XAFS應用介紹XAFS應用介紹1X射線吸收精細結構譜XAFS（實驗方法和應用）WebofScienceSearch:“EXAFS”or“XAFS”(butnot“XAS”–toomanyfalsehits)–1971-1975:8Publications–Lastyear:743Publications–Last10years:7,199PublicationsXAFS應用介紹X射線吸收精細結構譜XAFSWebofScienceSXAFS應用介紹XAFS應用介紹

XAFSBeamlineDesignParameter

位于第三代上海同步輻射裝置的BL14W1是一個高性能的X射線吸收譜光束線站。在一期的七條光束線站中BL14W1設計為通用吸收譜線站。BL14W1的光源是一個38極Wiggler插入件，最大磁場為1.2T，磁場周期為80mm.XAFS光束線的主要光學部件包括一個準直鏡，一個配有Si(111)和Si(311)的液氮冷卻雙晶單色器，一個聚焦鏡，一個高次諧波抑制鏡。光束線有聚焦和非聚焦兩種工作模式，其中，聚焦模式下能量范圍為4～22.5keV，非聚焦模式下的能量范圍為3.5~50keV。XAFS應用介紹XAFSBeamlineDesignParamete同步裝置束線能量范圍keV分辨率ΔE/E光通量@10kevPhs/sAS（澳大利亞）XAFS4-405×10-5~2×10-41012~1013SPing-8（日本）BL01B13.8-1133×10-5~3×10-4109~1011Diamond（英國）I-204-3410-4~10-51012BSRF（北京）1W1B4-301~3×10-42×1011SSRF（上海）BL14W14~505×10-5~2×10-41012～1013國內外同類線站性能比較XAFS應用介紹同步裝置束線能量范圍分辨率光通量@10kevASXAFS4-ExperimentalStationXAFS應用介紹ExperimentalStationXAFS應用介紹PotentialcapabilityMinimumDetectionLimit~1ppmItisageneralandhighperformanceXAFSbeamline,withhighflux、highsignal/noiseratioandfastdatacollection.XAFSanalyticaltechniquesatSSRF32元高純Ge探測器及XIA電子學系統4元Si漂移探測器及采集系統Lytle熒光電離室Oxford電離室五維樣品臺掠入射平臺低溫樣品室(4K)和高溫爐XAFS線站主要儀器設備XAFS線站主要實驗技術透射XAFS（TransmissionXAFS）熒光XAFS（FluoresceXAFS）掠入射XAFS（GrazingIncidentXAFS）原位XAFS（InsituXAFS）快速XAFS(QXAFS)XAFS應用介紹PotentialcapabilityItisageConventionalXAFSandQXAFSspectra(5Sec)ofCufoilatKedgemeasuredatBL14W1beamlineincomparisonwithstandardXAFSspectra(thedataisfromChicagoUniversityXAFSlibrary,whichwasmeasuredinAPS13ID)

comparisonwithAPSstandardXAFSspectraXAFS應用介紹ConventionalXAFSandQXAFSsSR-XAFS實驗框圖XAFS應用介紹SR-XAFS實驗框圖XAFS應用介紹XAFS在鈣鈦礦催化劑研究中的應用XAFS應用介紹XAFS在鈣鈦礦催化劑研究中的應用XAFS應用介紹汽車尾氣污染問題嚴重汽車尾氣的污染物，CO、HC以及NOx等，嚴重威脅到人類的生活，對其治理受到全球范圍的重視。世界上污染最為嚴重的二十個城市，出現頻率最高的就是中國的城市，占據60%。大氣污染問題與汽車尾氣排放具有很高的相關性。引起的呼吸系統疾病(主要是慢性阻塞性肺病)在我國城市居民主要疾病死亡構成中占12.6%，59%以上的司機患有不同程度的呼吸道疾病國內不斷提高汽車尾氣排放處理標準。國內在尾氣處理催化劑研究人員眾多。XAFS應用介紹汽車尾氣污染問題嚴重汽車尾氣的污染物，CO、HC以及NOx等Mazda:World’sfirstapplicationofsingle-nanocatalysttechnologyincatalyticconverters

XAFS應用介紹Mazda:World’sfirstapplicatiSelf-regenerationofaPd-perovskitecatalystforautomotiveemissionscontrol用XAFS手段研究催化材料的重生問題，研究其反應前后的結構變化，發現其在催化反應前后所處晶格和配位環境差異，解釋了其能長期保持高活性的原因。SPring-8Nature418,164-167(11July2002)XAFS應用介紹Self-regenerationofaPd-peroXAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹Improvingcatalyticconverters

為了提高催化劑的催化效率，科學家利用同步輻射裝置開展很多原位實時監測反應過程的研究。XAFS可以提供很重要的在金屬催化劑反應過程中，與局域結構和電子環境有關的原位動力學信息，他的動力學行為可以在ms,us,以至于ps.fs內研究。M.A.Newtonetal.,

NatureMaterials

2007,6,528-532;Angew.ChemInt.Ed.2007,45,8629-8631Fig.99:NormalisedPdKedgeenergydispersiveEXAFSspectraderivedduringaswitchfroma5%NO/Hefeedtoa5%CO/Hefeed(both75mlmin–1flow)at673Kovera1wt%Pd/10ZCAsample.Eachspectrumwasacquiredinca.250msecs.Forclarityonly1spectrum/secondisplotted.TheredtoyellowshadingisindicativeoftheswitchfromtheNOtoCOfeed.Fig.100:

Infraredspectra(averagedover9reversibleNO/COswitches)takenatthesametimeastheEXAFSspectrashowninFigure99,collectedwitha3Hzspectralacquistionspeed.Themajorgasphaseandsurfacefunctionalitiesobservedduringtheexperimentareindicated.Againtheshadingoftheflowofthegraphindicatesthechangeofreactivefeedstock.XAFS應用介紹Improvingcatalyticconverters國內的研究汽車尾氣凈化裝置及催化劑通過EXAFS研究助劑Fe的添加對催化劑Pt/Ba/Al2O3

中Pt物種微觀結構的影響，這種微觀結構的改變對催化劑組分間的作用和催化性能產生了顯著影響。MengMetal.AppliedCatalysisB:Environmental78(2008)38XAFS應用介紹國內的研究汽車尾氣凈化裝置及催化劑通過EXAFS研究助劑FeXAFS應用介紹XAFS應用介紹XAFS在電化學研究中應用XAFS應用介紹XAFS在電化學研究中應用XAFS應用介紹“Ethanolisoneofthemostidealreactantsforfuelcells,”saidBrookhavenchemistRadoslavAdzic.“It’seasytoproduce,renewable,nontoxic,relativelyeasytotransport,andithasahighenergydensity.Amajorhurdletothecommercialuseofdirectethanolfuelcellsisthemolecule’sslow,inefficientoxidation,whichbreaksthecompoundintohydrogenionsandelectronsthatareneededtogenerateelectricity.Specifically,scientistshavebeenunabletofindacatalystcapableofbreakingthebondsbetweenethanol’scarbonatoms.ButatBrookhaven,scientistshavefoundawinner.Madeofplatinumandrhodiumatomsoncarbon-supportedtindioxidenanoparticles,theresearchteam’selectrocatalystiscapableofbreakingcarbonbondsatroomtemperatureandefficientlyoxidizingethanolintocarbondioxideasthemainreactionproduct.Othercatalysts,bycomparison,produceacetalhydeandaceticacidasthemainproducts,whichmakethemunsuitableforpowergeneration.氫電池：儲存、運輸困難甲醇電池：CO中間物質乙醇電池：氧化困難，“Theabilitytosplitthecarbon-carbonbondandgenerateCO2atroomtemperatureisacompletelynewfeatureofcatalysis,”Adzicsaid.“Therearenoothercatalyststhatcanachievethisatpracticalpotentials.”XAFS應用介紹氫電池：儲存、運輸困難XAFS應用介紹XAFS應用介紹XAFS應用介紹ThemainabsorptionpeaksattheRhandPtedgeshaveaverysmallpotentialdependence,indicatingthatthesurfacesareonlyslightlyoxidized,unliketheprocessthatoccurswiththepureRhphase.ItislikelythatOH,whichispresentontheSnO2surfaceinaqueoussolutions,causesashiftinsurfaceoxidationofRhandPt(RhorPtOHformation)XAFS應用介紹ThemainabsorptionpeaksattMeasurementsofmetalmetal(RhPtandPtRh)coordinationnumbersNRh-PtandNPt-Rhenabledustoobtaintheaveragecompositionofthenanoparticles:x(Pt)/x(Rh)=NRh-Pt/NPt-Rh=2.1(0.3),inreasonablygoodagreementwiththeICPdatax(Pt)/x(Rh)=1.5(0.2).Theabsolutevaluesofthesecoordinationnumbersindicatethesamesizerange(13nm)asobtainedbyTEM.TheobtainedPtandRhcoordinationnumbershavesimilarvalues9.5(0.8)and10.8(0.8)respectively,consistentwithhomogeneousdistributionofPtandRhthroughouttheparticles.Inaddition,astheNPtPt/NPtRhandNRhPt/NRhRhratioswerefoundtobeconsistent,withthebulkratiosofPtandRhconcentrationsobtainedindependentlybyEXAFSandICP,weconcludethatthePtandRhformedaquasi-randomalloy.FurtherindependentevidencetowardsthatconclusionisthesimilaritybetweenthePtPt,PtRhandRhRhbondlengthsfoundbyourEXAFSanalysis:2.743?,2.725?,and2.705?,respectively,thatis,characterizedbyamuchsmallerspreadthanbetweenpurePt(2.775?)andRh(2.689?).XAFS應用介紹Measurementsofmetalmetal(RinsituIRRAStoidentifytheintermediatesandproductsofethanoloxidationXAFS應用介紹insituIRRAStoidentifytheXAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XASofPlatinumMonolayerFuelCellElectrocatalysts–Unambiguous,DirectCorrelationofSpectroscopyDatawithCatalyticProperties(a)ModelsofpseudomorphicmonolayersofPtonthreedifferentsubstratesinducingcompressivestrain(Ru(0001)andPd(111))andexpansivestrain(Au(111)).(b)SchematicofPtmonolayerelectrocatalystsubjecttosynchrotronX-rayK.Sasaki,R.R.Adzic.SynchrotronRadiatinNews,2009,22,17-21XAFS應用介紹XASofPlatinumMonolayerFuelXAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹StructuralandElectronicPropertiesofPlatinumNanoparticleSurfaceinanAqueousSystemProbedbyInSituX-rayAbsorptionSpectroscopyXAFS應用介紹StructuralandElectronicPropXAFS應用介紹XAFS應用介紹其他幾個與電池材料有關的例子XAFS應用介紹其他幾個與電池材料有關的例子XAFS應用介紹Dischargeofnewlithiumbatterymaterials:LixFePO4LixFePO4cathode0.1Hz,averagedover75spectra,lithiationspeedC/3,startingwithx=0.56.OxidationstatechangesfromFe3+toFe2+.FeK-edgeEdgeshiftatmd=0.5XAFS應用介紹DischargeofnewlithiumbatteLixNi0.5Mn0.5O2-cathodeMeasuredatNiK-andMnK-edgesalternatelyduringdischarge.0.1Hz,averagedover20spectra.LithiationspeedC/4.5,startingwithx=0.414.OxidationstatechangesfromNi4+overNi3+toNi2+.Dischargeofnewlithiumbatterymaterials:

LixNi0.5Mn0.5O2NiK-edgeXAFS應用介紹LixNi0.5Mn0.5O2-cathodeDischarLixNi0.5Mn0.5O2-cathodeMeasuredatNiK-andMnK-edgesalternatelyduringdischarge.0.1Hz,averagedover20spectra.LithiationspeedC/4.5,startingwithx=0.414.SignificantchangesintheEXAFS.Dischargeofnewlithiumbatterymaterials:

LixNi0.5Mn0.5O2NiK-edgeXAFS應用介紹LixNi0.5Mn0.5O2-cathodeDischarLixNi0.5Mn0.5O2-cathodeMeasuredatNiK-andMnK-edgesalternatelyduringdischarge.0.1Hz,averagedover20spectra.LithiationspeedC/4.5,startingwithx=0.414.OxidationstateofMnstaysinatetravalentstate.Dischargeofnewlithiumbatterymaterials:

LixNi0.5Mn0.5O2MnK-edgeXAFS應用介紹LixNi0.5Mn0.5O2-cathodeDischar直接甲醇燃料電池DMFCXAFS應用介紹直接甲醇燃料電池DMFCXAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹ElectrochemicalcellforinsituEXAFSoffuelcellelectrodesonstation16.5attheSRS,DaresburyPEMfuelcellforinsituEXAFSstudiesofanodeorcathodecatalystsonstation16.5attheSRS,Daresbury.Thecelldesignenablesthestudyofrealisticcatalystloadingsof≤1mgPtpercm-2ofelectrodeareaandoperatesunderfullyhumidifiedconditionsat80°C.XAFS應用介紹Electrochemicalcellforinsi優點缺點XAFS應用介紹優點缺點XAFS應用介紹時間分辨XAFS在動力學研究中應用XAFS應用介紹時間分辨XAFS在動力學研究中應用XAFS應用介紹QXAFS-催化-Pt/Al2O3-CO-氧化XAFS應用介紹QXAFS-催化-Pt/Al2O3-CO-氧化XAFS應用介XAFS應用介紹XAFS應用介紹時間分辨XAFS在反應動力學應用XAFS應用介紹時間分辨XAFS在反應動力學應用XAFS應用介紹時間分辨XAFS在反應動力學應用XAFS應用介紹時間分辨XAFS在反應動力學應用XAFS應用介紹FilmingchemicalreactionsThestudyoftransientstatesofmatterthatlastnanoseconds(10-9s),orevenpicoseconds(10-12s),isoneofthescientificchallengesthattheESRFhastakenupsuccessfully.Forexample,researchersobservedwhathappenstotheC2H4I2moleculeinwaterwhenhitbyaflashoflaserlight.Thepumpandprobetechniqueusedinthisexperimentmayalsohelpinthefuturetostudynanomaterialsandproteinsinaction.H.Iheeetal.,

Science2005,

309,1223XAFS應用介紹FilmingchemicalreactionsTheXAFS在多相催化中應用XAFS應用介紹XAFS在多相催化中應用XAFS應用介紹solidcatalystgasesSurfaceeventsMolecularunderstandingAtomicscaleconstructionDynamicprobeofoperatingstate在原子精度上設計、構筑高效催化劑；在分子精度上揭示反應物向產物的轉化；發展表征工具，原位、實時、高空間分辨地表征工作狀態催化劑，實現對催化過程本質的理解–DOEReport2007XAFS應用介紹solidcatalystgasesSurfaceeveActivationofaCuO/ZnO/Al2O3catalystCatalysisformsmethanolfromsynthesisgas:CO+2H2

→CH3OH.Alsohydrogencanbeproducedfromsyngasviathewater-gas-shiftreaction:CO+H2O→CO2+H2.CuO/ZnO-catalyst,asprepared:CuinsolidsolutionwithZnO,substitutingZn2+asCu2+.ReductionofcatalystinH2atmosphere:

Cureducedtometallicstate,migratestoZnOsurfaceCuformsparticlesoffewnmsize.ClustersizeandatomicstructureiscrucialforcatalyticactivitySmallerclusters

largerspecificsurface

higheractivity

lessmaterialneeded(expensive,evennoblemetals!)XAFS應用介紹ActivationofaCuO/ZnO/Al2O3AdvancingTime-resolvedMethodsinMonitoringandCharacterizationofCatalystsReductionofaCuO/ZnO/Al2O3methanolcatalystinH2atmosphere,observedwith50mstimeresolution.MeasurementsperformedatHASYLABincollaborationwiththegroupofB.S.Clausen.XAFS應用介紹AdvancingTime-resolvedMethodAnovelfastmonochromator:DrivesystemGoal:Faster(ms),widespectralrange,continuousmovementCurrentlyupto40Hzpossible

80spectra/s

12.5ms/spectrumXAFS應用介紹Anovelfastmonochromator:DrExperimentsatAPSundulator1-IDMonochromatorCatalyticreactorXAFS應用介紹ExperimentsatAPSundulator1CuO/ZnO-catalyst:ReductionCuOCuCuK-edgeDt=200sJ.-D.GrunwaldtandA.Baiker,ETHZürichXAFS應用介紹CuO/ZnO-catalyst:ReductionCuOCuO/ZnO-catalyst:ReductionCuOCuCuK-edgeDt=200sXAFS應用介紹CuO/ZnO-catalyst:ReductionCuOTomographicabsorptionspectroscopy:

Enteringthe3rddimensionXAFS應用介紹Tomographicabsorptionspectrom-XAFSin2Dand3DCharacterizationofmulticomponentsamplesonmm-scale

Valencedistributionofelements2D-mapping:0.25mm2with5mmresolution:10.000spectra

notfeasiblewithconventionalmethods,30s/scan

3.5days

oscillatingQEXAFSatmoderate10Hz

8min3D-Tomography:Evenmoretimeconsuming…FirstexperimentsatESRF(BM)andAPS(taperedundulator)FocussingwithX-raylenses

Focalsize6mmx2mm.

Even

dilutebiologicalsamplesinfluorescence

modepossible!XAFS應用介紹m-XAFSin2Dand3DCharacterizXANESm-tomographyrotationtranslationI1I2I0referencesampleL2horizontalfocalsize:6-10μmrefractivelensmonochromaticX-raysfromoscillatingmonochromatorCollaborationwithRWTHAachen(B.Lengeler)andTUDresden(C.Schroer)XAFS應用介紹XANESm-tomographyrotationtranX-rayAbsorptionSpectroscopicMicroscopy:FromtheMicro-totheNanoscaleXANEStomography:(a)schematicsketchofthesample.(b)TomographicreconstructionofthesampleonavirtualsectionatX-rayenergyE=8995eV.Fromthetomographicdataset,thefullXANESspectraateachlocationonthevirtualsectioncanbereconstructed.Twoexamplespectraforlocationsshownin(b)aredepictedin(c).(d)Relativeconcentrationsofmetallic,monovalent,andbivalentCuinsidetheglasscapillary.Theconcentrationofbivalentcopperisbelowthedetectionlimitofthemethod.AttenuationgeneratedbyelementsotherthanCuisshowninthelowerrightimage.XAFS應用介紹X-rayAbsorptionSpectroscopicMeasuredData

acquire10spectrain1secondsamplingrate:100kHz

102projections91pointsperprojectionAteachpositioninthescan:Acquisitionoftomographicdataset:over90.000spectrawith104pointseach>7GByteofrawdatarotationtranslationNearedgespectrum:Sample:CuO/ZnOcatalystinglasscapillaryXAFS應用介紹MeasuredDataacquire10spectCu/ZnOcatalystSampleinglasscapillary,outerdiameter500mm,innerdiameter400mm.Beamsize:10mmx10mmSamplebelow/aboveCuK-edgeReconstructedspectrawithreferencesC.G.Schroeretal.,Appl.Phys.Lett.82,3360(2003)Reconstructionatdifferentpositionsafterseveraloxidation/reductioncycles:Whathappenstothecatalystduringcatalysis?AllspectracanbedecomposedintocontentoftheCu-oxidesandCutoanswerthisquestion!XAFS應用介紹Cu/ZnOcatalystSampleinglassCu/ZnOcatalyst:CudistributionCu<Cu(I),1:1.8

Cu>Cu(I),1.26:1

Averageoverwholecrosssection:Cu:Cu(I)=51:49

Verydetailedinsituobservationofbehaviourofrealcatalysts!XAFS應用介紹Cu/ZnOcatalyst:CudistributiXAFS在表面有機金屬化學中應用XAFS應用介紹XAFS在表面有機金屬化學中應用XAFS應用介紹XAFS在有機金屬化學中應用-Zeolite-IrXAFS應用介紹XAFS在有機金屬化學中應用-Zeolite-IrXAFS應XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS在雙金屬納米粒子研究中應用XAFS應用介紹XAFS在雙金屬納米粒子研究中應用XAFS應用介紹Magneticnanoparticles

Iron-platinumnanoparticlesareknownfortheirinterestingmagneticproperties.AttheESRF,theyweresubjectedtosuccessivetreatments.Thestructuralchangesandtheirinfluenceontheelement-specificmagneticmomentsweremonitoredbytheanalysisoftheX-rayabsorptionnear-edgestructureandtheX-raymagneticcirculardichroism.ThesynthesisedFe50Pt50particleswereself-assembledonasiliconsubstrateandexposedtoasofthydrogenplasma.Theywerethenannealedat600°Cinorderto

achievethechemically-orderedL10phaseC.Antoniaketal.,Phys.Rev.Lett.

97,117201(2006).XAFS應用介紹Magneticnanoparticles

Iron-plXAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹XAFS應用介紹NearedgeX-rayabsorptionfinestructureC1s(C=C)→π*C=C：283.4eVC1s(C--H)→π*ring：285.2eVC1s(C--N)→π*ring：286.8eVσ*CCJ.AM.CHEM.SOC.9VOL.131,NO.18,2009XAFS應用介紹NearedgeX-rayabsorptionfin上海光源XAFS線部分研究結果XAFS應用介紹上海光源XAFS線部分研究結果XAFS應用介紹

Fe基超導材料高壓X射線吸收譜結構研究中科院物理所趙忠賢丁洪孫力玲用于XAFS實驗的金剛石CeFeAsO1-xFx鐵基超導材料結構高壓與超導臨界溫度關系高壓X射線吸收譜（XAFS)

2008年春日本和中國科學家發現一種新型超導體—鐵基超導材料。鐵基超導材料的發現為高溫超導研究和量子凝聚物理帶來了巨大的刺激和振奮，XAFS將從原子和電子結構上理解高溫超導的深層機制，利用SSRF高通量、高能量分辨的XAFS光束線，獲得了高質量高壓XAFS譜。

XAFS應用介紹Fe基超導材料高壓X射線吸收譜結構研究中科院物理所趙忠