如何设计催化剂

如何设计催化剂第1页/共35页Whatwouldoneliketoaccomplishintotalcatalystsynthesis?ShapeofthecavityPathtocavityAbilitytodesignandpositionancillarygroupsCompleteatomiccontrolofactivesite(metal,oxide)第2页/共35页MetalCrystalliteCatalyticActivePhaseSurfacearrangementofatomsCompositionNatureofsupportLocationofcrystalliteonsupport(defectsites)StructuresensitivityElectroniceffectLigandeffect第3页/共35页MetalclustersderivedfrommetalcarbonylcomplexesBCGatesJ.Molec.Catal.AChem163(2000)55Os5ConMgOIr4inzeolite第4页/共35页Size-selectiveclusterbeamdepositionofAunclustersonMgOHeiz,Sanchez,Abbet,Schneider,Chem.Phys.262(2000)189.MSsignalofC16O18OinTPDafterexposureto18O2andthenCO第5页/共35页AaronS.Eppler,

GüntherRupprechter,

LászlóGuczi,

andGaborA.Somorjai,J.Phys.Chem.B101(1997)9973.ArrayofPtonsilicaDepositionofmetalclustersusinglithographyInsufficientcontrolofshape,exactsize,andatomlocations;currentlimitonsmallestsizeachieved.第6页/共35页P-SO32-+Mn+(aq)→P-SO32-Mn+P-SO32-Mn++NaBH4→P-SO32-/MoPreparationofuniformsizedmetalparticlesusingfunctionalresinsCorain,Centomo,FerrariMeyer-Zaika,Schmid,Gold2003,October2003.第7页/共35页Controlofsurfacecoordinativeunsaturationsitesofaluminumoxide(Al2O3)bysynthesisActivesitesaresurfaceexposedAlions(Lewisacidsites).AlOAlOOAlOOOActivesite第8页/共35页AlAlORORROROROORNRH2H2OOH2RNAlAlOOOH2RNStrategy:useamine(Lewisbase)topreserveLewisacidity.AlORNRH2RORO2monomerCanmakemonomerAmineprotectionisretainedFinalsolidanactivecatalystKozlov,Kung,Xue,andKung,Angew.Chem.Int.Ed.42(2003)2415第9页/共35页Conversionofcyclopenteneoxideinreactionwithpiperidinecatalyzedbyvariousaluminas.●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.第10页/共35页Generationofactivesitebybuildingonawell-definedstructure第11页/共35页第12页/共35页第13页/共35页第14页/共35页001203cJ.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)3第15页/共35页29SiNMRof(Si-O)noligomerunitsAtom-by-AtomSynthesisofMetal-OxygenChainChang,Kung,andKung,Chem.Comm.submittted.第16页/共35页Metal-OxygenBackboneofDesignedSequenceandStructureOSiM第17页/共35页Moleculartemplating:A.KatzandM.E.Davis,Nature403(2000)286.Introducefunctionalgroupsatspecificlocationsinthecavity.Moleculesdiffusethroughsilicawallintoandoutofcavity.第18页/共35页PreparingsiteswithpredeterminedspacingDufaudandDavis,JACS125(2003)9403第19页/共35页Table3.SynthesisofBisphenolAwithSulfonicAcidFunctionalizedSBA-15Silicasandpara-TolueneSulfonicAcida

persiteyieldofbisphenolAbp,p'/o,p'molarratiocatalystfunctionalgroupGCcNMRdGCcNMRd

para-toluenesulfonicacidCH3aryl-SO3H362922.61-propanesulfonicacidCH3CH2CH2-SO3H9.6e

n.d.f

1.8e

n.d.11·SBA[Si]-CH2CH2aryl-SO3H131133.09·SBA[Si]-propyl-SO3H8.88.4106.410·SBA[Si]-propyl-SO3HHO3S-propyl-[Si]1818128.3VéroniqueDufaud*

andMarkE.Davis*,J.Am.Chem.Soc.,125(31),9403-9413,2003第20页/共35页Whatwouldoneliketoaccomplishintotalcatalystsynthesis?ShapeofthecavityPathtocavityAbilitytodesignandpositionancillarygroupsCompleteatomiccontrolofactivesite第21页/共35页Eliminatedporediffusioncontrol,Littleshapeselectivity.A.Corma,U.Diaz,M.E.Domine,V.Fornés,Angew.Chem.Int.Ed.39(2000)1499.(h00)第22页/共35页K.PolbornandK.Severin,Chem.Commun.(1999)2481-2482.MolecularImprintingCat.4madefrom2;controlcat.5madefrom1第23页/共35页RPRPActiveAtrestMolecularhingestocontrolaccessibilityofactivesites第24页/共35页Figure1Molecularmodelofendoclucanase12AandschematicmodeloftheDMAAm-enzymemolecularswitch.TheredresiduesrepresentthecatalyticglutamicacidsidechainsattheactivesiteofEG12A,thegreenresidueistheAsn55position,thepurpleresidueistheSer25position,andtheN-terminusisrepresentedasthebluecircle.TsuyoshiShimoboji,

EdmundLarenas,

TimFowler,

AllanS.Hoffman,*

and

PatrickS.Stayton*

BioconjugateChem.,

14(3),517-525,2003第25页/共35页Figure4CharacterizationofONPCenzymeactivitiesforfreeDMAAm-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),517-525,2003第26页/共35页MolecularSwitchingviaRedoxReductionbyascorbicacidOxidationwithammoniumpersulfateConformationalchangemonitoredbycirculardichroismS.ZahnandJ.W.Canary,Angew.Chem.Int.Ed.37(1998)305-第27页/共35页V.Balzani,A.Credi,F.M.Raymo,J.F.Stoddart,Angew.ChemieInt.Ed.39(2000)3348第28页/共35页J.Rebek,Jr.Acc.Chem.Res.17(1984)258V.Balzani,A.Credi,F.M.Raymo,J.F.Stoddart,Angew.ChemieInt.Ed.39(2000)3348第29页/共35页pH-DriventranslocationofNi(II)ionAmendola,Fabbrizzi,Mangano,Pallavicini,Acc.Chem.Res.34(2001)488.Translocationofmetalionissignaledbyquenching/revivaloftheemissionoffluorescentprobe(anthracenesubstituent)第30页/共35页Mesoporousbenzene-silicaS.Inagak