简介:Inthiswork,theinfluenceofCO2onthestructuralvariationandcatalyticperformanceofNa2WO4/Mn/SiO2foroxidativecouplingofmethanetoethylenewasinvestigated.ThecatalystwaspreparedbyimpregnationmethodandcharacterizedbyXRD,RamanandXPStechniques.AppropriateamountofCO2inthereactantgasesenhancedtheformationofsurfacetetrahedralNa2WO4speciesandpromotedthemigrationofOinMOx,Na,Wfromthecatalystbulktosurface,whichwerefavorableforoxidativecouplingofmethane.WhenthemolarratioofCH4/O2/CO2was3/1/2,enrichedsurfacetetrahedralNa2WO4speciesandhighsurfaceconcentrationofOinMOx,Na,Wweredetected,andthenhighCH4conversionof33.1%andhighC2H4selectivityof56.2%wereobtained.WithfurtherincreaseofCO2inthereagentgases,thecontentofactivesurfacetetrahedralNa2WO4speciesandsurfaceconcentrationofOinMOx,Na,Wdecreased,whilethatofinactivespecies(MnWO4andMn2O3)increaseddramatically,leadingtolowCH4conversionandlowC2H4selectivity.ItcouldbespeculatedthatNa2WO4crystalwastransformedintoMnWO4crystalwithexcessiveCO2addedunderthereactionconditions.PretreatmentofNa2WO4/Mn/SiO2catalystbymoderateamountofCO2beforeOCMalsopromotedtheformationofNa2WO4species.
简介:Wereportedabifunctionalmaterial,Cr-salenimplantedconjugatedmicroporouspolymer(Cr-CMP),whichisabletocaptureexcellentCO2amountsandhasaremarkablecatalyticactivitytowardsthecycloadditionreactionofCO2toepoxidesformingcycliccarbonatesatmildconditionswithoutadditionalsolvents.ThisheterogeneousCr-CMPcatalysthasasuperiorcatalyticactivitytoitsrelatedhomogeneouscatalystandcanbereusedmorethantentimeswithoutasignificantdecreaseincatalyticactivity.
简介:TheeffectofthecoadsorptionofCOandO2ontheZiff-Gulari-BarshadsurfacecatalyticreactionsysteminstudiedbyMonteCarlosimulation.ThecoadsorptionofbothspeciesaddsanextrareactionsteptotheclassicalZiff-Gulari-Barshadmodel.Itisshownthatthesecond-orderphasetransitionfromthereactivestatetotheO-passivatedstateintheZiff-Gulari-Barshadmodeliseliminated,andtheproductionrateofCO2increaseslinearlyalongthefractionycoofCOingasphasewhenitislow,inagreementwithexperimentalresults.WealsofindthattheincreaseoftheprobabilityofthecoadsorptionleadstothedecreaseofthecriticalvalueofycoofthediscontinuousphasetransitiontotheCO-passivatedstate.
简介:Recentadvancesontheuseofnanocarbon-basedelectrodesfortheelectrocatalyticconversionofgaseousstreamsofCO2toliquidfuelsarediscussedinthisperspectivepaper.Anovelgas-phaseelectrocatalyticcell,differentfromthetypicalelectrochemicalsystemsworkinginliquidphase,wasdeveloped.Thereareseveraladvantagestoworkingasphase,e.g.noneedtorecovertheproductsfromaliquidphaseandnoproblemsofCO2solubility,etc.Operatingundertheseconditionsandusingelectrodesbasedonmetalnanoparticlessupportedovercarbonnanotube(CNT)typematerials,longC-chainproducts(inparticularisopropanolunderoptimizedconditions,butalsohydrocarbonsuptoC8-C9)wereobtainedfromthereductionofCO2.Pt-CNTaremorestableandgiveinsomecasesahigherproductivity,butFe-CNT,particularusingN-dopedcarbonnanotubes,giveexcellentpropertiesandarepreferabletonoble-metal-basedelectrocatalystsforthelowercost.ThecontrolofthelocalizationofmetalparticlesattheinneroroutersurfaceofCNTisanimportactfactorfortheproductdistribution.ThenatureofthenanocarbonsubstratealsoplaysarelevantroleinenhancingtheproductivityandtuningtheselectivitytowardslongC-chainproducts.TheelectrodesfortheelectrocatalyticconversionofCO2arepartofaphotoelectrocatalytic(PEC)solarcellconcept,aimedtodevelopknowledgeforthenewgenerationartificialleaf-typesolarcellswhichcanusesunlightandwatertoconvertCO2tofuelsandchemicals.TheCO2reductiontoliquidfuelsbysolarenergyisagoodattempttointroducerenewablesintotheexistingenergyandchemicalinfrastructures,havingahigherenergydensityandeasiertransport/storagethanothercompetingsolutions(i.e.H2).
简介:Accuratelymeasuringthedifferentialmolecularabsorptioncrosssectionisthekeytoobtainingahigh-precisionconcentrationofatmospherictracegasesinadifferentialabsorptionlidar(DIAL)system.However,theCO2absorptionlineismeticulousat1.6μm,easilytranslatingandbroadeningbecauseofthechangeoftemperatureandpressure.Hence,measuringtheverticalprofileofatmospherictemperatureandpressuretocalculatetheverticalprofileoftheCO2weightparameterisnecessary.Ingeneral,measuringatmospherictemperatureandpressurehasacertainamountofuncertainty.Therefore,thisstudyproposestheconceptofabalancedon-linewavelength,wherethedifferentialmolecularabsorptioncrosssectionislargerandtheCO2weightparameterisinsensitivetotheuncertaintyofatmospherictemperatureandpressure.Inthisstudy,weanalyzedtheinfluenceofuncertaintyontheCO2weightparameterateverypreselectedwavelength,aswellasdeterminedanappropriatewavelengthnearoneoftheabsorptionpeaks.Ourresultshowsthat1572.023nmshouldbeoneoftheappropriatebalancedonlinewavelengths.ThemeasurementerrorsofthemixingratioofCO2moleculeinthiswavelengthareonly0.23%and0.25%andarecausedby1Ktemperatureerrorand1hPapressureerror,respectively.Thisachievementofabalancedon-linewavelengthwillnotonlydepresstherequirementofthelaser’sfrequencystabilizationbutalsothedemandformeasurementprecisionoftheatmospherictemperatureandpressureprofile.Furthermore,thisstudycanachievetheexactmeasurementoftheverticalprofileofatmosphericCO2basedonanindependentdifferentialabsorptionlaser.
简介:Thispaperreportsonthelongevityofglycerol-dry(CO2)reformingoverthelanthanum(La)promotedNi/Al2O3catalysts.TheXRDresultsshowedthattheNiparticlewaswell-dispersedinthepresenceofLapromoter.Inaddition,viatheNH3-TPDanalysis,itwasfoundthattheLapromoterhasreducedtheacidityofNicatalystwhichmayhaveexplainedthemitigationofcarbonlaydown.Itwasdeterminedthatthe3.0wt%La-promotedNi/Al2O3catalystpossessedthelargestBETspecificsurfaceareaof97m2g-1.Consequently,ityieldedthebestcatalyticlongevityperformancewithconversionattainedmorethan90%,evenafter72hofreactionduration.Significantly,itcanbeconfirmedthatthepresenceofCO2duringtheglyceroldryreformingwasessentialinreducingcarbondeposition,mostlikelyviagasificationpathway.Thishasensuredastabilityofcatalyticactivityforalongreactionperiod(72h).
简介:Aseriesofoxygenpermeabledual-phasecompositeoxides60wt%Ce0.8Gd0.2O2-δ-40wt%LnBaCo2O5+δ(CGO-LBCO,Ln=La,Pr,Nd,Sm,GdandY)weresynthesizedthroughasol-gelrouteandeffectsoftheLn3+cationsontheirphasestructure,oxygenpermeabilityandchemicalstabilityagainstCO2wereinvestigatedsystemicallybyXRD,SEM,TG-DSCandoxygenpermeationexperiments.XRDpatternsrevealthatthelargerLn3+cations(La3+,Pr3+andNd3+)successfullystabilizedthedouble-layeredperovskitestructureofsinteredLBCO,whilethesmallerones(Sm3+,Gd3+,andY3+)resultedinthepartialdecompositionofLBCOwithsomeimpuritiesformed.CGO-PBCOyieldsthehighestoxygenpermeationflux,reaching2.8×10-7mols-1cm-2at925?Cwith1mmthicknessunderair/Hegradient.TheTG-DSCprofilesin20mol%CO2/N2andoxygenpermeabilityexperimentswithCO2assweepgasshowthatCGO-YBCOdemonstratesthebestchemicalstabilityagainstCO2,possiblyduetoitsminimumbasicity.ThestableoxygenpermeationfluxofCGO-YBCOunderCO2atmosphererevealsitspotentialapplicationintheoxy-fuelcombustionrouteforCO2capture.
简介:TogaindeepinsightintotheMorphologicaleffectofNixMg1-xOcatalystsonthereactionofCO2reformingwithmethane,wedesignedandfabricatedthreedifferentspatialstructuralNixMg1-xOcatalysts.TheseNixMg1-xOcatalystswithspecificmodelssuchasrod,sheetandsphere,exhibitedvariousactivityandstabilityinCO2reformingreaction.HereinNixMg1-xOnanorodsdisplayedhighercatalyticactivity,inwhichmethaneconversionwasupto72%andCO2conversionwas64%at670°Cwithaspacevelocityof79,200mL/(gcath),comparedwithnanosheetandnanospherecounterparts.Furthermore,bothcatalystsofNixMg1-xOnanorodandnanosheetshowedahighresistancetowardcokedepositionandsinteringofactivesitesintheprocessofCO2reformingofmethane.
简介:FifteennewabsorptionlinesareobservedwhenstudyingCO2absorptionspectroscopybywavelengthmodulation(WM)techniquewithadistributedfeedbacklaser.TheovertonespectraofCO2around1.31μmandthecorrespondingspectralparameters(i.e.positions,intensities,self-broadeningcoefficients)arepresented.Theintensityoftheweakestlinedetectedis2.25163×10^-27cm^-1/(molecule·cm^-2)atthepressureof5Tort,withacorrespondingabsorptionof3.88×10^-8.
简介:合成了氰根桥联配合物Co[Fe(CN)5NO].5H2O,使用元素分析、热重分析、红外光谱、XRD对配合物进行了表征。红外光谱显示金属离子通过氰根桥联即FeII-CN-NiII传递磁相互作用,是属于桥式氰根配体的CN伸缩振动,而粉末XRD衍射图表明此化合物为面心立方体结构(FCC),空间群为Fm3m(225),晶格常数a=10.2856。通过对该配合物的直流变温磁化率和交流磁化率测定表明金属离子通过氰根传递弱反铁磁作用,根据Curie-Weiss定律,拟合数据获得居里常数C=1.55cm3·K/mol,顺磁居里温度θ=-1.87K。
简介:CO2photoreductionisanattractiveprocesswhichallowsthestorageofsolarenergyandsynthesisofsolarfuels.Manydifferentphotocatalyticsystemshavebeendeveloped,whilethealternativephoto-reactorsarestillinsufficientlyinvestigated.Inthiswork,photoreductionofCO2withH2OintoCH4wasinvestigatedinamodifiedconcentratingsolarreactor,usingTiO2andPt/TiO2asthecatalysts.TheTiO2andPt/TiO2sampleswereextensivelycharacterizedbydifferenttechniquesincludingpowderX-raydiffraction(XRD),N2adsorption/desorptionandUV–visabsorption.ThecatalyticperformanceoftheTiO2andPt/TiO2samplesinthegasphasewasevaluatedunderunconcentratedandconcentratedXe-lamplightandnaturesolarlightwithdifferentconcentratingratios.VariousparametersofthereactionsystemandthecatalystswereinvestigatedandoptimizedtomaximizethecatalyticperformanceofCO2reductionsystem.Comparedwiththenormallightirradiation,theTiO2andPt/TiO2samplesshowhigherphotocatalyticactivity(about6–7times)forreducingCO2intoCH4underconcentratedXe-lamplightandnaturesolarlight.Intherangeofexperimentallightintensity,itisfoundthattheconcentrationofthelightmakesitsuitableforthecatalyticreaction,andincreasestheutilizationefficiencyoftheTiO2andPt/TiO2sampleswhiledoesnotdecreasethequantumefficiency.
简介:Inthiswork,a2Dcovalenttriazine-basedframeworkwaspreparedbyusing1,3-dicyanobenzo[c]thiophene(DCBT)asmonomertoeffectivelycaptureCO2.TheresultingCTF-DCBTwascharacterizedbyFT-IR,XPS,PXRD,elementalanalysis,SEM,TEM,andN2adsorption-desorption.TheresultsindicatethatCTF-DCBTispartiallycrystallineandhasultramicropore(6.5A?)aswellashighheteroatomcontents(11.24wt%and12.61wt%forNandS,respectively).Inaddition,theBETsurfaceareaandtotalporevolumeofCTF-DCBTare500m2/gand0.26cm3/g,respectively.CTF-DCBTpossessesexcellentthermalstability(450°C)andchemicalstabilitytowardsboilingwater,4MHCl,and1MNaOH.TheCO2adsorptioncapacityofCTF-DCBTis37.8cm3/gat1barand25°C.Aftersixadsorption-desorptioncycles,thereisnoobviouslossofCO2uptakeobserved.Duetotheultramicroporeandhighheteroatomcontents,CTF-DCBThashighisostericheatsofadsorptionforCO2andhighselectivitiesofCO2overN2andCH4.At25°C,theCO2/N2andCO2/CH4selectivitiesare112.5and10.3,respectively,whicharehigherthanthoseofmostPOFs.BreakthroughcurvesindicatethatCTF-DCBTcouldeffectivelyseparateCO2/N2andCO2/CH4mixtures.
简介:CO2conversionviaphotocatalysisisapotentialsolutiontoaddressglobalwarmingandenergyshortage.PhotocatalysiscandirectlyutilizetheinexhaustiblesunlightasanenergysourcetocatalyzethereductionofCO2tousefulsolarfuelssuchasCO,CH4,CH3OH,andC2H5OH.Amongstudiedformulations,CubasedphotocatalystsarethemostattractiveforCO2conversionbecausetheCu-basedphotocatalystsarelow-costandabundancecomparingnoblemetal-basedcatalysts.Inthisliteraturereview,acomprehensivesummaryofrecentprogressonCu-basedphotocatalystsforCO2conversion,whichincludesmetalliccopper,copperalloynanoparticles(NPs),copperoxides,andcoppersulfidesphotocatalysts,canbefound.Thisreviewalsoincludedadetaileddiscussiononthecorrelationsofmorphology,structure,andperformanceforeachtypeofCu-basedcatalysts.Thereactionmechanismsandpossiblepathwaysforproductionsofvarioussolarfuelswereanalyzed,whichprovideinsightintothenatureofpotentialactivesitesforthecatalysts.Finally,thecurrentchallengesandperspectivefutureresearchdirectionswereoutlined,holdingpromisetoadvanceCu-basedphotocatalystsforCO2conversionwithmuch-enhancedenergyconversionefficiencyandproductionrates.
简介:InthispaperweusedMOF-5andCu3(BTC)2toseparateCO2/CH4andCH4/N2mixturesunderdynamicconditions.Bothmaterialsweresynthesizedandpelletized,thusallowingforameaningfulcharacterizationinviewofprocessscale-up.ThematerialswerecharacterizedbyX-raydiffraction(XRD)andscanningelectronmicroscopy(SEM).Byperformingbreakthroughexperiments,wefoundthatCu3(BTC)2separatedCO2/CH4slightlybetterthanMOF-5.BecausethecrystalstructureofCu3(BTC)2includesunsaturatedaccessiblemetalsitesformedviadehydration,itpredominantlyinteractedwithCO2moleculesandmoreeasilycapturedthem.Conversely,MOF-5withasuitableporesizeseparatedCH4/N2moreefficientlyinourbreakthroughtest.
简介:ThecorrelationbetweenphasestructuresandsurfaceacidityofAl2O3supportscalcinedatdifferenttemperaturesandthecatalyticperformanceofNi/Al2O3catalystsintheproductionofsyntheticnaturalgas(SNG)viaCOmethanationwassystematicallyinvestigated.Aseriesof10wt%NiO/Al2O3catalystswerepreparedbytheconventionalimpregnationmethod,andthephasestructuresandsurfaceacidityofAl2O3supportswereadjustedbycalciningthecommercialγ-Al2O3atdifferenttemperatures(600–1200C).COmethanationreactionwascarriedoutinthetemperaturerangeof300–600Catdifferentweighthourlyspacevelocities(WHSV=30000and120000mL·g-1h-1)andpressures(0.1and3.0MPa).ItwasfoundthathighcalcinationtemperaturenotonlyledtothegrowthinNiparticlesize,butalsoweakenedtheinteractionbetweenNinanoparticlesandAl2O3supportsduetotherapiddecreaseofthespecificsurfaceareaandacidityofAl2O3supports.Interestingly,NicatalystssupportedonAl2O3calcinedat1200C(Ni/Al2O3-1200)exhibitedthebestcatalyticactivityforCOmethanationunderdifferentreactionconditions.LifetimereactiontestsalsoindicatedthatNi/Al2O3-1200wasthemostactiveandstablecatalystcomparedwiththeotherthreecatalysts,whosesupportswerecalcinedatlowertemperatures(600,800and1000C).ThesefindingswouldthereforebehelpfultodevelopNi/Al2O3methanationcatalystforSNGproduction.
简介:Aseriesofamine-basedadsorbentsweresynthesizedusingsiliceousMCM-41individuallyimpregnatedwithfourdifferentamines(ethylenediamine(EDA),diethylenetriamine(DETA),tetraethylenepentamine(TEPA)andpentaethylenehexamine(PEHA))tostudytheeffectofaminechainlengthandloadingweightontheirCO2adsorptionperformancesindetail.TheadsorbentswerecharacterizedbyFT-IR,elementalanalysis,andthermo-gravimetricanalysistoconfirmtheirstructureproperties.Thermo-gravimetricanalysiswasalsousedtoevaluatetheCO2adsorptionperformanceofadsorbents.Longerchainamine-basedmaterialscanachievehigheramineloadingsandshowbetterthermalstability.TheCO2adsorptioncapacitiesatdifferenttemperaturesindicatethattheCO2adsorptionisthermodynamicallycontrolledoverEDAMCM41andDETA-MCM41,whiletheadsorptionoverTEPA-MCM41andPEHA-MCM41isunderkineticcontrolatlowtemperature.ThechainlengthofaminesaffectstheCO2adsorptionperformanceandtheadsorptionmechanismsignificantly.TheresultsalsoindicatethatCO2adsorptioncapacitycanbeenhanceddespiteofhighoperationtemperatures,ifappropriateamines(TEPAandPEHA)areapplied.However,adsorbentswithshortchainamineexhibithigheradsorptionanddesorptionratesduetothecollaborativeeffectofrapidreactionmechanismsofprimaryaminesandlessdiffusionresistanceofshorterchainlengthamines.