离子液体(共21张PPT)

CatalysiswithIonicLiquids:

ProgressandProspects

YouquanDENG

CentreforGreenChemistryandCatalysis

LanzhouInstituteofChemicalPhysics

ChineseAcademyofSciences

Lanzhou,730000,China

第1页，共21页。1.INTRODUCTION:WhatareionicliquidsRoomtemperatureILscontainorganiccationsandinorganicanions

N-alkylimidazoliumN-alkylpyridiniumquaternaryammonium

quaternaryalkylphosphoniumFunctionalgroupse.g.X=NH2,SO3H,CO2H,etc.incorporateduponthesidechainofImidazolium[CF3COO]-[CF3SO2]-[BF4]-[PF6]-[(CF3SO2)2N]-AirandwaterstableDecreasingcoordinatingabilibityIncreasinghydrophobicitySecondgenerationILsTypicalcations[AlCl4]-[AuCl4]-[PdCl4]2-TypicalanionsReactivetowaterFirstgenerationILsFunctionalILsThirdgenerationILsNew!Chloroaluminate

第2页，共21页。1.INTRODUCTION:PropertiesofionicliquidsLowermeltingpoint:＜-90oCNegligiblevaporpressure:GreensolventsLargeliquidrange

＞200oCSelectivedissolvability:‘liquid’zeoliteDesignable:Acidity,Density,HydrophilityDiversity:overatrillionpossibleGoodelectrechemicalsatbility:E.W.ca5VHighthermalstability>400oCILscontaning1-alkyl-3methylimidazoliumcationsStrongcoulombicforce:MuchdifferentfrommolecularsolventsILspossesssomespecialphysicalandchemicalpropertiesreasonablygoodelectricalconductivity(25mS/cm)第3页，共21页。1.INTRODUCTION:GeneralsituationofILsresearch

ca.

200papershaveappearedonthe226thACSNationalMeeting

HundredspatentsonILshavealsobeenissuedCatalysisOrganicsynthesisSeparation&analysisFunctionalmaterialslifesciencesThefigureillustratesthegrowthinpublicationsonILsAtleastanother500paperswillappearedbytheendof2003TherehasbeenmuchworkperformedonILsasreactionmediaorfunctionalmaterials

Lubricants,sensing&opticalmaterials

StationaryphaseforGC,treatingnuclearwasteElectrochemistryNanotechnologyCleanenergyHeack,Beckmannetc

Nano-metalparticles,filmElectrolytes,Electrodeposition

Electrolytesforsolarcell,batteryArtificialmuscle,drugreservoirs第4页，共21页。1.INTRODUCTION:GeneralresearchsituationofcatalysiswithILsILsascatalystsorreactionmediahavebeenreportedtohaveexcellentperformancesformanycatalyticreactionsCatalyticreactionsusingILsasreactionmediaCatalyticactivityenhanced

SelectivityimprovedEnzymecatalysisCatalyststabilityimprovedILsbiphasicsystemSeparationofdesiredproductsfromreactionwassimplifiedILsusedassubstituteofvolatileorganicsolventsCatalyticreactionmaybecomegreener

第5页，共21页。2.PROGRESS:CatalysiswithILs—BiocatalysisinILsLipase-CatalyzedPolytransesterificationofDVAandBDTheuseofILstoreplaceorganicsolventsinbiocatalyticprocesseshasrecentlygainedmuchattention

J.Am.Chem.Soc.,2003,byA.J.RusselletalPolyesterThefigureillustratesLipasepossesshigheractivityandstabilityinBMIMPF6ILthanthatintetrahydrofuranNoreactionoccurredinthehydrophilicILSinvestigated,egBMIMNO3DVABDNovozym435&porcinepancreaticlipaseintetrahydrofuranNovozym435&porcinepancreaticlipaseinBMIMPF6At50oCinthepresenceofDVAandBD第6页，共21页。2.PROGRESS:CatalysiswithILs—FunctionalILs

Recently,functionalILs,egBronstedacidicILsusedassolvent-catalystweredevelopedJ.Am.Chem.Soc.,2002,byJ.H.Davis,Jr.etalSulfonicacidgroupwasincorporatedSolidacids,duetonon-volatility,arebeingmorewidelyused,buttheyhaveshortcomingsaswellSuchBronstedacidicILhasnegligiblevaporpressure,andissomekindof‘solidlike’liquidacid

Nearly100％ofesterselectivityachieved

Isolationofdesiredproductscanbeobtainedbyasimpledistillation

TheILcouldbereused

SuchBronstedacidicILsisalsoaneffectivecatalystsforesterificationofalkeneswithaceticacid

第7页，共21页。EffectivecatalyticsynthesisofdisubstitutedureasfromaminesandCO2withoutadditionofdehydrationagentoptimalhomogeneouscatalystsystemRh+DMImBF4(D=n-decyl)Step2ReactionAcontinuousrunhasbeencarriedoutoveraperiodof5500h,andbuteneconversionandselectivitywerestableFunctionalmaterialsPureDMImBF4IsolationofdesiredproductscanbeobtainedbyasimpledistillationAnoptimumreactordesignmustbedevelopedquaternaryalkylphosphoniumILphysicallyconfinedintonanoporesofsilicagelasimmobilizedILscatalystRusselletalFlowphenomena,massandheatingtransfer,andreactionkineticsarerequired

Continuous-flowhydromylationinaScCO2-ILbiphasicsystemhasbeensuccessfullyestablished2.PROGRESS:CatalysiswithILs—CombinationwithScCO2

Science,2003,byD.J.Cole-HamiltonAdiagramofcontinuous-flowhydromylationinaScCO2-ILbiphasicsystemHigheraldehydeselectivityHigherratioofthelinear:thebranched

HydroformylationofhexenecatalysedbyRh

catalystSolventCon.%Sel.%1:bBMImPF69915.72:4BMImPF6+scCO24083.56:1第8页，共21页。PROGRESS:CatalysiswithILs—Dimerizationofalkenes

TheInstitutFrancaisduPétrole,IFPlaunchedthefirstcommercialprocessbasedonILs,knownastheDifasolprocess

TypicalDifasolprocess:butenesdimerizationtooctenesbasedonnickel(II)saltinionicliquid.IFPclaimthattheDifasolprocesswasmuchbetterthanotherdimerisationprocessesandwithoutanyothersolventAcontinuousrunhasbeencarriedoutoveraperiodof5500h,andbuteneconversionandselectivitywerestablePhaseseparatorDifasolreactionsectionSeparationofILandproductoccursrapidlyandcompletelyduetoinsolubilityIonicLiquidsinsynthesis,2002,byP.Wasserscheidetal第9页，共21页。2.PROGRESS：CatalysiswithIonicliquidsonlargescaleBASF'SSMARTIL:thefirstcommercialuseoftheILsinanorganicprocess

IntelligentILseparatesaslowerphasefromproductdeprotonation&recycling+++UsingN-methylimidazoletoscavengeacidthatisformedintheprocess.N-methylimidazoleisalsoacatalystHmIm-ClIL,formedduringreaction,separateasaclearliquidphasefromtheproductHmIm-Cl,afterdeprotonation,itcanbedistilledlikeanyotherorganicsolventandcanberecycledSuchprocessisonamultitonscaleinbatchreactorwithoutproducingsolidsManufacturingProcessofalkoxyphenlphosphines

C&ENews,2003,byM.Freemantle第10页，共21页。2.PROGRESS：CatalysiswithIonicliquidsinChina

Ionicliquid-catalystH2O-H2O21.Water/ILbiphasicreactionforbenzeneoxidationtophenolAqueousphaseH2O-H2O2IL+cat+benzeneCat＋IL＋benzeneH2O2phenolH2O-phenolIL＋catalystAschematicshowoftheaqueous/ILbiphasicreactionsystem1.OMImPF6(O=n-Octyl),Fe(O3SC12H25)3andbenzene:insolubleinwater2.OxidationofbenzeneoccurredatinterfacebetweenILandH2O,phenolwasinthewater3.H2O+phenolphasewasseparatedfromILphasebysimpledecantation

phenolreusedSolventCon.%Sel./%OMImPF65499Noionicliquid1671

ResultsofselectiveoxidationofbenzenetophenolaAlmost100%selectivityforphenolwasachievedThewater/ILsystemcouldbereusedGreenChem,2003,byY.Dengetal.Step1ChargingStep2ReactionStep3Separationa.At50℃for6.0h,C6H6/H2O2=1,第11页，共21页。2.ILs+Pdcomplexforcarbonylationofanilinetoaffordcarbamate

intermediatesforisocyanatesbynon-phosgeneroutes

2.PROGRESS：CatalysiswithIonicliquidsinChinaBMImBF4+Pd(1,10-phenanthroline)2+complexcatalystAim:

TodemonstratethatthediversityofILsmayformanoptimalhomogeneouscatalystsystemwithaspecificorganometalliccomplexltssolubilityinILscanbeadjustedthroughtuningtheILs.

Pd(phen)2Cl2isinsolubleinmostoforganicsolvents.

FTRamananalysis:someinteractionbetweenPd(phen)2Cl2andtheILO2MeOHILCon.(%)Sel.(%)TOFMBImBF4

99986104----2.199140ResultsofCarbonylationofanilinetoaffordcarbamateTOFreachedtoca.6100mol·mol-1·h-1,whichismuchhigherthanthatreportedinpreviousliterature.J.Catal.,2003,byY.Dengetal第12页，共21页。2.PROGRESS：CatalysiswithIonicliquidsinChina

3.ElectrochemicalactivationofCO2forthesynthesisofcycliccarbonatesthroughcycloadditionofCO2toepoxidesinILsAschematicshowofthereactionsystemMganodeCucathodeIL+substratePumpCO2gastankResultsofsynthesisofcycliccarbonatesinBMImBF4substrateCon.(%)Sel.(%)propyleneoxide92100epichlorohydrin6386styreneoxide7869Chem.Commun.2002,ByYDengetalGoodtoexcellentresultswereobtained.Thereactionwasconductedunderroomtemperatureandatmosphericpressurewithoutadditionalsupportingelectrolyteandco-catalyst

第13页，共21页。2.PROGRESS：CatalysiswithIonicliquidsinChina

4.EffectivecatalyticsynthesisofdisubstitutedureasinILwithCO2&aminesproductWater+IL+baseAfterreactionAfteraddingwaterSubs.ProductsYields(%)98a9393SymmetricureassynthesiswithCO2andaminesinIL(BMImCl)+CsOHa:thecatalystwasreusedatthethirdtimeEffectivecatalyticsynthesisofdisubstitutedureasfromaminesandCO2withoutadditionofdehydrationagentThecatalyticsystemcouldbereusedafterdistillationofwaterAngew.Chem.In.Edi.,2003,ChinesePatentCN1424310A,byY.DengetalAdditionofH2Ointothemixture,ILandbasewouldtransferintoH2Olayer,thedesiredproductwasprecipitated

H2O第14页，共21页。3.Prospects:CatalysiswithIonicliquids

Theresearchofcatalysisin/withILsisstillinitsearlystage.ThereisstilllargeresearchspaceforcatalysiswithILs.Theneedofgreencatalysisandcuriosityofchemiststothese‘unorthodox’liquidsmaystronglydrivethedevelopmentoftheresearchofILsandcatalysiswithILsDirectionsforpotentialfutureresearchofcatalysiswithILs:第15页，共21页。3.Prospects:Moleculardesign,synthesesandcharacterizationofcatalytictask-specificILs

Computersimulation,andspecificandinsitucharacterizationmethodsforthestudyoftheILsphysicochemicalproperties-catalyticperformancearehighlydesiredFunctionalgroupscanbeincorporateduponsidechainofimidazoliumcation,orotherquaternaryammonium

cationsChiralILsThepictureshowsthatthearrangementofboththechlorideanionsandimidazoliumcations第16页，共21页。3.Prospects:

HomogeneouscatalysisusingILsasreactionmedia

Homogeneouscatalysisofferanumberofimportantadvantagesinwhichreactionmediaplayanimportantrole.UsingILsasreactionmediamay

openupnewpossibilitiesforHomogeneouscatalysis

Foraspecifichomogeneouscatalyticreaction,ILsmayofferanumberofadvantages:ILsmayfunctionas‘soft’supporttoimmobilizeeithermetalcomplexornano-metalparticletoform‘solidlike’liquidcatalystsystem

NanoPtparticlesinBMIMPF6IL

DiversitySimpleseparationSelectivedissolvabilityGreenerreactionmediumNegligiblevaporpressureoptimalhomogeneouscatalystsystemInorganicChemistry2003,byJ.Dupoutetal第17页，共21页。3.Prospects:Developmentof

ImmobilizedILsCatalystsThechemicalindustrystillprefersheterogeneouscatalysts,itisdesirabletominimizetheamountofILsneededforapracticalprocessPreparationofsurfaceanchoredIL

ChemicalbondingofimidazoliumcationtosolidsurfacemaychangepropertiesoftheILs.J.Am.Chem.Soc,2002byJ.PMehnertetalILphysicallyconfinedintonanoporesofsilicagelasimmobilizedILscatalystAddingMetalcomplexornotIonicliquidsSi(OEt)4HCl/EtOH-H2OILsconfinedactascatalystormedia;silicagelwithdesiredsizesofporesandchannelsareusedasnano-reactorwithinletandoutlet.SizeofnanoporesisbigenoughtocontainILs;sizeofchannelissmallenoughtopreventILsfromleaching,butbigenoughforRandPtransport

One-potassemblyofILs,silicateesterviaasol-gelprocess

Thekeyconceptofdesigningsuchcatalystsysteminvolves:

Preparedsample第18页，共21页。PROGRESS:CatalysiswithILs—BiocatalysisinILsquaternaryalkylphosphoniumStep3SeparationDupoutetalDavis,Jr.ILphysicallyconfinedintonanoporesofsilicagelasimmobilizedILscatalystFTRamanspectraofILsconfinedinsilicagelweremarkedlydifferentwithbulkILsintermediatesforisocyanatesbynon-phosgeneroutesElectrolytes,ElectrodepositionNovozym435&porcinepancreaticlipaseintetrahydrofuranepichlorohydrinwithoutadditionalsupportingelectrolyteandco-catalystINTRODUCTION:GeneralresearchsituationofcatalysiswithILsN-methylimidazoleisalsoacatalystincorporateduponthesidechainofImidazolium3.Prospects:DevelopmenyofImmobilizedILscatalysts—PhysicalconfinementofILintonanoporesofsilicagel

PureDMImBF4+DMImBF4/silicagelFTRamanspectraofILsconfinedinsilicagelwerema