乙醇催化重整制氢研究进展课件

乙醇催化重整制氢研究进展1895乙醇催化重整制氢研究进展1895一、研究背景热值高能源危机环境友好应用广泛来源多样氢能天然气、煤和石油等化石燃料的日益枯竭重整制氢、电解水制氢、光生物制氢、光解水制氢。工业上，以天然气蒸汽重整制氢为主。无污染、无碳排放重要的传统化工原料，并且在燃料电池等领域具有广阔发展空间MattosLV,etal.Chem.Rev.2012,112(7):4094-4123.HuberGW.etal.Science,2003,300(5628):2075-2077.一、研究背景热值高能源危机环境友好应用广泛来源多样氢能生物质能生物质能开发与利用生物质发电生物材料石化产品替代品国家“十二五”规划生物甲醇生物乙醇生物柴油生物甘油0.1kg甘油/kg柴油生物质基醇类（bio-alcohols)ZhouCH,etal.Chem.Soc.Rev.,2008,37(3):527-549.AlonsoDM,etal.Chem.Soc.Rev.,2012,41(24):8075-8098.一、研究背景生物质能生物质能开发与利用生物质发电生物材料石化产品替代品国

生物质基醇类环境友好价廉易储运可再生Whybio-alcohols?Whysteamreforming?产氢效率高工艺成熟常压、中高温反应条件原料高效利用SteamreformingMattosLV,etal.Chem.Rev.2012,112(7):4094-4123.HuberGW.etal.Science,2003,300(5628):2075-2077.一、研究背景生物质基醇类环境友好价廉可再生Whybio-aBasisofEthanol/GlycerolSteamReforming

C2H5OH+3H2O→2CO2+6H2

RenewableBiodeg-radableLowtoxicityHighvaporis-ationheatEasyhandlingSulfurfreeC3H8O3+3H2O→3CO2+7H2

BasisofEthanol/GlycerolSteaReformingactivityonmetals

C2H5OH+3H2O→2CO2+6H2

Ethanolconversionsonsupportedsingle-componentcatalystsat573K,60000h-1ofGHSV,and1:3ofS/C,dilutedin86%He.Duan&Senken.,IndEngChemRes,2005,44,6381Reformingactivityonmetals镍基催化剂理性设计存在的挑战镍基催化剂具有较大的开发潜力，但其存在易积碳，活性组分易烧结等问题。催化剂性质镍颗粒大小金属分散度金属与载体相互作用催化剂制备不同镍基前躯体影响具有特殊结构的催化剂前躯体的制备催化剂测试乙醇蒸汽重整吸附强化乙醇蒸汽重整工程放大催化剂表征XRD、H2-TPR、TEM、XPS、TG,etc.设计和开发高活性和高稳定性的催化剂仍是生物质基醇类制氢工艺亟待解决的关键技术之一。一、研究背景镍基催化剂理性设计存在的挑战镍基催化剂具有较大的开发潜力，但Nickelparticlesize:Ni/γ-Al2O3<Ni/CeO2<Ni/ZrO2<Ni/MgOOSCofsupport:CeO2>ZrO2>γ-Al2O3>MgOAcidamount:MgO<CeO2<ZrO2<γ-Al2O3(A)NH3-TPRSprofilesofreducednickelcatalysts;(B)H2-TPRprofilesofsupportednickelcatalysts;(C)XRDpatternsofreducednickelcatalysts;(D)Oxygenstoragecapacity(OSC)testsofpureoxides.SurfacePropertiesofSupportsGongetal.PCCP2012,14,4066(Cover)Nickelparticlesize:OSCofsuSulfurpoisoningSinteringActivityCformationNickelChallengesforNickelSteam-ReformingcatalystsParticlesizeofNimetalSurfaceoxidationactivityImprovemetaldispersionandnanoconfinementeffecttostabilizenickelparticlesImprovesurfaceoxygenmobilityActivitySelectivityH2yieldProcessintensificationSorptionenhancedsteamreformingSulfurpoisoningSinteringActivImproveNidispersionandnanoconfinementeffectofNiNPsSkeletalNiNi@ZrO2Ni-CaO-Al2O3bi-functionalcatalystsImprovedispersionandnanoconfinementeffectImprovesurfaceoxygenmobilityProcessintensificationNickelprecursoreffectNickelPSstructureNickelHTLsstructureNickelperovskitestructureNi/MgO-CeO2catalystsImproveNidispersionandnanoImprovedDispersionofNi:theJourneyofRaneyNiGongetal.,PCCP

2012,14,3295hydratedaluminumEnhanceddispersionandsurfaceareaofNi;additivemetalscouldtunetheselectivityImprovedDispersionofNi:theReactionconditions:ethanolfeed,3.1h-1,S/C=4Catalysts:RaneyNireactionconditions:ethanolfeed,4.6h-1,350ºC

S/C=4Catalysts:raneyNireactionconditions:ethanolfeed,3.1h-1,S/C=4,350ºCLTSteamReformingtoProduceCO-FreeH205101520253035404550020406080100Time/hConversionorselectivity/%

EthanolconversionH2selectivityCO2selectivityCOselectivityCH4selectivityLow-TemperatureSteamReformingtoProduceCOFreeHydrogenGongetal.,PCCP

2012,14,3295Reactionconditions:ethanolfImproveNidispersionandnanoconfinementeffectofNiNPsSkeletalNiNi@ZrO2Ni-CaO-Al2O3bi-functionalcatalystsImprovedispersionandnanoconfinementeffectImprovesurfaceoxygenmobilityProcessintensificationNickelprecursoreffectNickelPSstructureNickelHTLsstructureNickelperovskitestructureNi/MgO-CeO2catalystsSupportedcatalystsPrecursorondispersionImproveNidispersionandnanoNi(CH3COO)2Ni-ACNi(NO3)2Ni-NNi(C7H7O2)2Ni-AANiCl2Ni-Cγ-Al2O3InfluenceofNickelPrecursorsonNickeldispersionXRDpatternsofthecatalystsafter700ºCreductionTEMimagesofthecatalystsafterreductionNickelparticlesize：Ni-AC<Ni-N<Ni-AA<Ni-CGongetal.,ACSSusChemEng

2013,doi:10.1021/sc400123fNi(CH3COO)2Ni(NO3)2Ni(C7H7O2)2InfluenceonGlycerolSteamReformingActivityInfluenceonGlycerolSteamReReactionconditions：550ºC，S/C=3，LHSV=6.6h-1，1atmTGcurveofthecatalystsafterreaction►Stability：Ni-AC>Ni-N>Ni-AA>Ni-C►cokedeposits：Ni-AC<Ni-N<Ni-AA<Ni-CTEMimagesafterreactionInfluenceonGlycerolSteamReformingStabilityReactionconditions：550ºC，S/CDifferentnickeldispersionandreducibilityGlycerolSteamReformingDifferentglycerolsteamreformingactivityandstabilityDifferentnickelprecursorsNi(CH3COO)2Ni(NO3)2Ni(C5H7O2)2NiCl2EffectofNickelPrecursorsonGlycerolSteamReformingGongetal.,ACSSusChemEng

2013,doi:10.1021/sc400123fDifferentnickeldispersionanImproveNidispersionandnanoconfinementeffectofNiNPsSkeletalNiNi@ZrO2Ni-CaO-Al2O3bi-functionalcatalystsImprovedispersionandnanoconfinementeffectImprovesurfaceoxygenmobilityProcessintensificationNickelprecursoreffectNickelPSstructureNickelHTLsstructureNickelperovskitestructureNi/MgO-CeO2catalystsHighdispersioncatalysts,methodtoresistsinteringImproveNidispersionandnanoZrOCl2NH4OHN2dryNanoarchitecturalDesignofNi@ZrO2CatalystConventionalNi/ZrO2NanoarchitecturalNi-ZrO2Gongetal.,ChemCommun

2013,49,4226ZrOCl2N2dryNanoarchitecturalNanoconfinmenteffectinNi@ZrO2catalyst

Ni@ZrO2Gongetal.,ChemCommun

2013,49,4226NanoconfinmenteffectinNi@ZrESRactivityandstabilityCatalyticactivityat723K.Solidsymbols:Ni@ZrO2catalyst;hollowsymbols:Ni/ZrO2catalyst.(b)Catalyticstabilityat873K.TheinsetsareTEMimagesoftheusedcatalystsGongetal.,ChemCommun

2013,49,4226ESRactivityandstabilityCataImproveNidispersionandnanoconfinementeffectofNiNPsSkeletalNiNi@ZrO2Ni-CaO-Al2O3bi-functionalcatalystsImprovedispersionandnanoconfinementeffectImprovesurfaceoxygenmobilityProcessintensificationNickelprecursoreffectNickelPSstructureNickelHTLsstructureNickelperovskitestructureNi/MgO-CeO2catalystsHighdispersioncatalysts,methodtoresistsinteringImproveNidispersionandnanoNanoconfinementofNiNPsbyphyllosilicatesstructureGongetal.,ACSSusChemEng2013,1,161NanoconfinementofNiNPsbyp(a)Ni/SiO2P(b)Ni/SiO2INiNPsstabilizedbythestructureGongetal.,ACSSusChemEng2013,1,161(a)Ni/SiO2P(b)Ni/SiO2INiNReactionconditions:ethanolfeedvelocity,2.5g·h/molfor(c)600,(b)500,and(a)400ºC,0.82g·h/molfor(d)700ºC;6vol%ofethanolingas;S/C=4,1atm.Stabilityteston(aandc)Ni/SiO2Pand(bandd)Ni/SiO2I.Reactionconditions:(aandb)400ºC,(candd)600ºC;1atm,ethanolfeedvelocity,10g·h/mol,ethanolinfeed,6vol%for400ºCreaction;ethanolfeedvelocity,16.4g·h/mol,ethanolinfeed,3vol%for600ºCTEMcharacterizationafter600ºCstabilitytest(aandb)TEMimagesand(candd)HRTEMimagesfor(aandc)Ni/SiO2Pand(bandd)Ni/SiO2I.InsetsareforstatisticsofNiparticlesize.CokedepositionrateonNi/SiO2PandNi/SiO2IActivityandstabilityonNi/PS-basedcatalystsGongetal.,ACSSusChemEng2013,1,161Reactionconditions:ethanolfNanoconfinementofNiNPsbyPSNanotubeNiPSCrispationReductionNiPSnanotubeNi/PSnGongetal.,ChemCommun,inpress,

doi:10.1039/c3cc43895cNanoconfinementofNiNPsbyPPhysical-chemicalpropertiesofNi/PSnGongetal.,ChemCommun,inpress,

doi:10.1039/c3cc43895cPhysical-chemicalpropertiesoReactivitycomparisonofdifferentNi/SiO2catalysts.Reactionconditions:1atm,400ºC,S/C=4,W/F=2.5g∙h/mol,EtOH/gas=6%Ethanolsteamreformingreactivityand(b)deactivationtestonthereducedcatalysts.Reactionconditions:(a)1atm,400ºC,S/C=4,W/F=10g·h/mol,EtOH/gas=2.5%;(b)1atm,400ºC,S/C=4,W/F=5g·h/mol,EtOH/gas=4.2%(a)EthanolsteamreformingstabilitytestonNi/PSn-600,reactionconditions:1atm,500ºC,S/C=4,W/F=10gh/mol,EtOH/gas=4.2%.(b)TEMimagesofthecatalystafterstabilitytest.ActivityandStabilityonNi/PSnGongetal.,ChemCommun,inpress,

doi:10.1039/c3cc43895cReactivitycomparisonofdiffeImproveNidispersionandnanoconfinementeffectofNiNPsSkeletalNiNi@ZrO2Ni-CaO-Al2O3bi-functionalcatalystsImprovedispersionandnanoconfinementeffectImprovesurfaceoxygenmobilityProcessintensificationNickelprecursoreffectNickelPSstructureNickelHTLsstructureNickelperovskitestructureNi/MgO-CeO2catalystsHighdispersioncatalysts,methodtoresistsinteringImproveNidispersionandnanoNanoconfinementofNiNPsbyPerovskitestructureNanoconfinementsinterresistIncreaseinterface,improvemetal-supportintertionWelldisperse,reducenickelparticlesizeGongetal.,unpublishedresultsNanoconfinementofNiNPsbyP图4-7还原后的催化剂TEM图STEMofthecatalystsafterreductionStabilitytestReactionconditions：S/C=3，LHSV=2.5h-1，550ºC，1atmActivityandStabilityonPerovskite-basedcatalystsGongetal.,unpublishedresults图4-7还原后的催化剂TEM图STEMofthecaImproveNidispersionandnanoconfinementeffectofNiNPsSkeletalNiNi@ZrO2Ni-CaO-Al2O3bi-functionalcatalystsImprovedispersionandnanoconfinementeffectImprovesurfaceoxygenmobilityProcessintensificationNickelprecursoreffectNickelPSstructureNickelHTLsstructureNickelperovskitestructureNi/MgO-CeO2catalystsHighdispersioncatalysts,methodtoresistsinteringImproveNidispersionandnanoXRDpatternsofthehydrotalcite-likeprecursors(a)NiMg6(b)NiMg8(c)NiMg10TransmissionelectronmicrographoftheNiMg6precursorFT-IRoftheNiMg6precursor(a)NiMg6(b)NiMg8(c)NiMg10Nanoconfinementbyhydrotalcite-likestructureGongetal.,IntJHydrogenEnergy,2010,35:6699-6708(Mg2++Ni2+)/Al3+=3XRDpatternsofthehydrotalciTemperatureprogramreductionoftheoxides

(a)NiMg6(b)NiMg8(c)NiMg10(d)NiOXRDpatternsoftheoxides(a)NiMg6(b)NiMg8(c)NiMg10HighDispersionofNickelCatalysts(a)(a)(c)Gongetal.,IntJHydrogenEnergy,2010,35:6699-6708TemperatureprogramreductionXRDpatternsofthereducedNiMg10catalystatdifferenttemperatures(a)973K(b)1023K(c)1123K(d)1173KConversion/composition(%)vsreductiontemperaturecurvesofethanolsteamreformingovertheNiMg10catalyst.Activityonhydrotalcitederivednickelcatalysts973K1073K1173KGongetal.,IntJHydrogenEnergy,2010,35:6699-6708XRDpatternsofthereducedNiImproveNidispersionandnanoconfinementeffectofNiNPsSkeletalNiNi@ZrO2Ni-CaO-Al2O3bi-functionalcatalystsImprovedispersionandnanoconfinementeffectImprovesurfaceoxygenmobilityProcessintensificationNickelprecursoreffectNickelPSstructureNickelHTLsstructureNickelperovskitestructureNi/MgO-CeO2catalystsImproveNidispersionandnanoOxygenmobilityofCeO2

basedsupportsPromoteWGSREnhanceadsorptionofwaterSuppresscarbondepositionImprovedispersionofnickelOxygenstoragecapacityRedoxrateH.Song,U.S.Ozkan,J.Catal.,2009,261:66-74J.A.Farmer,C.T.Campbell,Science,2010,329:933-935ImportanceofSurfaceOxygenMobilityOxygenmobilityPromoteEnhancIncreaseoxygenvacancyPromoteCe4+reductionEnhanceoxygenmobilityG.Balducci,M.S.Islam,J.Kasaparetal.Chem.Mater.2003,15:3781-3785X.Liu,K.Zhou,L.Wang,B.Wang,Y.Li,J.Am.Chem.Soc.2009,131:3140–3141MgadditionApproachforEnhancingOxygenMobilityIncreaseoxygenvacancyPromoteEnhancedOxygenMobilityofNi/CeOxGongetal.,AIChEJ.2012,58,516EnhancedOxygenMobilityofNiEthanolsteamreformingonNi/MgO-CeO2catalysts.Reactionconditions:Pressure:1atm,temperature:400ºC,S/C:4,EthanolfeedingW/F:33gh/molEthanolsteamreformingonNi/7MgCeandNi/10MgCeatdifferentreactionconditions.(a)Pressure:1atm,temperature:400ºC,S/C:4,ethanolfeedingW/F:11gh/mol;(b)Pressure:1atm,temperature:600ºC,S/C:4,ethanolfeedingW/F:33gh/mol(a)(b)CorrelationofOxygenMobilityandReactivityGongetal.,AIChEJ.2012,58,516EthanolsteamreformingonNi/CarbondepositionsontheNi/MgO-CeO2catalystsafter10hreaction(reactionconditions:1atm,400ºC,andethanolfeedingW/F33gh/mol);inset:carbondepositionperunitNiontheNi/MgO-CeO2catalystsProposedMechanismTheadditionofMggreatlyenhancestheOOSofCeO2,andsubsequentlyfacilitatetheconversionofethanolandremovalofdepositedcarbon.Gongetal.,AIChEJ.2012,58,516CarbondepositionsontheNi/MImproveNidispersionandnanoconfinementeffectofNiNPsSkeletalNiNi@ZrO2Ni-CaO-Al2O3bi-functionalcatalystsImprovedispersionandnanoconfinementeffectImprovesurfaceoxygenmobilityProcessintensificationNickelprecursoreffectNickelPSstructureNickelHTLsstructureNickelperovskitestructureNi/MgO-CeO2catalystsImproveNidispersionandnano(Ca2+Ni2+)1-xAl3+x(OH)2(An-)x/n•mH2OBi-functionalcatalysts:adsorptionandreformingBi-functionalCatalystsGongetal.,EngEnvironSci2012,5,8942(Ca2+Ni2+)1-xAl3+x(OH)2(An-)x/ComparisonofcyclicsorptioncapacityofNi–CaO–Al2O3catalysts(carbonationin50%CO2for45minat500Candcalcinationin100%N2for20minat700C).ComparationofNi–CaO–Al2O3catalystsintheSESREexperiment.Solidline:H2concentration,dashedline:CO2concentration,reactionconditions:1atm,500C,S/C?4,120min,desorptionconditions:1atm,700C,30minMultiplereaction–desorptioncyclesoftheCA3.0catalystandthemixtureofCaOandNi/Al2O3catalysts(reactionconditions:1atm,500C,S/C?4,90min,desorptionconditions:1atm,700C,30min)SorptionEnhancedsteamreformingGongetal.,EngEnvironSci2012,5,8942ComparisonofcyclicsorptionBi-functionalMechanismGongetal.,EngEnvironSci2012,5,8942Bi-functionalMechanismGonget三传一反（催化剂放大）理性设计（模型催化）活性位本质展望三传一反理性设计活性位本质展望Thankyouforyourattention!Thankyouforyourattention!乙醇催化重整制氢研究进展1895乙醇催化重整制氢研究进展1895一、研究背景热值高能源危机环境友好应用广泛来源多样氢能天然气、煤和石油等化石燃料的日益枯竭重整制氢、电解水制氢、光生物制氢、光解水制氢。工业上，以天然气蒸汽重整制氢为主。无污染、无碳排放重要的传统化工原料，并且在燃料电池等领域具有广阔发展空间MattosLV,etal.Chem.Rev.2012,112(7):4094-4123.HuberGW.etal.Science,2003,300(5628):2075-2077.一、研究背景热值高能源危机环境友好应用广泛来源多样氢能生物质能生物质能开发与利用生物质发电生物材料石化产品替代品国家“十二五”规划生物甲醇生物乙醇生物柴油生物甘油0.1kg甘油/kg柴油生物质基醇类（bio-alcohols)ZhouCH,etal.Chem.Soc.Rev.,2008,37(3):527-549.AlonsoDM,etal.Chem.Soc.Rev.,2012,41(24):8075-8098.一、研究背景生物质能生物质能开发与利用生物质发电生物材料石化产品替代品国

生物质基醇类环境友好价廉易储运可再生Whybio-alcohols?Whysteamreforming?产氢效率高工艺成熟常压、中高温反应条件原料高效利用SteamreformingMattosLV,etal.Chem.Rev.2012,112(7):4094-4123.HuberGW.etal.Science,2003,300(5628):2075-2077.一、研究背景生物质基醇类环境友好价廉可再生Whybio-aBasisofEthanol/GlycerolSteamReforming

C2H5OH+3H2O→2CO2+6H2

RenewableBiodeg-radableLowtoxicityHighvaporis-ationheatEasyhandlingSulfurfreeC3H8O3+3H2O→3CO2+7H2

BasisofEthanol/GlycerolSteaReformingactivityonmetals

C2H5OH+3H2O→2CO2+6H2

Ethanolconversionsonsupportedsingle-componentcatalystsat573K,60000h-1ofGHSV,and1:3ofS/C,dilutedin86%He.Duan&Senken.,IndEngChemRes,2005,44,6381Reformingactivityonmetals镍基催化剂理性设计存在的挑战镍基催化剂具有较大的开发潜力，但其存在易积碳，活性组分易烧结等问题。催化剂性质镍颗粒大小金属分散度金属与载体相互作用催化剂制备不同镍基前躯体影响具有特殊结构的催化剂前躯体的制备催化剂测试乙醇蒸汽重整吸附强化乙醇蒸汽重整工程放大催化剂表征XRD、H2-TPR、TEM、XPS、TG,etc.设计和开发高活性和高稳定性的催化剂仍是生物质基醇类制氢工艺亟待解决的关键技术之一。一、研究背景镍基催化剂理性设计存在的挑战镍基催化剂具有较大的开发潜力，但Nickelparticlesize:Ni/γ-Al2O3<Ni/CeO2<Ni/ZrO2<Ni/MgOOSCofsupport:CeO2>ZrO2>γ-Al2O3>MgOAcidamount:MgO<CeO2<ZrO2<γ-Al2O3(A)NH3-TPRSprofilesofreducednickelcatalysts;(B)H2-TPRprofilesofsupportednickelcatalysts;(C)XRDpatternsofreducednickelcatalysts;(D)Oxygenstoragecapacity(OSC)testsofpureoxides.SurfacePropertiesofSupportsGongetal.PCCP2012,14,4066(Cover)Nickelparticlesize:OSCofsuSulfurpoisoningSinteringActivityCformationNickelChallengesforNickelSteam-ReformingcatalystsParticlesizeofNimetalSurfaceoxidationactivityImprovemetaldispersionandnanoconfinementeffecttostabilizenickelparticlesImprovesurfaceoxygenmobilityActivitySelectivityH2yieldProcessintensificationSorptionenhancedsteamreformingSulfurpoisoningSinteringActivImproveNidispersionandnanoconfinementeffectofNiNPsSkeletalNiNi@ZrO2Ni-CaO-Al2O3bi-functionalcatalystsImprovedispersionandnanoconfinementeffectImprovesurfaceoxygenmobilityProcessintensificationNickelprecursoreffectNickelPSstructureNickelHTLsstructureNickelperovskitestructureNi/MgO-CeO2catalystsImproveNidispersionandnanoImprovedDispersionofNi:theJourneyofRaneyNiGongetal.,PCCP

2012,14,3295hydratedaluminumEnhanceddispersionandsurfaceareaofNi;additivemetalscouldtunetheselectivityImprovedDispersionofNi:theReactionconditions:ethanolfeed,3.1h-1,S/C=4Catalysts:RaneyNireactionconditions:ethanolfeed,4.6h-1,350ºC

S/C=4Catalysts:raneyNireactionconditions:ethanolfeed,3.1h-1,S/C=4,350ºCLTSteamReformingtoProduceCO-FreeH205101520253035404550020406080100Time/hConversionorselectivity/%

EthanolconversionH2selectivityCO2selectivityCOselectivityCH4selectivityLow-TemperatureSteamReformingtoProduceCOFreeHydrogenGongetal.,PCCP

2012,14,3295Reactionconditions:ethanolfImproveNidispersionandnanoconfinementeffectofNiNPsSkeletalNiNi@ZrO2Ni-CaO-Al2O3bi-functionalcatalystsImprovedispersionandnanoconfinementeffectImprovesurfaceoxygenmobilityProcessintensificationNickelprecursoreffectNickelPSstructureNickelHTLsstructureNickelperovskitestructureNi/MgO-CeO2catalystsSupportedcatalystsPrecursorondispersionImproveNidispersionandnanoNi(CH3COO)2Ni-ACNi(NO3)2Ni-NNi(C7H7O2)2Ni-AANiCl2Ni-Cγ-Al2O3InfluenceofNickelPrecursorsonNickeldispersionXRDpatternsofthecatalystsafter700ºCreductionTEMimagesofthecatalystsafterreductionNickelparticlesize：Ni-AC<Ni-N<Ni-AA<Ni-CGongetal.,ACSSusChemEng

2013,doi:10.1021/sc400123fNi(CH3COO)2Ni(NO3)2Ni(C7H7O2)2InfluenceonGlycerolSteamReformingActivityInfluenceonGlycerolSteamReReactionconditions：550ºC，S/C=3，LHSV=6.6h-1，1atmTGcurveofthecatalystsafterreaction►Stability：Ni-AC>Ni-N>Ni-AA>Ni-C►cokedeposits：Ni-AC<Ni-N<Ni-AA<Ni-CTEMimagesafterreactionInfluenceonGlycerolSteamReformingStabilityReactionconditions：550ºC，S/CDifferentnickeldispersionandreducibilityGlycerolSteamReformingDifferentglycerolsteamreformingactivityandstabilityDifferentnickelprecursorsNi(CH3COO)2Ni(NO3)2Ni(C5H7O2)2NiCl2EffectofNickelPrecursorsonGlycerolSteamReformingGongetal.,ACSSusChemEng

2013,doi:10.1021/sc400123fDifferentnickeldispersionanImproveNidispersionandnanoconfinementeffectofNiNPsSkeletalNiNi@ZrO2Ni-CaO-Al2O3bi-functionalcatalystsImprovedispersionandnanoconfinementeffectImprovesurfaceoxygenmobilityProcessintensificationNickelprecursoreffectNickelPSstructureNickelHTLsstructureNickelperovskitestructureNi/MgO-CeO2catalystsHighdispersioncatalysts,methodtoresistsinteringImproveNidispersionandnanoZrOCl2NH4OHN2dryNanoarchitecturalDesignofNi@ZrO2CatalystConventionalNi/ZrO2NanoarchitecturalNi-ZrO2Gongetal.,ChemCommun

2013,49,4226ZrOCl2N2dryNanoarchitecturalNanoconfinmenteffectinNi@ZrO2catalyst

Ni@ZrO2Gongetal.,ChemCommun

2013,49,4226NanoconfinmenteffectinNi@ZrESRactivityandstabilityCatalyticactivityat723K.Solidsymbols:Ni@ZrO2catalyst;hollowsymbols:Ni/ZrO2catalyst.(b)Catalyticstabilityat873K.TheinsetsareTEMimagesoftheusedcatalystsGongetal.,ChemCommun

2013,49,4226ESRactivityandstabilityCataImproveNidispersionandnanoconfinementeffectofNiNPsSkeletalNiNi@ZrO2Ni-CaO-Al2O3bi-functionalcatalystsImprovedispersionandnanoconfinementeffectImprovesurfaceoxygenmobilityProcessintensificationNickelprecursoreffectNickelPSstructureNickelHTLsstructureNickelperovskitestructureNi/MgO-CeO2catalystsHighdispersioncatalysts,methodtoresistsinteringImproveNidispersionandnanoNanoconfinementofNiNPsbyphyllosilicatesstructureGongetal.,ACSSusChemEng2013,1,161NanoconfinementofNiNPsbyp(a)Ni/SiO2P(b)Ni/SiO2INiNPsstabilizedbythestructureGongetal.,ACSSusChemEng2013,1,161(a)Ni/SiO2P(b)Ni/SiO2INiNReactionconditions:ethanolfeedvelocity,2.5g·h/molfor(c)600,(b)500,and(a)400ºC,0.82g·h/molfor(d)700ºC;6vol%ofethanolingas;S/C=4,1atm.Stabilityteston(aandc)Ni/SiO2Pand(bandd)Ni/SiO2I.Reactionconditions:(aandb)400ºC,(candd)600ºC;1atm,ethanolfeedvelocity,10g·h/mol,ethanolinfeed,6vol%for400ºCreaction;ethanolfeedvelocity,16.4g·h/mol,ethanolinfeed,3vol%for600ºCTEMcharacterizationafter600ºCstabilitytest(aandb)TEMimagesand(candd)HRTEMimagesfor(aandc)Ni/SiO2Pand(bandd)Ni/SiO2I.InsetsareforstatisticsofNiparticlesize.CokedepositionrateonNi/SiO2PandNi/SiO2IActivityandstabilityonNi/PS-basedcatalystsGongetal.,ACSSusChemEng2013,1,161Reactionconditions:ethanolfNanoconfinementofNiNPsbyPSNanotubeNiPSCrispationReductionNiPSnanotubeNi/PSnGongetal.,ChemCommun,inpress,

doi:10.1039/c3cc43895cNanoconfinementofNiNPsbyPPhysical-chemicalpropertiesofNi/PSnGongetal.,ChemCommun,inpress,

doi:10.1039/c3cc43895cPhysical-chemicalpropertiesoReactivitycomparisonofdifferentNi/SiO2catalysts.Reactionconditions:1atm,400ºC,S/C=4,W/F=2.5g∙h/mol,EtOH/gas=6%Ethanolsteamreformingreactivityand(b)deactivationtestonthereducedcatalysts.Reactionconditions:(a)1atm,400ºC,S/C=4,W/F=10g·h/mol,EtOH/gas=2.5%;(b)1atm,400ºC,S/C=4,W/F=5g·h/mol,EtOH/gas=4.2%(a)EthanolsteamreformingstabilitytestonNi/PSn-600,reactionconditions:1atm,500ºC,S/C=4,W/F=10gh/mol,EtOH/gas=4.2%.(b)TEMimagesofthecatalystafterstabilitytest.ActivityandStabilityonNi/PSnGongetal.,ChemCommun,inpress,

doi:10.1039/c3cc43895cReactivitycomparisonofdiffeImproveNidispersionandnanoconfinementeffectofNiNPsSkeletalNiNi@ZrO2Ni-CaO-Al2O3bi-functionalcatalystsImprovedispersionandnanoconfinementeffectImprovesurfaceoxygenmobilityProcessintensificationNickelprecursoreffectNickelPSstructureNickelHTLsstructureNickelperovskitestructureNi/MgO-CeO2catalystsHighdispersioncatalysts,methodtoresistsinteringImproveNidispersionandnanoNanoconfinementofNiNPsbyPerovskitestructureNanoconfinementsinterresistIncreaseinterface,improvemetal-supportintertionWelldisperse,reducenickelparticlesizeGongetal.,unpublishedresultsNanoconfinementofNiNPsbyP图4-7还原后的催化剂TEM图STEMofthecatalystsafterreductionStabilitytestReactionconditions：S/C=3，LHSV=2.5h-1，550ºC，1atmActivityandStabilityonPerovskite-basedcatalystsGongetal.,unpublishedresults图4-7还原后的催化剂TEM图STEMofthecaImproveNidispersionandnanoconfinementeffectofNiNPsSkeletalNiNi@ZrO2Ni-CaO-Al2O3bi-functionalcatalystsImprovedispersionandnanoconfinementeffectImprovesurfaceoxygenmobilityProcessintensificationNickelprecursoreffectNickelPSstructureNickelHTLsstructureNickelperovskitestructureNi/MgO-CeO2catalystsHighdispersioncatalysts,methodtoresistsinteringImproveNidispersionandnanoXRDpatternsofthehydrotalcite-likeprecursors(a)NiMg6(b)NiMg8(c)NiMg10TransmissionelectronmicrographoftheNiMg6precursorFT-IRoftheNiMg6precursor(a)NiMg6(b)NiMg8(c)NiMg10Nanoconfinementbyhydrotalcite-likestructureGongetal.,IntJHydrogenEnergy,2010,35:6699-6708(Mg2++Ni2+)/Al3+=3XRDpatternsofthehydrotalciTemperatureprogramreductionoftheoxides

(a)NiMg6(b)NiMg8(c)NiMg10(d)NiOXRDpatternsoftheoxides(a)NiMg6(b)NiMg8(c)NiMg10HighDispersionofNickelCatalysts(a)(a)(c)Gongetal.,IntJHydrogenEnergy,2010,35:6699-6708TemperatureprogramreductionXRDpatternsofthereducedNiMg10catalystatdifferenttemperatures(a)973K(b)1023K(c)1123K(d)1173KConversion/composition(%)vsreductiontemperaturecurvesofethanolsteamreformingovertheNiMg10catalyst.Activityonhydrotalcitederivednickelcatalysts973K1073K1173KGongetal.,IntJHydrogenEnergy,2010,35:6699-6708XRDpatternsofthereducedNiImproveNidispersionandnanoconfinementeffectofNiNPsSkeletalNiNi@ZrO2Ni-CaO-Al2O3bi-functionalcatalystsImprovedispersionandnanoconfinementeffectImprovesurfaceoxygenmobilityProcessintensificationNickelprecursoreffectNickelPSstructureNickelHTLsstructureNickelperovskitestructureNi/MgO-CeO2catalystsImproveNidispersionandnanoOxygenmobilityofCeO2

basedsupportsPromoteWGSREnhanceadsorptionofwaterSuppresscarbondepositionImprovedispersionofnickelOxygenstoragecapacityRedoxrateH.Song,U.S.Ozkan,J.Catal.,2009,261:66-74J.A.Farmer,C.T.