Self-Adjusting Metal-Organic Framework for Efficient Capture of Trace Xenon and Krypton.docx

1、Angewandte1GDChEineZeitschriftderGesellschaftDeutscherChemikerChemiewww.angewandte.deAkzeptierterArtikelTitel:Self-AdjustingMetal-OrganicFrameworkforEfficientCaptureofTraceXenonandKryptonAutoren:ZhengNiu,ZiwenFan,TonyPham,GauravVerma,KatherineA.Forrest,BrianSpace,PraveenK.Thallapally,AbdullahM.Al-En

2、izi,andShengqianMaDieserBeitragwurdenachBegutachtungundUberarbeitungsofortalsakzeptierterArtikel(AcceptedArticle;AA)publiziert.DiedeutscheUbersetzungwirdgemeinsammitderendgultigenenglischenFassungerscheinen.DieendgiiltigeenglischeFassung(VersionofRecord)wirdehestmoglichnachdemRedigierenundeinemKorre

3、kturgangalsEarly-View-BeitragerscheinenundkannsichnaturgemafivonderAAFassungunterscheiden.LesersolltendaherdieendgultigeFassung,sobaidsieveroffentlichtist,verwenden.FurdieAA-FassungtragtderAutordiealleinigeVerantwortung.Zitierweise:Angew.Chem.Int.Ed.2022,e202117807LinkzurVoR:https:/doi.Org/10.1002/a

4、nie.202117807WlLEY-VCHWlLEY-VCHCOMMUNICATIONSelf-AdjustingMetal-OrganicFrameworkforEfficientCaptureofTraceXenonandKryptonZhengNiu,*(aZiwenFan,同TonyPham,同GauravVerma,【加KatherineA.Forrest,对BrianSpace,回PraveenK.Thallapally,*IclAbdullahM.Al-Enizi,mShengqianMa*bla ZiwenFanandProf.Z.NiuCollegeofChemistry,

5、ChemicalEngineeringandMaterialsScience.SoochowUniversity,Suzhou215123,PeoplesRepublicofChinaE-mail:zhenaniuOb Dr.G.VermaandProf.S.MaDepartmentofChemistry,UniversityofNorthTexas.Denton,Texas76201.UnitedStatesE-mail:Shenaaian.MaunLeduc PraveenK.ThallapallyPhysicalandComputationalScienceDirectorate.Pac

6、ificNorthwestNationalLaboratory.Richland,Washington99354,UnitedStatesE-mail:praveen,thallaDallyDnnl.aovd Dr.T.PhamandDr.K.A.ForrestDepartmentofChemistry.UniversityofSouthFlorida,4202E.FowlerAvenue.Tampa.Florida33620,UnitedStatese Prof.B.SpaceDepartmentofChemistry,NorthCarolinaStateUniversity,2700Sti

7、nsonDr.,Raleigh,NC27607,UnitedStatestProf.A.M.Al-EniziDepartmentofChemistry,CollegeofScience,KingSaudUniversity,Riyadh11451,SaudiArabiaSupportinginformationforthisarticleisgivenviaalinkattheendofthedocument.usedtoseparateXeandKrfromnuclearreprocessingoff-gas,171whichisenergy-intensiveanduneconomic.A

8、lternatively,porousmaterialscancaptureXeandKrfromnuclearreprocessingoff-gaswithgreaterenergyefficiency.Amongvarioustypesofporousmaterials,metal-organicframeworks(MOFs)exhibitsuperiorXeandKrcaptureperformance(81comparedtoporousorganiccagecompoundsandtraditionalporousmaterialsincludingsilver-loadedzeo

9、litesandactivatedcarbons.冏ReportedMOFsforcapturingXeandKrcanbegroupedasa)rigidframework,whichexhibitsnosignificantstructuralchangeaftergasfilling(Scheme1A);andb)flexibleframework,whichexhibitsprofoundstructuralchangeaftergasfilling(Scheme1B).Therigidframeworkwithappropriatelysizedporecanaccommodatet

10、heXe/Kratomsbutthefine-tuningofporesizeisnotaneasytask.SomeflexibleMOFsshowthebreathingeffectsafterfillingwithXeorKrmoleculesandthusrealizetheseparationofXeandKr.”However,sincethebreathingeffecthasthethresholdconcentrationtothetargetgas,itisdifficulttobeappliedtothecaptureoftraceamountsofXeandKr.Abs

11、tract:Thecaptureofthexenonandkryptonfromnuclearreprocessingoff-gasisessentialtothetreatmentofradioactivewaste.AlthoughvariousporousmaterialshavebeenemployedtocaptureXeandKr,thedevelopmentofhigh-performanceadsorbentscapableoftrappingXe/Kratverylowpartialpressureasintheinthenuclearreprocessingoff-gasc

12、onditionsremainschallenging.Herein,wereportaself-adjustingmetal-organicframeworkbasedonmultipleweakbindinginteractionstocapturetraceXeandKrfromthenuclearreprocessingoff-gas.Theself-adjustingbehaviorofATC-Cuanditsmechanismhavebeenvisualizedbythein-situsingle-crystalX-raydiffractionstudiesandtheoretic

13、alcalculations.Theself-adjustingbehaviorendowsATC-Cuunprecedenteduptakecapacitiesof2.65and0.52cm3g1forXeandKrrespectivelyat0.1barand298K,aswellastherecordXecapturecapabilityfromthenuclearreprocessingoff-gas.OurworknotonlyprovidesabenchmarkXeadsorbentbutproposesanewroutetoconstructsmartmaterialsforef

14、ficientseparations.inrr解盗FlexibleframeworkSelf-adjustingframeworkiau”3vvv/ivvvxyjjculauaiivvv/iivv/traceXeandKrfromthenuclearreprocessingoff-gas.AsillustratedinScheme1C,differentfromtherigidframeworkandflexibleframework,theporesoftheself-adjustingframeworkcanPursuingthebalancebetweenenergydemandandt

15、heenvironmentisanemergingissueinourgeneration.111Albeitconfrontedwithsomenegativecriticisms,nuclearpowergenerationhaspreventedabout1.84millionairpollution-relateddeathsandreducedCO?emissionsby64billiontonsfromsupplementingfossilfuels.Therapidgrowthofnuclearindustrieshasgeneratedtonsofassociatedhigh-

16、levelradioactivewastewhichmustbesafelysequestered;otherwiseitwouldcauseseriousenvironmentalissues.131Inthetreatmentofnuclearfuelwastes,gaseousradioactivekryptonandxenonaredifficulttocapturecomparedwithotherspecies.141Forgaseousradioactivekryptonandxenon,thelonghalf-lifeof85Kr(t”2*10.8years)urgesitss

17、eparationandcapturefromtheoff-gastoavoidradioactivecontamination,whiletheradioactive135Xecancaptureaneutrontotransmutetostable136Xe,whichcanbeusedinthefieldfromlighting,laser,medicalimagingtoanaesthesia.151Furthermore,thecaptureofXeinthetreatmentofnuclearfuelwastecansignificantlylowerthepriceoftheXe

18、sincetheconcentrationofXeinthenuclearfissiongasis4500timeshigherthanintheatmosphere.161Currently,cryogenicdistillationtechnologyismostly1smartlyadjusttheirporesizeforthetargetgases,andremainunchangedforothergases.Inthisregard,wechooseanalkylporousMOF,anhydrousCu2(ATC)(denotedbyATC-Cu),(121whichhasas

19、emi-rigidframeworkandincludestwotypesofhydrogenrichcavities.TheframeworkofATC-Cucanadjustitsporestoaccommodatethetargetgases(Xe/Kr)yetremainunresponsivetothemaingasesofnuclearreprocessingoff-gas(N2andO2)atnormalpressureandtemperature.Takingadvantageoftheself-adjustingbehavior,ATC-Cudemonstratesthere

20、cordXeandKruptakecapacityat0.1barand298K,aswellasthebenchmarkXecapturecapabilityinthenuclearreprocessingoff-gas.ATC-Cuwassynthesizedaccordingtotheliteraturewithminormodifications(SeeSI).AsshowninFigure1A,fourCupaddlewheelsecondarybuildingunits(SBUs)wereconnectedbytheATCligandtoconstructa4,4-coordina

21、tednet.TheframeworkofATC-CuincludesCu-openmetalsitesandtwotypesofhydrogenrichpolyhedroncavities,CavityI(green)andCavityII(purple).ThesymmetrycenterofCavityIandthemidpointofC4axisofCavityIIaredefinedasthecentersofCavityIandII,respectively.Theaveragedistancebetweenthecenterandtheatomonthevertexofthepo

22、lyhedroncavity(denotedas(C-V)avhereafter)is3.90Aand3.85AforCavityIandII,respectively.CavityIhastwelveHatoms,whileCavityIIhaseightHatomsandeightoxygenatoms.(Figure1B)ThePXRDpatternoftheassynthesizedATC-Cusampleagreeswellwiththecalculatedpatternfromthesinglecrystaldata.Furthermore,theTAGdatarevealedth

23、atATC-Cuisstabletill270C.TheBrunauer-Emmett-Teller(BET)surfaceareaofATC-Cuisabout600m2g_1(Langmuirsurfacearea:667m2/g),whichwascalculatedfromtheN2sorptionisothermsat77K.Thegas-loadedsingle-crystalX-raydiffraction(SCXRD)experimentswereperformedtodetecttheimpactofN2,O2,Xe,andKrontheATC-Cuframework.113

24、1AfterexposingintoN2orO2atmosphereat298Kand1barfor12h,thecavitiesinATC-Curemainunchanged,indicatingthattheframeworkofATC-CushowsrigiditytowardN2andO2presumablyduetotheveryweakinteractions.However,afterloadingXetoATC-Cuunderthesamecondition,significantchangesoftheATC-Cuframeworkwereobserved.Different

25、fromtheO2andN2molecules,therelativelystrongerinteractionbetweenXeandH/OatomsonthecavitiesofATC-CumakethepartsofthecavitiesintheATC-CuframeworkcanshrinkandsmartlyfitXeatoms,andtherestcavitiesintheframeworkareenlargedtobalancetheinnerstressofthecrystal.AsshowninFigure1CandD,Xeatomsarelocatedatthecente

26、rofthecavitiesornearby.Comparedwith(C-V)avofCavityI,theaveragedistancebetweenXeandtheatoms(denotedas(Xe-V)avhereafter)onCavityIAandIIAdecreasesfrom3.90Ato3.67Aand3.75Arespectively.Meanwhile,theshapeoftheCavityIAandIBexhibitsthesignificantchanges:thelengthofCavityIchangesfrom6.24Ato5.53Aand6.77AforCa

27、vityIAandIBrespectively.(Figure1C)ThesimilarselfadjustingbehaviorcanalsobeobservedatCavityIBandIIB,yetthe(Xe-V)avofCavityIIBincreasesfrom3.85A(C-V)”ofCavityII)to3.94A.(Figure1D)AlthoughtheuptakeamountofKrinATC-CuislessthanthatofXe,wealsocanobservetheKratomsleadthechangeoflengthofcavities,whichindica

28、testhatthesimilarinteractionsasXe.(SchemeS1)Consequently,ATC-Cuexhibitstheself-adjustingbehaviorforXeandKr,whileexhibitingunresponsivetoN2andO2.Theaboveself-adjustingbehaviormaybeattributedtotheinteractionsbetweenXe/Kratomsandframeworkcausedlocaldynamics.Figure1.(A)ThecavitiesintheframeworkofATC-Cu;

29、(B)TheenlargedviewofCavityIandII;Thechangeofthe(C)CavityIand(D)cavityIIafteradsorbingN2,O2,andXe.(TheblueballinCavityIandIIstandforthecenterofthecavities,andthegoldballinCavityIA,IB,IIAandIIBstandfortheSCXRDdeterminedlocationofXeinATC-Cu).Figure2.Thein-situSCXRDdeterminedlocationsofXeatomsinthecavit

30、iesofATC-Cu.FurtherstudiesoftheXeandKrloadedATC-Cucrystalsrevealedthemechanismoftheself-adjustingbehaviorinATC-Cu.AspresentedinFigure2,therearefourprimarylocationsofXeatomsinATC-Cu,whicharebasedonmultipleC-H-Xe2interactions.Remarkably,althoughthesitebetweentwooppositeCupeddle-wheelexhibitsexcellentC

31、H4andC2H2adsorptioncapability,1141fewXeorKratomscanbeobservedatthesitefromin-situSCXRD.TheaboveresultssuggesttheCuunsaturatedmetalsiteisnotthepreferredXeorKradsorptionsite.ToexplorethepreferentialXeadsorptionsite,weemployedperiodicdensityfunctionaltheory(DFT)methodstodeterminetheabsoluteenergiesford

32、ifferentXeadsorptionsitesinATC-CuasrevealedthroughSCXRD.Thecalculationresultsindicatedthatthecontractivecavities,CavityIAandIIA,aretheenergeticallyfavorablesitesinATC-Cu,withthecalculatedenergyof39.38and41.56kJmol-1forXe1andXe2,whiletheexpandedCavityIBandIIBexhibitsthelowerenergyof37.45and31.28kJmol

33、-1,whichadsorptionisothermsforXe,Kr,N2,andO2werecollectedat298K.AsillustratedinFigure3A,theuptakeamountsofN2andO2forATC-CuissignificantlylowerthanXeandKr.TheXeuptakecapacityofATC-Cureaches2.65mmolgat298Kand0.1bar,aremuchlowerthanthecontractivecavities.Thecalculationresultsfurtherconfirmedtheself-adj

34、ustingbehaviorofATC-CuiscausedbythesynergisticeffectbasedonmultipleweakinteractionsbetweenXeandtheframework.CalculationsoftheadsorptionenergiesforKradsorbedabouttheanalogoussitesinATC-CurevealednotablylowerbindingenergiescomparedtothoseforXe(TableS10).respectivelyattains2.7and0.52mmolg1at1and0.1bar,

35、whicharetherecordvaluesundersimilarconditions.I810-11)(Figure3D)Uponreaching1barat298,ATC-Cucanadsorb5.0mmolgor0.95gcm3Xe,whichisevenhigherthanxenonhydrate(0.85gcm3).Furthermore,ATC-Cuexhibitsexcellentcycleperformance;asshowninFigure3B,theuptakeamountofXeexhibitsnodecreaseaftertencycles.Theexcellent

36、XeandKrcapabilityatlowpressuresandroomtemperaturessuggeststhatATC-CuisapromisingmaterialforXeandKrcaptureevenintheambientatmosphere.InspiredbythesignificantdifferenceintheuptakeamountbetweenXe/KrandN2/O2inATC-Cu,theselectivityofXe/N?andXe/O2aswellastheuptakeamountofXeinthemixturegas(400ppmXe,balance

37、dbyN2orO2)wasdeterminedusingtheIdealAdsorbedSolutionTheory(IAST).Meanwhile,theselectivityofKr/N2andKr/O?aswellastheuptakeamountofKrinthemixturegas(1000ppmKr,balancedbyN2orO2)at298Kand1barwasalsodeterminedbyIAST.AsdisplayedinFigureS7andS8,thecalculatedXe/NzandXe/Ozselectivityforthecorrespondingmixtur

38、egas(400ppmXe,balancedbyN2orO2)inATC-Cuare66and109respectivelyat298Kand1bar.For400ppmXeinN2and1000ppmKrinN2,thecalculateduptakeamountattainsto22.2mmolkgand4.2mmolkg1,respectively.Furthermore,theselectivityofXe/KrwasalsodeterminedusingIAST.TheXe/KrselectivityfortheKr/Xemixture(Xe/Kr=20/80v/v)is13.9,w

39、hichislowerthanCo-squarate,SB-MOF-1,CROFOUR-1-Ni,andMOF-Cu-H,buthigherthanotherMOFs(TableS4).(8J0-111Figure3.(A)TheXe,Kr,O2.andN2isothermsforATC-Cu；(B)Xeadsorption/desorptioncyclingdataofATC-Cu;Surveyof(C)Xeand(D)Kruptakeamountat298Kand0.1barinATC-Cuandothertop-performancematenals.654321o.aGO.GO.BEE

40、-ssaoDToinvestigatetheimpactoftheself-adjustingbehavioronthegasadsorptioncapabilityofATC-Cu,thesingle-componentcomparedfavorablywiththereportedporousmaterials.1810-111(Figure3C)Similarly,KruptakeamountofATC-Cuat298KIlliFigure4.(A)Columnbreakthroughexperimentfor400ppmXe.40ppmKr,21%O2,balancedwithN：at

41、298Kand1barforATC-Cu;(B)Columnbreakthroughexperimentfor1000ppmKr,21%O2,balancedwithN2at298Kand1barforATC-Cu.(C)Xeuptakeamountsoftopperformancematenalsfromcolumnbreakthroughexperimentfor400ppmXe.40ppmKr,21%O2.balancedwithN：at298Kand1bar;(D)Kruptakeamountsoftopperformancematenalsfromcolumnbreakthrough

42、experimentfor1000ppmKr,21%O2,balancedwithNjat298Kand1bar.GiventhehighselectivityofXeandKroverN2and02calculatedbyIAST,thecolumnbreakthroughexperimentswereperformedwithagasmixtureconsistingof400ppmXe.40ppmKrbalancedwithN2andO2.Thisconditionispresentinthenuclearreprocessingindustryandanymaterialthatisc

43、apabletoselectivelyseparateXeandKrovertheothergases,nearroomQ一。snuroIAIpQ8O(12)1314temperature,wouldpotentiallyreplacecryogenictechnology.Therefore,columnbreakthroughexperimentsatroomtemperatureonCu-ATCwereperformed,byfeedingairwith400ppmXeand40ppmKrandmonitoredusingamassspectrometerasshowninFigure4

44、A.TheretentiontimeofXeislongerthanthatofKrandothermaingasesintheairwhichindicatesthatATC-CucaneffectivelycaptureandseparateXefromagasmixtureusefulfornucleargasreprocessing.TheXeandKrcapacityofATC-CufromthebreakthroughexperimentismuchhigherthananyMOFsandporousorganiccagematerialswetestedthusfar.Assho

45、wninFigure4C,theequilibriumXecapacityfrombreakthroughexperimentsinATC-Cu(32mmol/kg)surpassedanyMOFsandporousorganiccagematerialswetestedthusfar.FurtherbreakthroughexperimentswereperformedonATC-CutodemonstratetheremovalofKrfromthegascompositionwithoutXe(1000ppmKr,78%N21and21%O2)atroomtemperature(Figu

46、re4B).TheKrcapacityofCu-ATCwasfoundtobe8mmolkg1,higherthanthehigh-performancematerialsincludingNiMOF-74,CC3,andSBMOF-1(Figure4D).Inconclusion,wereportedaself-adjustingframeworkinMOFforcapturingtraceXeandKrfromthenuclearreprocessingoffgas.Theself-adjustingbehaviorofATC-Cuhasbeenillustratedviagases-lo

47、adedSCXRDstudiesalongwiththeoreticalcalculations.Theuniqueself-adjustingframeworkendowstheATC-CutherecordXeandKruptakecapacityat0.1barand298K,aswellasthebenchmarkXecapturecapabilityinthenuclearreprocessingoff-gas.Thisworkprovidesanewroutetodesignandimplementnovelporousmaterialswiththeself-adjustingf

48、rameworkfordevelopinghigh-performanceseparationmaterials.AcknowledgementsTheauthorsthankthesupportfromtheRobertA.WelchFoundation(B-0027)andtheUSNationalScienceFoundation(ECCS-2029800).Z.N.acknowledgestheNationalNaturalScienceFoundationofChina(Grant22001186)andtheNationalScienceFoundationofJiangsuPro

49、vince(GrantBK20200853).T.P.,K.A.F.,andB.S.acknowledgestheNationalScienceFoundation(AwardNo.DMR-1607989),includingsupportfromtheMajorResearchInstrumentationProgram(AwardNo.CHE1531590).ComputationalresourcesweremadeavailablebyaXSEDEGrant(No.TG-DMR090028).ResearchComputingattheUniversityofSouthFloridaa

50、ndHigh-PerformanceComputingatNorthCarolinaStateUniversity.B.S.alsoacknowledgessupportfromanACSPetroleumResearchFundgrant(ACSPRF56673ND6).PKTthankDOE-OfficeofNuclearEnergyforsupport.Particularly,wethankKenMarsden(INL),JohnVienna(PNNL),PatriciaPaviet(PNNL)andKimberlyGray(DOENE).PartialsupportfromtheRe

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