution 259</p> <p>8.4.16 (Co, Cu)-Doped Calcium Titanate 259</p> <p>8.4.17 (Na, K)-Doped Bismuth Titanate 260</p> <p>8.4.18 Mg-Doped Barium Tantalate 261</p> <p>8.4.19 Lead-Free Ba(Fe0.5Nb0.5)O3 261</p> <p>8.4.20 B-Doped Mg4Nb2O9 261</p> <p>8.4.21 Ce-Doped Lutetium Aluminum Garnet 262</p> <p>8.4.22 Ce-Doped Barium Yttrium Garnet 263</p> <p>8.4.23 Aluminum Titanate 263</p> <p>8.4.24 Magnesium Aluminum Titanate 264</p> <p>8.4.25 Lanthanum Cobaltite 265</p> <p>8.5 Composite Ceramics 266</p> <p>8.5.1 Al2O3–ZrO2 Nanocomposite 266</p> <p>8.5.2 Alumina–Yttrium Aluminum Garnet 269</p> <p>8.6 Conclusions 269</p> <p>References 270</p> <p><b>9 Thin Film Deposition Techniques 277</b><br /><i>David Grosso, Cédric Boissière, and Marco Faustini</i></p> <p>9.1 Introduction 277</p> <p>9.2 General Aspects of Liquid Deposition Techniques 280</p> <p>9.2.1 A Multistep Process between Chemistry and Engineering 280</p> <p>9.2.2 Initial Solution (Sol–Gel Chemistry) 280</p> <p>9.2.3 Deposition Step (Solution Spreading) 283</p> <p>9.2.4 Evaporation Step (Progressive Concentration) 284</p> <p>9.2.5 Optional Patterning Processes 288</p> <p>9.2.6 Postdeposition Treatments (Stabilization, Consolidation, and Modification) 288</p> <p>9.3 Spin Coating 289</p> <p>9.3.1 Generalities on Spin Coating 289</p> <p>9.3.2 Fundamentals of Spin Coating 290</p> <p>9.3.3 Advantages and Drawbacks of Spin Coating 294</p> <p>9.3.4 Some Critical Examples of Films Prepared by Spin Coating 295</p> <p>9.4 Dip Coating 296</p> <p>9.4.1 Generalities on Dip Coating 296</p> <p>9.4.2 Fundamentals of Dip Coating 297</p> <p>9.4.2.1 Model for the Capillarity Regime 299</p> <p>9.4.2.2 Model for the Draining Regime 300</p> <p>9.4.2.3 Combining Models to Describe Simultaneously Both Regimes 301</p> <p>9.4.3 Advantages and Drawbacks of Dip Coating 302</p> <p>9.4.4 Some Critical Examples of Films Prepared by Dip Coating 302</p> <p>9.5 Alternative and Emerging Techniques 304</p> <p>9.5.1 Roll-to-Roll Coating Techniques 304</p> <p>9.5.2 Droplet-Assisted Deposition (Aerosol and Inkjet) 304</p> <p>9.5.3 Electro-assisted Deposition 308</p> <p>9.6 General Perspectives 310</p> <p>References 310</p> <p><b>10 Monolithic Sol–Gel Materials 317</b><br /><i>Raz Gvishi</i></p> <p>10.1 Introduction 317</p> <p>10.2 Principles of Sol–Gel Monolith Fabrication 319</p> <p>10.2.1 Hydrolysis and Condensation 319</p> <p>10.2.2 Role of Drying in Monolith Fabrication 320</p> <p>10.2.3 Chemical Composition Effects 321</p> <p>10.2.3.1 Metal Alkoxide Precursor Types 321</p> <p>10.2.3.2 pH Effect: Type of Catalyst Used 321</p> <p>10.2.3.3 H2O: Si Molar Ratio (R) 322</p> <p>10.2.3.4 Steric Effect of Precursor Ligand Groups 323</p> <p>10.2.3.5 Functionality of Organically Modified Silanes 323</p> <p>10.3 Routes for Fabrication of Monoliths 324</p> <p>10.3.1 Xerogel Monoliths 325</p> <p>10.3.1.1 Methods for Preparing Nonsilica Xerogel Monoliths 325</p> <p>10.3.1.2 Methods for Preparing Silica Xerogel Monoliths 327</p> <p>10.3.2 Organically Modified Silane Monoliths 329</p> <p>10.3.2.1 ORMOSIL Inorganic–Organic Hybrid Monoliths in One Phase 330</p> <p>10.3.2.2 Hybrid Monoliths by Fast Sol–Gel (FSG) Process 331</p> <p>10.3.3 Multiphasic Composite Hybrid Monoliths 333</p> <p>10.3.4 Aerogel Monoliths 338</p> <p>10.4 Summary 339</p> <p>References 340</p> <p><b>11 Hollow Inorganic Spheres 345</b><br />Atsushi Shimojima</p> <p>11.1 Introduction 345</p> <p>11.2 General Strategies 345</p> <p>11.2.1 Templating Methods 345</p> <p>11.2.2 Template-Free Methods 347</p> <p>11.3 Typical Synthesis Procedures 347</p> <p>11.3.1 Hollow Silica Particles 347</p> <p>11.3.2 Hollow Mesoporous Silica Particles 350</p> <p>11.3.3 Hollow Organosilica Nanoparticles 354</p> <p>11.3.4 Hollow Crystalline Silicate Particles 355</p> <p>11.3.5 Hollow Titania (TiO2) Particles 357</p> <p>11.3.6 Hollow Particles of Other Metal Oxides 359</p> <p>11.4 Applications 360</p> <p>11.4.1 Antireflective Coatings 360</p> <p>11.4.2 Catalysis 361</p> <p>11.4.3 Lithium Ion Battery 362</p> <p>11.4.4 Biomedical Applications 363</p> <p>11.5 Summary 365</p> <p>References 365</p> <p><b>12 Sol–Gel Coatings by Electrochemical Deposition 373</b><br /><i>Liang Liu and Daniel Mandler</i></p> <p>12.1 Introduction 373</p> <p>12.2 Mechanism of the Sol–Gel Electrochemical Deposition 374</p> <p>12.3 Manipulation of the Sol–Gel Electrochemical Deposition 379</p> <p>12.3.1 Effect of Deposition Parameters 379</p> <p>12.3.2 Electrochemical Deposition of Nanostructured Silica Thin Films 383</p> <p>12.3.3 Selective Electrochemical Deposition on Patterns 385</p> <p>12.3.4 Local Electrochemical Deposition of Sol–Gel Films by Scanning Electrochemical Microscopy 386</p> <p>12.4 Electrochemical Codeposition of Sol–Gel-Based Hybrid and Composite Films 388</p> <p>12.4.1 Electrodeposition of Sol–Gel-Based Hybrid Films 389</p> <p>12.4.2 Electrodeposition of Sol–Gel-Based Composite Films 390</p> <p>12.5 Applications of Electrochemically Deposited Sol–Gel Films 394</p> <p>12.5.1 Corrosion Protection and Adhesion Promotion 394</p> <p>12.5.2 Electrochemical Sensors 397</p> <p>12.5.3 Biocomposite Films 400</p> <p>12.5.4 Other Applications 405</p> <p>12.6 Summary 408</p> <p>Abbreviations for Silanes 409</p> <p>Acknowledgments 410</p> <p>References 410</p> <p><b>13 Nanofibers and Nanotubes 415<br /></b><i>Il-Doo Kim and Seon-Jin Choi</i></p> <p>13.1 Introduction 415</p> <p>13.2 Nanofibers 415</p> <p>13.2.1 Electrospinning Process 416</p> <p>13.2.2 Polymer Nanofibers 417</p> <p>13.2.3 Metal Nanofibers 419</p> <p>13.2.4 Metal Oxide Nanofibers 421</p> <p>13.2.5 Multicomposite Nanofibers 424</p> <p>13.2.6 Graphene-Functionalized Nanofibers 426</p> <p>13.3 Nanotubes 427</p> <p>13.3.1 Direct Synthetic Methods of Nanotubes 427</p> <p>13.3.1.1 Hydrothermal Synthetic Routes 427</p> <p>13.3.1.2 Electrochemical Synthetic Routes 428</p> <p>13.3.1.3 Electrospinning Routes 428</p> <p>13.3.2 Indirect Synthetic Methods of Nanotubes 431</p> <p>13.3.2.1 AAO Templating Routes 431</p> <p>13.3.2.2 Inorganic Layer Templating Routes 432</p> <p>13.3.2.3 Polymer Templating Routes 434</p> <p>13.3.2.4 Electrospun Nanofiber Templating Route 436</p> <p>13.4 Summary and Future Perspectives 439</p> <p>References 439</p> <p><b>14 Nanoarchitectures by Sol–Gel from Silica and Silicate Building Blocks 443</b><br /><i>Pîlar Aranda, Carolina Belver, and Eduardo Ruiz-Hitzky</i></p> <p>14.1 Introduction 443</p> <p>14.2 Porous Clay Nanoarchitectures Using Sol–Gel Approaches 444</p> <p>14.3 Porous Nanoarchitectures from Delaminated Clays 450</p> <p>14.4 Fibrous Silicates as Building Blocks in Sol–Gel Nanoarchitectures Derived from Clays 457</p> <p>14.5 Conclusion 464</p> <p>Acknowledgments 465</p> <p>References 465</p> <p><b>15 Sol–Gel for Metal Organic Frameworks (MOFs) 471</b><br /><i>Kang Liang, Raffaele Ricco, Julien Reboul, Shuhei Furukawa, and Paolo Falcaro</i></p> <p>15.1 Introduction 471</p> <p>15.2 Design and Synthetic Strategies of MOF–Sol–Gel-Based Structures 472</p> <p>15.2.1 MOFs Hosting Sol–Gel-Based Structures 472</p> <p>15.2.2 Surface Chemical Functionalization of Sol–Gel Materials and Ceramics for MOF Technology 475</p> <p>15.2.2.1 Nano/Microparticles 475</p> <p>15.2.2.2 Thin Films 476</p> <p>15.2.2.3 Membranes and Monoliths 477</p> <p>15.2.3 Engineered Ceramics and Hybrid Materials for Controlled MOF Nucleation and Growth 478</p> <p>15.2.3.1 Nano/Microparticles 478</p> <p>15.2.3.2 Thin Films and Membranes 479</p> <p>15.2.4 Conversion from Ceramics for the Fabrication of MOFs 480</p> <p>15.3 Conclusion and Remarks 482</p> <p>Acknowledgments 483</p> <p>References 483</p> <p><b>16 Silica Ionogels and Ionosilicas 487</b><br /><i>Peter Hesemann, Lydie Viau, and André Vioux</i></p> <p>16.1 Introduction 487</p> <p>16.2 Ionogels 488</p> <p>16.2.1 Brief Presentation of ILs 488</p> <p>16.2.2 Sol–Gel in Ionic Liquids 489</p> <p>16.2.2.1 Formic Acid Solvolysis Sol–Gel Way 490</p> <p>16.2.2.2 Hydrolysis Sol–Gel Way 491</p> <p>16.2.2.3 Mesoporous Silicas from Ionogels 492</p> <p>16.2.2.4 Particulate Ionogels 492</p> <p>16.2.3 Applications of Ionogels 493</p> <p>16.2.3.1 Conducting Properties of Confined ILs 493</p> <p>16.2.3.2 Hybrid Host Matrices for Ionogel Electrolytes 494</p> <p>16.2.3.3 Ionogel Electrolytes for Lithium Batteries 495</p> <p>16.2.3.4 Proton-Conducting Ionogel Membranes 495</p> <p>16.2.3.5 Ionogel Electrolytes for Solar Cells 495</p> <p>16.2.3.6 Ionogels Incorporating Task-Specific Solutes 495</p> <p>16.2.3.7 Ionogels for Drug Release Systems 497</p> <p>16.3 Ionosilicas 497</p> <p>16.3.1 Definitions 497</p> <p>16.3.1.1 Synthesis of Ionosilicas 498</p> <p>16.3.2 Synthesis of Surface-Functionalized Ionosilicas 498</p> <p>16.3.2.1 Postsynthesis Grafting Reactions 500</p> <p>16.3.2.2 Cocondensation Reactions 500</p> <p>16.3.3 Hybrid Ionosilicas 504</p> <p>16.3.4 Ionic Nanoparticles and Ionic Nanoparticle Networks 505</p> <p>16.3.5 Applications of Ionosilicas 506</p> <p>16.3.5.1 Catalysis 506</p> <p>16.3.5.2 Anion Exchange Reactions 507</p> <p>16.3.5.3 Molecular Recognition 507</p> <p>16.4 Conclusion 508</p> <p>References 508</p> <p><b>17 Aerogels 519</b><br /><i>Shanyu Zhao, Marina S. Manic, Francisco Ruiz-Gonzalez, and Matthias M. Koebel</i></p> <p>17.1 Introduction and Brief History 519</p> <p>17.2 Synthesis and Processing 521</p> <p>17.2.1 Gel Preparation 521</p> <p>17.2.1.1 Silica Gels 521</p> <p>17.2.1.2 Nonsilica Inorganic Oxide Gels 527</p> <p>17.2.1.3 Organic and Biopolymer Gels 529</p> <p>17.2.1.4 Exotic Gels 534</p> <p>17.2.2 Gel Aging and Solvent Exchange 535</p> <p>17.2.2.1 Aging Process 535</p> <p>17.2.2.2 Effect of Solvent Exchange 536</p> <p>17.2.3 Gel Modification and Chemical Functionalization 537</p> <p>17.2.4 Gel Drying 538</p> <p>17.2.4.1 Freeze-Drying 539</p> <p>17.2.4.2 Ambient Pressure Drying 540</p> <p>17.2.4.3 Supercritical Drying 543</p> <p>17.2.4.4 High-Temperature Supercritical Drying 544</p> <p>17.2.4.5 Low-Temperature Supercritical Drying 545</p> <p>17.3 Characterization Methods 546</p> <p>17.3.1 Structural Characterization 547</p> <p>17.3.2 Chemical Characterization 548</p> <p>17.3.3 Thermal Characterization 549</p> <p>17.3.4 Mechanical Characterization 550</p> <p>17.3.5 Optical Characterization 552</p> <p>17.4 Selected Examples and Applications 553</p> <p>17.4.1 Aerogels for Superinsulation 554</p> <p>17.4.1.1 Silica Aerogels 555</p> <p>17.4.1.2 Organic Aerogels 555</p> <p>17.4.2 Aerogels for Catalysis: Chemistry Applications 556</p> <p>17.4.2.1 Silica-Based Aerogel 556</p> <p>17.4.2.2 Alumina-Based Aerogel 556</p> <p>17.4.2.3 Titania-Based Aerogel 557</p> <p>17.4.2.4 Zirconia-Based Aerogel 557</p> <p>17.4.2.5 Carbon Aerogels 557</p> <p>17.4.2.6 Other Mixed Oxides Composite Aerogels 558</p> <p>17.4.3 Aerogels for Supercapacitor and Battery Research 558</p> <p>17.4.4 Aerogels in Space Exploration 558</p> <p>17.4.5 Aerogels for Biomedical Applications 559</p> <p>17.5 Trends, Conclusion, and Outlook 559</p> <p>17.5.1 Small Volume–High Specialization 559</p> <p>17.5.2 Large Volume–High Performance 560</p> <p>17.5.3 Outlook 561</p> <p>References 562</p> <p><b>18 Ordered Mesoporous Sol–Gel Materials: From Molecular Sieves to Crystal-Like Periodic Mesoporous Organosilicas 575</b><br /><i>Sílvia C. Nunes, Paulo Almeida, and Verónica de Zea Bermudez</i></p> <p>18.1 Introduction 575</p> <p>18.2 Synthesis Mechanisms of Periodic Mesoporous Silica Materials 577</p> <p>18.2.1 Liquid Crystal Templating 578</p> <p>18.2.2 Cooperative Self-Assembly 578</p> <p>18.2.3 Evaporation-Induced Self-Assembly Mechanism 579</p> <p>18.2.4 Soft Templating 580</p> <p>18.3 Functionalization of Periodic Mesoporous Silica Materials 582</p> <p>18.3.1 Postsynthetic Grafting 583</p> <p>18.3.2 Direct Synthesis 583</p> <p>18.4 Periodic Mesoporous Organosilicas 584</p> <p>18.4.1 Synthesis Mechanisms 584</p> <p>18.4.2 Multifunctionalization 586</p> <p>18.4.3 Periodic Mesoporous Organosilicas with Amorphous Wall Structure 587</p> <p>18.4.4 Periodic Mesoporous Organosilicas with Crystal-Like Wall Structure 587</p> <p>18.4.5 Functionalization of Crystal-Like Periodic Mesoporous Organosilicas and Figures of Merit 591</p> <p>18.5 Future Trends 595</p> <p>Acknowledgments 596</p> <p>References 596</p> <p><b>19 Biomimetic Sol–Gel Materials 605</b><br /><i>Carole Aimé, Thibaud Coradin, and Francisco M. Fernandes</i></p> <p>19.1 Introduction 605</p> <p>19.2 Natural Sol–Gel Materials 606</p> <p>19.2.1 Biogenic Oxides 606</p> <p>19.2.2 Biochemical Conditions of Silica Formation 609</p> <p>19.2.3 Chemical Features of Biogenic Silica 610</p> <p>19.2.3.1 Silica Deposit in Higher Plants 610</p> <p>19.2.3.2 Diatoms Frustule 611</p> <p>19.2.3.3 Sponges Spicule 612</p> <p>19.2.4 Properties and Applications 614</p> <p>19.2.5 Overview 617</p> <p>19.3 Biomimetic Sol–Gel Chemistry 618</p> <p>19.3.1 Chemical Background from Biosilicification Processes 618</p> <p>19.3.1.1 Silaffins 618</p> <p>19.3.1.2 Silicateins 620</p> <p>19.3.2 Silicatein-Derived Biomimetic Sequences: From Proteins to Amino Acids 624</p> <p>19.3.2.1 Enzymes and Peptides 624</p> <p>19.3.2.2 Rational Design 625</p> <p>19.3.3 Silaffins-Derived Biomimetic Sequences Based on Polyamines 628</p> <p>19.3.3.1 Long-Chain Polyamines: Silica Formation and Morphogenesis Control 628</p> <p>19.3.3.2 Short-Chain Amines 629</p> <p>19.3.3.3 R5 Peptide 630</p> <p>19.3.4 Overview 630</p> <p>19.4 Biohybrid Materials from Bioinspired Mineralization Strategies 631</p> <p>19.4.1 Mineralization of Biomacromolecules 632</p> <p>19.4.1.1 Proteins 632</p> <p>19.4.1.2 Polysaccharides 635</p> <p>19.4.1.3 Complex Coacervates 636</p> <p>19.4.2 Mineralization of Microorganisms 637</p> <p>19.4.3 Materials and Devices Based on Biomimetic and Bioinspired Mineralization 638</p> <p>19.4.4 Overview 641</p> <p>19.5 Conclusions 641</p> <p>References 642</p> <p><b>Volume Two: Characterization and Properties of Sol-Gel Materials</b></p> <p><b>Part Three Characterization Techniques for Sol–Gel Materials 651</b></p> <p>20 Solid-State NMR Characterization of Sol–Gel Materials: Recent Advances 653<br /><i>Florence Babonneau, Christian Bonhomme</i></p> <p><b>21 Time-Resolved Small-Angle X-Ray Scattering 673</b><br /><i>Johan E. ten Elshof, Rogier Besselink, Tomasz M. Stawski, Hessel L. Castricum</i></p> <p><b>22 Characterization of Sol–Gel Materials by Optical Spectroscopy Methods 713</b><br /><i>Rui M. Almeida, Jian Xu</i></p> <p><b>23 Properties and Applications of Sol–Gel Materials: Functionalized Porous Amorphous Solids (Monoliths) 745</b><br /><i>Kazuki Nakanishi</i></p> <p><b>24 Sol–Gel Deposition of Ultrathin High-κ Dielectric Films 767</b><br /><i>An Hardy, Marlies K. Van Bael</i></p> <p><b>Part Four Properties 787</b></p> <p><b>25 Functional (Meso)Porous Nanostructures 789</b><br /><i>Andrea Feinle, Nicola Hüsing</i></p> <p><b>26 Sol–Gel Magnetic Materials 813</b><br /><i>Lucía Gutiérrez, Sabino Veintemillas-Verdaguer, Carlos J. Serna, María del Puerto Morales</i></p> <p><b>27 Sol–Gel Electroceramic Thin Films 841</b><br /><i>María Lourdes Calzada</i></p> <p><b>28 Organic–Inorganic Hybrids for Lighting 883</b><br /><i>Vânia Teixeira Freitas, Rute Amorim S. Ferreira, Luis D. Carlos</i></p> <p><b>29 Sol–Gel TiO2 Materials and Coatings for Photocatalytic and Multifunctional Applications 911</b><br /><i>Yolanda Castro, Alicia Durán</i></p> <p>30 Optical Properties of Luminescent Materials 929<br /><i>Sidney J.L. Ribeiro, Molíria V. dos Santos, Robson R. Silva, Édison Pecoraro, Rogéria R. Gonçalves, José Maurício A. Caiut</i></p> <p><b>31 Better Catalysis with Organically Modified Sol–Gel Materials 963</b><br /><i>David Avnir, Jochanan Blum, Zackaria Nairoukh</i></p> <p><b>32 Hierarchically Structured Porous Materials 987</b><br /><i>Ming-Hui Sun, Li-Hua Chen, Bao-Lian Su</i></p> <p><b>33 Structures and Properties of Ordered Nanostructured Oxides and Composite Materials 1031</b><br /><i>María Luz Martínez Ricci, Sara A. Bilmes</i></p> <p><b>Volume Three: Application of Sol-Gel Materials</b></p> <p><b>Part Five Applications 1055</b></p> <p><b>34 Sol–Gel for Environmentally Green Products 1057</b><br /><b>Rosaria Ciriminna, Mario Pagliaro, Giovanni Palmisano</b></p> <p><b>35 Sol–Gel Materials for Batteries and Fuel Cells 1071</b><br /><i>Jadra Mosa, Mario Aparicio</i></p> <p><b>36 Sol–Gel Materials for Energy Storage 1119</b><br /><i>Leland Smith, Ryan Maloney, Bruce Dunn</i></p> <p><b>37 Sol–Gel Materials for Pigments and Ceramics 1145</b><br /><i>Guillermo Monrós</i></p> <p><b>38 Sol–Gel for Gas Sensing Applications 1173</b><br /><i>Enrico Della Gaspera, Massimo Guglielmi, Alessandro Martucci</i></p> <p><b>39 Reinforced Sol–Gel Silica Coatings 1207</b><br /><i>Antonio Julio López, Joaquín Rams</i></p> <p><b>40 Sol–Gel Optical and Electro-Optical Materials 1239</b><br /><i>Marcos Zayat, David Almendro, Virginia Vadillo, David Levy</i></p> <p><b>41 Luminescent Solar Concentrators and the Ways to Increase Their Efficiencies 1281</b><br /><i>Renata Reisfeld</i></p> <p><b>42 Mesoporous Silica Nanoparticles for Drug Delivery and Controlled Release Applications 1309</b><br /><i>Montserrat Colilla, Alejandro Baeza, María Vallet-Regí</i></p> <p>43 Sol–Gel Materials for Biomedical Applications 1345<br /><b>Julian R. Jones</b></p> <p>44 <b>Self-Healing Coatings for Corrosion Protection of Metals 1371</b><br />George Kordas, Eleni K. Efthimiadou</p> <p><b>45 Aerogel Insulation for Building Applications 1385</b><br /><i>Bjørn Petter Jelle, Ruben Baetens, Arild Gustavsen</i></p> <p><b>46 Sol–Gel Nanocomposites for Electrochemical Sensor Applications 1413</b><br /><i>Pengfei Niu, Martí Gich, César Fernández-Sánchez, Anna Roig</i></p> <p>Index 1435</p>