Editedby RasmusFehrmann, AndersRiisager,and MarcoHaumann SupportedIonicLiquids RelatedTitles Serp,P.,Philippot,K.(eds.) Gruttadauria,M.,Giacalone,F. Nanomaterials inCatalysis Catalytic Methodsin AsymmetricSynthesis 2013 AdvancedMaterials,Techniques,and ISBN:978-3-527-33124-6 Applications (Alsoavailableindigitalformats) 2011 Zhang,W.,Cue,B.(eds.) ISBN:978-0-470-64136-1 (Alsoavailableindigitalformats) GreenTechniquesforOrganic SynthesisandMedicinal SeriesEditor:Anastas,P. Chemistry VolumeEditors:Leitner,W.,Jessop,P.G., Li,C.-J.,Wasserscheid,P.,Stark,A. 2012 Handbook ofGreen ISBN:978-0-470-71151-4 (Alsoavailableindigitalformats) Chemistry – GreenSolvents Behr,A.,Neubert,P. 3-VolumeSet 2010 AppliedHomogeneous ISBN:978-3-527-31574-1 Catalysis (Alsoavailableindigitalformats) 2012 ISBN:978-3-527-32641-9 Edited by Rasmus Fehrmann, Anders Riisager, and Marco Haumann Supported Ionic Liquids Fundamentals and Applications TheEditors AllbookspublishedbyWiley-VCHare carefullyproduced.Nevertheless,authors, Prof.Dr.RasmusFehrmann editors,andpublisherdonotwarrantthe TechnicalUniversityofDenmark informationcontainedinthesebooks, DepartmentofChemistry includingthisbook,tobefreeoferrors. Building207 Readersareadvisedtokeepinmindthat 2800Kgs.Lyngby statements,data,illustrations,procedural Denmark detailsorotheritemsmayinadvertentlybe inaccurate. Dr.AndersRiisager LibraryofCongressCardNo.:appliedfor TechnicalUniversityofDenmark DepartmentofChemistry Building207 BritishLibraryCataloguing-in-Publication 2800Kgs.Lyngby Data Denmark Acataloguerecordforthisbookisavailable fromtheBritishLibrary. Dr.MarcoHaumann FAUErlangen-Nu¨rnberg Bibliographicinformationpublishedbythe LSfu¨rChem.Reaktionstechnik DeutscheNationalbibliothek Egerlandstr.3 TheDeutscheNationalbibliothek 91058Erlangen liststhispublicationintheDeutsche Germany Nationalbibliografie;detailedbibliographic dataareavailableontheInternetat <http://dnb.d-nb.de>. (cid:2)c 2014Wiley-VCHVerlagGmbH&Co. KGaA,Boschstr.12,69469Weinheim, Germany Allrightsreserved(includingthoseof translationintootherlanguages).Nopart ofthisbookmaybereproducedinany form–byphotoprinting,microfilm,orany othermeans–nortransmittedortranslated intoamachinelanguagewithoutwritten permissionfromthepublishers.Registered names,trademarks,etc.usedinthisbook, evenwhennotspecificallymarkedassuch, arenottobeconsideredunprotectedbylaw. PrintISBN:978-3-527-32429-3 ePDFISBN:978-3-527-65481-9 ePubISBN:978-3-527-65480-2 mobiISBN:978-3-527-65479-6 oBookISBN:978-3-527-65478-9 CoverDesign Formgeber,Mannheim, Germany Typesetting LaserwordsPrivateLimited, Chennai,India PrintingandBinding MarkonoPrintMedia PteLtd,Singapore Printedonacid-freepaper V Contents Preface XV ListofContributors XVII 1 Introduction 1 RasmusFehrmann,MarcoHaumann,andAndersRiisager 1.1 ACenturyofSupportedLiquids 1 1.2 SupportedIonicLiquids 2 1.3 ApplicationsinCatalysis 5 1.4 ApplicationsinSeparation 5 1.5 CoatingofHeterogeneousCatalysts 6 1.6 MonolayersofILonSurfaces 7 1.7 Conclusion 7 References 8 PartI ConceptandBuildingBlocks 11 2 IntroducingIonicLiquids 13 TomWelton 2.1 Introduction 13 2.2 Preparation 13 2.3 LiquidRange 14 2.4 Structures 16 2.4.1 TheLiquid/SolidInterface 17 2.4.2 TheLiquid/GasInterface 19 2.5 PhysicalProperties 20 2.5.1 TheLiquid/SolidInterface 21 2.5.2 TheLiquid/GasInterface 21 2.5.3 Polarity 22 2.5.4 ChromatographicMeasurementsandtheAbrahamModelof Polarity 24 2.5.5 InfiniteDilutionActivityCoefficients 24 2.6 EffectsofIonicLiquidsonChemicalReactions 26 2.7 IonicLiquidsasProcessSolventsinIndustry 29 2.8 Summary 30 References 31 VI Contents 3 PorousInorganicMaterialsasPotentialSupportsforIonicLiquids 37 WilhelmSchwieger,ThangarajSelvam,MichaelKlumpp,and MartinHartmann 3.1 Introduction 37 3.2 PorousMaterials – anOverview 39 3.2.1 History 39 3.2.2 PoreSize 40 3.2.3 StructuralAspects 41 3.2.4 Chemistry 43 3.2.5 Synthesis 43 3.3 Silica-BasedMaterials – Amorphous 48 3.3.1 SilicaGels 48 3.3.2 PrecipitatedSilicas 49 3.3.3 PorousGlass 49 3.4 LayeredMaterials 51 3.5 MicroporousMaterials 52 3.5.1 Zeolites 52 3.5.2 AlPOs/SAPOs 54 3.5.3 HierarchicalPorosityinZeoliteCrystals 55 3.6 OrderedMesoporousMaterials 56 3.6.1 Silica-BasedClassicalCompounds 58 3.6.2 PMOs 60 3.6.3 MesoporousCarbons 61 3.6.4 OtherMesoporousOxides 61 3.6.5 AnodicOxidizedMaterials 62 3.7 StructuredSupportsandMonolithicMaterials 63 3.7.1 MonolithswithHierarchicalPorosity 64 3.7.2 HierarchicallyStructuredReactors 65 3.8 Conclusions 66 References 66 4 SyntheticMethodologiesforSupportedIonicLiquidMaterials 75 ReinoutMeijboom,MarcoHaumann,ThomasE.Mu¨ller,and NormenSzesni 4.1 Introduction 75 4.2 SupportMaterials 76 4.3 PreparationMethodsforSupportedIonicLiquids 77 4.3.1 IncipientWetnessImpregnation 77 4.3.2 Freeze-Drying 79 4.3.3 SprayCoating 80 4.3.4 ChemicallyBoundIonicLiquids 82 4.3.5 IL–SilicaHybridMaterials 89 4.4 Summary 91 References 91 Contents VII PartII SynthesisandProperties 95 5 PoreVolumeandSurfaceAreaofSupportedIonicLiquidsSystems 97 FlorianHeym,ChristophKern,JohannesThiessen,andAndreasJess 5.1 ExampleI:[EMIM][NTf ]onPorousSilica 98 2 5.2 ExampleII:SCILLCatalyst(CommercialNicatalyst)Coatedwith [BMIM][OcSO ] 99 4 Acknowledgments 103 Symbols 104 Abbreviations 104 References 104 6 TransportPhenomena,Evaporation,andThermalStabilityofSupported IonicLiquids 105 FlorianHeym,ChristophKern,JohannesThiessen,andAndreasJess 6.1 Introduction 105 6.2 DiffusionofGasesandLiquidsinILsandDiffusivityofILsin Gases 106 6.2.1 DiffusivityofGasesandLiquidsinILs 106 6.2.2 DiffusionCoefficientofEvaporatedILsinGases 108 6.3 ThermalStabilityandVaporPressureofPureILs 109 6.3.1 DrawbacksandOpportunitiesRegardingStabilityandVaporPressure MeasurementsofILs 109 6.3.2 ExperimentalMethodstoDeterminetheStabilityandVaporPressure ofILs 110 6.3.3 DataEvaluationandModelingMethodology 110 6.3.3.1 EvaluationofVaporPressureandDecompositionofILsbyAmbient PressureTGatConstantHeatingRate 110 6.3.3.2 EvaluationofVaporPressureofILsbyHighVacuumTG 114 6.3.4 VaporPressureDataandKineticParametersofDecompositionof PureILs 116 6.3.4.1 KineticDataofThermalDecompositionofPureILs 116 6.3.4.2 VaporPressureofPureILs 116 6.3.5 GuidelinestoDeterminetheVolatilityandStabilityofILs 118 6.3.6 CriteriafortheMaximumOperationTemperatureofILs 118 6.3.6.1 MaximumOperationTemperatureofILswithRegardtoThermal Decomposition 118 6.3.6.2 MaximumOperationTemperatureofILswithRegardto Evaporation 120 6.4 VaporPressureandThermalDecompositionofSupportedILs 120 6.4.1 ThermalDecompositionofSupportedILs 121 6.4.2 MassLossofSupportedILsbyEvaporation 123 6.4.2.1 EvaporationofILsCoatedonSilica(SILP-System) 123 6.4.2.2 EvaporationofILsCoatedonaNi-Catalyst(SCILL-System) 132 6.4.2.3 EvaluationofInternalSurfaceAreabytheEvaporationRateof SupportedILs 132 VIII Contents 6.4.3 CriteriafortheMaximumOperationTemperatureofSupported ILs 134 6.4.3.1 MaximumOperationTemperatureofSupportedILswithRegardto ThermalStability 134 6.4.3.2 MaximumOperationTemperatureofSupportedILswithRegardto Evaporation 135 6.5 Outlook 137 Acknowledgments 138 Symbols 138 Abbreviations 140 References 140 7 IonicLiquidsattheGas–LiquidandSolid–LiquidInterface – CharacterizationandProperties 145 ZlataGrenobleandStevenBaldelli 7.1 Introduction 145 7.2 CharacterizationofIonicLiquidSurfacesbySpectroscopic Techniques 146 7.2.1 TypesofInterfacialSystemsInvolvingIonicLiquids 146 7.2.2 OverviewofSurfaceAnalyticalTechniquesforCharacterizationof IonicLiquids 146 7.2.3 StructuralandOrientationalAnalysisofIonicLiquidsatthe Gas–LiquidInterface 147 7.2.3.1 PrinciplesofSum-FrequencyVibrationalSpectroscopy 147 7.2.4 Cation-SpecificIonicLiquidOrientationalAnalysis 148 7.2.5 Anion-SpecificIonicLiquidOrientationalAnalysis 154 7.2.6 IonicLiquidInterfacialAnalysisbyOtherSurface-Specific Techniques 157 7.2.7 IonicLiquidEffectsonSurfaceTension 162 7.2.8 IonicLiquidEffectsonSurfaceChargeDensity 163 7.3 OrientationandPropertiesofIonicLiquidsattheSolid–Liquid Interface 165 7.3.1 SurfaceOrientationalAnalysisofIonicLiquidsonDrySilica 165 7.3.2 CationOrientationalAnalysis 166 7.3.3 AlkylChainLengthEffectsonOrientation 167 7.3.4 CompetingAnionsandCo-adsorption 168 7.3.5 ComputationalSimulationsofIonicLiquidonSilica 168 7.3.6 IonicLiquidsonTitania(TiO ) 170 2 7.4 Comments 172 References 173 8 SpectroscopyonSupportedIonicLiquids 177 PeterS.Schulz 8.1 NMR-Spectroscopy 178 8.1.1 SpectroscopyofSupportandIL 178