Zr的添加对稀燃天然气汽车尾气净化催化剂Pd—Pt／AI203'l生能的影响

SEPTEMBER物理化学学WUIHUAXUEXUEBAOACTAPHYS一CSIN2015，319，17711779L771ARTICLE】DOI103866PKUWHXB201507141WWWWHXBPKUEDUCNZR的添加对稀燃天然气汽车尾气净化催化剂PDPTAI203L生能的影响胡伟王云，尚鸿燕，徐海迪Z，S钟琳11陈建军龚茂初陈耀强，四川大学化学工程学院，成都610064；四川大学新能源与低碳技术研究院，成都610064；，四川大学化学学院，绿色化学与技术教育部重点实验室，成都610064摘要PDPT双金属基甲烷氧化催化剂的催化活性、抗水热老化性和耐硫性在一个通有模拟稀燃天然气汽车尾气成分的固定床反应器中进行检测研究发现ZR掺杂的PDPFFAI2O3PDPUZQA10XO【3州2提高了催化的催化活性、抗水热老化性和耐硫性以共沉淀法制备ZRAI的摩尔比分别为01、025075、0505、075025GL10的材料为载体材料双金属催化剂的活性组分分别为15W，质量分数的PD和03W的PT，活性组分PD、PT通过共浸渍的方法浸渍到以上载体材料上制备得到一系列整体式催化剂分别采用低温N2吸脱附、X射线衍射XRD、H2程序升温还原HTPR、O2程序升温氧化O一TPDX射线光电子能谱对制各的催化剂进行表征结果显示ZR的加入使催化剂的载体材料结晶度提高，活性组分的分散度也得到了相应的提高同时二价PD物种与周围电子密度分别增加相比于PDPTAI203LLPDPTZRO2催化剂，在不同条件预处理后ZR的添加对催化剂的性能有明显的提高，其中催化剂PD_PTZR05AL0_5O175展现了最好的催化活性、抗水热老化性以及耐硫性关键词铝锆不同摩尔比载体天然气燃料发动机催化性能中图分类号0643EFFECTSOFZRADDITIONONTHEPERFORMANCEOFTHEPDPTAI203CATALYSTFORLEANBURNNATURAIGASVEHICLEEXHAUSTPURIFICATIONHUWEIWANGYUNSHANGHONGYANXUHAIDIL。ZHONGLINCHENJIANJUNGONGMAPCHUCHENYAPQIANGR。，COLLEGEOFCHEMICALENGINEERING,SICHUANUNIVERSITY,CHENGDU610064,RCHINA；2INSTITUTEOFNEWENERGYANDLOWCARBONTECHNOLOGY,SICHUANUNIVERSITY,CHENGDU610064，PRCHINA；KLABORATORYOFGREENCHEMISTRYTECHNOLOGYOFMINISTRYOFEDUCATION，COLLEGEOFCHEMISTRY,SICHUANUNIVERSITY,CHENGDU610064,PRCHINAABSTRACTTHECATALYTICACTIVITY，HYDROTHERMALAGINGRESISTANCE，ANDSULFURTOLERANCEOFAPDPTBASEDMETHANEOXIDATIONCATALYSTWEREEVALUATEDINAFIXEDFLUIDIZEDBEDREACTORCONTAININGSIMULATEDIEANBURNNATURALGASVEHICLEEXHAUSTGASESZIRCONIUMDOPEDPDPTAI2O3PDPTZRXAL1XOF31，2WASFOUNDTOSIGNIFICANTLYIMPROVETHECATALYTICACTIVITY，HYDROTHERMALAGINGRESISTANCE，ANDSULFURTOLERANCEZRMODIFIEDALUMINASUPPORSWEREPREPAREDBYCOPRECIPITATIONWITHMOLARRATIOSOFZRTOA10F01，0。25075O505，075025，AND10THEPDPTBIMETALLICCATALYSTSCONTAINING15W，MASSFRACTIONPDAND03WPTSUPPOSEDONTHEABOVEMODIFIEDCOMPOSITESUPPOSWEREPREPAREDBYTHECOIMPREGNATINGMETHODRECEIVEDMAY4，2015；REVISEDJULY14，2015；PUBLISHEDONWEBJULY14，2015CORRESPONDINGAUTHORSCHENYAOQIANG，EMAILNIC7501SOUEDUON；TELFAX862885418451ZHONGLIN，EMAILZHONGLINSCUEDUCATHEPROJCOTWASSUPPORTEDBYTHENATIONALNATURALSCIENCEFOUNDATIONOFCHINA21173153，PROJECTFROMSICHUANPROVINCIALENVIRONMENTOFFICE，CHINA2OL1HB002，ANDSCIENCEANDTECHNOLOGYSUPPORTPROJECTOFSCIENCEANDTECHNOLOGYDEPARTMENTOFSICHUANPROVINCE，CHINA2012FZ0008国家自然科学基金21173153，四川省环境保护厅项目201IHB002及四川省科技厅科技支撑项目2012FZ0008资助EDITORIAL0FFICEOFACTAPHYSICOCHIMICASINICA1772ACTAPHYSCHIMSIN2015VOL31THECATALYSTSWERECHARACTERIZEDBYN2ADS0RPTJON，DESORPTION，XRAYDIFFRACTIONXRD，H2TEMPERATUREPROGRAMMEDREDUCTIONH2TPR，O2TEMPERATUREPROGRAMMEDDESORPTION，ANDXRAYPHOTOELECTRONSPECTROSCOPYXPSTHERESULTSSHOWTHATTHECRYSTALLINITYOFTHESAMPLES，DISPERSIONOFTHEACTIVECOMPONENT，NUMBEROFPDSPECIES，ANDELECTRONDENSITYAROUNDPDSPECIESINCREASEAFTERADDITIONOFZRO2TOAI2O3SUPPORTSCOMPAREDWITHTHEACTIVITYRESULTSOFPDPTAI2O3ANDPDPTZRO2CATALYSTSAFTERDIFFERENTPRETREATMENTCONDITIONS，THEPERFORMANCEOFTHECATALYSTISGREATLYENHANCEDBYADDINGZRO。INTHEAI203SUPPORTS，ANDPDPTZR0SA105O175SHOWSTHEBESTCATALYTICACTIVITY，STRONGESTHYDROTHERMALAGINGRESISTANCE，ANDHIGHESTSULFURTOLERANCEAMONGTHEINVESTIGATEDCATALYSTSKEYWORDSALUMINUM；ZIRCONIUM；DIFFERENTMOLARRATIOS；SUPPORT；NATURALGASFUELLEDVEHICLECATALYTICPERFORMANCE1LNTRODUCTIONNATURALGAS【NGRESOURCESAREABUNDANT，ANDUSEDWIDELYASENERGYSOURCEININDUSTRYANDAUTOMOTIVEVEHICLEOWINGTOTHEIRLOWEXHAUSTEMISSION，WITHTHEDEVELOPMENTOFTHENATURALGASFIELDS，THENUMBEROFNATURALGASVEHICLESISINCREASINGSYNCHRONOUSLYBESIDESTHEECONOMICNEEDS。COMPRESSEDNATURALGASVEHICLESNGVSWITHLOWCOANDLOWNOXEMISSIONSHAVEMOREECOFRIENDLYADVANTAGESTHANGASOLINEANDDIESELVEHICLES一ESPECIALLYTHEOPERATIONOFNGVSUNDERLCAL1BURNCONDITIONSCOULDREDUCETHEPOLLUTANTSMOREEFFECTIVELYANDIMPROVETHERMALEFFICIENCYCOMPAREDWITHTHESTOICHIOMETRICCONDITION一ALTHOUGHENGINETECHNOLOGIESHAVEBEENIMPROVEDTOINCREASECOMBUSTIONEMCIENCYANDDECREASEEMISSIONTHEMAININGREDIENTSOFEXHAUSTSTILLCONTAINHC，CO，ANDN；MOREOVER，METHANEISTHEMAINCOMPONENT90一95、OFTHETOTALHYDROCARBONTHATMAKESMORECONTRIBUTIONSTOGLOBALCLIMATEWARL1INGTHANCARBONDIOXIDEWHENTHEEMISSIONRATESAREEQUALITYL6THEREFOREITISVERYURGENTTOREDUCEMETHANEEMISSIONEFFECTIVELYINTHENGVEXHAUSTNOBLEMETALPT，PD，RHCATALYSTS，ESPECIALLYPALLADIUMCATALYSTSHAVEBEENRECOGNIZEDASONEOFTHEBESTCATALYSTSTOREDUCEMETHANEEMISSIONS，0THENVGCATALYSTSAREUSUALLYWORKINGINTHEHARSHENVIRONMENTTHEHIGHTEMPERATURE，HIGHWATERCONTENT，ANDHIGHSULFURCONTENT，WHICHMAKESTHEACTIVESITEOFCATALYSTSBEEASYTOBEPOISONEDANDSINTEREDABOUT10一15VOLUMEFRACTIONWATERVAPORWHICHEXISTSINTHENVGEXHAUSTWOULDINDUCESINTERINGOFACTIVESITE1EADINGTOTHEDECREASEOFCHDCONVERSIONUNDERLEANBUMCONDITIONSTHESULFIDESCONTAINEDINTHEEXHAUSTGASALSOCAUSEDEACTIVATIONOFTHECATALYSTSINFACT，THESYNERGISTICEFFECTEXISTINGBETWEENWATERANDSULFURINTHEEXHAUSTOFNGVSCANACCELERATETHEDEACTIVATIONOFCATALYSTS。TTHUSTHEHYDROTHERMALAGINGRESISTANCEANDSULFURTOLERANCEOFPALLADIUMSUPPORTEDCATALYSTSFORMETHANECONVERSIONNEEDTOBEIMPROVEDLAPISARDI，PERSSON，”YANG，”CORRO，ANDNARUIETA1REPORTEDTHATTHEADDITIONOFPTTOPDCOULDIMPROVETHECATALYTICACTIVITY，THERMOSTABILITY，ANDSULFURRESISTANCETHEVFOUNDTHATTHEADDITIONOFPTTOTHEPDCATALYSTSCOULDWEAKENTHEPD一0BONDANDAFFECTTHEADSORPTIONOFMETHANEANDOXYGENALSOTHEPROBABILI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ICACTIVITYITSDIFFRACTIONPEAKSWERELOCATEDAT2304。，505。，602。34,37ASSHOWNINFIG7B，THE20VALUESOFZR048AL052O174SHIFTTOLOWERVALUESWITHINCREASINGTHECONTENTOFZR，INDICATINGTHATMOREANDMOREZIRCONIUMENTEREDINTOTHEZR048A1052O174，WHICHFORMEDMOREEXCELLENTSOLIDSOLUTION，BUTTHESOLIDSOLUTIONZR048AL052OLL74OFPDPTZR075ALO25O1625APPEAREDOBVIOUSLYSPLITPHASEAT20304OTABLE4TEXTURALPROPERTIESOFTHEZKL0SUPPOS0O，CO一芒8C0O1776ACTAPHYS一CHIMSIN2015VOL312E。FIG7XRDPATTERNSOFTHEPREPAREDPDPFFZLDL10OCATALYSTSYA12O3；OA1052ZR048O174；VMONOCLINICZRO2；TETRAGONALZRO2FORPDPTZRO，。MONOCLINICZRO，ANDTETRAGONALZRO，WEREPRESENTED，ANDTHECONTENTOFMONOCLINICZRO，PHASEWASPRIMARYTHEZIRCONIACRYSTALLITESMAYBLOCKTHEPOREOFSOMEALUMINAWHICHCANEXPLAINTHESURFACEAREADROPFROMBET34H，TPRRESULTSH，TPREXPERIMENTSWEREUSEDTOEVALUATETHERELATIONSHIPBETWEENTHEREDUCIBILITYANDTHEACTIVITYOFCATALYSTSITWASREPORTEDTHATLOWERREDUCTIONTEMPERATUREANDLARGERPEAKAREAIMPLIEDHIGHERCATALYTICACTIVITYTHEH2TPRPROFILESOFTHEPDPTZRA1103H2ARESHOWNINFIG8ITINDICATEDTHATTHELOWTEMPERATUREOFREDUCTIONPEAKSCONCENTRATEDABOUT100。CWASATTRIBUTEDTOTHEREDUCTIONOFPDSPECIES，。WHILETHEPEAKSATABOUT150。CWEREASSIGNEDTOTHEREDUCTIONOFPTO，ITCANBESEENTHAT，WITHTHEADDITIONOFZIRCONIUMTOALUMINUMTHEREDUCTIONTEMPERATUREOFPD0DROPPEDFIRSTLYANDTHENSTARTEDTOINCREASETHELOWESTREDUCTIONTEMPERATUREWAS70。CWHICHWASATTRIBUTEDTOPDPTZROSA1050L75SAMPLE，ANDTHEHIGHESTWASL03。CFORPDPTZRO，SAMPLEFORPTO2，THEREDUCTIONTEMPERATUREPROFILESHOWEDTHESIMILARTRENDTOTHELAWOFPDOANDL30AND150。CWERETHELOWESTANDHIGHESTREDUCTIONTEMPERATURES，RESPECTIVELYITWASREPORTEDTHATLOWERREDUCTIONTEMPERATUREIMPLIEDHIGHERCATALYTICACTIVITYFORTHECATALYSTAWIDELYACCEPTEDREDOXMECHANISMSUGGESTEDTHATPDOWASTHEMAINACTIVESPECIESFORTHEOXIDATIONOFCHD，THERESULTSOFH2TPRWERECONSISTENTWITHTHERESULTSOFTHECATALYTICACTIVITYTHEDIFFERENCESINREDUCTIONTEMPERATUREFORPDPT87PDPFFAI2O383C，一JPD_P忆R0A10SOZSDP1PTZROSAI01_PDP忆R05AISOS10332PDPTZRO25010015020025030035077。CFIG8H2TPRPROFILESOFTHEFIVECATALYSTSTHECATALYSTSMAYBEDUETODIFFERENTSTRENGTHINTERACTIONBETWEENNOBLEMETALANDTHESUPPORTSASSHOWNINFIG8，PDPTZRO5A1O50175CATALYSTHADTHEHIGHESTPEAKINTENSITYANDTHEBIGGESTPEAKAREAOFH2TPRTHERESULTSINDICATEDTHATTHEINTERACTIONSBETWEENTHENOBLEMETALOXIDEANDTHESUPPORTSWERETHEWEAKESTAMONGTHEFIVECATALYSTSANDTHATTHENOBLEMETALOXIDECANBEREDUCEDEASILY“INTERESTINGLY，PDPTZRO2SHOWNTHELOWESTACTIVITYFORTHEMETHANEOXIDATIONHADASMA11ESTREDUCTIONPEAKAREAAMONGTHECATALYSTSBOTHTHEREDUCTIONTEMPERATUREANDTHEPEAKAREASHOWEDTHATPDPTZRO5A1O50L75COULDEXHIBITBETTERCATALYTICACTIVITYTHANTHEOTHERS，WHICHWASCONSISTENTWI