1001-3555201204-0366-102012-02-262012-07-28.1983.Emaillicpcas@gmail.com.*Emailxlwang@lzb.ac.cn.ERC730000O643.32A1HeteropolyacidPolyoxometalate-....12..MO6MO4、、..11∶12Keggin.XM12O40n-X=PSiGeM=WMoPW12O403-SiW12O404-PMo12O403-1a22∶18Dawson.X2M18O62n-X=MoWM=PAsKeggin.1b3.cd.4.efγ-Kegginsandwich.1Fig.1Structureofheteropolyanions1..2..3.“”.4.、、、.264Vol.26No.420128JOURNALOFMOLECULARCATALYSISCHINAAug.20125...2070..2、、、3....、B、、H3PW12O40PW12>H4PW11VO40>H3PMo12O40PMo12~H4SiW12O40SiW12>H4PMo11VO40~H4SiMo12O40SiMo12>>HClHNO3.MoWV.Misonosurface-typebulk-typeIandII2.POM..I.IIeII+.IIIPOM..2Fig.2Modelofsruface-typeandbulk-typeIandII2.1.、4.Radbil56-.Sil-va7.8、14-9.10DRIFTS..2.2、、.KegginDawson..B..SiO211121314ZrO21516177634.Dias18H3PW12O40NbOH2n+H3-nPW12O40n-3H3PW12O40B.19MOF.Cu3BTC2MOF.POM/Cu3BTC2.、.MOF.3aCu3BTC2bH3PW12O40Fig.3athetunnelstructureofCu3BTC2bImmobilizedH3PW12O40inthetunnelJohanA.Martens20HPW/Cu3BTC2HPW/Cu3BTC2.HPW/Cu3BTC2Y...21、Keggin.110℃..4Fig.4POMmodifiedILscatalyst.1422-28.Zieba29MxH3-xPW12O40M=KorCsx=22.5and3.K2K2.30/PyBS3PW12O40.2.3、、Friedel-Crafts.SnO2H3PW12O4031、3233Friedel-Crafts863265Fig.5HPAsaltscatalyzedesterexchangereaction34.Nikunj35γ-Al2O3pw12Friedel-Crafts.36.α-37-394041.2.4BrnstedL.Ferreira42SiO297%.Castanheiro42-.H3PW12O40>H4SiW12O40>H4PMo12O40>H4SiMo12O40.98%.6Fig.6ImobilizedheteropolyacidcatalyzedacetalizationAkihiro43γ-SiW10O32H2O22l-O24-Knovenagel96%6LewisH+Brnsted.7γ-SiW10O32H2O22l-O24-KnovenagelFig.7γ-SiW10O32H2O22l-O24-catalyzedKnovenagelreaction.4420∶1dr99%ee../.8Fig.8ChiralityammoniumsaltofPOM4598%99.9%...9Fig.9POMammoniumsaltcatalyzedPrinsreaction2.5Emma46γ-SiW10O36Cu2N326-97%TON100000..TON.4713-48Hosomi-Sakurai4950.963410γ-SiW10O36Cu2N326-Fig.10γ-SiW10O36Cu2N326-catalyzedcyclopropanationreaction3Keggin..、、、.....3.1C-H.MirkhaniSchiffFeCu5152..Mizuno53..Neumann54-57.Mostafa58Daw-sonα2-K8HP2V3W15O62..Cavaleiro59SandwichM4H2O2PW9O342M=CoMnandFe.FeTON.3.260-64.Mizuno65gamma-SiW10O368-99%99%.66..-.11Fig.11SynthesisofPOM/ILnanosphereGhamati67.98%.3.368-71.Neu-07326man72sandwichPdⅡPd-POMPdCl20.5Q12WZn3H2O2ZnW9O342.....Mizuno73γ-KegginZnacac2sandwich...12ZnsandwichFig.12ZncoordinatedSandwichtypyPOM3.4Corma74Heck.60..13Fig.13POM/LDHcatalyzedhydroxylreaction75H3PW12O401-.....14a.bFig.14asynthesisofnanowireboxdationofsulfurtosulphone76.K6PW9V3O40·4H2O1734..15K6PW9V3O40·4H2OFig.15K6PW9V3O40·4H2O/PyridineN-oxidesystem77787980.4、.1..2.、..3..1KozhevnikovIV.Catalysisbyheteropolyacidsandmulti-componentpolyoxometalatesinliquid-phasereactionsJ.ChemicalReviews1998981171-1982WeinstockIA.Homogeneous-phaseelectron-transferre-actionsofpolyoxometalatesJ.ChemicalReviews1998981113-1703CormaA.Inorganicsolidacidsandtheiruseinacid-cata-lyzedhydrocarbonreactionsJ.ChemicalReviews1995953559-6144MisonoM.Heterogeneouscatalysisbyheteropolycom-poundsofmolybdenumandtungstenJ.CatalysisRe-views-ScienceandEngineering1987292-3269-3215Radbil'ABetal.CamphenehydrationcatalyzedbyheteropolyacidsJ.RussianJournalofAppliedChemis-try2000732253-2566Radbil'ABetal.Acid-catalyzedalkoxylationandhy-drationofcampheneJ.RussianJournalofOrganicChemistry200036111618-16227daSilvaKAKozhevnikovIVGusevskayaEV.Hy-drationandacetoxylationofcamphenecatalyzedbyheteropolyacidJ.JournalofMolecularCatalysisa-Chemical20031921-2129-1348AlhanashAKozhevnikovaEFKozhevnikovIV.Gas-phasedehydrationofglyceroltoacroleincatalysedbycae-siumheteropolysaltJ.AppliedCatalysisa-General2010378111-189OnoY.Heteropolyacidcatalysis-auniqueblendofacid-baseandredoxpropertiesJ.PerspectCatal1992431-46410ChengLMYeXP.ADRIFTSStudyofCatalyzedDe-hydrationofAlcoholsbyAlumina-supportedHeteropolyAcidJ.CatalysisLetters20091301-2100-10711YamamotoYetal.DirectadditionofaceticacidtoethylenetoformethylacetateinthepresenceofH4SiW12O40/SiO2J.AppliedCatalysisa-General20083441-255-6012SopaAetal.Ethanetoaceticacidoxidationoversup-portedheteropolyacidsJ.AppliedCatalysisa-General20052851-2119-12513KostovaNGetal.MechanochemicalapproachforpreparationofMo-containingbeta-zeoliteJ.JournalofPhysicsandChemistryofSolids2007685-61169-117214BrahmkhatriVPatelA.12-Tungstophosphoricacidan-choredtoSBA-15Anefficientenvironmentallybenignreusablecatalystsforbiodieselproductionbyesterifica-tionoffreefattyacids.AppliedCatalysisa-General20114031-2161-17215SakthivelRKemnitzE.AcetylationofanisoleonTPA/ZrO2.IndianJournalofChemicalTechnology200815136-4016Bravo-SuarezJJPaez-MozoEAOyamaST.Interca-lationofdecamolybdodicobaltateIIIanioninlayereddoublehydroxidesJ.ChemistryofMaterials20041671214-122517AmirinejadMetal.Cesiumhydrogensaltofheteropoly-acids/Nafionnanocompositemembranesforprotonex-changemembranefuelcellsJ.JournalofMembraneScience20113771-289-9818DiasJAetal.Preparationandcharacterizationof27326H3PW12O40supportedonniobiaJ.MicroporousandMesoporousMaterials20101321-2103-11119SunCYetal.Highlystablecrystallinecatalystsbasedonamicroporousmetal&#x2212organicframeworkandpolyoxometalatesJ.JournaloftheAmericanChemicalSociety200913151883-188820MartensJAetal.ConvenientsynthesisofCu3BTC2encapsulatedKegginheteropolyacidnanoma-terial