教你如何设计催化剂Kung课件

TowardsTotalDesignofHeterogeneousCatalystsHaroldH.KungChemicalEngineeringDepartmentNorthwesternUniversityEvanston,IL60208-3120October13,2003Whatwouldoneliketoaccomplishintotalcatalystsynthesis?ShapeofthecavityPathtocavityAbilitytodesignandpositionancillarygroupsCompleteatomiccontrolofactivesite(metal,oxide)MetalCrystalliteCatalyticActivePhaseSurfacearrangementofatomsCompositionNatureofsupportLocationofcrystalliteonsupport(defectsites)StructuresensitivityElectroniceffect

LigandeffectSize-selectiveclusterbeamdepositionofAunclustersonMgOHeiz,Sanchez,Abbet,Schneider,Chem.Phys.262(2000)189.MSsignalofC16O18OinTPDafterexposureto18O2andthenCOAaronS.Eppler,

GüntherRupprechter,

LászlóGuczi,

andGaborA.Somorjai,J.Phys.Chem.B101(1997)9973.ArrayofPtonsilicaDepositionofmetalclustersusinglithographyInsufficientcontrolofshape,exactsize,andatomlocations;currentlimitonsmallestsizeachieved.P-SO32-+Mn+(aq)→P-SO32-Mn+P-SO32-Mn++NaBH4→P-SO32-/MoPreparationofuniformsizedmetalparticlesusingfunctionalresinsCorain,Centomo,FerrariMeyer-Zaika,Schmid,Gold2003,October2003.AlAlORORROROROORNRH2H2OOH2RNAlAlOOOH2RNStrategy:useamine(Lewisbase)topreserveLewisacidity.AlORNRH2RORO2monomerCanmakemonomerAmineprotectionisretainedFinalsolidanactivecatalystKozlov,Kung,Xue,andKung,Angew.Chem.Int.Ed.42(2003)2415Conversionofcyclopenteneoxideinreactionwithpiperidinecatalyzedbyvariousaluminas.●PPD-Al2O3,◊SG-Al2O3-200,○SG-Al2O3-500-H2O-200,▲SG-Al2O3-500-H2O,ΔPA-Al2O3-500-H2O-200■PA-Al2O3-500-H2O,□blank.Xue,Kung,Kozlov,Popp,andKung,Catal.Today,2003.Generationofactivesitebybuildingonawell-definedstructure001203cJ.M.Thomas,etal.Nature398(1999)227;Angew.Chem.Int.Ed.39(2000)2310.Hexane()OxidationTwoCo(III)ionsinCoAlPO-18atthedesireddistanceapartinCo/P=0.1samples.CoAlPO-36oflargerporestructureandshape,producesmuchmore3-oland3-one.ImportanceincontrollingrelativelocationofsitesRajaandThomas,J.Molec.Catal.181(2002)3Metal-OxygenBackboneofDesignedSequenceandStructureOSiMMoleculartemplating:A.KatzandM.E.Davis,Nature403(2000)286.Introducefunctionalgroupsatspecificlocationsinthecavity.Moleculesdiffusethroughsilicawallintoandoutofcavity.PreparingsiteswithpredeterminedspacingDufaudandDavis,JACS125(2003)9403Whatwouldoneliketoaccomplishintotalcatalystsynthesis?ShapeofthecavityPathtocavityAbilitytodesignandpositionancillarygroupsCompleteatomiccontrolofactivesiteEliminatedporediffusioncontrol,Littleshapeselectivity.A.Corma,U.Diaz,M.E.Domine,V.Fornés,Angew.Chem.Int.Ed.39(2000)1499.(h00)K.PolbornandK.Severin,Chem.Commun.(1999)2481-2482.MolecularImprintingCat.4madefrom2;controlcat.5madefrom1Figure1Molecularmodelofendoclucanase12AandschematicmodeloftheDMAAm-enzymemolecularswitch.TheredresiduesrepresentthecatalyticglutamicacidsidechainsattheactivesiteofEG12A,thegreenresidueistheAsn55position,thepurpleresidueistheSer25position,andtheN-terminusisrepresentedasthebluecircle.TsuyoshiShimoboji,

EdmundLarenas,

TimFowler,

AllanS.Hoffman,*

and

PatrickS.Stayton*

BioconjugateChem.,

14(3),517-525,2003Figure4CharacterizationofONPCenzymeactivitiesforfreeDMAAm-EG12Aconjugatesinsolutionatasfunctionofpolymersizeandconjugationsite.Theenzymeactivitiesweremeasuredfor100nMconjugatesusingONPC(8mM)asasubstrateandnormalizedtotheactivityofN55CorS25CEG12Acontrolsas100%ateachtemperature.EG12A-M10,10kDaDMAAm-EG12Aconjugate;EG12A-M6,6kDaDMAAm-EG12Aconjugate;EG12A-M3,3kDaDMAAm-EG12Aconjugate;andEG12A+M10,physicalmixtureofenzymeplus10kDaDMAAm.TsuyoshiShimoboji,

EdmundLarenas,

TimFowler,

AllanS.Hoffman,*

and

PatrickS.Stayton*

BioconjugateChem.,

14(3),517-525,2003J.Rebek,Jr.Acc.Chem.Res.17(1984)258V.Balzani,A.Credi,F.M.Raymo,J.F.Stoddart,Angew.ChemieInt.Ed.39(2000)3348pH-DriventranslocationofNi(II)ionAmendola,Fabbrizzi,Mangano,Pallavicini,Acc.Chem.Res.34(2001)488.Translocationofmetalionissignaledbyquenching/revivaloftheemissionoffluorescentprobe(anthracenesubstituent)Mesoporousbenzene-silicaS.Inagakietal,Nature,416(2002)304Single-walledcarbonnanotubeSingle-walledmetal-oxygennanotubeControlofnanoreactorwallpropertiesM.C.Kung3-DMacroporousmaterialAfterR.C.Schroden,C.F.Blanford,B.J.Melde,B.J.S.Johnson,A.Stein,Chem.Mater.13(2001)1074.Dr.AhnSynthesisofwaferswithahighdensityofmicronsizestraightchannelsConclusion: