锆簇金属有机骨架材料(Zr-MOFs)的合成总结

序号配体条件结构来源1ZrOCl2.8H2O(200mg),H3TATB(60mg)and0.6mLtrifluoroaceticacidin12mLofDEFwereultrasonicallydissolvedinaPyrexvial.Themixturewasheatedat120ºCinanovenfor12h.Aftercoolingdowntoroomtemperature,whitepowdercrystallineprecipitatewasharvestedbyfiltrationPCN-777Angew.Chem.Int.Ed.2014,53,1–72Allsamplesweresynthesizedviaarefluxmethodinvolvingthereactionof2-sulfoterephthalicacidwithZrCl4inwaterunderrelativelyconcentratedconditions.Forthesamplewithnoadditivesduringsynthesis(1),monosodium2-sulfoterephthalicacid(5g,18.6mmol)wasdissolvedinminimalwater,andthenpassedthroughDOWEX50WX8protonexchangeresintoobtain2-sulfoterephthalicacid.Thewaterwasthenremovedbyrotaryevaporation,then40mLoffreshultrapurewaterwasaddedtodissolvethesolid.Separately,ZrCl4(2.5g,10.7mmol)wasdissolvedin15mLofultrapurewater(caution,highlyexothermic),thenthetwosolutionsweremixedtomakeaclear,slightlypinksolutionwithpH1.Thesolutionwasthenheatedtoreflux,andafter~3minutesawhiteprecipitateformed.Refluxwascontinuedfor16hours,DOI:10.1021/jacs.5b07267J.Am.Chem.Soc.XXXX,XXX,XXX−XXXthenthesolutionwascooledandthesolidwasrecoveredbycentrifugation.Thesolidwasthenwashed2xwithultrapurewater,thenrefluxedforanother16hoursinultrapurewatertopurify.3Synthesisof14nmUiO-66-N3(Zr6O4OH4(C8H3O4-N3)62-Azido-1,4-benzenedicarboxylicacid(50mg,0.24mmol)wasdissolvedin1mLofN,NDimethylformamide(DMF).Inaseparatevial,zirconylchlorideoctahydrate(21mg,0.066mmol)wasdissolvedin3mLofDMF.Thetwosolutionsweremixedtogetherina10mLscintillationvial,andaceticacid(300µl)wasaddedtothereactionmixture.Thesolutionwasheatedat90˚Cfor18htoyieldUiO-66-N3(Zr6O4OH4(C8H3O4-N3)6.MOFnanoparticleswerepurifiedbycentrifugation(15000rpm,90min)followedbysolventexchange(3xDMFand3xNANOpureH2O)overa48hperiod.MOFnanoparticlesweresuspendedinH2Oforcharacterizationandfunctionalizationwith纳米级别dx.doi.org/10.1021/ja503215w|J.Am.Chem.Soc.2014,136,7261−72644DUT-67.ZrCl4/HfCl4(230mg/320mg,1mmol)wasdissolvedinthemixtureofDMF(12.5mL)andNMP(12.5mL)bysonicationfor10min.2,5-Thiophenedicarboxylicacid(H2tdc)(110mg,0.67mmol)wasaddedtoresultingsolutionandsonicatedadditional5min.Afterthataceticacid(7mL,117mmol)wasaddedtothesolutionandsonicatedfor10min.Theresultingmixturewasdistributedto10Pyrextubes,whichweresubsequentlytemperedat120°Cfor48h.TheresultedpowderwasseparatedbycentrifugationandwashedseveraltimeswithDMFuntilsupernatantsolutionbecamecolorless.Thepowderwasfilteredanddriedunderargonatmosphereforhalfanhour.Yield:224mg(71.5%)forDUT-67(Zr)and259mg(63.9%)forDUT-67(Hf).ThesinglecrystalsofDUT-67wereobtainedusingthesameprocedure,but10mLofaceticacidinsteadof7mLwereadded.dx.doi.org/10.1021/cg301691d|Cryst.GrowthDes.2013,13,1231−12375ZrCl4/HfCl4(230mg/320mg,1mmol)wasdissolvedinDMF(25mL)bysonicationfor10min.H2tdc(258mg,1.5mmol)wasaddedtoresultingsolution,andthemixturewassonicatedadditional5min.Afterthataceticacid(11mL,183mmol)wasaddedandthemixturewassonicatedforfurther10min.Thereactionmixturewasdistributedto12Pyrextubes,whichweresubsequentlytemperedat120°Cfor72h.ThewashinganddryingprocedurewasthesameasappliedtoDUT-67.Yield:384mg(53.9%)forDUT-67(Zr)and453mg(52.3%)forDUT-67(Hf).ThesinglecrystalsofDUT-68(Zr)wereobtainedusingthesamesyntheticprotocol,bututilizinglargeramountofmodulator.AsolutionofH2eddb(65mg,0.24mmol),ZrCl4(60mg,0.25mmol),2.5mLofaceticacid(HOAc)in16mLofN,N-dimethyl-formamide(DMF)wassealedina20mLglassvialandheatedat1201Cfor48h.TheresultingcolorlesscrystalswerecollectedandwashedwithDMFandacetone,andthendriedinair(yield72mg).JournalofSolidStateChemistry223(2015)104–108ZrCl4(24mg)wasdissolvedin8mLofN,N-dimethylformamide(DMF)ina25mLpyrexvial,towhich1.0gbenzoicacidwasadded.Themixturewasheatedin85ºCovenfor1hoursandcooledtotheroomtemperature.Then,H6TBPP(20mg)wasaddedtotheabovesolution,whichwassonicatedforawhile.Theresultingmixturewasheatedin120ºCovenfor96hourstoyieldabout14mgofdarkredcrystals(yield:38.89%basedonChem.Sci.,2015,6,3466–3470|3467H6TBPP).ThecrystalsobtainedwerefilteredandwashedwithDMF.Elementalanalysescalcd(%)forFJI-H6(Afteractivationandabsorbedsmallamountofwater,thecrystalhasaformulaof[Zr6O4(OH)4(H2TBPP)3]n·~20nH2O):UiO-66a0.24gZrOCl2*8H2Owasdissolvedin20mlDMF/1.6mlHAcunder5minsonication.Terephthalicacid(0.136g,0.82mmol,1.1eq)wasaddedandthemixturewassonicatedfor5minmoreandplacedinto120Cpreheatedovenfor1day.Solutionwasdecanted/centrifuged,precipitatewaswashedDMF4timesandacetone4timesover12hours.Thematerialwasevacuated12hatRTfollowedby12hat120C(ramp1C/min).UiO-66b0.24gZrOCl2*8H2Owasdissolvedin32mlDMF/3gbenzoicacidunder5minsonication.Terephthalicacid(0.136g,0.82mmol,1.1eq)wasaddedandthemixturewassonicatedfor5minmore,distributedto4vialsandplacedinto120Cpreheatedovenfor1day.Precipitatewasfiltered,washedDMF4timesandacetone4timesover12hours.Thematerialwasevacuated12hatRTfollowedby12hat120C(ramp1C/min).Yieldoftheactivatedmaterial–0.15g.UiO-66f0.24gZrOCl2*8H2Owasdissolvedin20mlDMF/0.8mlHCOOHunder5minsonication.Terephthalicacid(0.136g,0.82mmol,1.1eq)wasaddedandthemixturewassonicatedfor5minmoreandplacedinto120Cpreheatedovenfor1day.Sol