Editedby DavidLevyand MarcosZayat TheSol-GelHandbook Related Titles Kickelbick,G.(ed.) Ruiz-Hitzky,E.,Ariga,K.,Lvov,Y.M.(eds.) HybridMaterials Bio-inorganicHybridNanomaterials Synthesis,Characterization,andApplications Strategies,Syntheses,Characterizationand Applications SecondEdition 2015 2008 PrintISBN:978-3-527-33844-3(Alsoavailableina PrintISBN:978-3-527-31718-9(Alsoavailableina varietyofelectronicformats) varietyofelectronicformats) Liu,X.Y.,Li,J.L.(eds.) Tadros,T.F.(ed.) SoftFibrillarMaterials Self-OrganizedSurfactantStructures FabricationandApplications 2011 2013 PrintISBN:978-3-527-31990-9(Alsoavailableina PrintISBN:978-3-527-33162-8(Alsoavailableina varietyofelectronicformats) varietyofelectronicformats) Tadros,T.F. Tadros,T.F.(ed.) 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DerivedNanomaterials DispersionofPowders InLiquidsandStabilizationofSuspensions 2009 PrintISBN:978-0-470-72117-9(Alsoavailableina 2012 varietyofelectronicformats) PrintISBN:978-3-527-32941-0(Alsoavailableina Hamley,I.W. varietyofelectronicformats) IntroductiontoSoftMatter SyntheticandBiologicalSelf-Assembling Materials 2007 PrintISBN:978-0-470-51609-6(Alsoavailableina varietyofelectronicformats) Edited by David Levy and Marcos Zayat The Sol-Gel Handbook Volume 1: Synthesis and Processing Volume 2: Characterization and Properties of Sol-Gel Materials Volume 3: Application of Sol-Gel Materials TheEditors AllbookspublishedbyWiley-VCHarecarefully produced.Nevertheless,authors,editors,and Prof.DavidLevy publisherdonotwarranttheinformationcontained Inst.CienciadeMateriales inthesebooks,includingthisbook,tobefreeof deMadrid,ICMM-CSIC errors.Readersareadvisedtokeepinmindthat SorJuanaInesdelaCruz3 statements,data,illustrations,proceduraldetailsor 28049Madrid otheritemsmayinadvertentlybeinaccurate. Spain LibraryofCongressCardNo.:appliedfor Dr.MarcosZayat BritishLibraryCataloguing-in-PublicationData Inst.CienciadeMateriales Acataloguerecordforthisbookisavailablefromthe deMadrid,ICMM-CSIC BritishLibrary. SorJuanaInesdelaCruz3 28049Madrid Bibliographicinformationpublishedbythe Spain DeutscheNationalbibliothek TheDeutscheNationalbibliothekliststhis publicationintheDeutscheNationalbibliografie; detailedbibliographicdataareavailableonthe Internetat<http://dnb.d-nb.de>. 2015Wiley-VCHVerlagGmbH&Co.KGaA, Boschstr.12,69469Weinheim,Germany Allrightsreserved(includingthoseoftranslation intootherlanguages).Nopartofthisbookmaybe reproducedinanyform–byphotoprinting, microfilm,oranyothermeans–nortransmittedor translatedintoamachinelanguagewithoutwritten permissionfromthepublishers.Registerednames, trademarks,etc.usedinthisbook,evenwhennot specificallymarkedassuch,arenottobeconsidered unprotectedbylaw. PrintISBN:978-3-527-33486-5 ePDFISBN:978-3-527-67084-0 ePubISBN:978-3-527-67083-3 MobiISBN:978-3-527-67082-6 oBookISBN:978-3-527-67081-9 Typesetting ThomsonDigital,Noida,India PrintingandBinding MarkonoPrintMediaPte Ltd,Singapore Printedonacid-freepaper V Contents Preface XXXI ListofContributors XXXIII VolumeOne: SynthesisandProcessing PartOne Sol–GelChemistryandMethods 1 1 ChemistryandFundamentalsoftheSol–GelProcess 3 UlrichSchubert 1.1 Introduction 3 1.2 HydrolysisandCondensationReactions 4 1.2.1 Silica-BasedMaterials 4 1.2.1.1 Precursor(s) 9 1.2.1.2 Catalyst(pH) 9 1.2.1.3 AlkoxoGroup/H ORatio(R ) 9 2 w 1.2.1.4 Solvent 10 1.2.1.5 Electrolytes 10 1.2.2 MetalOxide-BasedMaterials 11 1.3 Sol–GelTransition(Gelation) 17 1.3.1 HydrolyticSol–GelProcesses 17 1.3.2 NonhydrolyticSol–GelProcesses 22 1.3.3 Inorganic–OrganicHybridMaterials 22 1.4 AgingandDrying 24 1.5 PostsynthesisProcessing 26 1.6 ConcludingRemarks 26 References 27 2 NonhydrolyticSol–GelMethods 29 RupaliDeshmukhandMarkusNiederberger 2.1 Introduction 29 2.2 NonaqueousSol–GelRoutestoMetalOxideNanoparticles 31 2.2.1 Surfactant-AssistedSynthesis 31 VI Contents 2.2.2 Solvent-ControlledSynthesis 33 2.2.2.1 BenzylAlcoholRoute 33 2.2.2.2 tert-ButylAlcoholRoute 37 2.2.2.3 EtherRoute 37 2.2.2.4 AcetophenoneRoute 38 2.2.2.5 CarboxylicAcidRoute 39 2.2.2.6 BenzylamineRoute 39 2.2.3 Microwave-AssistedSynthesis 40 2.3 NonaqueousSol–GelSynthesisbeyondMetalOxides 43 2.3.1 Composites 43 2.3.2 Organic–InorganicHybridMaterials 44 2.3.3 MetalSulfides 46 2.3.4 Metals 47 2.4 ChemicalReactionandCrystallizationMechanisms 48 2.4.1 Introduction 48 2.4.2 OverviewoftheMainChemicalReactions 49 2.4.3 ClassicalandNonclassicalCrystallizationMechanisms 51 2.4.4 SelectedExamples 51 2.5 AssemblyandProcessing 56 2.5.1 Introduction 56 2.5.2 NanoparticleArraysandSuperlattices 57 2.5.3 OrientedAttachmentandMesocrystals 59 2.5.4 Films 60 2.6 SummaryandOutlook 63 References 63 3 IntegrativeSol–GelChemistry 71 M.Depardieu,N.Kinadjian,D.Portehault,R.Backov,andClémentSanchez 3.1 Introduction 71 3.2 Designof0DStructures 72 3.2.1 AerosolProcessing 72 3.2.2 Capsules 75 3.2.2.1 SimpleEmulsionsPreparation 76 3.2.2.2 MineralizationoftheWaxDispersion 76 3.2.2.3 Temperature-TriggeredRelease 77 3.2.2.4 IntroducingaHydrophilicCompartment 79 3.2.2.5 Water@Wax@WaterEmulsionFormulation 80 3.2.2.6 Water@Wax@WaterEmulsionMineralization 80 3.2.2.7 Temperature-TriggeredRelease 81 3.2.2.8 Wax@Water@OilEmulsionFormulation 83 3.2.2.9 Wax@Water@OilEmulsionMineralization 84 3.2.2.10 Temperature-TriggeredRelease 85 3.3 Designof1DMacroscopicStructures 88 3.3.1 Electrospinning 89 3.3.1.1 AFirstCase:TiO FibersforDye-SensitizedSolarCells 89 2 Contents VII 3.3.1.2 CouplingSol–GelReactionsandElectrospinning 90 3.3.2 Extrusion 93 3.3.2.1 V O FibersasAlcoholSensor 94 2 5 3.3.2.2 CompositeFibersPreparedwiththeHelpofPolymerDehydration/ Reticulation 96 3.4 DesignofExtended2DStructures 99 3.5 DesignofExtended3DStructures 99 3.5.1 Foams 99 3.5.1.1 SilicaFoams:Si-(HIPE) 101 3.5.1.2 Eu3+@Organo-Si-(HIPE):PhotonicProperties 101 3.5.1.3 Pd@Organo-Si-(HIPE):CyclingHeckCatalysisReactions 103 3.5.1.4 Enzyme@Organo-Si-(HIPE):HighEfficiencyBiocatalysts 104 3.5.1.5 Si-(HIPE)asHardTemplatetoCarbonaceousFoamsand Applications 106 3.5.1.6 Carbon-(HIPE)asLiIonNegativeElectrodes 107 3.5.1.7 LiBH4@Carbon-(HIPE)forHydrogenStorageandRelease 107 3.5.2 Aerogels 112 3.5.3 DenseNanostructuredMonoliths 112 3.6 Conclusions 113 References 115 4 SyntheticSelf-AssemblyStrategiesandMethods 121 AlexandraZamboulis,OlivierDautel,andJoëlJ.E.Moreau 4.1 Introduction 121 4.2 TemplatedSynthesisofInorganicMaterials 122 4.2.1 Self-AssemblyofMesoporousSilicas 123 4.2.2 HydrothermalRearrangementandPostsynthesisTreatment 125 4.2.3 Self-AssemblyofThinFilms 126 4.2.4 Self-AssemblyofFunctionalizedMesoporousSilicas 127 4.3 Self-AssembledOrganosilicas 128 4.3.1 ControlofthePoreStructure:TemplatedSynthesisofMesoporous BridgedSilsesquioxanes 129 4.3.2 Self-OrganizedOrganosilicas 132 4.3.3 Self-AssemblySyntheticStrategiesforOrganosilicaswithOptical Properties 139 4.3.3.1 TowardanH-Aggregation/CardPackStacking 141 4.3.3.2 FromaJ-toanH-Aggregation 149 4.3.3.3 TranscriptionoftheJ-AggregationfromthePrecursortothe Material 153 4.4 Conclusions 154 References 154 5 ProcessingofSol–GelFilmsfromaTop-DownRoute 165 PlinioInnocenziandLucaMalfatti 5.1 Introduction 165 VIII Contents 5.2 Top-DownProcessingbyUVPhotoirradiation 167 5.2.1 UVCuringofOxides 167 5.2.2 UVCuringofHybridSol–GelFilms 169 5.2.3 UVPhotoirradiationofMesoporousFilms 170 5.2.4 NanocompositeSo–GelFilmsbyUVPhotoirradiation 173 5.3 LaserIrradiationandWriting 174 5.3.1 Thermal-InducedEffects 174 5.3.2 Laser-InducedMicrofabrication 175 5.3.3 NanofabricationbyTwo-orMultiphotonAbsorption 177 5.4 ElectronBeamLithography 178 5.5 Top-DownProcessingbyHardX-Rays 181 5.6 SoftX-RayLithography 184 References 186 6 Sol–GelPrecursors 195 VadimG.Kessler 6.1 Introduction 195 6.2 SimpleSiliconAlkoxides 196 6.3 FunctionalandMixedLigandSiliconAlkoxidesforMoreFacile Hydrolysis 197 6.4 FunctionalSiliconAlkoxides:PrecursorsofHybridMaterials 198 6.5 SimpleMetalAlkoxides 200 6.5.1 CommerciallyAvailableSimpleMetalAlkoxide 202 6.5.2 CustomarySynthesisofMetalAlkoxidePrecursors 209 6.5.2.1 InteractionofMetalswithAlcohols 209 6.5.2.2 AlcoholysisofComplexesDerivedfromVolatileAcidsWeakerThan Alcohols 209 6.5.2.3 BasicAlcoholysisofMetalHalides:MetathesisReaction 210 6.5.2.4 AlcoholysisofMetalOxides 210 6.5.2.5 ElectrochemicalOxidationofMetalsinAlcohols 211 6.5.2.6 AlcoholInterchangeReaction 211 6.6 FunctionalandMixedLigandMetalAlkoxidesforMoreFacile HydrolysisandStabilizationofResultingColloids 212 6.7 PrecursorandSolventChoiceforNonhydrolyticSol–GelProcesses 213 6.8 SynthesisofComplexMaterials:Single-SourcePrecursorApproach 214 6.9 Sol–GelPrecursorsforSpecialApplications:Biomedicaland Luminescent 215 Abbreviations 216 References 216 PartTwo Sol–GelMaterials 225 7 NanoparticlesandComposites 227 GuidoKickelbick 7.1 Introduction 227