Hyunsoo Park, Ohmin Kwon, and Jihan Kim - Park, Kwon, Kim - 2021 - Unknown

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pubs.acs.org/JPCCArticleComputationalIdentificationofConnectedMOF@COFMaterialsHyunsooPark,OhminKwon,andJihanKim*CiteThis:J.Phys.Chem.C2021,125,5897−5903ReadOnlineACCESSMetrics&MoreArticleRecommendationsABSTRACT:Covalent-organicframeworks(COFs)areregardedaspromisingcandidatesformanydifferentenergy/environmentalapplications,butthesematerialsaremoredifficulttosynthesizecomparedtootherporousmaterialssuchasmetal−organicframeworks(MOFs).Herein,wedevelopedacomputationalscreeningalgorithmthatusesMOFsassubstratesinordertotheoreticallyallowheteroepitaxialgrowthofthree-dimensionalCOFs(3DCOFs).ThealgorithmdetailstheinterfaceofMOF@COFattheatomic/molecularlevelinordertocreate3DCOFsusingabottom-upapproach.Consequently,19pairsofMOF@COFresultedfromthealgorithmareselectedascandidatesforheteroepitaxialgrowthof3DCOFsonthesurfaceofMOFs.■INTRODUCTION2DCOFs.Zhangandco-workersdemonstratedthatNH2-MIL-68@TPA-COFhybridmaterialcanbeusedasanCovalent-organicframeworks(COFs)aresynthesizedusing1−6effectivephotocatalystforthedegradationofRhodamineorganicbuildingunitslinkedbystrongcovalentbonds.30B.Kimandco-workersdevelopedametal-dopedNH2-MIL-BecauseCOFshavealargesurfacearea,enhancedchemical/7−11125(Ti)@LZU1hybridmaterialthatshowsexcellentphoto-thermalstability,andtunableporesize,theyhavebeencatalystperformanceforbothhydrogenationanddehydrogen-regardedaspromisingcandidatesforgasstorageand3112−1415−19ation.Lanandco-workersreportedthatNH2-UIO-66@separation,photocatalysts,andoptoelectronicdevi-20−22TAPA-1compositematerialcanbeusedasasuitableces.Unfortunately,unliketheirmorerenownedcounter-3223,24photocatalystforH2evolution.Hanandco-workerspartmaterialofmetal−organicframeworks(MOFs),demonstratedthatPCN-222-CO@TAPA-1showsthedeace-synthesisofCOFswithhighcrystallinitystillremainsatalization-Knoevenagelcondensationcascadereactionwithsignificantchallengegiventhatthestrongcovalentbondslead33highperformanceasabifunctionalcatalyst.Inaddition,topartialcrystallinitywiththepresenceofamorphous25variousMOF/COFcompositematerialssuchasNH2-MIL-networks.Three-dimensional(3D)COFsareespecially3435125(Ti)@CTF-1,IRMOF-3@LZU1,NH2-MIL-88B@TP-DownloadedviaUNIVOFCONNECTICUTonMay15,2021at21:01:29(UTC).difficulttosynthesizecomparedtotwo-dimensional(2D)3637TTA,NH2-UIO-66@LZU1,NH2-MIL-125@TAPB-COFsasthevanderWaalsinteractionsfromtheπ-orbital3839PDA,NH2-UIO-66@TP-PDA(orTP-TPE),andNH2-overlapfoundin2DCOFsprovideadditionaldrivingforceto40Seehttps://pubs.acs.org/sharingguidelinesforoptionsonhowtolegitimatelysharepublishedarticles.26UIO-66@TFPT-DETHhavebeenreported.readilyformstackedlayers,whichismissingin3DCOFs.ToUnfortunately,despitemanyofthereportedsuccessfulfacilitatesynthesisof3DCOFs,manyresearchworkshaveaforementionedworks,wesurmisethattherearemanyfailedbeenreportedtoincreasethecrystallinityofCOFsusingexperimentalattemptsatsynthesizingMOF@COFmaterialsvarioussubstrates.Forexample,Dichtelandco-workersviaintegrating3DMOFsand3DCOFs.Itcanbeintuitedthatdemonstratedthat2DCOFspossessimprovedcrystallinitytoenhancethelikelihoodofsynthesizingcleanandcrystallinewhen2DCOFsaresynthesizedastheorientedthinfilmson27,283DMOF@3DCOFstructures,thecompositematerialwouldsingle-layergraphene(SLG).Additionally,Gaoandco-needtobedesignedfromabottom-upapproachwhereworkersutilizedaporousα-Al2O3substratetosynthesize3D29detailedanalysiswouldneedtobeconductedattheatomicCOF-320membranes.TheyshowedthatCOF-320possessesandmolecularleveltoselectthebestpairofcandidateahighdegreeofcrystallinitywhengrownonaporousα-Al2O3substrate.Nonetheless,theusageoftemplatestosynthesize3DCOFshavestillbeenchallengingbecausethechemicalReceived:December29,2020environmentoftheinterfacesbetweenthetwomaterialsofRevised:February24,2021compositesisunknown.Published:March5,2021Recently,MOFshavebeenusedtocreateMOF/COFcompositematerialswiththeinterfaceformedviaimineformationfromamine-functionalizedMOFsandimine-based©2021AmericanChemicalSocietyhttps://dx.doi.org/10.1021/acs.jpcc.0c115515897J.Phys.Chem.C2021,125,5897−5903

1TheJournalofPhysicalChemistryCpubs.acs.org/JPCCArticleFigure1.(a)Clustermodelofamine-functionalizedBDCthatwasgeometricallyoptimizedbyGaussian09.ThecenterofmassofBDCismarkedasagreencircleandablackcircleindicatestheregionwherethenitrogenatomofthefunctionalgroupcanbelocated.(b)TwosnapshotsoftherotationalmotionofBDCinIRMOF-3.Fourpossiblepositionsoftheaminegroupinamine-functionalizedBDCaremarkedasnitrogenatoms.Blue,gray,red,andwhiteatomsrepresentnitrogen,carbon,oxygen,andhydrogen,respectively.materials.Previously,ourgroupdevisedarationalcomputa-experimentallysynthesized449COFs(other4002DCOFstionalalgorithmtoidentifyMOF@MOFstructuresandsixintheCoRECOFdatabasewereignoredasourfocuswasonnewMOF@MOFstructuresweresuccessfullysynthesized3DMOF@3DCOFmaterials).The3DCOFsintheCoRE41fromourtheoreticalpredictions.CriticaltothisalgorithmCOFdatabaseincludetheCOFswithhighcrystallinity(i.e.,wasaninsightthatthelinkerfromoneMOFcansuccessfully48COF-300,COF-303,LZU-79,andLZU-111).formcoordinationbondstothemetalnodeofthesecondLatticeMatching.LatticematchingisknownasakeyMOFandthattwoconstituentMOFsshouldpossesssimilarfactortoenhancethelikelihoodofheteroepitaxialgrowthforlatticeparameters.Additionally,variousheterostructures41,42,49−51thecompositematerials.ZurandMcgilldevelopedsuccessfullysynthesizedwithheteroepitaxialgrowthoftheanalgorithmthatcanpredictheteroepitaxialgrowthatthesecondaryMOFononeMOFseedhavebeenreported.42In52surfaceforcompositematerialsusingthelatticematching.Athecurrentwork,wedevelopedacomputationalscreeningkeyaspectofthelatticematchingalgorithmistomatchalgorithmthatcanrationallyidentifyMOF@COFmaterialstranslationalsymmetryinlatticesoftwocrystalmaterialsattheusingtheknowninteractionsbetweentheMOFsandtheinterfaces.Tothisend,thedistinct(100),(010),and(001)COFsattheatomicandmolecularlevel.WebelievethatthisMillerplaneswereusedfortheCOFsandthedistinctMillerbottom-upapproachcanbeusedtodesignnewMOF@COFplaneswithindices−1≤h,k,andl≤1wereusedforthematerialsthatcanfacilitatesynthesisofthisclassofcompositeMOFs.Tarziaandco-workers53usedthesamelatticematchingmaterials.algorithmforhigh-throughputscreeningofMOFsforheteroepitaxialalignmentonthesubstratesurfaces.The■METHODScriterionofthelatticematchingwasvalidatedascomparingFormationofCOFsentailsmanykindsofreactionssuchastheresultsofexperimentaldata,andsimilarcriteriawereusedboronatedanhydrideformation,nitrilecyclotrimerization,inthisworkaswell:(1)themaximumareaofsuperlatticeswas43borosilicateformation,andimineformation.Inthiswork,setlessthanninetimesthe(001)planeareaofCOFs,and(2)wedecidedtouseMOFsasatheoreticalsubstratetoformthelengthtoleranceforsuperlatticeparametermatchingwascompositeMOF@COFmaterialsandexploredvarioussettobelessthan10%,andtheangletolerancewassettobepossibilitiesinwhichCOFscouldbesynthesizedontopof2%.MOFsviasequentialreactions.Unfortunately,asfarasweChemicalBondingattheInterface.Chemicalbondingknow,itisdifficulttodirectly“connect”componentsof3Dattheinterfaceplaysacriticalroleonwhetherthetwo53−55COFstotheMOFsandassuch,weoptedtofirstfunctionalizecomponentmaterialsformacleansurfaceattheinterface.thelinkersoftheMOFstructurestoinducetheimine-basedToidentifychemicalbonding,chemicalconnectionpoints(i.e.,reactionbetweenthefunctionalgroupsoftheMOFsandtheatomsthatparticipateinbonding)ofMOFsandCOFsshouldimine-basedCOF.Asimilarreactionmechanismhasbeenbedefined.AttheinterfaceofMOF@COFmaterials,theexploredinthepasttosuccessfullysynthesizeMOF@2DCOFaminegroupinamine-functionalizedBDCofMOFsandthematerials.Inthiswork,wefocusedononlyinteractionswithaldehydeprecursorofCOFsarereactedbytheimineamine-functionalizedMOFsinspiteofthelackofthenumberformationreaction.Assuch,H2OmoleculesescapebyaofMOFsgiventhatthesearetheonesthataremostlikelytocondensationreactionandthenitrogenatomsoftheaminebesynthesizedinpractice.groupremain.Theremainingnitrogenatomsinamine-functionalizedBDCaredefinedasthechemicalconnection■SCREENINGALGORITHMpointsforMOFs.Likewise,thenitrogenatomsofimine-basedDatabaseConstructionforAmine-FunctionalizedCOFsaredefinedasthechemicalconnectionpointsforCOFs,MOFsandImine-BasedCOFs.Thelistofamine-function-anditisourhypothesisthatthesetwoconnectionpointsalizedMOFs44werefoundbyusingConquest,41whichisawouldneedtobewithinclosespatialvicinityofoneanotherprimaryprogramforsearchingandretrievinginformationfromacrossallthesupercellsoftheentirecrystaltoenhancethe45likelihoodofformingacleanandlargecrystallinecompositetheCambridgeStructuralDatabase(CSD).TheamineandnitrogroupwereselectedasthefunctionalgroupofMOFsformaterial.theimine-basedreaction.Atotalof537MOFshavingeitherWiththatsaid,identificationofthechemicalconnectionamine-functionalizedBDC(1,4-benzenedicarboxylicacid)orpointsoftheMOFsiscomplicatedduetothefactthattheirnitro-functionalizedBDCwerecollectedduetotheirfunctionalgroupscanrandomlyattachtoanyoneofthefour46prominence.FortheCOFs,493DCOFswerecollectedhydrogenatomsoftheBDClinker(seeFigure1afor47fromtheCoRECOFdatabase,whichconsistsofillustration).Also,therotationaldegreeoffreedomcannot5898https://dx.doi.org/10.1021/acs.jpcc.0c11551J.Phys.Chem.C2021,125,5897−5903

2TheJournalofPhysicalChemistryCpubs.acs.org/JPCCArticleFigure2.SchematicdiagramthatindicatestheoverallprocedureofscreeningforMOF@COFmaterials.Figure3.Screeningschemeforheteroepitaxialgrowthofthe3DCOFonMOFasthesubstratewhichconsistsofthreesteps:(1)latticematching,(2)identifyingconnectionpointsoftheMOFandCOF,and(3)unitcelltranslationoftheCOFwithMOFfixed.TworepresentativecandidatesofMOF@COFareIRMOF-3@DL-COF-1for(a)andUIO-66(Eu)@PI-COF-4for(b).TheconnectionpointsofCOFsaremarkedbygreenatomsandthoseofMOFsaremarkedbylargegraycircles.beignoredasshowninFigure1bwhichshowstwosnapshotsaccount,theBDCintheMOFsshouldbeconsideredtofreelywithdifferentorientationsoftheBDClinkers.Morrisandco-rotateinthesescreeningstudies.Assuch,itisassumedthattheworkersreportedthattheactivationenergyoftherotationofaminegroupscanalsofreelyrotateandstaywithinacircleofatheaminegroupis1.8±0.6kcalmol−1,andthefull180°specificradiusatthecenterofmassofBDC.Todeterminetherotationofthephenylenegroupinamine-functionalizedBDCspecificradiusvalue,aclustermodelofBDCwasgeometrically(i.e.,IRMOF-3)wasobtainedtobe5.0±0.2kcalmol−1byoptimizedusingtheGaussian0957packagewiththe6-31G+5658NMRrelaxationmeasurement.Althoughtheseactivation(d)basissetandB3LYPfunctional.ThecalculatedoptimalenergieswerecalculatedforjusttheIRMOF-3structure,itdistancebetweentheaminegroupandthecenterofmassofprovidesevidencethattherotationalmotionofBDChaslowBDCis2.817Å.Therefore,thechemicalconnectionpointsofactivationenergyinMOFs.WhentakingthesevaluesintoMOFsareintherangewitharadiusof2.817Åatthecenterof5899https://dx.doi.org/10.1021/acs.jpcc.0c11551J.Phys.Chem.C2021,125,5897−5903

3TheJournalofPhysicalChemistryCpubs.acs.org/JPCCArticleFigure4.ComputationalmodelofIRMOF-3@DL-COF-1for(a)andUIO-66(Eu)@PI-COF-4for(b).ThetopredregionindicatestheCOFandthebottomblueregionindicatestheMOF.TheyareoptimizedusingtheForcitemoduleinMaterialsstudio.ThechemicalconnectionpointsofMOF@COFaremarkedaslargegreenatoms.Figure5.Screeningschemeforheteroepitaxialgrowthofthe3DCOFonMOFasthesubstratewithYUXQOY@PI-COF-4whichhaveamaximumASOis0.75.TheconnectionpointsofCOFsaremarkedbygreenatomsandthoseofMOFsaremarkedbylargegraycircles.massofBDC.ThesechemicalconnectionpointsaremarkedaswhereSmisthenumberofbindingatomsandScisthenumberblackcirclesinFigure1.ofconnectionpointsoftheCOFinaunitcell.WhenASOis1,ChemicalConnectionPointsMatching.TofindoptimalallconnectionpointsoftheCOFarewithintheradiusofthepairsofMOFsandCOFsthatcanconnectviathechemicalconnectionpointsoftheMOF.Incontrast,whenASOis0,connectionpoints,wesetthecriterionthatthenitrogenatomsnoneoftheconnectionpointsoftheCOFsareclosetotheofimine-basedCOFs(connectionpointsofCOFs)hadtobeMOF.Toexaminethelikelihoodofheteroepitaxialgrowthofwithin2.817ÅfromthecenterofmassofthebenzeneringoftheCOFsonthesubstrate,onlythepairsofMOF/COFwithBDC(connectionpointsofMOFs).ToexaminewhetheraASOlargerthan0.5wereselectedaspotentialcandidates.ThegivenMOF/COFpairsatisfiedthiscriterion,theunitcellofoverallscreeningprocedureissummarizedinFigure2.theMOFwasfixedwhiletheunitcelloftheCOFwastranslatedinunitsof0.5Åtoseeifanyofthesecombinations■RESULTSANDDISCUSSIONledtoasuccessfulmatch.ToquantifytheinterfacialbindingofOurscreeningalgorithmidentifiedatotalof19MOF@COFtheCOFsintherangebetween0and1,ASO(atomicsite49pairsashighpotentialcandidatesforsynthesis.Altogether,overlap)isdefinedasthereare9MOF@COFpairswithamaximumASOof1,meaningthatalliminenitrogenatomsoftheseCOFsareSmASO=within2.817ÅfromthecenterofmassofBDClinkersintheScMOFs.Figure3showsarepresentativeillustrationexampleof5900https://dx.doi.org/10.1021/acs.jpcc.0c11551J.Phys.Chem.C2021,125,5897−5903

4TheJournalofPhysicalChemistryCpubs.acs.org/JPCCArticle(a)IRMOF-3@DL-COF-1and(b)UIO-66(Eu)@PI-COF-4.Table1.NineteenPairsofMOF@COFinwhichtheAsshowninFigure3a,IRMOF-3isacubicstructurewithaMaximumASOIsLargerthan0.5latticeparameterof(25.75×25.75×25.75Å)whileDL-MOF@COF-1-borisalsoacubicstructurewithalatticeparameterofMOFCOFCOF(26.56×26.56×26.56Å).Bycleavingboththematerialsrefcode(Millercommonname(Milleralongthe(100)Millerplane,themismatchratioofthelatticeplane)commonnameplane)ASOisonly3.1%.AfterpassingthroughthelatticematchingEDUSUR(001)IRMOF-3(Zn)DL-COF-1(100)1.0criterion,theunitcelloftheCOFwassubsequentlytranslatedDQAMUG3D-CuPor-COF(100)1.0alongthefixedMOFunitcelltofindtheoptimalconfiguration(010)thatminimizesthedistancesbetweenthesechemicalDQAMUGPI-COF-4(001)1.0connectionpoints.Finally,allconnectionpointsoftheDL-(010)COF-1-borarewithinthoseofIRMOF-3asshowninthefinalEZIPEK(100)NH2-UIO-66PI-COF-4(001)1.0(Eu)stepofFigure3a.UsingthisMOF@COFstructure,aEZIPEK(100)NH2-UIO-663D-CuPor-COF(100)1.0computationalmodelwasgeneratedandgeometrically(Eu)59optimizedusingtheForcitemoduleinMaterialsStudioKOKKOL(110)NH2-MIL-88bDL-COF-1(100)1.0(Figure4a).(Fe)ThesecondrepresentativeMOF@COFpair(i.e.,UIO-KOKKOL(110)NH2-MIL-88bPI-COF-4(001)1.066(Eu)@PI-COF-4)isshowninFigure3b.UIO-66(Eu)isa(Fe)cubicstructurewithalatticeparameterof(21.71×21.71×XIVNEW(100)PI-COF-4(001)1.021.71Å)whilePI-COF-4isatetragonalstructurewithalatticeYUXQOY(101)DL-COF-1(100)1.0DIYKED(110)DL-COF-1(100)0.667parameterof(20.49×20.49×32.20Å).BycleavingboththeDIYKED(010)PI-COF-4(001)0.75materialsalongthe(001)Millerplane,themismatchratioisEDUSUR(100)IRMOF-3(Zn)3D-CuPor-COF(100)0.6885.6%.Figure3bshowstheoptimalminimumdistanceoftheEWILON(100)NH2-UIO-66PI-COF-4(001)0.5chemicalconnectionpointsoftheMOFandtheCOFusing(Zr)translationalmotionoftheunitcelloftheCOF.AllchemicalEWILON(100)NH2-UIO-663D-CuPor-COF(100)0.688connectionpointsoftheCOFarematchedwiththeMOFas(Zr)thesubstrate.ThecomputationalmodelisalsogeneratedinRUPNEW(100)CAU-1(Al)DL-COF-1(100)0.5Figure4binthesameway.WOBHOMNH2-MIL-88b3D-CuPor-COF(100)0.75Furthermore,thereare10MOF@COFpairswitha(101)(Zn)maximumASObetween0.5and1.Figure5showsaWOBHOMNH2-MIL-88bPI-COF-4(001)0.5(101)(Zn)representativeexampleofYUXQOY@PI-COF.YUXQOYisYUXQOY(101)3D-CuPor-COF(100)0.625anorthorhombicstructurewhichconsistsoftheamine-YUXQOY(100)PI-COF-4(001)0.7560functionalizedBDClinkerand4,4′-bipy.Thelatticeparameteris(11.72×13.70×21.05Å).Thesuperlattice(21.05×40.10Å)oftheMOFcleavedbythe(100)Millerplanearematchedwiththesuperlattice(20.49×40.98Å)of■theCOFcleavedbythe(001)Millerplane.ThelengthAUTHORINFORMATIONmismatchratioofthelatticeis2.20%.However,thesetwoCorrespondingAuthormaterialsonlyhaveamaximumASOof0.75whentranslatingJihanKim−DepartmentofChemicalandBiomoleculartheunitcelloftheCOFasshowninFigure5.YoucanseethatEngineering,KoreaAdvancedInstituteofScienceandoneoutoffourgreenchemicalconnectionpointsareoutsideTechnology(KAIST),Daejeon34141,RepublicofKorea;thecircularregionoftheMOFconnectionpoints.Assuch,orcid.org/0000-0002-3844-8789;Email:jihankim@theremightbeaneedformorestrainforallofthesepointstokaist.ac.krmatchwithoneanother.Informationregardingall19MOF@AuthorsCOFcandidatesaresummarizedinTable1.HyunsooPark−DepartmentofChemicalandBiomolecularEngineering,KoreaAdvancedInstituteofScienceand■CONCLUSIONSTechnology(KAIST),Daejeon34141,RepublicofKorea;Wehavedevelopedanovelalgorithmthatpredicthetero-orcid.org/0000-0001-9388-173Xepitaxialgrowthof3Dimine-basedCOFsonthesurfacesofOhminKwon−DepartmentofChemicalandBiomolecularamine-functionalizedMOFsandidentified19pairsofMOF@Engineering,KoreaAdvancedInstituteofScienceandCOFwhichcanbeexperimentallysynthesizedbyusingtheTechnology(KAIST),Daejeon34141,RepublicofKorea;MOFsassubstratesandinducingheteroepitaxialgrowthfororcid.org/0000-0002-1090-0737thecorrespondingCOFcandidates.WebelievethatthisCompletecontactinformationisavailableat:bottom-updesigncanovercomesomeofthechallengesforhttps://pubs.acs.org/10.1021/acs.jpcc.0c11551synthesizingof3DCOFsandmightfacilitategrowinglargecrystalswiththeaidofthesubstrateMOFs.Also,asaNotescomputationalgroup,althoughwedonothavethecapacitytoTheauthorsdeclarenocompetingfinancialinterest.synthesizethesematerialsourselves,futurecollaborationwithexperimentalgroupswouldbefruitfulinleadingtosuccessful■ACKNOWLEDGMENTSsynthesisofthesematerials.Itisouropinion,giventhelowThisworkwassupportedbySamsungResearchFunding&crystallinityfoundinmostCOFs,choosingCOFswithhighIncubationCenterofSamsungElectronicsunderProjectcrystallinitywouldfacilitatethesynthesisprocess.NumberSRFC-MA1702-07.5901https://dx.doi.org/10.1021/acs.jpcc.0c11551J.Phys.Chem.C2021,125,5897−5903

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