SAPO-34分子篩合成實例解決的基礎問題Si原子是如何進入分子篩骨架的如何控制Si原子在分子篩骨架中的分布分子篩的合成與制備結構&組成催化性能DICPAl(1Si)Al(1Si)Al(3Si)Al(4Si)HigherSi/AlStrongeracidicsitesDICPXRDspectraofas-synthesizedsamplesDICPCrystallizationcurveofSAPO-34DICPIRresultsDICPAssignmentoftheIRbandsinframeworkvibrationregionoftheas-synthesizedsamplesCrystalli-zationTimeStructureTypeAsym.StretchSym.StretchT-OBendingP-O-Al(P-O-P)O-P-OSi-OP-O(Al-O)D-6RingsPO4(Si,Al)O4SiO4RingsChannel0hGel12251090785730-618570520470365-0.5hGel-1070-730-618570-475365-1hCrystal12151100-730635570530480-3801.5hCrystal12151100-730635570530480-380DICPInfluenceofcrystallizationonthecompositionofsolidsamplesRelativecontentcurveoftemplateintheas-synthesizedsamplesDICP31PNMRofthegelsamplesinthefirststepsofthecrystallizationprocessThestirredmixinggeloftherawsources(silicasol,pseudoboehmite,orthophosphoricacidandwater)Thestirredmixinggelofa.andtemplate(TEA).Theb.gelafteraging(theinitialstateofthecrystallization).

DICP27AlMAS(a),31PMAS(b)and29SiCP/MAS(c)NMRspectraofas-synthesizedsamplesintheearlierstageofcrystallizationabcDICP27AlMASNMRspectraofcalcinedanddehydratedsamplesintheearlierstageofcrystallizationDICPChangesoftheAl(IV),P(IV)andSi(IV)relativecontent(a)andrelativeproportion(b)oftheas-synthesizedsampleswithcrystallizationtime(a)relativecontent(b)relativeproportionDICP晶粒以Si(4Al)方式生長(2.5h)初始凝膠(0h)重排聚合形成晶核(0.5h)晶粒生長~80%Si直接進入骨架Si(nAl)n=0-4結構形成(26h)Si取代P2Si取代Al+PSi直接參與相對結晶度~80%SAPO-34晶化機理模型DICP4.分子篩的基本性質基本特點多孔晶體，規整孔道結構大比表面積結構多樣性組成多樣性高熱穩定性，水熱穩定性基本性質離子交換性質吸附性質固體酸堿性質DICPDICPDICPDICPDICPDICPDICP5.分子篩的表征XRD：

晶相，晶胞參數，晶體結構電子顯微鏡：晶貌，組成吸附－脫附：比表面積，孔徑，孔容、酸堿性等紅外光譜（IR)：－OH；酸堿性質；骨架；表面物種NMR：結構微環境分析；酸堿性質熱重－差熱：熱穩定性，酸堿性，吸附（脫附）性質，積碳分析注意：XRD圖隨組成也有變化DICP去除模板劑前后XRD圖有變化DICPXRD測定結晶度一般測定8個主峰即可也可用于測定雜晶相對結晶度Sumofpeakheights(unknown)Sumofpeakheights(standard)%Crystalinity=DICPXRD測定Si/Al比晶粒必須大于0.3微米組成變化引起晶胞參數變化，XRD呈現規律性可以測定Si/Al判斷晶體中是否有不均勻Al分布DICP％Al＝16.5－30.8

HZSM-5DICPIR法測定Si/Al只對特定體系適用組成規律變化會體現在IR光譜中DICPDICP分子篩酸性的測定酸堿中和（指示劑法）TPDIR1H-NMR31P-NMRTPD和IR最常用DICPH-MAS-NMRspectrumofHYzeoliteDICPIRspectraofHYzeolitewithoutandwithadsorbedpyridine

HYHY+Pyridine(sodalite)(supercage)(B)(Lewis)DICPPyridineadsorptionondifferentzeolitessamplesP.A.Weyrich,W.F.Holderich,Appl.Catal.A158(1997)145.DICP

++MethodAcidTypeAcidLocation(Int./Ext.)AcidAmountAcidStrengthMajorDrawbacksBr?nstedLewisTitration

─++AccessibilityTPD(Basesadsorption)

++─+±Diffusion&Non-acidicadsorptionIR(hydroxyls)+───+SamplepreparationIR(Basesadsorption)+++±±Samplepreparation1HNMR(hydroxyls)+──±+Wateradsorption31PNMR

(TMP)++─+

(B)─(L)+

(L)─(B)Volatile,Oxidization&Toxicity31PNMR(PhosphineOxides)++++(B,L)+(B,L)WeakerbasicityComparisonofVariousAcidCharacterizationMethodsDICPNH3-TPDofH-ZSM-5Zhaoetal.,J.Phys.Chem.B,106,4462(2002)DICP1H&27AlMASNMRofH-ZSM-5SpinningRate=5.0kHzSpinningRate=5.5kHzDICPIntroducingthePlayersTMP(Trimethylphosphine)Sizeca.0.55nmTMPO(TrimethylphosphineOxide)Sizeca.0.55nmTBPO(TributylphosphineOxide)Sizeca.0.82nmZSM-5(10-MR)DICPSamplePreparationProceduresTMPAdsorptionthermaldecomposition

oftrimethylphosphinesilveriodidecomplexontothedehydratedH-ZSM-5at473KTMPO(TBPO)AdsorptionH-ZSM-5dehydration723K;24haddTMPO/TBPOdissolvedinCH2Cl2underN2gloveboxLoadedSampleCH2Cl2evacuationvesselagitatedatRT;12h323KunderN2gloveboxpackingintoMASrotor31PMASNMRDICPTMP/Br?nstedacidsiteTMPO/Br?nstedacidsite

IonicPairComplex

HydrogenBondedComplexLunsfordetal.,J.Am.Chem.Soc.,107,1540(1985)Muelleretal.,J.Phys.Chem.B,102,2890(1998)

InteractionsBetweenProbeMoleculesandBr?nstedAcidSitesHigherAcidicStrength

O-HBondStrength

31PChemicalShift

(downfield)FormationofTMPH+complexDICP31PMASNMR(TMP/H-ZSM-5/26)Assignments-4ppm:

TMPH+/Br?nstedacidsites-50ppm:

TMP/Lewisacidsites-62ppm:

Physisorbed

TMPNOTE:Acidsiteswithdifferentstrengths

cannotbedifferentiated!!CP/MASDecouplingWithoutdecouplingSpinningRate=7kHzLBLunsfordetal.,JACS,107,1540(1985)DICP31PMASNMR(TMPO/H-ZSM-5)1501209060300Chemicalshift(ppm)HZSM-5/15HZSM-5/26HZSM-5/75HZSM-5/15(Partiallyhydrated)******************MobileTMPO

Uptofive31Presonancewereobserved@86,75,67,63and53ppmforTMPO/Br?nsted

IncreasingSi/Al

AcidicStrength

NoLewisacidsitesobserved

Thenewlyobserved30ppmpeakcanbeascribedduetomobileTMPO

TMPOcanprobesbothinternalandexternalacidsitesSpinningRate=10kHzDICPCorrelationofResultsObtainedfromTMPOandTBPO(a)TMPO(b)

TBPO********646948(P)58(P)7074SpinningRate=10kHzZhaoetal.,J.Phys.Chem.B,106,4462(2002)

AdsorptionofTMPOandTBPOonAl-MCM-41(Si/Al=70;poresize=2.54nm)ChemicalShift(

)

c

1(

1-c)

2(

2-c)TMPO3969(30)64(25)TBPO4774(27)70(23)Muelleretal.,J.Phys.Chem.B,102,2890(1998)

MechanismofAcidSiteFormationinAl-MCM-41?DICP31PMASNMRofCrystallineTBPODICPAcidPropertiesofH-ZSM-5Determinedby

31PMASNMRinConjunctionwithICP

TMPO(Internal+External)

(

)/ppm86(47)75(36)67(28)63(24)53(14)43(4)30Sample(Si/Al)H-ZSM-5/150.5%(---,0.005)22.4%(0.165,

---)37.5%(0.258,

0.017)36.6%(0.242,0.027)3.0%(0.021,---)

H-ZSM-5/266.9%(0.014,0.010)45.4%(0.159,---)22.7%(0.067,0.012)25.0%(0.063,0.025)----

----H-ZSM-5/753.5%(0.003,0.002)69.8%(0.108,---)----(---,0.002)26.7%(0.032,0.009)----

----TBPO(External)

(

)/ppm92(45)----75(28)71(24)----54(7)47Sample(Si/Al)H-ZSM-5/1510.5%----35.0%54.5%------------H-ZSM-5/2622.3%----25.2%52.5%------------H-ZSM-5/7515.4%----17.6%67.0%----

(1)

refertochemicalshiftdifferencew.r.t.crystallineTMPO(39ppm)orTBPO(47ppm).(2)

Datainparenthesesdenote(Int.,Ext.)acidconcentrationsin(0.05)mmol/gcat.(3)Assume1:1relationbetweenadsorbateandBr?nstedacidsite.ICPprobidesconcentrationsofAl,SiandP.DICP31PNMRChemicalShiftAssignmentsforVariousCatalystsAdsorbedwithTMPOandTBPODICPDistributionofAcidSitesforVariousCatalystsDICP6.分子篩的催化性能分子篩的特點多孔晶體

孔道結構規整Shapeselectiveeffect

比表面積大Highactivity

組成可調變性酸、堿性可調離子交換性氧化還原性能TS-1，?..

結構可調變性據反應特點選擇分子篩Shape-selectiveeffect規整孔道結構使分子篩具有特殊的催化性能ReactantshapeselectivityProductshapeselectivityReactantshapeselectivityandproductshapeselectivityarestronglydependingoncrystalsizeandactivityRestrictedtransitionstateshapeselectivityRestrictedtransitionstateshapeselectivityisindependentofcrystalsizeandactivity,butdependsonporeandcavitydiametersandonzeolite’sstructuresDICPReactantshapeselectivityProductshapeselectivityDICPReactantshapeselectivityDehydrationofn-andiso-butanolonCa-XandCa-ADICPProductshapeselectivityCH3OHC5-C11，汽油C2-C4，烯烴ZSM-5SAPO-34MTGMTOCH3OH＋toluene

p-xylene改性ZSM-5DICPLiquidPhaseAlkylationofNaphthaleneoverLargePoreZeolitesRRBackgroundPENPBN塑料液晶中間體---中法PICS項目T-butylationofNaphthalenewitht-butanolReactionResultsreactiontime=2hsNo1-TBNRestrictedtransitionstateshapeselectivityDisproportionationofdialkylbenzeneovermediumporezeolite(HMd,ZSM-5)雙分子反應，形成中間過渡態需要較大的空間Theactivityonvariouszeolites(ZSM-5,ZSM-4,Mordenite,Y)werecorrelatedwiththeireffectiveporesize.DICP分子篩催化的液相有機反應酸堿功能芳烴的親電取代反應烷基化酰化鹵化脂肪族化合物的親核取代反應酯化

縮合反應異構化、重排消去、加成分子篩催化的液相有機反應金屬功能氧化反應酸性－金屬雙功能Cat:TS-1,...DICP重要的分子篩A:(detergents,desiccationandseparation);FAU:X(desiccation,purification,separation)andY(separation,catalysis);MOR:(adsorptionandcatalysis);LTL:KL-typezeolite(catalysis:aromatization);MFI:SilicaliteandZSM-5(adsorptionandcatalysis);BEA:Beta-typezeolite(catalysis:cumene);MTW:zeoliteMCM-22(catalysis:ethylbenzene,probablycumene?);CHA:SAPO-34(methanoltoolefinsorMTOprocess-demonstrationunit);FER:Ferrierite(skeletalisomerizationofn-butenes-demonstrationunit);AELand/orTON:SAPO-11andpossiblyZSM-22(improvementofpourpointforpetroleumcutsbystraightlongparaffinisomerization);Structuresnotrevealed(foraromaticC8isomerization):oneiscertain(IFP)andthesecondispossible(UOP).DICP7.規整孔道介孔材料DICPMobilresearchersin1992,cationicsurfactantporesize1.5-10nm,highsurfaceareas1200m2/glowhydrthermalstability,basicconditionHexagonal(p6m)LiquidcrystaltemplateroutesCubicIa3dlamellarMCM-41MCM-48MCM-50ANewFamilyofMesoporousMaterialsM41SDICP介孔材料的形成機理1.層狀機理：1993年G.D.Stucky1996年日本Inagaki:pHdecreasingThemechanismforformationofFSM-16

2.棒狀機理：1994年M.E.DavisA.Monnieretal.Science,261,1299(1993)C.Chen,etal.MicroporousMater.,4,1(1995)S.B.Inagaki,CHEMSOCJPN69,1449(1996)

DICP介孔材料的形成機理CooperativeAssemblyApproach:Q.Huoetal.Nature,368,317(1994).DICPmicroporouszeolitesMCM-41poresize<1.1nmporesize2-6nmApplications:catalysis,separation,adsorption,sensor,nanodeviceandfabricationofnanostructuredmaterialsadvantageinthemassdiffusionandtransportbecauseoftheirinterconnectingnetworksBicontinuoushelix3DcubicmesostructureIa3d,MCM-48J.Thomas,O.Terasakietal.,Acc.Chem.Res.

2001,34,583-594DICPCubicCagedMesoporousSilicaSBA-1lowtemperaturesynthesis,-5°C,acidsynthesis,largeheadgroupsurfactant,C16H33N(Et)3BrwelldefinedmorphologyanepitaxialphasetransformationO.Terasaki,T.Tatsumi,JACS,2002,123,12089Q.Huoetal.Nature,368,317(1994).DICP

3Dcagedstructure,cubicIm3mtriblockcopolymerwithlongEOchainsF127,EO106PO70EO106,F108,F98,Brij700,acidsynthesis,highlyorderedXRDpatternsN2sorptionisothermsD.Zhao,etal.J.Am.Chem.Soc.

1998,120,60248.0nmLargePoreCubicCagedSBA-16O.Terasaki,D.Zhaoetal.Nature408,449(2000)100110111Cellparametera=13.3nmWindowsize2.3nmCavitysurfaceSpherediameterd=9.5nm

XRDpatternsStructuremodelDICPMesoporousSilicaMCM-48andCarbonsCMK-4R.Ryooetal.,J.Phys.Chem.B,103,7743,1999.S.Jun,S.H.Joo,R.Ryoo,etal.,J.Am.Chem.Soc.,122(43);10712-10713,2000.S.Joo,R.Ryooetal.,MicroporousMesoporousMater.,44-45,153-158,2001.DICPD.Zhao,Science,1998,279,548TEMimagesoMesoporousSilicaSBA-15blockcopolymertemplatingacidicsynthesisconditionlargeporesize(4.6~40nm)thermallyandhydrothermallystablehighlyorderedthicksilicawall,microporouswallshighsurfaceareas(~1000m2/g)porevolume(1.0—2.5cm3/g)N2sorptionisothermsXRDpatternsD.Zhao,etal.J.Am.Chem.Soc.

1998,120,6024S.-H.Joo,R.Ryoo,M.Jaroniec,J.Phys.Chem.B2002,106,4640N2sorptionisothermsinitialpartsof

plotsDICPSynthesisofMesoporousMaterials

Surfactant

+Inorganicsource

hydrothermalSyntheticCharactersforMesoporousMaterials：1.lowtemperature,-5°C~RT,<150°C2.fastformationrate<1min3.compositionisvariable,tetrahedron,octahedron4.non-aqueoussynthesis,surfactanttemplating5.morphologycontrolStructurecharacters:1.non-perfectcrystal,longrangeorder(nocode)2.amorphousinorganicwalls3.weckinteraction(H-bonding,ligand,vanderWaals)4.hydrothermallyunstablepH,mediamesoporousmaterialsDICPSynthesisRoutestoMesoporousMaterialsQ.Huoetal.Nature,368,317(1994).S.A.Bagshaw,etal.Science,269,1242(1995)J.Y.Ying,ANGEWCHEMINTEDIT38,56(1999)D.Zhao,Science,1998,279,548MCM-41(p6m),MCM-48(Ia3d),MCM-50(L),SBA-6(Pm3n),SBA-8(cmm),FUD-2(Fd3m)

f,I+…X…H+SS=nonionicsurfactant,blockcopolymersNon-silicaoxidemesostructures,e.g.W,MoSBA-3(p6m),SBA-1(pm3n),SBA-2(P63/mmc),MHS,MUX,worm-likedirorderedmesoporeHexagonal,cubicmesostructures,Nb,TaSBA-15(p6m),SBA-16(Im3m),SBA-12(P63/mmc),

SBA-11(Pm3m),FDU-1(Im3m),FDU-4,5SBA-13,14DICP8.分子篩研究的幾個熱點方向DICPSessionsin13-IZCMineralogyofnaturalzeoliteZeolitenucleationandgrowthNewmethodsofzeolitesynthesisIsomorphoussubstitutionsSynthesisofnewmaterialsFundamentalsofmicelletemplatingNewmesoporousmolecularsievesSyntheseswithnon-ionicsurfactantsCrystalstructuredeterminationHost-guestchemistryPost-synthesismodificationIn-situspectroscopyandcatalysisFrameworksandacidsitesFrameworks,cations,clustersModellingandtheoreticalstudiesAModellingandtheoreticalstudiesBPrinciplesofadsorptionAdsorptionandseparationprocessDiffusion:fundamentalapproachZeolitemembranesandfilmsNanocompositefundamentalsandapplicationsAdvancedmaterialsMicro-andmesoporous

materialsinfinechemistryNewroutestohydrocarbonactivationConversionofaromaticsCatalysisforoilrefiningSelectiveoxidationandsulfurresistanceConfinementandphysicalchemistryforcatalysisNewapproachestocatalystpreparationEnvironmentalcatalysisEnvironment-friendlyapplicationsofzeolitesZeolitemineralsandhealthsciencesDICP幾個熱點方向傳統分子篩研究仍持續保持活力AvelinoCorma,MariaJ.Diaz-Cabanas,JoaquinMarti