简介:UsingvanderWaalscorrecteddensityfunctionaltheory(vdW-DF)methodwehaveinvestigatedtheadsorptionofacetonemoleculeonpristineandPt-dopedgraphene.Severalactivesitesforboththeinteractingsystemshavebeenconsideredintheadsorptionprocessincludingfullgeometryoptimization.Wehaveanalyzedthestructuralandelectricalpropertiesofenergeticallyfavorableconfigurations.TheresultsshowthatadsorptionofacetonemoleculeonthePt-dopedgrapheneisenergeticallypreferable.Thebindingenergyandbondingdistancearedeterminedtobe-5.277eVand2.206A,respectively,accompanyingwithchargetransferof1.11e.Furthermore,thePt-0bondisrathersignificantlyelongatedwhenacetoneisadsorbedonPt-dopedgraphene.Comparedtopristinegraphene,thePt-dopedgraphenehasstrongerinteractionwiththeacetoneandmayprovidemoresensitivesignaiforasingleacetonemolecule.Meanwhile,practically,thebandgapofPt-dopedgraphenewouldbecomereducedafteracetoneadsorption.Consequently,ourfirst-principlesstudypresentsevidenceforacoherentbenchmarkfortheapplicabilityofPt-dopedgrapheneforacetoneadsorptionanddetection.
简介:Anenvironmentallyfriendlyprecursor,adenosine,hasbeenusedasadualsourceofCandNtosynthesizenitrogen-dopedcarboncatalystwith/withoutFe.Ahydrothermalcarbonizationmethodhasbeenusedandwateristhecarbonizationmedia.Themorphologyofsampleswith/withoutFecomponenthasbeencomparedbyHRTEM,andtheresultshowsthatFecanpromotethegraphitizationofcarbon.Furtherelectro-chemicaltestshowsthattheoxygenreductionreaction(ORR)catalyticactivityofFe-containingsample(C–FeN)ismuchhigherthanthatoftheFe-freesample(C–N).Additionally,theintermediatesofC–FeNformedduringeachsyntheticprocedurehavebeenthoroughlycharacterizedbymultiplemethods,andthefunctionofeachprocedurehasbeendiscussed.TheC–FeNsampleexhibitshighelectro-catalyticstabilityandsuperiorelectro-catalyticactivitytowardORRinalkalinemedia,withitshalf-wavepotential20mVlowerthanthatofcommercialPt/C(40wt%).Itisfurtherincorporatedintoalkalinepolymerelectrolytefuelcell(APEFC)asthecathodematerialandledtoapowerdensityof100mW/cm~2.
简介:ThehighlydispersedPt–ReOX(x≤1)sitesca.0.5nminsizewereformedviaasuccessiveandstronginteractionoftheReprecursorwithtitaniaandthenofthePtcomplexwithdepositedlow-valentrheniumoxideclusters.Thesize,chargeandchemicalcompositionwerecharacterizedbymeansofHRTEM/STEMwithEDXmapping,XPS,andFTIRS.ThesesiteswithRe/Pt=2wereshowntobehighlyactiveandselectiveinthehydrogenationofcarboxylicacidtoalcoholunderverymildconditions(T=130°C,P=50bar).ThereactionrateconstantforthehydrogenationofhexanoicacidincreasedlinearlywiththePtcontent.Asforthehomogeneouspincer-typeRu-organiccomplexes,theactivePt–ReOXsitescandissociateheterolyticallythemolecularhydrogenwiththeformationofhydroxylgroupsandPthydrideforhydrogenationofthecarboxylicgroup.Indeed,TOFof20h-1andselectivityof98%–99%areapproachingthevaluestypicalofhomogeneouscatalysts.Thefirstorderkineticsdescribedwelltheexperimentaldataobtainedinawiderangeofreactionconditions.
简介:Theaerobicoxidationofglycerolprovidesaneconomicallyviableroutetoglyceraldehyde,dihydroxyacetoneandglycericacidwithversatileapplications,forwhichmonometallicPt,AuandPdandbimetallicAu–Pt,Au–PdandPt–PdcatalystsonTiO2wereexaminedunderbase-freeconditions.PtexhibitedasuperioractivityrelativetoPd,andAu–PdandPt–PdwhileAuwasessentiallyinactive.ThepresenceofAuontheAu–Pt/TiO2catalystsledtotheirhigheractivities(normalizedperPtatom)inawiderangeofAu/Ptatomicratios(i.e.1/3–7/1),andtheonewiththeAu/Ptratioof3/1exhibitedthehighestactivity.SuchpromotingeffectisascribedtotheincreasedelectrondensityonPtviatheelectrontransferfromAutoPt,ascharacterizedbythetemperature-programmeddesorptionofCOandinfra-redspectroscopyforCOadsorption.Meanwhile,thepresenceofAuonAu–Pt/TiO2,mostlikeduetotheobservedelectrontransfer,changedtheproductselectivity,andfacilitatedtheoxidationofthesecondaryhydroxylgroupsinglycerol,leadingtothefavorableformationofdihydroxyacetoneoverglyceraldehydeandglycericacidthatwerederivedfromtheoxidationoftheprimaryhydroxylgroups.ThesynergeticeffectbetweenAuandPtdemonstratesthefeasibilityintheefficientoxidationofglyceroltothetargetedproducts,forexample,byrationaltuningoftheelectronicpropertiesofmetalcatalysts.
简介:Variousagriculturalcropresiduesincludingcornstover,corncob,andsorghumstalkwithamoisturecontentof75wt%weresubjectedtoalongpretreatment(12-60h)withsupercriticalCO2(scCO2),atlowtemperature(50-80℃)andapressureof17.5-25.0Mpa.Thesugaryieldsfromtheenzymatichydrolysis(EH)ofthepretreatedsampleswereasmuchasthree-tofourfoldgreaterthanthoseaffordedbytherawmaterials.However,whenpretreatmentwasconductedwithinashorttime(e.g.0.5h),aspreviouslyreportedintheliterature,onlyaslightincreaseintheEHsugaryieldswasobserved.TheproposedscCO2pretreatmentmechanismdemonstratedtheroleofmoistureinthesystem.Wetting,softening,andswellingwereobservedtomainlyaffectthelignocellulosewhenasuitableamountofwaterwasadded.Finally,thesampleswereanalysedbyX-raydiffractionandscanningelectronmicroscopy,beforeandafterpretreatment,toinvestigatethechangesinthemicroscopicstructureofthebiomass.
简介:Anovelgas-phaseelectrocatalyticcellcontainingalow-temperatureprotonexchangemembrane(PEM)wasdevelopedtoelectrochemicallyconvertCO2intoorganiccompounds.TwodifferentCu-basedcathodecatalysts(CuandCu-C)werepreparedbyphysicalvapordepositionmethod(sputtering)andsubsequentlyemployedforthegas-phaseelectroreductionofCO2atdifferenttemperatures(70-90℃).ThepreparedelectrodesCuandCu-CwerecharacterizedbyX-raydiffraction(XRD),X-rayphotoemissionspectroscopy(XPS)andscanningelectronmicroscopy(SEM).Asrevealed,CuispartiallyoxidizedonthesurfaceofthesamplesandtheCuandCu-Ccathodiccatalystswerecomprisedofaporous,continuous,andhomogeneousfilmwithnanocrystallineCuwithagrainsizeof16and8nm,respectively.Theinfluenceoftheappliedcurrentandtemperatureontheelectro-catalyticactivityandselectivityofthesematerialswasinvestigated.Amongthetwoinvestigatedelectrodes,thepureCucatalystfilmshowedthehighestCO2specificelectrocatalyticreductionratesandhigherselectivitytomethanolformationcomparedtotheCu-Celectrode,whichwasattributedtothehigherparticlesizeoftheformerandlowerCuO/Curatio.Theobtainedresultsshowpotentialinterestforthepossibleuseofelectrical「enewableenergyforthetransformationofCO2intovaluableproductsusinglowmetalloadingCubasedelectrodes(0.5mgCucm2)preparedbysputtering.
简介:Carbon-supportedPdnanoparticleswerepreparedbymicrowaveheating-glycolreductionmethod,andcharacterizedbyawidearrayofexperimentaltechniquesincludingX-raydiffractionspectroscopy(XRD)andtransmissionelectronmicroscopy(TEM).TheelectrooxidationbehaviorsofethanolonthePd/Celectrodeinalkalinemediawereinvestigatedusingcyclicvoltammetry(CV),chronoamperometry(CA),electrochemicalimpedancespectroscopy(EIS)andsinglecellperformancemethods.Pd/Celectrodeforethanoloxidationshowedhighelectro-catalyticactivityandlongtermstability.However,itisobservedthatthecurrentdensitydecreaseswiththeincreasingofthepotentialandnegativeimpedancepresentsinthepotentialfrom-0.1to0.1V.Thedecreasingcurrentdensityandthenegativeimpedancecouldbeduetotheadsorbedintermediatesspeciesthatinhibitedthefurtheroxidationofethanol.BasedonthechemicalreactionanalysisandEISspectra,equivalentcircuitsrelatingtovariouspotentialzoneshavebeenobtained.TheseresultsrevealthedynamicadsorptionofintermediatesspeciesonPdsurfaces.Significantly,itisclarifiedthattheadsorptionbehaviorbeginsfromthemaximumcatalysisofelectro-catalysisandendsintheformationofthepalladium(II)oxidelayerontheelectrodesurface.
简介:TheCprogramminglanguageisexpressiveandflexible,butnotsafe;asitsexpressivepowerandflexibilityareobtainedthroughunsafelanguagefeatures,andimproperuseofthesefeaturescanleadtoprogrambugswhosecausesarehardtoidentify.SinceCiswidelyused,anditisimpracticaltorewriteallexistingCprogramsinsafelanguages,sowaysmustbefoundtomakeCprogramssafe.ThispaperdealswiththeunsafefeaturesofCandpresentsasurveyonexistingsolutionstomakeCprogramssafe.Wehavestudiedbinary-levelinstrumentationtools,sourcecheckers,source-levelinstrumentationtoolsandsafedialectsofC,andpresentacomparisonofdifferentsolutions,summarizedthestrengthsandweaknessesofdifferentclassesofsolutions,andshowmeasuresthatcouldpossiblyimprovetheaccuracyoralleviatetheoverheadofexistingsolutions.
简介:ThefirststarsintheearlyUniversewereformedabout400millionyearsafterthebigbang.VerificationoftheexistenceofthesestarsisimportantforourunderstandingoftheevolutionoftheUniverse[1].IthasbeenpredictedthatforPopulation-IIIstellarproductionyields,theabundancesofodd-Zelementsareremarkablydeficientcomparedtotheiradjacenteven-Zelements[2].Astronomersaresearchingforlong-lived,lowmassstarswiththeuniquenucleosyntheticpatternmatchingthepredictedyields[3].
简介:The12C+13Csystemhasbeenstudiedextensively,becauseofthesimilarityoftheentrancechanneltotheastrophysicallyimportant12C+12Creaction[1??3].Untilnow,threedifferentmethodshavebeenexploitedtoperformthefusioncrosssectionmeasurementsfor12C+13CundertheCoulombbarrier:(1)measuringtheyieldofcharacteristicrays,(2)thetotal-rayyieldsusingNaIsummingdetectorsand(3)theactivityofthereactionresidue24Na(T1=2=15.0h).Recently,thefusioncrosssectionof12C+13Chasbeenmeasureddownto0.9nbthroughtheactivitymeasurementbyourgroup[4].Althoughthestatisticalmodelcalculationsinallthesethreemethodshavebeenroutinelyusedtoconverttheobservedpartialcrosssectionsintothetotalfusioncrosssections[5],thesystematicuncertaintyinducedbythestatisticalcorrectionshasnotbeenstudiedverywell.