AJournaloftheGesellschaftDeutscherChemiker AngewandChteemieInternationalEdition eptedArticle Title:MixedMetal-OrganicFrameworkwithMultipleBindingSitesforEfficientC2H2/CO2Separation Authors:BanglinChen,JunkuoGao,XuefengQian,RuibiaoLin,RajamaniKrishna,HuiWu,andWeiZhou ThismanuscripthasbeeneptedafterpeerreviewandappearsasaneptedArticleonlinepriortoediting,proofing,andformalpublicationofthefinalVersionofRecord(VoR).ThisworkiscurrentlycitablebyusingtheDigitalObjectIdentifier(DOI)givenbelow.TheVoRwillbepublishedonlineinEarlyViewassoonaspossibleandmaybedifferenttothiseptedArticleasaresultofediting.ReadersshouldobtaintheVoRfromthejournalwebsiteshownbelowwhenitispublishedtoensureuracyofinformation.TheauthorsareresponsibleforthecontentofthiseptedArticle. Tobecitedas:Angew.Chem.Int.Ed.10.1002/anie.202000323Angew.Chem.10.1002/ange.202000323 LinktoVoR:/10.1002/anie.202000323/10.1002/ange.202000323 AngewandteChemieInternationalEdition 10.1002/anie.202000323 eptedManuscript COMMUNICATION MixedMetal-OrganicFrameworkwithMultipleBindingSitesforEfficientC2H2/CO2Separation JunkuoGao,*XuefengQian,Rui-BiaoLin,*RajamaniKrishna,HuiWu,WeiZhou,*BanglinChen* Abstract:TheC2H2/CO2separationisparticularlychallenging owingtotheirhighsimilarityinphysicalpropertiesandmolecularsizes,butofindustrialsignificance.Hereinwereportamixedanicframework(M’MOF)[Fe(pyz)Ni(CN)4](FeNi-M'MOF,pyz=pyrazine)withmultiplefunctionalsitespactone-dimensionalchannelsof~4.0ÅforchallengingC2H2/CO2separation.ThisMOFshowsnotonlyaremarkablevolumetricC2H2uptakeof133cm3cm−3butalsoanexcellentC2H2/CO2selectivityof24underambientcondition,resultinginthesecondhighestC2H2-capturedamountof4.54molL−1thatoutperformsmostpreviousbenchmarkmaterials.Theseparationperformanceofthismaterialhasbeenvalidatedbydynamicbreakthroughandneutrondiffractionexperiments,whichisdrivenbyπ-πstackingandmultipleintermolecularinteractionsbetweenC2H2moleculesandthebindingsitesofFeNi-M'MOF.Besides,thismaterialcanbefacilelysynthesizedbymixingmethodatroomtemperatureandiswaterstable,jointlyhighlightingFeNi-M'MOFasapromisingmaterialforC2H2/CO2separation. anicframeworks(MOFs)haveemergedasverypromisingporousmaterialsforadsorptivegasseparationbecausetheyintegratethemeritsoftunableporesizesandfunctionalporesurfacethatcanrealizenotonlymolecularsievingeffectbutalsopreferentialgasbinding.[1]PlentyofMOFshavebeenexploredforsimplifyingvariousgasseparationandpurificationschemes,rangingfrommatureonessuchascarbondioxidecapture(CO2)frommethaneandnitrogentomorechallengingolefin/paraffinandalkyne/alkeneseparations.[2]ForC2H2andCO2gasmolecules,theirveryhighsimilarityinphysicalproperties(differinboilingpointby~3%and~6K),andidenticalmolecularshapes/sizes(3.3×3.3×5.7Å3forC2H2,3.2×3.3×5.4Å3forCO2)withbothicdiametersof∼3.3Å,makeitverydifficultandchallengingtorealizeefficientporousmaterialsfor [*]Prof.J.Gao,Mr.X.QianInstituteofFunctionalPorousMaterials,TheKeylaboratoryofAdvancedTextileMaterialsandManufacturingTechnologyofMinistryofEducation,SchoolofMaterialsScienceandEngineeringZhejiangSci-TechUniversityHangzhou310018(China)Email:jkgao@Prof.J.Gao,Dr.R.-
B.Lin,Prof.B.ChenDepartmentofChemistryUniversityofTexasatSanAntonioOneUTSACircle,SanAntonio,TX78249-0698(USA)Email:ruibiao.lin@utsa.edu;banglin.chen@utsa.eduDr.R.KrishnaVan’tHoffInstituteofMolecularSciencesUniversityofAmsterdamSciencePark904,1098XHAmsterdam(TheNetherlands)Dr.H.Wu,Dr.W.ZhouNISTCenterforNeutronResearchNationalInstituteofStandardsandTechnologyGaithersburg,MD20899-6102(USA)Email:wzhou@nist.gov Supportinginformationforthisarticleisgivenviaalinkattheendofthedocument. C2H2/CO2separationunderambientconditions.[3]AfewultramicroporousMOFsfeaturingbareoxygenorfluorinebasesiteshavebeendevelopedtopreferentiallybindC2H2moleculesthroughH-bondinginteractionsorbindCO2moleculesthroughelectrostaticinteractions,showinghighC2H2/CO2selectivitybutlowC2H2uptake.[4]AnotherapproachistoincorporatestrongadsorptionbindingsitesmainlyopenmetalsitesintoMOFswithlargeporevolumestoboosttheuptakecapacityofthepreferredgasmolecules.[5]UTSA-74representsauniqueexamplewithopenmetalcentersoftwoessiblesites,whichcanbindtwoC2H2butoneCO2molecules,differingfromitsisomerMOF-74whichadsorbssimilaramountsofC2H2andCO2underthesamecondition.[5c]Thoughprogresseshavebeenmadeoverthepastseveralyears,theuptakecapacityversusselectivitytrade-offstillposesadauntingchallengeforaddressingC2H2/CO2separation.[6] ThevastdatabaseofreportedMOFstructuresparativeanalysestotargetpotentialcandidateswithdualfunctionalities,featuringmoderateporevolumesandessiblefunctionalsites,torealizebothhighgasuptakeandseparationselectivities.Amongplentifulligands,cyanideisashortandhighlybasicligandthatisfeasibletoconstructrobustMOFswithmodestporeaperturesize,suchasPrussianblueandpounds.[7]ForthoseMOFswithmetalloligands,theopenmetalsitesonligandsareessibleforgasmolecules,whereasexpectednarrowporestructuresoriginatingpactligandsenforceadditionalmultipleintermolecularinteractionstoform,asdemonstratedbyaseriesofmixedanicframeworks(M’MOFs).[8]Inthisregard,aHofmann-typeMOF[Fe(pyz)Ni(CN)4](FeNi-M'MOF,pyz=pyrazine)discoveredin2001,showingopennickelsitesandpolarizedsurfacesaswellpactporechannelsof~4.0Å,isparticularlyinteresting.[9]Thehighdensityoffunctionalsitesandultramicroporewouldcollaborativelyenforcegasseparationwithhighgasuptakeandseparationselectivities.Hereinweinvestigatethemixediron/nickelMOFFeNiM'MOFforpotentialC2H2/CO2separation.InthisMOF,C2H2moleculesarefoundtopreferentiallybindontoanicmoietiesandopenNisitesthroughπ-πstackingandmultipleintermolecularinteractions,respectively,whereasCO2moleculesmainlydistributeontheopenNisitesthroughrelativelyweakinteractions.Inthiscontext,FeNi-M'MOFshowsaveryhighC2H2/CO2selectivityof24thatissuperiortotheperformingMOFswhileretainingaremarkableC2H2uptakecapacityof133cm3cm−3,andthusanexcellentC2H2-capturedcapacityof4.54molL−1at298Kand1barfor50:50C2H2/CO2separation,whichisclosetothatofthebenchmarkUTSA-74andexceedsthoseofotherout-performingMOFs.[5c] FeNi-M'MOFisapillared-layerM’MOF,inwhichtheFe[Ni(CN)4]layerisconnectedbythepyzpillars.TheNiatomsshowsquare-planarcoordinationgeometrywhileFeatomsareoctahedrallycoordinated.TheNiatomsarecoordinatedbycarbonatomsoffourdifferentcyangroups,whereastheFeatomsarefullycoordinatedbynitrogenatomsfromfourdifferentcyangroupsandtwopyzlinkers.Fe[Ni(CN)4]layersarethenconnectedbypyzlinkersintoaworkwithone-dimensionalchannelsofabout4.15×4.27or3.94×4.58Å
2. Thisarticleisprotectedbycopyright.Allrightsreserved. AngewandteChemieInternationalEdition 10.1002/anie.202000323 COMMUNICATION TheopenmetalsitesdensityofFeNi-M'MOFisabout9.2mmolcm−3,whichishigherthanthatofmostMOFs,asshowninTableS2. Figure1.ThecrystalstructureofFeNi-M'MOFviewedalongthea/baxis.Fe,Ni,
C,N,HinFeNi-M'MOFarerepresentedbyorange,green,gray,blueandwhite,respectively. FeNi-M'MOFwassynthesizedatroomtemperatureinwaterandmethanol.[10]ByaddingthesolutionofK2[Ni(CN)4]intothemixedmethanolandwatersolutionofFe2+andpyz,theFeNi- M'MOFmicrocrystallinepowderswereobtainedafterstirringfor30minutes.ThepowderX-raydiffraction(PXRD)ofproductsindicatedthatthoseproductshaveagoodcrystallinityandmatchwellwiththesimulatedXRDpattern,indicatingthepurityofFeNiM'MOF.TheresultantFeNi-M'MOFwasfurthervalidatedbyelementalanalysis(EA),thermogravimetryanalysis(TGA),energydispersivespectroscopy(EDS)andX-rayphotoelectronspectroscopy(XPS)analysis(seesupportinginformation).ThisMOFalsoexhibitsanexcellentwaterstabilityasshowninFigureS2.Aftersoakinginwaterfor30days,thecrystallinityofFeNiM'MOFisstillretained.TheTGAcurveindicatedthatFeNiM'MOFexhibitsaconsiderablethermalstabilityupto200oC(FigureS4).ThethermalstabilityofFeNi-M'MOFwasalsoconfirmedbyvariabletemperaturePXRD(FigureS5),indicatingthatFeNi-M'MOFcanmaintainitscrystallinestructureuntil~200oC.Thefastandfacilesynthesismethod,excellentwaterstabilityandgoodthermalstabilityindicateFeNi-M'MOFisapromisingseparationmaterialforscale-upsynthesis. TheBrunauer-Emmett-Teller(BET)surfaceareaofFeNiM'MOFwasmeasuredtobe383m2g−1byN2sorptionexperimentat77KasshowninFigure2a.Theexperimentaltotalporevolumeis~0.25cm3g−1,andslightlysmallerthanthetheoreticalonecalculatedfromthecrystalstructure(0.30cm3g−1),whichcanbeattributedtotheinsufficientfillingofN2moleculesintheultramicroporousporechannels. eptedManuscript Figure2.(a)N2sorptionisothermsforFeNi-M'MOFat77K.(b)C2H2andCO2sorptionisothermsforFeNi-M'MOFat298K.(c)ComparisonofIASTselectivitiesforequimolarC2H2/CO2mixturesinFeNi-M'MOF,FePt-M'MOFandothermaterialsintherangeof0-1barat298K.(d)ComparisonofC2H2/CO2adsorptionselectivityandvolumetricC2H2uptakeat1barinFeNi-M'MOF,FePt-M'MOFandotherporousmaterials. Thisarticleisprotectedbycopyright.Allrightsreserved. eptedManuscript AngewandteChemieInternationalEdition 10.1002/anie.202000323 COMMUNICATION TheC2H2andCO2gasadsorptionisothermsofFeNi-M'MOFweremeasuredat273Kand298K.AsshowninFigure2b,thevolumetricC2H2uptakecapacityofFeNi-M'MOFis133cm3cm−3(4.29mmolg−1)at1barand298K,whichishigherthanthoseofmanyotherMOFs,suchasDICRO-4-Ni-i(52cm3cm−3),[4e]ZJU60a(96cm3cm−3),[11]Cu[Ni(pdt)2](108cm3cm−3),[6a]SNNU-45(113cm3cm−3),[6b]TIFSIX-2-Cu-i(116cm3cm−3),[4f]PCP-33(128cm3cm−3),[12]parabletothoseofUTSA-74(144cm3cm−3),[5c]FJU-90a(146cm3cm−3),[6c]andZn-MOF-74(150cm3cm−3)[13].TheCO2uptakeofFeNi-M'MOFis84cm3cm−3(2.72mmolg−1)at1barand298K.At1barand273K,C2H2andCO2uptakesofFeNi-M'MOFareupto145and102cm3cm−3respectively,asshowninFigureS8.Interestingly,thePtanalogue[Fe(pyz)Pt(CN)4](FePt-M'MOFFigureS10-12)showsmuchloweruptakecapacitiesforC2H2andCO2(100and105cm3cm−3,respectively),indicatingthepotentialbindingcontributionofNisitesinthistypeofMOFforC2H2molecules.Toevaluatetheseparationperformanceofthismaterial,idealadsorbedsolutiontheory(IAST)wasemployedtocalculatetheadsorptionselectivity.AsshowninFigure2c,at100kPaand298K,theC2H2/CO2(50/50)selectivityofFeNi-M'MOFis24.TheselectivityofFeNi-M'MOFishigherthanthoseofmostMOFs,suchasZn-MOF-74(1.92),[5c]FJU-90a(4.3),[6c]UTSA-74a(8.2),[5c]JCM-1(13.4),[4b]DICRO-4-Ni-i(13.9),[4e]andbenchmarkHOF-3a(21).[14]Itshouldbenotedthatboththeuptakecapacityandseparationselectivitycansignificantlyaffectthepracticalperformanceofanadsorbent.HOF-3ahasahighselectivity,butthelowuptakeofC2H2reduceditsseparationperformance.Incontrast,FeNi-M'MOFcanaddresssuchtrade-offbetweentheadsorptioncapacityandselectivityasshowninFigure2d.ThehighselectivityandhighC2H2adsorptioncapacityofFeNiM'MOFjointlyrevealitsbrightseparationpotentialforC2H2/CO2. TransientbreakthroughsimulationswereconductedtodemonstratetheC2H2/CO2separationperformanceofFeNiM'MOF.ThesimulationsinFigure3ademonstratetheFeNiM'MOFisofpotentialuseforthischallengingseparationofC2H2/CO2mixtures.TheC2H2/CO2mixtures(50/50)wereusedasfeedstomimictheindustrialprocessconditions.PureCO2firstelutedthroughthebed,wheretheCO2purityis99.95%,andfollowedbythebreakthroughofC2H2afteracertaintimeτbreakthatFeNi-M'MOFhasbeensaturatedbyC2H2.TheC2H2capturedamountofFeNi-M'MOFis4.54molL−1basedonthesimulatedcolumnbreakthrough,whichisclosetothatofthebenchmarkUTSA-74(4.86molL−1)[5c]andhigherthanthoseofmostout-performingMOFs,suchasZn-MOF-74(4.06molL−1),[5c]FJU-90a(4.16molL−1),[6c]PCP-33(4.16molL−1)[12].ordingly,FeNi-M'MOFshowsnotonlyahighC2H2/CO2selectivityandhighC2H2uptakebutalsohighC2H2-capturedcapabilityfromgasmixture,enablingthismaterialahugeC2H2/CO2separationpotential.Basedonexperimentalbreakthroughstudies,wefurtherevaluatedtheperformanceofFeNi-M'MOFinnearpracticalseparationprocessesforC2H2/CO2mixture(50/50v/v)asshowninFigure3b.Indeed,FeNi-M'MOFexhibitsexcellentC2H2/CO2mixturesseparationperformanceat298K.CO2wasfirstelutedthroughtheadsorptionbedwithoutanydetectableC2H2,whereasthelatterwasretainedintheMOFcolumnforaremarkableperiodpriortosaturatetheMOF.TheretainedtimeofpureCO2andC2H2forC2H2/CO2(50/50v/v)mixtureonFeNi-M'MOFareupto24and 40minrespectively.ordingly,thecaptured-C2H2wascalculatedtobe4.10molL−1withaseparationfactorof1.7. Figure3.(a)TransientbreakthroughsimulationsforseparationofequimolarC2H2/CO2mixtureusingFeNi-M'MOFat298K,withapartialpressureof50kPaforeach.(b)ExperimentbreakthroughcurvesforequimolarC2H2/CO2mixtureinapackedcolumnwithFeNi-M'MOFat298Kand1bar. Theisostericheatofadsorption(Qst)hasbeenusedtoevaluatethestrengthofinteractionbetweentheadsorbentandtheadsorbate,whichiscalculated(FigureS13)fromtheadsorptionisothermsat273and298K.TheQstvaluesare27~32.8and~24.5kJmol−1ofFeNi-M'MOFforC2H2andCO2,respectively.TheQstvalueofC2H2inFeNi-M'MOFislowerthanthoseofotherMOFssuchasHKUST-1(39kJmol−1),[15]FeMOF74(47.5kJmol−1),[16]andSIFSIX-2-Cu-i(41.9kJmol−1),[1e]andparabletothatofUTSA-74(31kJmol−1).[5c]ThesedataindicateFeNi-M'MOFhasalowerregenerationenergyforC2H2production,whichwouldbebeneficialforpracticalapplication. TounderstandtheseparationperformanceofFeNi-M'MOF,theadsorptionmodesofC2H2inFeNi-M'MOFwereestablishedbyDFT-Dcalculations(FigureS14).ThemodelingstructuresindicatedthattherearetwobindingsitesforC2H2inFeNi-M'MOF.SiteⅠlocatedinthemiddleoftwoadjacentpyzrings,whereC2H2wasadsorbedthroughtheπ-πinteractionsbetweenC2H2andpyzrings(FigureS14a).TheC2H2staticbindingenergyinsiteⅠisupto41.4kJmol−
1.SiteⅡlocatedinthemiddleoftwoadjacentNiopenmetalsites,whereC2H2moleculewasadsorbedthroughtheinteractionsbetweenC≡CandNiopenmetalsitesandwasperpendiculartocaxis.TheC2H2staticbindingenergyinthissiteis29.9kJmol−1,whichissmallerthanthatofsiteⅠ(FigureS14b). Furthervisualizationofthesehost-guestinteractionswascarriedoutthroughhigh-resolutionneutronpowderdiffractionexperiments.ThecrystalstructureunderlowC2D2loadingwasmeasuredfirst(Figure4a).Asexpected,C2D2moleculespreferentiallydistributeonsiteⅠ.C2D2moleculeswereidentifiedbetweenthetwopyzringsthroughπ-πstacking(3.552Å).TheC2D2moleculesshowatitlingangleof27.4ºfromthe[001]direction(crystallographiccaxis)(FigureS15a).Inadditional,multipleintermolecularinteractionswerealsoobservedbetweenC2D2andFeNi-M'MOF(Dᵟ+···Nᵟ-:2.977Å,Cᵟ-···Nᵟ-:3.808Å,Figure4candFigureS15b).Incontrast,thepreferentialCO2bindingsiteislocatedattheopenNisite(Figure4b).TheelectronegativeOᵟ-atomsofCO2interactwiththepositiveopenmetalsiteNiᵟ+.However,thedistanceacrossthechannelisinsufficientforfavorableNiᵟ+···Oᵟ-=C=Oᵟ-···Niᵟ+interactionstoforminthestructure.Thus,CO2moleculeswereadsorbednearthecenterofthechannelandparalleltothechannel.Oᵟ-atomof Thisarticleisprotectedbycopyright.Allrightsreserved. eptedManuscript AngewandteChemieInternationalEdition 10.1002/anie.202000323 COMMUNICATION CO2insertsbetweentheadjacenttwoNiᵟ+atomsfromdifferentlayersandthedistanceofOᵟ-···Niᵟ+are3.746and3.325Å,respectively(Figure4d).Thistypeinteractionisrelativelyweak,beingconsistentwiththegentleadsorptionisothermandlowQstofCO2inFeNi-M'MOF.ThemultiplebindingsitesofFeNiM'MOFforgasmoleculesanditsdifferentbindingmodestowardC2H2andCO2,enableFeNi-M'MOFtoselectiveadsorptionC2H2fromCO2withbothhighC2H2uptakeandremarkableC2H2/CO2selectivity. Figure4.NeutrondiffractioncrystalstructureofFeNi-M'MOF⊃C2D2(a)andFeNi-M'MOF⊃CO2(b),viewedfroma/baxis.AdsorptionbindingsitesofC2D2(c)andCO2(d)forFeNi-M'MOF.Fe,Ni,
C,N,
O,HinFeNi-M'MOFandCO2arerepresentedbyorange,green,gray,blue,red,andwhite,respectively;CandDinC2D2arerepresentedbyorangeandwhite,respectively.ThelabelleddistanceismeasuredinÅ. Insummary,thehighlyselectiveC2H2/CO2separationhasbeenessfullyrealizedbyamixediron/nickelMOFFeNiM'MOFfrommetalloligandapproach.ThestructuralfeaturesofcyanonickelateandoptimalporechannelsinthisMOFallowC2H2moleculestointeractonmultiplebindingsites,withbothveryhighC2H2uptakeandC2H2/CO2selectivityinvolumetricratio.Theso-calleddualfunctionalityinthismaterialenablethisMOFstoserveasoneofthebestmaterialsforC2H2/CO2separationintermsofC2H2-capturedcapability.ThisworkalsoillustratesanoutstandingexampletofurtherrevealthehugeseparationpotentialofMOFadsorbents,especiallyforchallenginggasseparationandpurification.Theactiveongoingresearchaffordstremendousopportunitiesforenergy-efficientseparation. Acknowledgements ThisworkwassupportedbytheZhejiangProvincialNaturalScienceFoundationofChina(LY20E020001),NationalNaturalScienceFoundationofChina(51602301and51672251)andWelchFoundation(AX-1730).J.G.acknowledgestheFundamentalResearchFundsofZhejiangSci-TechUniversity(2019Q007). Conflictofinterest Theauthorsdeclarenoconflictofinterest. Keywords:anicframeworks•gasseparation• acetylene•Hofmann•openmetalsites __________________________________________________ [1]a)
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