Deactivation Mechanism Study for Sulfur-Tolerance Enhanced NiO Nanocatalysts of Lean Methane Oxidation - Wu et al. - 2021 - Unknown

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pubs.acs.org/JPCCArticleDeactivationMechanismStudyforSulfur-ToleranceEnhancedNiONanocatalystsofLeanMethaneOxidationJianzhouWu,KaiminDu,JianweiChe,ShihuiZou,LipingXiao,HisayoshiKobayashi,andJieFan*CiteThis:J.Phys.Chem.C2021,125,2485−2491ReadOnlineACCESSMetrics&MoreArticleRecommendations*sıSupportingInformationABSTRACT:Thetreatmentofleanmethanefromsulfur-containingexhaustsofnaturalgasvehiclesisimportant,butchallenging,becauseofthestrongandirreversiblecatalystpoisoningbysulfurspecies.Herein,sulfur-toleranceenhancedNiOnanocatalysts(NiO-SPP)arepreparedviasurfacepolymericphosphate(SPP)modificationofNiONPs,andaself-catalyzedsulfation(SCS)mechanismisproposedtorevealtheinsightsontheboostedsulfur-tolerancecapacity.IntheSCSmechanism,thesulfationprocessisdividedintotwosteps,namely,(1)theinitialsulfationprocessand(2)theself-catalyzedsulfationprocessacceleratedbypreviouslyformedsulfates.StabilityanddurabilitytestsofNiONPsandNiO-SPPrevealthattheimprovedsulfur-tolerancecapacityviaSPPmodificationshouldbeattributedtotworeasons,namely,theexternalreasonastheprotectiononthesurfacestructureofNiO-SPP,andtheinternalreasonasthedecelerationoftheinitialsulfationrate.Specifically,characterizationsandanalysesofthecatalystsbeforeandafterstabilitytestsindicatethattheSPPmodificationcouldefficientlycutdowntheinteractionpossibilityofactivesiteswithsulfurspecies.OnthebasisoftheSCSmechanism,theinitialsulfationrateofNiONPsunderlong-termdeactivationtestsiscalculatedtobe12.8timesthatofNiO-SPP,andtheself-catalyzedsulfationrateconstantforNiONPsistwicethatofNiO-SPP.TheSPPmodificationofcatalystsandtheSCSmechanismprovideareferencefortheimprovementofcatalystdurabilityontheperspectiveofdeactivation.■INTRODUCTIONprocessofPdMOCsasanexample,theactivesitePdOcould11Theuseofnaturalgasasanenergysourceislikeadouble-besulfatedintopalladiumsulfatebySO2,andthesulfationedgedsword.Methane,themaincomponentofnaturalgas,isprocesswouldbegreatlyenhancedwiththepresenceof12thehydrocarboncompoundwithhighestH/Cratio,whichsteam.ThedurabilityofMOCsinthepresenceofbothSO2makesnaturalgasacleanfuelcomparedtooilandcoal.1,2andH2Oispathetic,andenhancementoverthesulfur-However,leakandemissionofunburnedmethanecanleadtotolerancecapacityisofurgencyforpotentialindustrialpotentialdamagetotheenvironment.3−6Forinstance,theapplications.applicationofnaturalgasasvehiclesfuelcanrelativelycutInconsiderationofthecostofMOCs,variousnon-nobledowntheemissionofcarbondioxide,butmethaneinthetransitionmetaloxides(suchasFe,Co,Ni,Mn,Zr,Ce,andDownloadedviaUNIVOFPRINCEEDWARDISLANDonMay16,2021at12:41:18(UTC).13−20exhaustcouldpossiblyleadtoseveregreenhouseeffectduetotheircompositeswithacomparisonchartinTableS1ofSeehttps://pubs.acs.org/sharingguidelinesforoptionsonhowtolegitimatelysharepublishedarticles.itsexceptionalcapacityintrappingheatescapingfromthetheSupportingInformation)havebeenstudiedforcomplete7earth.CH4oxidation.Amongthem,NiOhasexhibitedremarkableThetreatmentoftheleanmethaneintheexhaustisof21−2425performance,butitssulfurresistancecapacityislow.significance,andcatalyticoxidationwithtransitionmetalFormetal-basedMOCs,toslowdownthepoisoningprocess,acatalysts,suchasnickeloxide(NiO)andpalladium(Pd),isanchangeofthechemicalsurroundingsforactivesitesisan8efficientapproach.Thecatalystsforexhausttreatmentusuallyefficientapproach,includingadjustmentofsupportsandworkunderconditionsof(A)lowtemperature(typicallylessfunctionalizationoftheactivesites.8,26−29Recently,surfacethan500−550°C),(B)leanmethane(500−1000ppm),(C)ligandmodificationhasemergedasaneffectiveandelegantlargeamountofwatervapor(10−15%)andCO2(15%),(D)strategytotunethesubstratesandproductsadsorptionlargeexcessofoxygen,and(E)thepresenceofSOx(∼1ppm)9andNOx.Sulfurdioxide(SO2),generatedbythecombustionofsulfurcomponentsinnaturalgas(includinghydrogenReceived:December14,2020sulfideandthiols10),willpoisontheactivesitesofmethaneRevised:January12,2021oxidationcatalysts(MOCs)andshrinkthecatalyticcapacityofPublished:January21,2021MOCs.ThepoisoningprocessofMOCsbySO2canbeconsideredachemicalreactionbetweenSO2andactivesites,leadingtotheformationofsulfates.Takingthesulfation©2021AmericanChemicalSocietyhttps://dx.doi.org/10.1021/acs.jpcc.0c111172485J.Phys.Chem.C2021,125,2485−2491

1TheJournalofPhysicalChemistryCpubs.acs.org/JPCCArticleFigure1.MethanecatalyticoxidationactivityofNiONPsandNiO-SPPwithcorrespondingTEMimages.Scalebar,50nm.Testconditions:150mgofcatalysts,0.2%CH,6%O,93.8%N,andGHSV40000mL·g−1·h−1.422cat.propertiesofmetallicnanoparticlesthroughpotentiallyalteringfor2hwillleadtoNiONPs,whicharethesubstratesfor30−34thestericandelectronicpropertyofthecatalystsurface.furtherSPPmodification.TheSPPmodificationprocessis39Inthiswork,NiOnanoparticles(NPs)arepreparedthroughbasedonthepreviouswork.Typically,0.2gofNiONPswasthermaldecompositionofnickeloxalatedihydrateasMOCs,dispersedinto100mLofdeionizedwater,followedbythewhicharefurthersurfacepolymericphosphate(SPP)modifiedadditionofHNO3toadjustthepHvalueofthesolutionto1.toNiO-SPP.TheperformanceanddurabilityofthetwoThesuspensionwasstirredatroomtemperaturefor2hbeforecatalystsaretestedunderthreedifferentconditions.Aself-centrifugation.Then,theprecipitatewasdispersedinto100catalyzedsulfation(SCS)mechanismisappliedtodiscussthemLofNaH2PO4·2H2Oaqueoussolution(themolarratioofPdeactivationprocessofNiONPsduringthecatalyticleantoNiwas1.2:1).AftervigorouslystirringatroomtemperaturemethaneoxidationprocesswithSO2.Themechanismisfor10h,solidproductwasobtainedbycentrifugation.AfterproposedbasedontheFinkeandWatzkytwo-stepnucleationwashingwithdeionizedwaterandethanol,theproductwasmechanism(FWmechanism),aclassicalnanoparticledriedat40°Cinvacuumandfurthercalcinedat500°Cinthe35−38nucleationandgrowthmodel.Thesulfationprocessofairfor2htoobtaintheSPPmodifiedNiONPs,whichisNiONPscanbedividedintotwosteps,namely,(1)theinitialdenotedasNiO-SPP.sulfationprocessand(2)theself-catalyzedsulfationprocessCharacterization.Thefollowingtechniqueswereusedtoacceleratedbypreviouslyformedsulfates.Twokineticcharacterizesamplesbeforeoraftercatalysis.parameterscanbeabstractedviathemechanism,kiandks,(a)X-raydiffraction(XRD),recordedonaRigakuUltimawhicharetheapparentsulfationrateconstantforthetwoIVdiffractometerwithCuKαradiation(40kV,40mA,steps.AlthoughtheSPPmodificationcutsdowntheactivityof10°·min−1from20°to70°).NiONPs,thesulfur-tolerancecapacityislargelyimproved.(b)Transmissionelectronmicroscopy(TEM),performedDetailedcharacterizationsandanalyses,includingFT-IR,XPS,onaHitachiHT7700,withanaccelerationvoltageofTEM,SEM,andDFTcalculations,revealtheprotectionof100kV.SPPmodificationagainstsulfur.Long-termdeactivationtests(c)Scanningtransmissionelectronmicroscopy(SEM)andforthecatalystsindicatethedecelerationoftheinitialsulfationenergydispersiveX-ray(EDX)spectroscopemapping,ratebySPPmodification.performedonaHitachiSU-8010equippedwithEDX.(d)Fourier-transforminfrared(FT-IR)spectra,recordedon■EXPERIMENTALSECTIONaNicoletiS10FT-IRspectrometer.Materials.Nickel(II)oxalatedihydrate(NiC2O4·2H2O,(e)X-rayphotoelectronspectroscopy(XPS),performedon99%)andnickelsulfatehexahydrate(NiSO4·6H2O,99.9%aVGScientificESCALABMarkIIspectrometermetalsbasis)wereacquiredfromAladdinIndustrialCo.,equippedwithtwoultrahighvacuum(UHV)chambers.China.Sodiumdihydrogenphosphatedihydrate(NaH2PO4·AllbindingenergieswerereferencedtotheC1speakat2H2O,AR)andnitricacid(HNO3,AR)werepurchasedfrom284.8eVofthesurfaceadventitiouscarbontocorrectSinopharmChemicalReagentCo.,Ltd.,China.Awatertheshiftcausedbythechangeeffect.purificationsystem(Milli-QReference,Millipore,Merck)was(f)Thermogravimetricanalysis(TGA),performedonaappliedtoproduceultrapurewaterwitharesistivityabove1.82Mettler-ToledoTGA/DSC11100SFinstrument.Typi-×105Ω·mat25°C.Allreagentswereusedwithoutfurthercally,4mgofthesamplewasheatedfromroomtemperatureto800°Catarateof10°C·min−1in50purification.Allthegasesinvolvedinthecatalytictests,mL·min−1ofOflow.includingCH4/N2(1mol%methane),O2/N2(20mol%O2),2highpurityN2(99.999%),SO2/N2(100ppmofSO2),andH2ActivityTest.Catalytictestsofmethanecombustionunder(99.999%),werepurchasedfromHangzhouJingongwuziconventionalconditionswereperformedinafixed-bedquartzCo.,Ltd.,China.reactor(8mmi.d.,450mmlong)operatingatatmospherePreparationofNiONPsandTheirSurfacePolymericpressure.Thefeedflowwas100mL·min−1with0.2vol%CH,4Phosphate(SPP)Modification.NiONPsweresynthesized6vol%O2andN2.Theywereconductedwith150mgofbythethermaldecompositionofcommercialnickeloxalate.catalystsdilutedwithquartzsand(80−100mesh)tomakeupThecalcinationofnickeloxalatedihydrateat500°Cintheaira3cmlongbed(1.5mLvolume).Thetemperatureofthe2486https://dx.doi.org/10.1021/acs.jpcc.0c11117J.Phys.Chem.C2021,125,2485−2491

2TheJournalofPhysicalChemistryCpubs.acs.org/JPCCArticleFigure2.(A)StabilitytestsofNiONPsandNiO-SPPwithTEMimagesafterthetests.Scalebar,50nm.Testconditions:150mgofcatalysts,reactiontemperature500°C;N:conventionalconditions,0.2%CH4,6%O2,93.8%N2;W:H2Oconditions,0.2%CH4,6%O2,15%H2O,and78.8%N;S:SOconditions,0.2%CH,6%O,15%HO,1ppmofSO,and78.8%N;GHSV40000mL·g−1·h−1.(B)FT-IRand(C)XPS2242222cat.(Ni2p1/2,O1s,andS2p)analysisoftheas-synthesizedcatalystsandafterstabilitytests.catalyticbedwasmeasuredwithathermocouple.Thefeedand■RESULTSANDDISCUSSIONthereactionproductswereanalyzedonlinewithagasPerformanceofNiO-BasedCatalysts.CatalystsofNiOchromatograph(GC).NPs(preparedviathermaldecompositionofnickeloxalate)StabilityTest.TheapparatususedforstabilitytestistheandNiO-SPP(preparedviaSPPmodificationofas-synthesizedsametothatfortestingtheactivityofthecatalysts.Indetail,NiONPs)weretestedtodeterminetheactivityandstability.150mgofcatalystswasinvolvedwithareactiontemperatureatTheactivitiesofthecatalyststowardleanmethaneoxidationareshowninFigure1.A150mgportionofeachcatalystwas500°C.Theperformanceofcatalystswasevaluatedinitiallyused,andaschematicillustrationofthereactionapparatusisinunderconventionalconditions(100mL·min−1feedwith0.2%FigureS1oftheSupportingInformation(SI).NiONPsCH4,6%O2andN2)for2h,followedbytheintroductionofexhibitbetteractivity,indicatingthattheSPPmodificationHO(HOconditions,100mL·min−1feedwith0.2%CH,6%224succeeded.Indetail,the10%CH4conversiontemperatureO2,15%H2OandN2)for2h.Afterward,1ppmofSO2was(T10)forNiONPsisabout300°C,T50350°C,andT90400introducedintothereactionsystem(SO2conditions,100mL·°C,while,forNiO-SPP,theT10isabout350°C,T50400°C,min−1feedwith0.2%CH4,6%O2,15%H2O,1ppmofSO2andT90445°C.AccordingtotheTEMimagesofthetwoas-synthesizedcatalysts,thereisnoobviousdifferenceinparticleandN2),andthetestlastedfor8h.Forthelong-termappearanceandsize.TheSPPmodificationshouldbeofathindeactivationtest,thecatalystsunderwentSO2conditions(100coverageofphosphateovertheNiONPssurfacewithpartialmL·min−1feedwith0.2%CH,6%O,15%HO,1ppmof422activesitescovered,whichissupportedbycharacterizationsinSO2andN2)forover24huntiltheactivityislow.ThegasFigureS2,includingFT-IRspectra,XPSspectra,GTAresults,hourlyspacevelocity(GHSV)foreverytestis40000mL·andXRDpatterns.Becauseofthelossofsomeactivesites,the−1−1catalyticactivitydropsafterthemodification.gcat.·h.Thestabilitytestisinthesequenceofconventional-Thetwocatalystsfurtherunderwentstabilitytests(FigureH2O-SO2conditions.Thisisdesignedtoensurethatthe2).Similartotheconditionsfortheactivitytest,after150mgactivityofcatalystsunderconventionalandH2Oconditionsisofcatalystswasloadedinthereactionapparatus,thecatalystsstable,andtheactivitylossunderSconditionsismainlycausedweretestedat500°Cinconventionalconditions(denotedasbytheinteractionofSO2andNiO.Nconditions)for2h,H2Oconditions(denotedasW2487https://dx.doi.org/10.1021/acs.jpcc.0c11117J.Phys.Chem.C2021,125,2485−2491

3TheJournalofPhysicalChemistryCpubs.acs.org/JPCCArticleFigure3.SEMimagesandEDX-mappingresultsofthespent(A)NiONPsand(B)NiO-SPP.Scalebar,2μm.conditions)for2h,andSO2conditions(denotedasSpolymericphosphate.Thesurfacechemicalcompositionsofallconditions)for8h,sequentially.AsshowninFigure2A,withinthesesamplesarelistedinTableS2.Moreover,asshownintheinitial2h(theNconditions),χismaintainedat99%.AfterTableS3,densityfunctionaltheory(DFT)calculationsrevealtheintroductionofH2O(theWconditions),χshrinksrapidlythattheinteractionbetweensulfuroxidespecies(SO2andtoabout90%,whichshouldbeattributedtotheformationofSO3)andthesurfacesofNiONPsismuchstrongerthanthatsurfacehydroxylgroupsontheactivesites.Furthermore,theofNiO-SPP.Hence,thealmostunchangedsurfacestatusofintroductionofSO2(theSconditions)leadstoasignificantNiO-SPPshouldbenotedastheexternalcauseforsulfur-lossincatalyticactivityonNiONPsafter8hstabilitytest,tolerancecapacity.whilethedeactivationforNiO-SPPisrelativelysmall.ThecatalystswerefurtheranalyzedviaSEMandEDX-ComparingtheTEMimagesofthespentcatalystswithmapping.AsshowninFigure3,forspentNiO-SPP,thesignalthoseofas-synthesizedcatalysts,NiONPssufferedsevereofSisveryweakandScanbeconsiderednonexistenceinthesinteringduringthedeactivationprocess,whilethesizeofsample,whilethatsignalisquiteclearforNiONPs.InNiO-SPPhardlychanged.AsshowninFigureS4,NiSO4iscombinationwithalltheevidenceabove,itcanbestatedthatinactivetowardtheleanmethaneoxidation.Probably,itisthebettersulfur-tolerancecapacityforNiO-SPPistheeasiertoformsulfatesovertheNiONPssurfacenakedtoSO2,preventionofSPPtowardactiveNiOfromSO2:reducingleadingtotheenlargementofcatalysts,whilethesulfationthecontactpossibilitybetweenNiOandSO2,deacceleratingprocesswouldbedeceleratedbytheSPPmodification.thesulfationprocess,andthusprotectingthecatalyst.MoreexaminationshavebeenperformedtoanalyzetheProposaloftheSelf-CatalyzedSulfation(SCS)possiblemechanismforthebettersulfur-tolerancecapacityofMechanismforCatalystDurabilityTests.FromtheNiO-SPPindetail.OnthebasisoftheFT-IRspectraofNiOperspectiveofnanoparticlegeneration,thedeactivationNPsbeforeandafterstabilitytests,spentNiONPsexhibitanprocessofNiONPsduringthecatalyticoxidationofleanobvioussurfacesulfate(SO2−)peakat1080cm−1(FiguremethanecanbeconsideredasthegrowthprocessofNiSO442B).40ForNiO-SPP,duetothatthepeaksofphosphorusnanoparticleswithNiONPsasprecursor.Onthebasisofthe−12−FWmechanism,thesulfationofNiONPsisconsideredatwo-(800−1200cm)overlappedthepeaksofSO4,itisdifficultstepreaction.Asshowninfollowingexpressions,step1isthetotellthesurfacestatuschangeofNiO-SPPviaFT-IR,andXPSanalysisisutilized.Figure2CdisplaystheNi2p,O1s,andformationofNiSO4fromNiOwithSO2andO2.WithinthisS2pXPSspectraofas-synthesizedandspentNiONPsandperiod,theapparentreactionrateconstantisdenotedask1,whichistheconstantofthenucleationprocess.ThenucleationNiO-SPP.Foras-synthesizedNiONPs,theNi2ppeakat3+processforthecatalystsulfationistheinitialformationof855.5eVisattributedtoNispecies,andthepeakat853.7eV2+41NiSO4.Step2isaself-catalyzedreaction,wherethepreviouslytoNispeciesalongwithitssatellitepeakat860.8eV.The−generatedNiSO4instep1actsasacatalystacceleratingtheO1speakat530.8eVisassignedtoOspecies,andthepeak2−42subsequentsulfationprocedure,leadingtotherapidat529.1eVtoOspecies.Noticeably,allthreepeaksofNideactivationoftheNiOcatalyst.Similarly,therateconstant2pforspentNiONPsafterstabilitytestupshift,andasimilark2istreatedasakineticparameterofnanoparticlegrowth.upshiftisobservedforO1s,indicatingtheformationofsulfatespeciesandtheretractionofelectronsfromNiO.ForNiO-Step1NiO++→SO22ONiSO41k(1a)SPP,allpeaksofNi2p(855.8,853.9,860.9eV)andO1s(531.0,529.4eV)aremaintained.AccordingtotheS2pXPSStep2NiO+++→SO22ONiSO4NiSO42kspectra,itisclearthatsulfurspeciesarepresentintheformof(1b)sulfateswithbindingenergyintheregionof167−171eVforItshouldbenoticedthatthetwostepsoftheself-catalyzed43spentNiONPs,whilenoobvioussignalforspentNiO-SPPsulfationprocessofNiONPsiscontinuousanddependent.arises.ThepeaksofNi2pandO1sarealsoupshifted(0.2eVOncethereisNiSO4generatedoverthesurfaceofNiONPs,upshiftinNi2pand0.3upshiftinO1s)afterSPPthecatalyzedformationprocessofNiSO4isstarted,andthemodification,revealingastronginteractionbetweenNiOandnewlyformedNiSO4wouldbefurtherinvolvedinthe2488https://dx.doi.org/10.1021/acs.jpcc.0c11117J.Phys.Chem.C2021,125,2485−2491

4TheJournalofPhysicalChemistryCpubs.acs.org/JPCCArticleFigure4.Long-termdurabilitytestforNiONPsandNiO-SPPunderSconditionswithfittedtrendsbasedontheSCSmechanism.Testconditions:150mgofcatalysts,reactiontemperature500°C,0.2%CH4,6%O2,15%H2O,1ppmofSO2,and78.8%N2,andGHSV40000mL·g−1·h−1.Table#1displaysfittedparametersbasedontheSCSmechanism,andTable#2showsthedeactivationtimeforcatalystsreachingthecat.99%,90%,50%,10%,and1%oftheinitialactivity.generationprocess.ItisdifficultandirrationaltodividetheThecatalystsdeactivationplotsareinFigure4withtrendstwosteps,theinitialsulfationandthesubsequentsulfationfittedbytheSCSmechanism.Accordingtothefittingresults,processes,intotwoseparatedprocedures.OnceanyexposedtheSCSmechanismisofgoodfitnesstodescribetheNiOonthesurfaceofcatalystsissulfated,thedeactivationrelationshipbetweenχandtduringthesulfationprocessofprocesswouldstop,includingboththeinitialsulfationandthecatalysts.IncomparisonwithNiONPs,thebettersulfur-subsequentsulfation.Moreover,itisworthnotingthat,tolerancecapacityforNiO-SPPshouldbeattributedtothealthoughH2Oisnotincludedineq1,H2Oactsascatalystmuchsmallervalueofki,namely,thattheformationofsulfateandacceleratesthesulfationprocess,anditsinfluenceshouldovertheNiO-SPPsurfaceismoredifficultthanthatofNiObeconsideredaspartofthesulfationrateconstants.NPsduetothesurfaceprotectionviaSPPmodification.Accordingly,thereactionkineticsforthesulfationofNiOSpecifically,theinitialsulfationrateofNiONPsisabout12.8NPscanbedescribedaseq2timesthatofNiO-SPP,andtheself-catalyzedsulfationrateconstantforNiONPsisabouttwicethatofNiO-SPP.Besides,kk120+[]NiOdeactivationtimeforthecatalystsreachingthe99%,90%,50%,[NiO]=tk1ek(Nkk12+[]×iO0)t+10%,and1%oftheinitialactivityiscalculatedbasedonthe[]NiO02(2)SCSmechanism.TheSPPmodificationcanprovideabout3.3timesthedurability(activitydropsto1%oftheinitialactivity)where[NiO]tand[NiO]0aretheconcentrationsofsurfaceimprovementforthecatalyst.ThefarsmallerinitialsulfationactiveNiOatreactiontimesoftand0,andtisthetimeonstream.TheconcentrationofsurfaceactiveNiOreferstotherateofNiO-SPPshouldberegardedastheinternalcauseforratiobetweenthemolenumberofactiveNiOonthecatalystsulfur-tolerancecapacity.Thus,toimprovethesulfur-tolerancesurfaceandthemolenumberoftotalNiO.Tomakeeq2capacity,modificationstowardtheenhancementofcatalystsappropriateforthedescriptionofthepracticalmethanedesorptionabilityonSO2andtheinhibitionofinitialsulfationoxidationprocess,eq3isderivedrateshouldbeemphasized.kkis+χ0■χ=CONCLUSIONStkiek()kkis+×χ0t+TheactivityanddurabilityofNiONPsandNiO-SPPforleanχs(3)0methaneoxidationhavebeentestedtogaininsightsintotheenhancedsulfur-tolerancecapacityofNiO-SPP,andtheSCSwhereχistheconversionofmethane,χtandχ0refertotheconversionattand0,kiistheapparentinitialsulfationratemechanismisproposedandappliedtoexplainthephenom-constant,andksistheapparentself-catalyzedsulfationrateenon.ThesulfationprocessofNiOnanoparticlescanbeconstant.Herein,eq3isdenotedastheself-catalyzedsulfationtreatedasaprocedureofatwo-stepNiSO4nanoparticle(SCS)mechanism.Detaileddiscussiononthewholegrowth,whereinitiallyformedNiSO4wouldbeinvolvedinthederivationofequationsaboveisintheSI.continuoussulfation,andacceleratesthedeactivationprocessToacquireinsightsintothemechanismofsulfur-tolerancebyactingasacatalyst.Characterizationsandanalyses,boostviaSPPmodification,theas-synthesizedcatalystsfurtherincludingFT-IR,XPS,TEM,SEM,DFTcalculations,etc.,underwentlong-termdeactivationtestsunderSconditionsaremadeonthestructuraltransformationandtheperformancewiththeproposedSCSmechanism.Typically,150mgofthechangeofcatalystsunderSconditions.Ithasbeenuncoveredcatalystswasloadedintothereactionapparatus,andinitiallythatSPPmodificationcanprovidesulfur-tolerancecapacityfortheprocessofmethaneoxidationproceededundertheWNiONPs.Theexternalreasonfortheenhancedsulfur-conditions.Afterreactingfor2h,once1ppmofSO2wastolerancecapacityistheprotectiononthesurfacestructureofintroducedintothesystem,thedatarecordingofmethaneNiO-SPP,andtheinternalreasonisthedecelerationoftheconversionwasstarted,andthereactionwascontinueduntilinitialsulfationrate.TheSPPmodificationprovidesastrategytheconversionwaslow.toslowdownthesulfationprocessofNiO-basedcatalysts,and2489https://dx.doi.org/10.1021/acs.jpcc.0c11117J.Phys.Chem.C2021,125,2485−2491

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