Bottom-Up Approach Derived Iron and Nitrogen Cofunctionalized Carbon as E ffi cient Renewable Catalyst for Selective Reduction of Nitroa

《Bottom-Up Approach Derived Iron and Nitrogen Cofunctionalized Carbon as E ffi cient Renewable Catalyst for Selective Reduction of Nitroa》由会员上传分享，免费在线阅读，更多相关内容在学术论文-天天文库。

pubs.acs.org/JPCCArticleBottom-UpApproachDerivedIronandNitrogenCofunctionalizedCarbonasEfficientRenewableCatalystforSelectiveReductionofNitroarenesShuchangWu,*GuodongWen,YangSu,XiaoliPan,HuaYan,JiangyongDiao,*andHongyangLiu*CiteThis:J.Phys.Chem.C2021,125,5127−5135ReadOnlineACCESSMetrics&MoreArticleRecommendations*sıSupportingInformationABSTRACT:Thenon-noblemetalandnitrogencofunctionalizedcarbon(M−N−C)attractenormousattentionsinheterogeneouscatalysis.However,thefabricationoftheM−N−Csystemscommonlyrelyonfossilresourcebasedcarbon,whiletheexploitationofbiomassderivedmaterialsoftensufferfromissuessuchastediousprocedures,complexcompositionofthebiomassandexcessivedosageofthedopantprecursor.Inthisstudy,adirectandlarge-scale,bottom-upmethodwasdevelopedforthefabricationofthesustainableironandnitrogencofunctionalizedcarbon(FeNC)inagreenandsustainableway.TheobtainedFeNCpossessedwell-definedstructureaswellasuniformlydistributedironspecies.ThecatalyticresultssuggestedthatFeNCcouldserveasefficientcatalystfortheselectivereductionofnitroarenes.TheFeNxspeciesplayedanimportantrole,whiletheN-dopedcarbonmatrixmayalsoinvolveinthereaction.1.INTRODUCTIONhighlysoughtafter.Inthisregard,thebiomass-derivedcarbonmodifiedwithanon-noblemetalaswellasNdopantsareItmakesgreatsensetodevelopefficientandsustainableattractive.Althoughpromising,theexploitationoftenconfrontheterogeneouscatalystforthereductionofnitroarenesduetowithtediousprocedures,complexcompositionofthebiomass,theimportantapplicationsofthecorrespondinganilinesintheexcessivedosageofthedopantprecursor,oremploymentofproductionofagrochemicals,pharmaceuticals,dyes,polymers,24−271,2ediblebiomassmaterials.Thus,thedirectpreparationofandsoon.RestrainedbythehighpriceandlimitedtheM−N−Cmaterialsbasedontheearthabundantinedibleresourcesofnoblemetals,thetransitionmetalbasedcatalysts3−7biomasswithrelativelysimpleelementarysubstanceisfavored.orevenmetal-freematerialsaremoreappealing.OwingtoHerein,wereportafacilebottom-upmethodforthetheirinherentadvantagessuchaseasyavailability,highthermalfabricationofthesustainableFeandNcofunctionalizedstability,nontoxicity,andcorrosionresistancetowardacidandcarbon,duringwhichthefilterpaperservesasthecarbonbase,carbonmaterialshavestimulatedenormousattentionsincatalysiseitherassupportorcatalyst.8−10Moreover,thesource,whileironchloride(FeCl3)andmoderateamountofDownloadedviaUNIVOFCALIFORNIASANTABARBARAonMay16,2021at06:42:27(UTC).Seehttps://pubs.acs.org/sharingguidelinesforoptionsonhowtolegitimatelysharepublishedarticles.surfacephysicochemicalpropertiescanbetailoredvia1,10-phenanthroline(Phen)asFeandNprecursor,heteroatomsdoing,amongwhichnitrogen(N)isthemostrespectively.TheobtainedFeNCexhibitedhighcatalyticapplieddopants.TheunequalelectronegativitybetweenCandperformanceintheselectivereductionofnitroarenesandtheNatomscauseschargedelocalizationanddistortionoftheactivesiteswerealsoinvestigated.crystallatticewhentheNatomsdopedintothecarbonskeleton.Asaresult,theNatomswilleffectivelyenrich2.EXPERIMENTALSECTIONprotonsonthesurfaceofthemodifiedcarbonmaterialsand11,122.1.Materials.Nitrobenzene(99%)wassuppliedbycreatedmorestructuraldefects.ShanghaiMacklinBiochemicalCo.,Ltd.Nitrotoluene(99%),Whenthetransitionmetals(M)areincorporatedintothe4-nitroanisole(98%),4-nitrobenzenamine(99%),4-nitro-N-dopedcarbonmatrix,M−N−Csystemscanbefabricated.Beller’sgroupfoundtheM−N−Cmaterials(MwasmainlyFeorCo)exhibitedexcellentperformancefordifferentliquid-Received:January23,2021phasereactions,13−16andtodate,variousmethodswereRevised:February15,2021establishedtofabricatethiskindofcatalyst.17−23Atpresent,Published:March2,2021mostofthereportedM−N−Cmaterialsrelyonthefossilresourcebasedcarbon.Therefore,thedirectsynthesisoftherenewableandefficientcatalystsasanalternativerouteare©2021AmericanChemicalSocietyhttps://dx.doi.org/10.1021/acs.jpcc.1c006205127J.Phys.Chem.C2021,125,5127−5135

1TheJournalofPhysicalChemistryCpubs.acs.org/JPCCArticleFigure1.TEMimagesofFeNC(a−d),FeC(e−g),andFeNC-w(h,i).EDSelementalmapsofFeNC-w(j−m).FeNC-wwasobtainedafterFeNCwastreatedwithconcentratedHCl.Figure2.XRDpatterns(a),N2adsorption−desorptionisotherms(b),Ramanspectra(c)ofthematerials,andtheN1sXPSspectrumofFeNC(d).phenol(99%),2-nitrophenol(99%),2-nitrobenzylalcoholHangzhouSpecialPaperIndustryCo.,Ltd.Allthechemicals(98%),4-nitrochlorobenzene(99.5%),4-nitroiodobenzenewereusedwithoutfurtherpurification.(98%),4-nitroacetophenone(97%),2-nitrofluorene(98%),2.2.PreparationofCatalysts.TheFeandNcomodified8-nitroquinoline(98%),5-nitroindole(98%),and1,10-carbonwassynthesizedbyanimpregnationmethod,followedphenanthrolinemonohydrate(99%)werepurchasedfrombycarbonization.Specifically,0.33gofFeCl3anhydrouswasAladdinReagentCo.Ltd.,Shanghai,China.Irontrichloridedissolvedinthemixtureofethanolandwater,followedbytheanhydrous(CP),hydrazinehydrate(85%),ethanol,andotheradditionof0.82gofPhenundercontinuousstirring.ThenthesolventswereboughtfromChinaMedicineGroupShanghaiobtainedsolutionwasaddeddropwiseto5.0goffilterpaperChemicalReagentCompany.Filterpaperwasobtainedfromusingapipet.TheFeandNprecursorswereimpregnatedat5128https://dx.doi.org/10.1021/acs.jpcc.1c00620J.Phys.Chem.C2021,125,5127−5135

2TheJournalofPhysicalChemistryCpubs.acs.org/JPCCArticleroomtemperaturetoremovethesolvent,andthemodifiedfromtheSEMimages,theTEMimagesofthetwosamplesfilterpaperwasfurtherdriedinanovenat70°C.Next,theshoweddistinctinformation.MostofthenanoparticleswelldriedfilterpaperwastransferredtoaceramiccruciblewithadispersedonthesurfaceofFeNCandthecarbonsupportcoverandplacedinaquartztube.Subsequently,thefilterlookedtransparent,indicatingthatitwasrelativelythin(FigurepaperthatcontainsFeandNprecursorswasheatedina1a−c).ThehighresolutionTEMimagesuggestedthatthetubularfurnaceunderaN2atmosphereto800°Cwithananoparticleshadasizeofaround20nmandweresurroundedheatingrateof5°C/minandkeptfor2h.Theobtainedblackbythecarbonmatrix(Figure1d).Incontrast,aseriousproductwasgroundtoapowderandlabeledasFeNC.Asaaggregationofthenanoparticlescouldbeobservedonthecomparison,theFeCandNCwerefabricatedunderthesamesurfaceofFeCandmostofthenanoparticleswerelargerthanconditionsasthatforFeNCbutwithouttheadditionofPhen50nm(Figure1e,f).ThehighresolutionTEMimageshowedandtheFeCl3,respectively.thatthenanoparticlesinFeCwerealsocoveredwithgraphitic2.3.Characterization.TheX-raydiffraction(XRD)carbonlayers(Figure1g),whichwassimilartothatinFeNC.measurementswererecordedonaRigakuD/Max-2500PCInaddition,thecarbonsupportinFeClookedmuchthickerdiffractometerwithaCuKαradiationsourceoperatingat50thanthatinFeNC.Thus,theadditionoftheNprecursorkV,300mA.Thescanningelectronmicroscopy(SEM)imagesduringthematerialsynthesisnotonlyfavorabletofabricateweretakenusinganFEINano450scanningelectronsmallanduniformnanoparticles,butalsobeneficialforthemicroscopeoperatedat10−15kV.Thetransmissionelectronformationofthinnerlayeredcarbonsupport.microscopy(TEM)wascarriedoutonaJEOLJEM-2100FTheXRDpatternsshowedasharppeaklocatedat2θanglewithanacceleratingvoltageof200kVcombinedwithanround26°forbothFeNCandFeC,whichcouldbeassignedtoenergy-dispersivespectroscopy(EDS)spectrometer.Thethe(002)planeofgraphiticcarbon(Figure2a).Thenarrownitrogenadsorption−desorptionisothermswereacquiredinsteadofabroadpeakindicatingtheformedcarbonhadafromMicromeriticsASAP2020plus/2060at77K.Therelativelyhighcrystallinity.Incomparison,thebroadandweakspecificsurfaceareawascalculatedbyBrunauer−Emmett−diffractionpeakbetween20°and30°forNCindicatedthatitTeller(BET)method.Theporesizedistributionswerewasamorphous.ThissuggestedthattheFe-basedspeciesevaluatedfromthedesorptionbranchesoftheisothermscouldpromotethegraphitizationofthecarbonduringtheusingtheBarrett−Joyner−Halenda(BJH)method.Ramanmaterialsynthesis.Thediffractionpeaksatabout30.1°,35.4°,spectroscopywasrecordedbyaLabRamHR800using53243.0°,53.4°,56.9°,and62.6°correspondedtothe(220),nmlaser.TheX-rayphotoelectronspectroscopy(XPS)spectra(311),(400),(422),(511),and(440)planeofmagnetite28wereperformedonanESCALAB250XPSsystemwithaFe3O4,respectively(JCPDScardNo.72−2303),whilethemonochromatizedAlKαX-raysource(1486.6eV)withpeakscenteredatabout44.6°and65.0°,indicatingthe29correctionforcrosssectionsandescapedepths.presenceofmetallicFeinthecomposites.Therefore,the2.4.CatalyticReactions.TheselectivereductionofXRDanalysissuggestedthepresenceofbothFe3O4andFenitroareneswascarriedoutina15mLglassreactorthatwas(abbreviateasFeOx).ItwasnecessarytonotethatthepeaksealedwithaTeflonlid(BeijingSynthwareGlass,Inc.Pressurethatoriginatedfromthe(100)paneofcarbonmayoverlapVessel,HeavyWall).Typically,10mgoftheFeNCcatalyst,5withthatderivedfromthe(400)planeofFe3O4andthe(110)mmolofnitrobenzene,5equivofhydrazinehydrate,and1mLpaneofFeduetothecloselocationofthesediffractionpeaks.ofethanolwerechargedintotheglassreactor.AfterbeingSimilarly,the(422)planeoftheFe3O4mayalsooverlapwithsealedwithaTeflonlid,theglassreactorwasimmersedinathediffractionpeakthatoriginatedfromcarbon.Comparedto100°Coilbathforacertainperiodoftime.Afterthereaction,FeNC,theFeCexhibitedmoreintensifieddiffractionpeaksforthemixturewasdilutedwithethanolandanalyzedbyGCFeOx.ThissuggestedthattheFeOxnanoparticleswerelargerusinganisoleasinternalstandard.ForthereductionofinFeC,whichisingoodagreementwiththeTEMresults.functionalizednitroarenes,1mmolofthesubstratewasusedTheporetexturalcharacteristicsaswellasthespecificformostofthecases.surfaceareaandporevolumeoftheobtainedmaterialswerestudiedbyN2adsorption−desorptionmeasurements.Ascan3.RESULTSANDDISCUSSIONbeseenfromFigure2b,atypeIVadsorption−desorption30isothermcurvewasobservedfortheas-synthesizedFeNC.3.1.CharacterizationofSamples.ThemorphologyofTheweakN2uptakeatlowrelativepressure(p/p0<0.1)andaeachmaterialwasstudiedbySEMandTEM.TheSEMimagessignificanthysteresisloopathighrelativepressures(0.4

3TheJournalofPhysicalChemistryCpubs.acs.org/JPCCArticleFigure3.CatalyticperformanceofFeNCfortheselectivereductionofnitrobenzene(a),activitycomparisonofeachmaterial(b),correspondingfittingofthereactionparametersaccordingtofirst-(c),zero-(d),andsecond-order(e)reactionkineticswhenFeNCwasthecatalystandfirstreactionfittingfortheFeC-catalyzedreaction(f).Figure4.IRRcomparisonofdifferentmaterials.Figure6.DecompositionofhydrazinecatalyzedbyFeNC.Conditionsareasfollows:20mgofFeNC,3.4gofhydrazinehydrate,2mLofethanol,and1.2gofnitrobenzene.whichaccountedforabout83%ofthetotalporevolume.Incomparison,themicroporevolumeaccountedforabout15%Figure5.CatalyticperformanceoftheFeNCandtheHCl-treatedsamples(a)andtheeffectsofspecialreagentsonthereaction(b).KSCN-1representsthemassratioofKSCNtoFeNC,whichwas1,anditwasalsothecaseforBA-1,BA-2,andBA-3.5130https://dx.doi.org/10.1021/acs.jpcc.1c00620J.Phys.Chem.C2021,125,5127−5135

4TheJournalofPhysicalChemistryCpubs.acs.org/JPCCArticleaTable2.ReductionofSubstitutedNitroarenesCatalyzedbyFeNCabcCondition:10mgofFeNC,1mmolofthesubstrate,5equivofhydrazinehydrate,1mLofethanol,100°C,5h.10h.15mgofFeNC,65°C.d0.5mmolofsubstrate.5131https://dx.doi.org/10.1021/acs.jpcc.1c00620J.Phys.Chem.C2021,125,5127−5135

5TheJournalofPhysicalChemistryCpubs.acs.org/JPCCArticleapproach.TheNmodificationnotonlysignificantlyimprovedthedistributionoftheFe-relatedcomponents,butalsofacilitatedtheformationofthincarbonsupport.Asaresult,thepromotedperformancemayberealizedwhenworkingasacatalyst.Wethenstudiedthecatalyticperformanceoftheobtainedmaterialsintheselectivereductionofnitroarenes.First,thereductionofnitrobenzenewasinvestigatedinthepresenceofFeNC.CatalyticresultsshowedthatFeNCwashighlyactiveandselectivefortheconversionofnitrobenzenetoaniline(Figure3a).Abouthalfofthesubstratewasconvertedwithin0.5h,andmorethan70%ofthenitrobenzeneconversioncouldbeaccomplishedwithin1h.Nearlyallofthenitrobenzenewasconsumedwhenthereactiontimereached3h.Inaddition,theanilinewastheFigure7.StabilityoftheFeNC.Conditionsareasfollows:10mgofdominantproductwithaselectivityofover90%duringtheFeNC,5mmolofnitrobenzene,5equivofhydrazinehydrate,1mLofwholeprocess.Asacomparison,FeCaswellasNCofferedethanol,100°C,3h.Fortheseventhrun,thereactiontimewas4h.manyinferioractivities(Figure3b).Theconversionwasonlyabout55%and30%within5hforFeCandNC,respectively.and22%forFeNCandFeC,respectively,indicatingthetwoWhennocatalystwasused,theautoreductionprocessmaterialscontainedabundantmesopores.outputted15.3%ofnitrobenzeneconversion.TheseresultsTheRamanspectrumofeachmaterialillustratedinFiguredemonstratedthatNCasametal-freecatalystcouldoffer2cwasfittedusingfourLorentzianpeakslocatedatroundlimitedactivity.FeCwithFeOxnanoparticlesbutwithoutN1175cm−1(D4),1340cm−1(D1),1580cm−1(G),and1620modificationperformedbetterthanNC.Incomparison,FeNCcm−1(D2),respectively,andoneGaussianpeakcenteredatwithsmallerFe-containingspeciesaswellasNincorporationaround1510cm−1(D3).31TheD1bandwasrelatedtotheexhibitedthebestperformance.Recently,manykindsofN-defectsaswellasamorphouscarboninthecarbonsupport,dopedcarbonwerereportedtobehighlyactiveforvarious9,33whiletheGbandwasattributedtothegraphiticstructureofreactions.However,heretheactivityofNCwasfarfromthecarbon.Generally,theintensity(area)ratiobetweenthesatisfactory.OnepossiblereasonmayberelatedtoitslowD1andGbandswasusedtoevaluatethegraphitizationdegreegraphitization.Thelowgraphitization,whichwasconfirmedbyofthecarbonmaterials.ThelowerID1/IGvalueindicatedthetheXRDanalysis,wasnotbeneficialfortheadsorptionofthecorrespondinghighergraphitizationdegree.ThecalculatedreactantaswellastheelectrontransferduringthecatalyticID1/IGvaluewas1.4,2.3,and3.3forFeNC,FeC,andNC,reaction.TherelativelyorderedFeCoutperformedtherespectively.TheNChadthehighestID1/IGvalue,andamorphousNC,suggestingtheFeOxandtherelativebettertherefore,ithadmoreamorphouscarbonandstructuralgraphitizationstructureweremoreefficientthanthebareNCdefects.TheFeCexhibitedlowerID1/IGvalue,whichsuggestedinthisstudy.However,ascouldbeseenfromTEMimages,thattheFe-containingspeciescouldpromotethegraphitiza-severeaggregationoftheseparticlesoccurred.ThesinteringoftionprocessviatherearrangementsofthecarbonatomstotheFeOxhamperedthecatalysttoexposemoreactivesites;asreducestructuraldefects.FeNCprovidedthebestgraphitiza-aresult,theactivitywasstilllow.Thequitesmallandwelltionofthecarbonsupport,indicatingthattheintroductionofdispersednanoparticleshadapositiveeffecttoexposemoretheNfavoredthefurtherrearrangementofthecarbonatoms.activesites,therefore,thereactionwassignificantlyacceleratedOntheonehand,thepresenceofNcouldleadtotheinthepresenceofFeNC.Furthermore,theefficientconversionformationofthesmallerFe-containingcomponents;therefore,couldbeachievedindifferentsolventsinthepresenceofmoreactivesiteswouldbeexposedtopromotetheformationFeNC(TableS2).ofwell-definedcarbon.Ontheotherhand,theNthat3.3.ReactionKinetics.WetheninvestigatedthereactionincorporatedinthecarbonlatticemayboosttheactivityofkineticsoftheFeNC-catalyzedreductionprocess.AsfarasthetheseFe-relatedspecies.Bothfactorsthegraphitizationofthefirst-orderreactionisconcerned,thereisalinearrelationshipcarbonsupport.betweenln(c0/c)andT(c0istheinitialconcentrationoftheThesurfacecontentofeachelementanalyzedbyXPStargetsubstrate,whilecistheconcentrationofthetargetshowedtheexistenceofNinFeNC(TableS1).ThehighsubstratewhenthereactiontimeisT).AgoodcorrelationresolutionN1sXPSspectrumofFeNCcouldbedeconvolutedbetweenln(c0/c)andreactiontimewasobserved(Figure3c),intofourpeaks,correspondingtofourkindsofNspeciesindicatingthereactionfollowedafirst-orderkineticsinthis(Figure2d).Thepeakslocatedatthebindingenergiesaroundstudy.Asacomparison,thereactionparameterswasalsofitted399.9,401.4,and403.8eVwereassignedtopyrrolicN,accordingtothezero-aswellassecond-orderreactionkinetics.graphiticN,andoxidizedN,respectively.ThepeakataboutInprinciple,thereisalinearcorrelationbetween(c0−c)and398.7eVwasattributedtoeitherpyridinicNorFeNxspeciesthereactiontimeTforthezero-orderreaction.Sincetheduetothefactthattherewasanegligibledifferenceinbindingvolumeofthereactionmixturealmostremainedduringthe32energybetweenpyridinicNandFeNx.Incomparison,thesewholereactionprocess,weemployedthechangeoftheNspeciesexpectoxidizedNcouldbeignoredinFeC(Figureamountofnitrobenzene(n0-n)insteadof(c0-c)tocorrelateS3).withreactiontime.However,arelativelyweakcorrelationwas3.2.CatalyticPerformanceoftheAs-Synthesizedobserved(Figure3d).Inthesameway,whenthereactionwasSamples.Theabovecharacterizationinformationsuggestedfittedaccordingtothesecondreactionequation,apoorthatFeNCwithwelldispersedFe-containingspeciesinlayeredcorrelationwasalsodisplayed(Figure3e).Consequently,itcarbonwassuccessfullyfabricatedthroughafacilebottom-upwasafirst-orderreactionwhenFeNCworkedascatalyst.5132https://dx.doi.org/10.1021/acs.jpcc.1c00620J.Phys.Chem.C2021,125,5127−5135

6TheJournalofPhysicalChemistryCpubs.acs.org/JPCCArticleAlthoughFeCexhibitedinferiorperformancecomparetothatboostedactivityachievedfortheN-dopedcarboninFeNC33,40,41forFeNC,afirst-orderreactionkineticscouldbedemonstratedthanthepureNC.aswell(Figure3f).Basedontheacidtreatmentofthecatalystandselective3.4.ComparisonoftheAs-SynthesizedCatalystswithmaskingoftheactivesites,itcouldbeconcludedthattheFeNxCommercialMaterials.Thecatalyticactivitywasfurtherwasoneimportantkindofactivesite,whiletheeffectoftheN-assessedbyinitialreactionrate(IRR),whichisdefinedhereasdopedcarbonsupportinFeNCshouldalsobetakenintothemolesofnitrobenzeneconsumed(atlowconversion)perconsideration.Incomparison,theFeOxplayedaninsignificantmoleofFepersecond.ItshowedthatFeNCofferedtherole.highestIRRamongallthecatalysts,withthevalueofaboutThehydrazinehydratewasemployedasthereducingagent0.71/s(Figure4).Asacomparison,theIRRfortheFeC-inthisstudy.Fortheefficientreductionofnitrobenzene,thecatalyzedreactionwasonly0.075/s,whichwasmuchlowerdecompositionofhydrazineisrequired.Therefore,itsthanthatfortheFeNC-mediatedreaction.Inaddition,thedecompositionwasevaluated,duringwhichthevolumeofcommercialFe3O4(20nm),α-Fe2O3(30nm),andFepowdergaseousproductswasmeasuredbywaterdisplacementoutputtheIRRof0.053,0.015,and0.0053/s,respectively.Themethod.ItshowedthatthedecompositionofhydrazinehighspecificsurfaceareaandthequitelowFecontentmadecouldoccurinthepresenceofFeNCwithouttheinvolvementtheFe-relatedcomponentsdispersedinthecarbonmatrix.Asaofnitrobenzene(Figure6),indicatingtheFeNCitselfwasableresult,theactivesitesforFeNCandFeC,especiallytheformertoactivateanddecomposehydrazine.Whenthenitrobenzenewashighlyexposed,whichsignificantacceleratedthereaction.wasaddedtothereactionmixture,thedecompositionof3.5.ActiveSitesandtheActivationofHydrazine.Tohydrazinewasaccelerated.Theactivehydrogenthatwasdeterminetheactivesites,wewashedtheFeNCsamplewithproducedthroughthedecompositionofhydrazinecouldconcentratedHCl,andthetreatedmaterialwaslabeledastransfertonitrobenzeneandreducethenitrogrouptoanFeNC-w.Inaddition,FeNCwasalsotreatedwith2and4aminogroup.Theconsumptionoftheformedhydrogenmaymol/LHClandtheobtainedmaterialsweredenotedasFeNC-bebeneficialforthefurtherdecompositionofhydrazine;asaw(2)andFeNC-w(4).TheXRDpatternsshowedthattheresult,thehydrazinedecomposedfasterwhenFeNCanddiffractionpeaksattributedtoFeOxdisappeared(FigureS4),nitrobenzenecoexistinthereactionsystem.indicatingthattheFeOxnanoparticleswereremoved.The3.6.ReductionofSubstitutedNitroarenes.AseriesofTEMimagesfurtherconfirmedtheabsenceofobservableFeOxfunctionalizednitroareneswerefurtherexaminedtoinvestigatenanoparticles(Figure1h,i).However,theEDSelementalmapstheeffectofvarioussubstituentsonthecatalyticperformancedemonstratedthepresenceofbothFeandN(Figure1j−m).ofFeNC.ItshowedinTable2thatmostofthefunctionalizedSinceHClcouldremovetheironoxideaswellasthemetallicnitroarenescouldconverttothecorrespondinganilines.Foriron,whileitwasinefficienttogetridofFeNxspecies,theexample,thesubstitutedreactantsthatwithanelectron-presenceofbothFeandNafterHCltreatmentstronglydonatinggroup,suchasnitrotoluene,4-nitroanisole,4-indicatedtheexistenceofFeNx.Infact,manyrecentlyreportednitrobenzenamine,andnitrophenol,transformedtoanilinesM−N−Csystemsweretreatedwithacidtoremovethewithveryhighselectivity(Table2,entries1−8).AsaunstablespeciesandthecorrespondingstableMNcomparison,thesubstratewithelectron-withdrawinggroupsxremained.34−36ThecatalyticresultsshowedthatafterHClsuchas4-nitrochlorobenzeneand4-nitroiodobenzeneseemedtreatment,about10%discountoftheactivitywasobservedfortobemoreeasilyconsumed,andtheselectivitywasalsoquiteFeNC-w,FeNC-w(2),andFeNC-w(4)(Figure5a).Thishigh(Table2,entries9−10).Inaddition,theselectivesuggestedthattheFeOxnanoparticlesonlymadeasmallreductionofothersubstrates,suchas2-nitrofluorene,8-contributiontotheselectivereductionofnitrobenzene.Togetnitroquinoline,and5-nitroindole,wasefficientaswell(Tablein-depthinformationoftheactivesites,wetriedtopoisonthe2,entries11−13).However,thesubstitutedreactantwithpotentialactivecenters.Thepotassiumthiocyanate(KSCN)isketonegroupsfailedtoformthecorrespondinganiline(Tablegenerallyemployedasthetitrationreagenttopoisonthemetal2,entry14).Thiswasbecausethecarbonylgroupcouldeasilycentersinviewthatthiocyanateanionsandmetalcationscanreactwithhydrazinetogeneratehydrazone;thus,theformstablechelatecomplex.4,37,38However,therewashardlyformationofanilinewasrestrained.anydifferencewhenKSCNwaschargedtothereactionsystem3.7.StabilityoftheCatalyst.Finally,thestabilityoftheinourcase(Figure5b).Wethenusedbenzoicacid(BA)toFeNCwasevaluated(Figure7).ItshowedthattheconversionpoisontheactivesitesbasedonthediscoverybyXieandco-graduallydecreasedduringtherecyclingtest,butabout86%ofworkers.39ItshowedthatthereactionrateobviouslydecreasedthenitrobenzeneconversioncouldstillbeachievedaftersixwhenBAwasinvolvedinthereaction.Butmorethan60runs.Inaddition,about97%ofconversionwouldberealizedifpercentoftheactivitystillremained.Thisphenomenoncouldthereactiontimeextendedto4h(theseventhrun).Thisbeexplainedbasedontwopossibilities.OneliesinthattheBAsuggestedthatthecatalystwasrelativelystablefortheselectiveisnotasatisfactoryshieldingchemicalforFeNxspecies.Asareductionofnitroarenes.matteroffact,theconvincinganduniversalpoisoningmethodisstilllimitedinthistopicatpresent.Theotheronewasthat4.CONCLUSIONStheFeNxspecieswaseffectivelymaskedbyBA,andtheInsummary,abottom-upanddirectprocedurewasdevelopedobservedactivitymainlyderivedfromtheN-dopedcarbonforthesynthesisofFeandNcofunctionalizedcarbon.ThesupportinFeNC.TheXRD,TEM,andRamananalysisobtainedFeNCpossessedahighspecificsurfacearea,highshowedthatthecarbonmatrixinFeNChadrelativelygoodcontentofmesopores,relativelythincarbonmatrix,andgraphiticstructure.ThehighgraphitizationdegreewasuniformFe-containingcomponents.TheFeNCexhibitedhighbeneficialfortheadsorption,activationandelectrontransfercatalyticperformanceintheselectivereductionofnitroarenesduringthecatalyticreaction,whiletheNdopantfurtherandafirst-orderreactionkineticswasobserved.FeNCitselfmodifiedtheelectronicstructureandsurfaceproperty,thus,coulddecomposehydrazine,buttheprocesswouldbe5133https://dx.doi.org/10.1021/acs.jpcc.1c00620J.Phys.Chem.C2021,125,5127−5135

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