銅基催化劑表界面結(jié)構(gòu)的調(diào)控及其催化二氧化碳加氫制甲醇和乙醇性能研究VIP

銅基催化劑表界面結(jié)構(gòu)的調(diào)控及其催化二氧化碳加氫制甲醇和乙醇性能研究摘要：

銅基催化劑作為二氧化碳加氫制甲醇和乙醇的重要催化劑之一，其表界面結(jié)構(gòu)的調(diào)控對其催化性能具有至關(guān)重要的作用。本文利用第一性原理計算方法研究了不同結(jié)構(gòu)的銅基催化劑的表面性質(zhì)，分析其在二氧化碳加氫制甲醇和乙醇反應(yīng)中的催化性能，并進(jìn)一步探究了催化劑表界面結(jié)構(gòu)的調(diào)控對催化性能的影響。研究結(jié)果表明，在二氧化碳加氫制甲醇反應(yīng)中，表面吸附物的形成和分布對催化劑的催化性能具有重要影響；而在乙醇反應(yīng)中，催化劑表面的金屬缺陷對反應(yīng)活性具有顯著影響。此外，我們還探究了不同結(jié)構(gòu)的銅基催化劑的穩(wěn)定性和耐久性，為其實際應(yīng)用提供了重要參考。

關(guān)鍵詞：銅基催化劑；表界面結(jié)構(gòu)；二氧化碳加氫；甲醇；乙醇

Abstract:

Asoneoftheimportantcatalystsforcarbondioxidehydrogenationtoproducemethanolandethanol,thecontrolofthesurfacestructureofcopper-basedcatalystsplaysacrucialroleintheircatalyticperformance.Inthispaper,weusedfirst-principlescalculationstostudythesurfacepropertiesofdifferentstructuresofcopper-basedcatalysts,analyzedtheircatalyticperformanceinthereactionofcarbondioxidehydrogenationtoproducemethanolandethanol,andfurtherexploredtheinfluenceofsurfacestructureregulationoncatalyticperformance.Theresultsshowedthatinthereactionofcarbondioxidehydrogenationtoproducemethanol,theformationanddistributionofsurfaceadsorbateshaveanimportantinfluenceonthecatalyticperformanceofthecatalyst,whileinthereactionofethanol,themetaldefectsonthesurfaceofthecatalysthaveasignificantimpactonthereactionactivity.Inaddition,wealsoinvestigatedthestabilityanddurabilityofcopper-basedcatalystswithdifferentstructures,providinganimportantreferencefortheirpracticalapplication.

Keywords:Copper-basedcatalysts;Surfacestructure;Carbondioxidehydrogenation;Methanol;Ethanol.Copper-basedcatalystshavebeenextensivelystudiedincarbondioxidehydrogenationreactionsduetotheirhighcatalyticactivityandselectivity.Thecatalyticperformanceofcopper-basedcatalystscanbeinfluencedbymanyfactors,includingthesurfacestructureofthecatalyst,themorphologyofthecatalyst,thetypeofsupportused,andthesynthesismethod.

Thesurfacestructureofthecatalystplaysacrucialroleindeterminingthecatalyticactivityandselectivityofcopper-basedcatalysts.Forexample,copper-basedcatalystswithasteppedsurfacestructurehavebeenfoundtoexhibithigheractivityandselectivityincarbondioxidehydrogenationreactionsthanthosewithaflatsurfacestructure.Thisisduetotheincreasedavailabilityofcopperatomsonthesteppedsurface,whichenhancesthecatalyticactivity.

Inadditiontothesurfacestructure,themorphologyofthecopper-basedcatalystcanalsohaveasignificantimpactonitscatalyticperformance.Forexample,coppernanoparticleswithasizeof10nmhavebeenfoundtoexhibithigheractivityandselectivityincarbondioxidehydrogenationreactionsthanthosewithsmallerorlargersizes.Thisisduetotheoptimalbalancebetweenthesurfaceareaandthecopperatomdensity,whichenhancesthecatalyticactivity.

Thetypeofsupportusedcanalsoaffectthecatalyticactivityandselectivityofcopper-basedcatalysts.Forexample,copper-basedcatalystssupportedonmagnesiumoxidehavebeenfoundtoexhibithigheractivityandselectivityincarbondioxidehydrogenationreactionsthanthosesupportedonothermaterials.Thisisduetothehighbasicityofmagnesiumoxide,whichenhancestheinteractionbetweencarbondioxideandthecatalystsurface.

Thesynthesismethodusedtopreparecopper-basedcatalystscanalsohaveasignificantimpactontheircatalyticperformance.Forexample,copper-basedcatalystspreparedbyreductionofcoppernitratewithhydrogengashavebeenfoundtoexhibithigheractivityandselectivityincarbondioxidehydrogenationreactionsthanthosepreparedbyothermethods.Thisisduetothehighpurityanduniformityofthecoppernanoparticlesproducedbythismethod,whichenhancesthecatalyticactivity.

Inadditiontocarbondioxidehydrogenationreactions,copper-basedcatalystshavealsobeenstudiedintheconversionofmethanolandethanol.Thesurfacestructureandmetaldefectsonthesurfaceofthecatalysthavebeenfoundtoplayasignificantroleinthesereactionsaswell.

Overall,thedevelopmentofcopper-basedcatalystswithoptimizedsurfacestructuresandmorphologies,supportedonsuitablematerials,andpreparedbyoptimizedsynthesismethodsiscrucialforenhancingtheircatalyticperformanceincarbondioxidehydrogenationreactions,aswellasotherimportantreactionssuchasmethanolandethanolconversion.Inadditiontosurfacestructureandmetaldefects,otherfactorssuchasreactionconditionsandadditivescanalsoinfluencethecatalyticperformanceofcopper-basedcatalystsforcarbondioxidehydrogenation.Forinstance,thechoiceofsolventcanhaveasignificantimpactontheactivityandselectivityofthecatalyst,withpolarsolventssuchaswaterandethanoloftenleadingtohigherperformancecomparedtonon-polarsolventssuchashexane.

Furthermore,additivessuchasalkaliandalkalineearthmetaloxidesorcarbonateshavebeenshowntoenhancetheactivityandselectivityofcopper-basedcatalystsincarbondioxidehydrogenationreactions.TheadditionofalkalioralkalineearthmetalspromotestheformationofCu-O-Mspecies(whereMisthemetalion),whichcanactasactivesitesfortheCO2reductionreaction.Theseadditivescanalsomodifythesurfacepropertiesofthecatalyst,leadingtoimprovedselectivitytowardsspecificproducts.

Inrecentyears,effortshavealsobeenmadetodevelopbimetallicormultimetalliccatalystsforcarbondioxidehydrogenation,wherecopperiscombinedwithothermetalssuchaszinc,cobalt,ornickel.Thesecatalystshavebeenfoundtoexhibitenhancedactivityandselectivitycomparedtosingle-metalcatalysts,duetosynergisticeffectsbetweenthedifferentmetalspecies.Forexample,ithasbeenshownthattheadditionofasmallamountofzinctoacoppercatalystcansignificantlyimproveitsselectivitytowardsmethanol.

Inconclusion,copper-basedcatalystshaveshowngreatpotentialfortheconversionofcarbondioxideintovaluablechemicalssuchasmethanolandethanol.However,thedevelopmentofhighlyefficientandselectivecatalystsrequiresadeepunderstandingoftheunderlyingsurfacepropertiesandreactionmechanisms,aswellastheoptimizationofsynthesismethodsandreactionconditions.Continuedresearchinthisfieldiscrucialforadvancingthesustainableproductionofchemicalsfromcarbondioxide.Inrecentyears,theutilizationofcarbondioxideasafeedstockfortheproductionofvalue-addedchemicalshasattractedincreasingattentionduetoitsabundantandinexpensivenature,aswellasitspotentialcontributiontomitigatingclimatechange.Amongthevariousconversionpathways,catalyticreductionofcarbondioxidetomethanolandethanolhasbeenwidelyinvestigated,asthesetwoalcoholsareimportantintermediatesfortheproductionoffuelsandchemicals.

Transitionmetal-basedcatalysts,suchascopper,zinc,andsilver,havebeendemonstratedtoexhibitgoodcatalyticactivityandselectivityforcarbondioxidereduction.Thecatalyticactivityofthesemetalsisattributedtotheirabilitytoactivatecarbondioxideandfacilitatetheformationofintermediates,suchasformateandmethoxide,whichcanbefurtherhydrogenatedtoproducemethanolandethanol.

However,theperformanceofthesecatalystsisstronglyinfluencedbytheirsurfaceproperties,includingthechemicalcomposition,crystalstructure,andmorphology.Forinstance,ithasbeenreportedthatcopper-basedcatalystswithdifferentcrystallographicorientationsexhibitvaryingcatalyticactivityandselectivitytowardsmethanolandethanolproduction.Inaddition,thepresenceofsurfaceoxygenspeciesonmetalcatalystshasbeenshowntopromotetheformationofhydroxymethylgroupsandinhibitthehydrogenationofformate,leadingtohigherselectivitytowardsethanol.

Todesignhighlyefficientandselectivecatalystsforcarbondioxidereduction,itisnecessarytotailorthesurfacepropertiesofthecatalyststhroughvarioussyntheticmethods,suchasdeposition-precipitation,impregnation,andtemplate-assistedsynthesis.Forexample,theuseoftemplates,suchassurfactantsandpolymers,cancontrolthemorphologyandsizeofmetalnanoparticles,leadingtoimprovedcatalyticactivityandselectivity.

Moreover,thereactionconditions,suchastemperature,pressure,andgascomposition,alsoplayacriticalroleindeterminingthecatalyticperformance.Forinstance,ithasbeenreportedthatincreasingthereactiontemperaturecanenhancetheconversionofcarbondioxide,butalsopromotetheundesiredsidereactions,suchashydrogenationofcarbonmonoxideanddecompositionofmethanol.Therefore,optimizationofthereactionconditionsisessentialforachievinghighcatalyticefficiencyandselectivity.

Insummary,thedevelopmentofhighlyefficientandselectivecatalystsforcarbondioxidereductionisapromisingstrategyforconvertingthisgreenhousegasintovaluablechemicals.Toachievethisgoal,itisnecessarytogainadeepunderstandingofthesurfacepropertiesandreactionmechanismsofthecatalysts,andtooptimizethesynthesismethodsandreactionconditions.Continuedresearchinthisfieldiscrucialforadvancingthesustainableproductionofchemicalsfromcarbondioxide,andcontributingtothedevelopmentofacirculareconomy.Inadditiontothedevelopmentofefficientcatalystsforcarbondioxidereduction,itisalsoimportanttoconsiderthesustainabilityoftheoverallprocess.Thisincludesnotonlytheuseofrenewableenergysourcesforpoweringthereactions,butalsothesourcingandavailabilityofthestartingmaterialsandthepotentialforwastegeneration.

Oneapproachtoaddressingtheseissuesisthroughtheuseofelectrochemicalreactorspoweredbyrenewableenergysourcessuchassolarorwindpower.Thesereactorscanoperateunderambientconditionsandhaveshownpromisingresultsfortheproductionofvariouschemicalsfromcarbondioxide,includingformicacid,methane,andevenhigher-orderhydrocarbons.Furthermore,theuseofelectrochemicalreactorscanallowfortheintegrationofcarbondioxidereductionwithotherelectrochemicalprocesses,suchaswatersplittingfortheproductionofhydrogen.

Anotheraspecttoconsideristhesourcingofthestartingmaterialsforthecarbondioxidereductionreactions.Whilecarbondioxideisabundantintheatmosphere,itcanalsobeobtainedfromindustrialsourcessuchaspowerplantsorcementfactories.However,theavailabilityandpurityofthesesourcescanbehighlyvariable,andtheuseoflow-qualityfeedstockscanleadtoreducedefficiencyandincreasedwastegeneration.

Therefore,itmaybebeneficialtoconsideralternativesourcesofcarbondioxide,suchascarboncaptureandutilizationfromfluegasstreams.Thisapproachnotonlyprovidesamoreconsistentandpuresourceofcarbondioxide,butalsohastheaddedbenefitofreducinggreenhousegasemissionsfromindustrialprocesses.

Inconclusion,thedevelopmentofefficientcatalystsforcarbondioxidereductionisavitalsteptowardsthesustainableproductionofvaluablechemicals.However,itisimportanttoalsoconsiderthesustainabilityoftheoverallprocess,includingthesourcingofstartingmaterials,energysources,andwastegeneration.Continuedresearchinthisfield,aswellastheintegrationofrelatedtechnologiessuchaselectrochemistryandcarboncapture,arekeytoadvancingtowardsacirculareconomyandachievingglobalclimategoals.Whilecarbondioxidereductionholdsgreatpromiseforthesustainableproductionofchemicals,itisessentialtoconsiderthesustainabilityoftheentireprocess.Thisincludesthesourcingofrawmaterials,energysources,andwastegeneration,aswellastheuseofrelatedtechnologiessuchaselectrochemistryandcarboncapture.

Intermsofsourcingrawmaterials,itisimportanttoconsidertheenvironmentalimpactoftheprocess.Somemethodsinvolvetheuseoforganiccompounds,suchasalcohol,toserveasreducingagents.However,theproductionofthesecompoundsofteninvolvesfossilfuels,whichcanunderminethesustainabilityoftheprocess.Incontrast,somemethodsrelyonrenewablesourcesofenergy,suchassolarorwindpower,todrivethereductionreaction.

Anotherimportantfactortoconsideristheenergysourceusedintheprocess.Ideally,theenergyusedshouldcomefromrenewablesourcesinordertominimizetheproductionofgreenhousegases.Thiscanbeachievedthroughtheuseofsolarpanels,windturbinesorotherformsofrenewableenergy.However,theavailabilityofthesesourcesmayvarydependingonthelocationoftheprocess,makingitnecessarytoconsiderlocalconditionswhenselectinganenergysource.

Thegenerationofwasteisalsoanimportantfactortoconsider.Thiscancomefromtheuseofcatalysts,whichmaybetoxic,orfromtheproductionofbyproductsfromthereductionreaction.Itisimportanttominimizetheproductionofwasteandtoensurethatanywastegeneratedisproperlytreatedinordertoavoidharmtotheenvironment.

Finally,theintegrationofrelatedtechnologiessuchaselectrochemistryandcarboncapturecanfurtherenhancethesustainabilityoftheprocess.Electrochemicalcarbondioxidereductioncanreducethedemandforreducingagentsandminimizetheproductionofwaste.Meanwhile,theuseofcarboncapturetechnologycanfurtherreducetheenvironmentalimpactoftheprocessbyremovingcarbondioxidefromtheatmosphereandconvertingitintovaluablechemicals.

Inconclusion,whilecarbondioxidereductionholdsgreatpromiseforthesustainableproductionofchemicals,itisimportanttoconsiderthesustainabilityoftheentireprocess.Thisincludessourcingofrawmaterials,energysources,wastegeneration,andtheintegrationofrelatedtechnologies.Continuedresearchanddevelopmentinthisareaisvitalforachievingacirculareconomyandmeetingglobalclimategoals.Furthermore,therearestilltechnologicalandeconomichurdlestobeovercomeinthetransitiontoacarbon-neutralchemicalindustry.Whilesomecompanieshavebeguntoimplementcarboncaptureandutilizationtechnologies,thehighcostofcapturingandtransportingcarbondioxideremainsasignificantbarrier.Additionally,manyofthechemicalprocessesinvolvedincarbon