Surface Science and Methods in Catalysis, 529-0611-00L

Dr. Sharon Mitchell, Prof. Javier Prez-Ramrez

Advanced Catalysis Engineering, Institute for Chemical and Bioengineering
ETH Zrich, Switzerland
X-ray diffraction
Incidentradiation Reflectedradiation
d
Transmittedradiation
u u
1
Coursesynopsis
Threehoursofinput:PracticallyorientedguidetopowderXRDincatalysis,onlythebasic
theoreticalconceptswillbecovered.
Lectures1and2(3hours):
- Keycrystallographicconceptsandbasicsofdiffraction
- PracticalaspectsofXRD
- AnalysisofXRDdiffractiondata
- Insitustudiesandcomplementarytechniques
Lecture3(1hour):
- Workedexamples
Refertostandardtextbooksforfurtherdetails:
C.Suryanarayana, M.G.Norton.XrayDiffraction,APracticalApproach,1998,pp.207221.
C.Hammond.Thebasicsofcrystallographyanddiffraction,2
nd
ed.OUP,2001.
2
Keycrystallographicconcepts
The (220) planes
of atoms in NaCl
The (200) planes
of atoms in NaCl
3
Arrangementsofatoms/moleculesinsolids
High Low Sampletemperature
Decreaseinentropy
Strongcrystalforcesforming
Order
High
Low
AG= A HTAS
Increaseinentropy
Weakinteratomicinteraction
CrystallinesolidsOrderedthreedimensionalarrayofatoms.
Infiniterepetitionrequiredfordiffraction.
4
Keycrystallographicconcepts
c
b
a

Theunitcell:Aninfinitelyrepeatingbox
Conventionsoflatticedescription
- Theunitcellmustbeinfinitelystackable
usingonlytranslation.
- Thethreesmallestnoncoplanarvectors
a,b,andc describetheunitcell,with
interedgeanglesof,,and.
5
Keycrystallographicconcepts
Requirementforinfinitestackability:Areallrotationalsymmetriesinfinitelystackable?
1fold
2fold
3fold
4fold
6fold
5fold
7fold
Yes No
6
Keycrystallographicconcepts
Crystalsystems:Onlycertainrotationalsymmetries(1,2,3,4,6)areallowed
7typesofcrystalsystems:
Crystal system Cell lengths Cell angles
Cubic a=b=c ===90
Tetragonal a=b,c ===90
Orthorhombic a,b,c ===90
Hexagonal a=b,c ==90,=120
Rhombohedral a=b=c ==
Monoclinic a,b,c ,==90
Triclinic a,b,c ,,
Decreasing
symmetry
7
Keycrystallographicconcepts
What'sinthebox?Addingatomstotheunitcell
8
Keycrystallographicconcepts
Howmanyperiodicdistancesarethere
withinalattice?
a) b)
c) d)
b
a
9
Keycrystallographicconcepts
Howmanyperiodicdistancesarethere
withinalattice?
- Alatticeplaneisaplanewhich
intersectsatomsofaunitcellacross
thewholethreedimensionallattice.
- Therearemanywaysofconstructing
latticeplanesthroughalattice.
- Theperpendicularseparation
betweeneachplaneiscalledthed
spacing.
a) b)
c) d)
b
a
d d
d
d
10
Keycrystallographicconcepts
Howdowedescribelatticeplanes?
- Eachplaneintersectsthelatticeat
a/h,b/k,andc/l.
- h, k, and l, areknownastheMiller
indices (hkl) andareusedtoidentify
eachlatticeplane.
a)(110) b) (110)
c)(010) d)(230)
b
a
d d
d
d
11
Keycrystallographicconcepts
Howdowedescribelatticeplanes?
Andinthreedimesions:
Plane perpendicular to y cuts at , 1,
(010)plane
This diagonal plane cuts at 1, 1,
(110)plane
12
Relationshipbetweendspacingandlatticeconstants
XRDbasictheory
System d
hkl
Cubic
Tetragonal
Orthorhombic
Hexagonal
Rhombohedral
Monoclinic
Triclinic
Increasinglycomplexwith
decreasingsymmetry.
Simplestfororthogonal
crystalsystems
13
Keycrystallographicconcepts
Summary:
- Orderinginmaterialsgivesrisetostructuralperiodicity whichcanbedescribedintermsof
translational,rotational andothersymmetryrelationships.
- Crystallinematerialscomposedofinfinitearrayofidenticallattice points.
- Theunitcell isthesmallestthreedimensionalboxwhichcanbestackedtodescribethe3D
latticeofasolid.Theedges(a,b,andc)andinteredgeangles(,|,and)oftheunitcellare
knownasthelatticeparametersofacrystallinesolid.
- Relationshipbetweenunitcell,crystalsystems,andBravais lattices.
- Latticeplanesaretwodimensionalplaneswhichintersectthethreedimensionallatticeina
periodicway,withafixedperpendicularseparationknownasthedspacing.
- Millerindicesdefinetheorientationoftheplanewithintheunitcell.
14
Basictheoryof(Xray)diffraction
Incidentradiation Reflectedradiation
d
Transmittedradiation
u u
15
- The periodic lattice found in crystalline structures may act as a diffraction grating for wave
particles or electromagnetic radiation with wavelengths of a similar order of magnitude (10
10
m
/ 1 ).
- For solids there are three particles/waves with wavelengths equivalent to interatomic
distances and hence which will interact with a specimen as they pass through it: Xrays,
electrons, and neutrons.
Whenwilldiffractionoccur?
Sample
Xrays,
electrons,
neutrons
Detector
Diffraction
I
0
I
t
I
0
=I
t
transmittance
I
0
=I
t
diffractionand/orabsorbance
Sample
1
XRDbasictheory
16
Incidentradiation Reflectedradiation
d
Transmittedradiation
u u
- Inmaterialswithacrystallinestructure,Xraysscatteredbyorderedfeatureswillbe
scatteredcoherently inphaseincertaindirectionsmeetingthecriteriaforconstructive
interferencesignalamplification.
- TheconditionsrequiredforconstructiveinterferencearedeterminedbyBraggslaw.
BraggsLaw
n =2dsinu
=Xraywavelength
d =distancebetween
latticeplanes
u =angleofincidence
withlatticeplane
n =integer
XRDbasictheory
17
Whattypeofmaterialscanwestudy?
Gas:Nostructuralorder seenothing.
Liquid/Amorphoussolids:Orderoverafewangstroms broaddiffractionpeaks
Orderedsolids:Extensivestructuralorder sharpdiffractionpeaks.
Twotypesoforderedsolids:
1) Single
crystals
2)Polycrystalline
powders
Large crystalrequired.
Crystalorientation known.
Eachlatticeplaneonlypresentinone
orientation.
Nooverlapofreflections.
Reflectionintensitiesmaybeaccurately
measured.
Mostcommonin heterogeneouscatalysis
Assume allcrystalorientationspresent.
Each latticeplanepresentatall
orientations.
Many overlappingpeaks.
Reflectionintensitiesdifficultto
determine.
XRDbasictheory
18
Single
crystal
Xrays
Powder/
polycrystalline
Xrays
2u
I
Singlecrystals
- Xraysdiffractedfromasinglecrystal
produceaseriesofspotsinasphere
aroundthecrystal.(Ewald sphere)
- Eachdiffractionpeakuniquely
resolved.
Powders
- AllorientationspresentContinuous
debyerings.
- Lineardiffractionpatternwithdiscrete
reflectionsobtainedbyscanning
througharcthatintersectseachdebye
coneatasinglepoint.
1)
2)
Whatdoweobserve?
XRDbasictheory
19
Electrondensity
- Xraysscatteredbyelectrons
Greatertheatomicnumber,Z,thehigherthescatteringfactorofa
givenelement(directlyproportional).
Intensityproportionaltosumofthescatteringfactorsofatomsina
givenlatticeplane. I ,F,
2
Multiplicity
- ForPowdersamplesallplaneswithequivalentdspacingoverlap.
Intensitydependentonnumberofoverlappingplanes.
Whatdeterminestheintensityofthediffractionpeak?
XRDbasictheory
20
BraggsLaw:=2dsinu
- Toobservediffractionfromagivenlatticeplane,Braggslawmaybesatisfiedby
varyingeitherthewavelength,, ortheBraggangle, u.
Monochromaticdiffraction:
Varyu
Braggconditionmetonceatatime.
- Withafixedwavelength(laboratorysource)dataiscollectedasafunctionof
increasingdiffractionangleuptoagivenvalueofd(resolutiondependent).
Lauediffraction:
Vary.
Braggconditionmetmanytimessimultaneously.
Fasterbutgreatercomplexityindataanalysis.
Requiressynchrotronwhichisexpensive.
HowcanwesatisfytheBraggequation?
XRDbasictheory
21
Xraydiffraction
Measurementanddataanalysis
22
WheredoXrayscomefrom?
- TwoprincipalmethodsforXraygeneration:
1) Firebeamofelectronsatmetaltarget.
Ionizationofinnershellelectronsresultsinformationof
anelectronhole.
Relaxationofelectronsfromuppershells.Theenergy
differenceAE(10
10
m)isreleasedintheformofXrays
ofspecificwavelengths.
- CommonlyusedmetalsareCuK

( =1.5418)andMo
K

( =0.71073).
- VeryInefficient.Mostenergydissipatedatheat (requires
permanentcooling).
XRDpracticalaspects
23
WheredoXrayscomefrom?
- TwoprincipalmethodsforXraygeneration:
2)Accelerateelectronsinaparticleaccelerator
(synchrotronsource).Electronsacceleratedat
relativisticvelocitiesincircularorbits.Asvelocities
approachthespeedoflighttheyemitelectromagnetic
radiationintheXrayregion.
- TheXraysproducedhavearangeofwavelengths
(whiteradiationorBremsstrahlung).
- ResultsinhighfluxofXrays.
- Laueexperiment
I

Minimumandmaximum determined
byinitialkineticenergy
XRDpracticalaspects
24
HowdowemeasuretheXraydiffractionpatternofasolid?
Powderdiffractometer
Sampleholder
Detector
Electrongun
XRDpracticalaspects
25
Sampleholder
Focused
primary
beam
Diffracted
beam
Transmitted
beam
S
a
m
p
l
e
Focusingprimary
monochromator
Classic transmission geometry
(DebyeScherrer geometry)
- Bestforsampleswithlowabsorption.
- Capillariescanbeusedassampleholders
(measurementofairsensitivesamples/
suspensions).
Sampleholder
Sample
Primary
beam
Diffracted
beam
Classic reflection geometry
(BraggBrentano geometry).
- Bestforstronglyabsorbingsamples.
- Requiresflatsamplesurface.
- Easilyadaptedforinsitu investigations.
Diffractometer geometries:
XRDpracticalaspects
26
HowdowepresentXraydiffractiondata?
- Theintensityofthediffractionsignalisusuallyplottedagainstthediffractionangle2u [],
butd[nm]or1/d[nm
1
]mayalsobeused.
- A2u plotispointlessifthewavelengthusedisnotstatedbecausethediffractionanglefora
givendspacingisdependentonthewavelength. Themostcommonwavelengthusedin
PXRDis1.54(CuK).
- Thesignalsinadiffractogram arecalled(Braggordiffraction)peaks,lines,orreflections.
XRDdataanalysis
27
AnatomyoftheXRDpattern
Informationcontentofanidealizeddiffractionpattern.
XRDdataanalysis
28
HowpreciselycanweanalyzeanXraydiffractionpattern?
XRDdataanalysis
Differencesbetweentheoryandreality:
- Modelsbasedonidealsystems(SampleandXrays).
Reliantonseveralkeyassumptions.
x
y

Infinitelattice
Allcrystallite
orientationspresent
FormonochromaticXRD
Single,constant,
Instrumentalfactors?
Whatimpactdotheseassumptionshaveforrealexperiment?
29
XRDdataanalysis
1)Signal whatyouwant
+2)Background
+3)Noise
Diffractionpattern whatyouget
Experimentallyrecordeddiffractionpattern:
30
PreciseanalysisofXRDdatarequiresseparationofthesamplesignalfromthebackgroundand
noise.
Strategiestoimprovesignal/noiseratio:
-Increasingintensityofincomingbeam(synchrotronsource).
- Shorterwavelength(lessabsorption).
- Increasingamountofsamplebeam(illuminatedarea)
- Increasingthecountingtime(squarerootlaw!)
Separationofsignalandbackground:
- Nottrivial Iterativerefinementbetterthanbackgroundsubtraction.
- Normallyshouldonlybeusedfortoaiddatavisualizationandnotduringdataanalysis.
XRDdataanalysis
Canweimproveaccuracyofanalysis?
31
Xraywavelength:EffectofK
1+2
radiation
TheK
2
lineliestotherightandhasabout1/2oftheintensityofthecorrespondingK
1
line.
Theseparationbetweenthetwopeaksincreaseswithincreasingdiffractionangle.
HowwellthetwopeaksareresolvedalsodependsontheFWHMofthepeaks.
Majorityofmonochromators usedinlaboratoryXRDunabletoseparateK
1
andK
2
radiation.
Thus,eachBraggreflectionwilloccurtricewithslightlydifferentdiffractionangles.
XRDdataanalysis
32
XRDdataanalysis
Informationfrompeakintensity?
Absoluteintensitiesvarydependingonbothexperimentalandinstrumentalparameters.
I ,F,
2
I=kL(u)p(u)A(u)m,F
hkl
,
2
WhereIistheintensityofthereflection(hkl)andF istheamplitudeofthediffractedXray
beam(thestructurefactor).
k =constantforagivensample
L(u)=Lorentzcorrection:Geometriccorrectiontoallreflections
p(u) =polarizationcorrection:Xraywavesarepolarised
A(u) =absorptioncorrection:SomeXrayswillbeabsorbedbythesample
m =multiplicitycorrection.AlllatticeplaneswhichhavethesameBragganglesuperimposed.
Verydifficulttodeconvolve intensitiesofindividualreflections.
Relativereflectionintensitiesofmoreusethanabsoluteintensity.
33
XRDdataanalysis
Areallcrystalliteorientationspresent?
Preferredorientationonflatsamplemount
Sampleholder
Sample
Primary
beam
Diffracted
beam
Certaincrystalshapesfavour stackingina
particularway(e.g.needlesorplatelike).
Notallcrystalorientationspresent
Intensitydistributiondifferentfrom
expected.
Thiseffectisknownas:
preferredorientation.
34
XRDdataanalysis
SowhatcanwedeterminefromXRDdata?
1)Phasedetermination
Identificationofcrystallinephases.
2)Quantitativephaseanalysis
Relativecompositionofmixedphases.
5)Structuresolution
Completestructurerefinementofunknownphases.
4)Analysisofcrystallitesizeandstrain
Estimationofsizeofcrystalline
domainanddisorder.
3)Calculationoflatticeparameters
Structuralvariationsunder
differentconditions.
35
1)Phasedetermination (Qualitative)
Mostcommonuseinheterogeneouscatalysisisforphaseidentification.Eachdifferent
crystallinesolidhasauniqueXraydiffractionpatternwhichactslikeafingerprint.
e.g.TiO
2
Threecommonlyoccurringstructures.
Phaseswithsamechemical
compositionhavedifferentXRDpatterns.
XRDenablesrapiddeterminationof
form.
Needs:Peakpositionsandapproximaterelativeintensities.
Tools:Crystalstructuredatabases.PossibletosimulatethePXRDpattern ofknowncrystal
structuresfromthereportedcrystalinformationfile(.cif)usingseveralavailablesoftware.
XRDdataanalysis
36
1)Phasedetermination
Method:Matchdiffractionpatternagainstreferencedata.
Thiscouldbethediffractionpatternorthecorrespondingpeaklist(positionsandintensities).
Thereferencecouldbeanexperimentallycollected(e.g.fromknownmaterial),orsimulated
diffractionpattern.
Thematchingprocess:Manualorautomated.
SimulatingXRDdata:Forknowncrystalstructures.
XRDdataanalysis
Search forpreviouslyreportedstructuresindatabase.
Findsuitable.cif fileandopenwithviewingprogramsuchasMercury,MaterialsStudio
etc.
Calculatepowderdiffractionpatternusingsuitableparameters.
37
Searchterms:
- Literaturereference
- Crystalstructure
- Chemicalname
- Composition
- Experimentaldata
1)Phasedetermination:Findingreferencestructures
XRDdataanalysis
Search
38
XRDdataanalysis
Results
1)Phasedetermination:Findingreferencestructures
Usefulinformation:
Generateslistofreported
structures.
- Canselecthighqualitydata
only.
Datainwhichallexperimental
parametersarereported.
Ingeneralmorerecentdatais
higherquality(Improvementsin
diffractometers).
39
XRDdataanalysis
Usefulinformation:
- Cellparameters
Usefulforcomparativepurposes
- Bibliographicreference.
Preparationandexperimental
details.
- Temperatureofdatacollection
Thermalexpansion
Changesinlatticeparameters
Changesinpeakpositions.
- RValue
Indicationofdataquality
1)Phasedetermination:Findingreferencestructures
Download.cif file
40
XRDdataanalysis
1)Phasedetermination:SimulatingthePXRDpatternofareferencestructure
Structure
visualization
- Atomic
coordination,
unitcell,etc.
Simulationof
PXRDpattern
- Selectscan
range,,and
FWHM.
Comparesimulatedpatternswithmeasureddata
41
Q: HowmanypeaksmustmatchbetweenareferencePDFpatternandameasured
diffractogram?
A: Generally,all expectedreflectionsshouldbeseeninthediffractogram,otherwiseitisnot
avalidmatch.
XRDdataanalysis
1)Phasedetermination:FAQ
Exceptions?
- Lowsignaltonoise ratio. Weakreflectionsnotvisible.
- Strongpreferredorientationeffect.Differentrelative
intensitieswithasystematicdependenceonhkl.
- Anisotropicdisorder.FWHMofthepeaksshowa
systematicdependenceonhkl
42
Q: HowmanypeaksmustmatchbetweenareferencePDFpatternandameasured
diffractogram?
A: Generally, allexpectedreflectionsshouldbeseeninthediffractogram,otherwiseitisnot
avalidmatch.
XRDdataanalysis
1)Phasedetermination:FAQ
Q:Whatifthemeasuredpatterncontainsmore
reflectionsthanthereference?
A: Morethanonephasepresent.
Keepthereferencepattern,continuesearchingfor
referencestoexplaintheadditionalpeaks.Proceed
untilallpeaksaccountedfor.
43
Deviationsinrelativeintensities
- Preferredorientationeffects.Thedeviationofintensitiesshouldbesystematicwithhkl.
CheckbyapplyingaRietveldfitincludingapreferredorientationmodel.
- Incorrectidentification(Notlikely).
- Isostructural phase.Presenceofsubstitutional impuritiesofsimilaratomicsizebutdiffering
Zmaygiverisetodeviationinintensity.Verifysamplecomposition
XRDdataanalysis
1)Phasedetermination:FAQ
Deviationsinpeakpositions
- Thermalexpansion
- Isostructural phase.Presenceofsubstitutional
impuritiesofsimilarZbutdifferingatomicsize.
Verifysamplecomposition.
Isomorphism:InsteadofAO
2
,youmayhaveA
1x
B
x
O
2
,BO
2
,AO
2x
,...
44
2)Quantitativephaseanalysis
Determiningtherelativeproportionsofcrystallinephasepresentinanunknownsample.
Ratioofpeakintensitiesvarieslinearlyasafunctionofweightfractionsforanytwo
phases(e.g.AandB)inamixture.
b)QuantificationbywholepatternfittingusingRietveld methodismoreaccuratebutmore
complicatedapproach.
XRDdataanalysis
Thiscancrudelybeestimatedbyfreehand
scalingofXRDpatterns.
Needs:I
A
/I
B
value forallphasesinvolved.
Tools:Calibrationwithmixturesofknown
quantities.
Fastandgivessemiquantitativeresults.
45
2)Quantitativephaseanalysis:Seeingtheinvisible,ismyproductreallysinglephase?
DeterminationofamorphouscontentofasamplecontainingcrystallinephaseA.
Useinternalstandardofknowncrystallinity(spiking/referenceintensityratio)
Needs:AppropriateXRDstandardB.
Nooverlapofreflectionsofstandardwithphasetobedetermined.
Highcrystallinity,uniformparticlesize.
Carefulsamplepreparation
Method:KnownamountstandardBisaddedtospecimencontainingphaseA.
XRDdataanalysis
Al
2
O
3
(Corundum)
SiO
2
(Quartz)
ZnO
I
(hkl)A
X
A
I
(hkl)B
X
B
=k
46
3)Calculationoflatticeparameters
DiffractionanglerelatedtodspacingviaBraggequation.
XRDdataanalysis
Step1:Identifypeaksindiffractionpattern
47
3)Calculationoflatticeparameters
DiffractionanglerelatedtodspacingviaBraggequation.
XRDdataanalysis
Step2: Calculatecorrespondingdspacings.
48
3)Calculationoflatticeparameters
XRDdataanalysis
Step3: IndexthePXRDpattern
Easiestifcrystalsystemknownand
forhighersymmetrye.g.Cubic.
Iterativeprocess.
Oncehkl determinedcancalculate
latticeparametersa,b,c etc.
Reflection 2 sin
2
sin
2
/sin
2

min
n(sin
2
/sin
2

min
) h
2
+k
2
+l
2
hkl
1 38.43
2 44.67
3 65.02
4 78.13
49
Relatinglatticeplanestocrystalsymmetry
PredictedBraggpositionsforprimitivecells
with =1.54.
18 21 24 27 30 33 36
triclinic
tetragonal
monoclinic
orthorhombic
hexagonal
cubic
2u (
0
)
- Increasingsymmetrydecreasein
numberofreflectionsobserved.
- Withcertainsymmetriesreflections
fromdifferentlatticeplanescancel
outSystematicabsences.
Peakmultiplicitiesdecreasefromcubictotriclinic:
e.g.cubic d
(100)
=d
(100)
=d
(010)
=d
(010)
=d
(001)
=d
(001)
orthorhombic d
(100)
=d
(100)
d
(010)
=d
(010)
d
(001)
=d
(001)
XRDdataanalysis
50
4)Analysisofcrystallitesizeandstrain
XRDdataanalysis
Whatfactorsdeterminethepeakprofile?
Canwegainusefulinformation?
Idealsampleanddiffractometer
Zerowidthdiffractionlines
Realmeasurement
Diffractionlineshavefinitewidth.
Peakprofile.
51
4)Analysisofcrystallitesizeandstrain
XRDdataanalysis
Whatfactorsdeterminethepeakprofile?
XRDpeakprofileshapeandwidtharetheresultofimperfectionsinboththeexperimental
setupandthesample.
Instrumentalbroadening
Dependentonexperimentalsetup(e.g.samplesize,
slitwidths,goniometer radius).
Functionof2.
Determinedbymeasurementofasuitablereference.
Samplebroadening
Periodicityincrystalsisnotinfiniteascrystalshave:
Finitesizesizebroadening.Mostapparentincrystalssmallerthanca 100nm.
Latticeimperfections(e.g.dislocations,vacancies,substitutional)strainbroadening.
52
4)Analysisofcrystallitesizeandstrain
XRDdataanalysis
Whichofthesediffractionpatternscomesfromananocrystalline material?
Exactsamesample!
Measuredusingdifferentdiffractometers,withdifferentopticalconfigurations.
Instrumentalcontributionmustbeknowntodeterminesamplebroadening.
66 67 68 69 70 71 72 73 74
2u(deg.)
I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
53
Thetermsizeneedstobecarefullydefined:
XRDdataanalysis
4)Analysisofcrystallitesizeandstrain
54
XRDdataanalysis
4)Analysisofcrystallitesize:TheScherrerequation
( )
u

u
cos
2
L
K
B
size
=
Publishedby
Scherrer in1918
Relatespeakwidthto
crystallinedomainsize
B istheFWHMofthepeakprofile(correctedforinstrumentalbroadening)
L Volumeaverageofcrystalthicknessindirectionnormaltoreflectingplanes.
K isconstantofproportionality.
Diffractionangleofthereflection.
isthewavelength.
Assume:Crystalsuniformsizeandshape.
Scherrerconstant,K:Dependentoncrystalshape
0.94forsphericalcrystalswithcubicsymmetry.
55
XRDdataanalysis
SignificanceofapparentcrystalthicknessL
-Volumeaveragedcrystalthickness,L,dependenton
crystalshape.Examples:
a) CubiccrystalliteL =L
c
=crystalliteedgelength
(forreflectionsoflatticeplanesparalleltothecubefaces)
b)SphericalcrystalliteLL
c
=crystallitediameter
L
Vol
=3/4L
c
(forallreflections)
4)Analysisofcrystallitesize:Howdoesthesizebroadeningeffecttranslatetocrystalsize?
Influenceofcrystalliteshape,domainstructure,sizedistributionetc.
56
XRDdataanalysis
- Latticestrain(microstrain)arisesfromdisplacementsoftheunitcellsabouttheirnormal
positions.
- Oftencausedbydislocations,surfacerestructuring,latticevacancies,interstitials,
substitutionals,etc.
- Verycommoninnanocrystalline materials.
4)Analysisofmicrostrain broadening
B
xtra|n
(20) = 4s

tan0
Strainisusuallyquantifiedas
0
=d/d,withdthe
idealizeddspacingandd themostextremedeviation
fromd.
Thepeakbroadeningduetostrainisassumedvaryas:
26.5 27.0 27.5 28.0 28.5 29.0 29.5 30.0
2u []
I
[
a
.
u
.
]
57
XRDdataanalysis
Severalfactorscontributetotheobservedpeakbroadening, B
obs
:
B
obs
=B
instr
+B
sample
= B
instr
+B
size
+B
strain
- TheinstrumentalbroadeningB
instr
canbedeterminedexperimentallywithadiffraction
standardorcalculatedwiththefundamentalparametersapproach.
- Theseparationofthesizeandthestraineffectonthesamplebroadening,however,ismore
complicatedanddependsonthemethodused.
Mostmethodsconsiderthefollowingangulardependencies:
B
size
1/cos
B
strain
tan
Note:BroadeningmayalterFWHMortheintegralbreadthofthepeak (peakshape).
4)Size/strainanalysis:peakbroadeningsummary
58
XRDdataanalysis
Donottrusttheresultsintermsofabsolutevalues.
Useaconstantprocedureforaseriesofsamples.
Relyonrelativetrends.
Donotseriouslycompareresultsfromdifferentsources.
Dontbesurprisedifotheranalyticalmethods(e.g. TEM)yielddifferentresults.
Publishresultswithdetaileddescriptionofdeterminationprocedure
Warning:Unfortunately,peopletendtobelieveinnumbers.Uncertaintieswhichdonotappear
aserrorbarsareeasilyforgotten.Thus,ifyougiveresultsfromanXRDsize/strainanalysisto
otherpeople(e.g. asatableinyourthesis),beawarethattheywillprobablybetakenmore
seriousthantheyshould...
4)Practicalaspectsofsize/strainanalysis:Conclusions
59
5)Crystalstructuredetermination(Rietveldanalysis)
RietveldrefinementisanautomatedprocedurewhichsimulatestheXRDpatternsofmodel
systems(theoreticalorknown)andcalculatesthedifferenceoffitwithmeasureddata.
WhatcanRietveldrefinementtellus?
- Latticeparameters - Quantitativephaseanalysis - Atomicpositions - Crystallinity
- Atomicoccupancy - Phasetransitions - Structurefactors - Grainsize
Whatdoweneed?
Modelcrystalstructureofeachcrystallinecomponent.
Goodqualitydata.
XRDdataanalysis
Rawdata
Structural
model
Rietveld
refinement
Refined
model
60
5)Crystalstructuredetermination(Rietveldanalysis)
RietveldrefinementisanautomatedprocedurewhichsimulatestheXRDpatternsofmodel
systems(theoreticalorknown)andcalculatesthedifferenceoffitwithmeasureddata.
Howdoweobtainaninitialstructuralmodel?Trialanderror
- Solidsolutionsusuallyadoptsimilarstructuretypesastheirparentcompounds;
e.g.NaSr
4x
Ba
x
B
3
O
9
(0x4)
- Compoundswithsimilarchemicalformulamayhavesimilarstructurese.g.YBa
2
Cu
3
O
7
and
NdBa
2
Cu
3
O
7
Note:100%fitcorrespondstoallphasesmodeledwhichmaynotbe100%sample
(amorphousmaterial/unknownphasesetc.).
XRDdataanalysis
Rawdata
Structural
model
Rietveld
refinement
Refined
model
61
5)Rietveldanalysis:Calculationofspectrum
XRDdataanalysis
62
Principles
Tominimizetheresidualfunction:
where:
Rietveld,ActaCryst.22,151,1967.
Profilefitting
XRDdataanalysis
63
28.5 29.0 29.5 30.0
2u(deg.)
I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
Empiricallyfitexperimentaldatawitha
seriesofequations.
Methods:
SinglePeak
Wholepattern
(complicatedifmorethanonephase).
Rietveld(calculatedstructure).
Backgroundtypicallyassumedtobelinear.
Peakfittingprecisepeakparameters(position,intensity,FWHM,shape).
Profilefitting
XRDdataanalysis
64
DiffractionpeaksusuallycontainbothGaussianandLorentziancontributions.
Difficulttodeconvolve
MostdatafittedwithaprofilefunctioncombiningbothGaussianandLorentziancomponents:
pseudoVoigt(linearcombination) PearsonVII(exponentialmixing)
NonambientXRD
Insitu XRD
XRDunderNonambient conditions:
Elevatedorreducedtemperature.
Elevatedorreducedpressure.
Vacuum.
Definedgasatmosphere.
Whyisthisimportant?
Knowledgeofstructureuselessifthestructurechangesundercatalyticreactionconditions.
inoperandoXRD.
Whatcanwelearn?
Temperatureorpressureinducedphasetransitions Solid/solidreactions
Solid/gasreactions Formationofreactionintermediates
Timeresolvedmeasurements reactionkinetics
65
NonambientXRD
Insitu XRD
Characterizationoftheactivecatalyst
Activation/deactivationbehaviorofthecatalyst
Characterizationofcatalystprecursormaterials
Investigationofsomecatalystpreparationsteps
(e.g. insitucalcination)
Investigationofcatalystmaterialreactivity
(oxidation,reduction,decompositionreactions)
Cluesforunderstandingactivity/mechanisms
Structureactivity
correlations
Preparation/structure
correlations.
(chemicalmemory)
Knowledge
basedcatalysis
design
Example:Iftheonsettemperaturesofreductionandcatalyticactivitycoincide,wemay
suspectthatlatticeoxygenisinvolvedinthecatalyticreactionmechanism.
Inthecontextofcatalysis,theapplicationofinsitu XRDmayhelpwith:
66
NonambientXRD
Insitu XRD:Synchrotronstudies
- HigherfluxRapiddataacquisition
- HigherintensityGreaterpenetration.
- Permitsstudyofliquidphasereactions(alsorelevanttocatalystsynthesis).
67
NonambientXRD
Insitu XRD:Synchrotronstudies
- HigherfluxRapiddataacquisition
- HigherintensityGreaterpenetration.
- Permitsstudyofliquidphasereactions(alsorelevanttocatalystsynthesis).
68
Hightemperature/
pressurestudies
NonambientXRD
Insitu XRD:Synchrotronstudies Example
69
D3
D2
D1
**
* *
*
*
6MgO+Al
2
O
3
+H
2
OMg
4
Al
2
(OH)
14
.xH
2
O(LDH)
Diffractionpatternsrecordedat150C
2 D1=6 18.5,D2=18 50,D3=28 100
Precursorfor
spinelbase
catalysts
NonambientXRD
Insitu XRD:Synchrotronstudies Example
70
6MgO+Al
2
O
3
+H
2
OMg
4
Al
2
(OH)
14
.xH
2
O(LDH)
Precursorfor
spinelbase
catalysts
Obtainmentoftimeresolveddata:
Kineticsofconsumptionand
growthofcrystallinephases.
Reactionrateincreaseswith
temperatureinagreementwith
Arrheniuskinetics.
NonambientXRD
Insitu XRD:Synchrotronstudies
71
Obtainmentoftimeresolveddata:
Kineticsofconsumptionand
growthofcrystallinephases.
Detectionofatleasttwotransient
phases.
PreparationofalayeredPerovskitebymoltensaltrouteat800C.
K
2
CO
3
:CaCO
3
:Nb
2
O
5
+RbClinexcessRbCa
2
Nb
3
O
10
Note:Dataispresentedasintensity
versusenergy().
NonambientXRD
InoperandoXRD
Onlinemonitoringofthegasphaseby:
massspectrometry(hightimeresolution,butoftenonlysemiquantitative),
gaschromatography(lowertimeresolution(minutesscale),butbetter
quantification).
Totakefulladvantageofinsitu investigationson
catalystsunderoperationconditions,thecatalytic
activitymustbemonitoredsimultaneously.
Providescommonscaletocorrelatethe
resultsofdifferentinsitumethods.
72
NonambientXRD
InsituXRD:Relevanceforcatalysis
Xraydiffractioncharacterizestheaveragebulkstructureofcrystallinematerial.
Aretheresultsobtainedrelevantforcatalysis?
Dependsonsystemunderinvestigation,XRDmaygivecluesrelevantforcatalysis,since:
Thereisnosurfacewithoutbulk,andnobulkwithoutsurface.Modificationsofthebulk
structurewillprobablyaffectthesurfacestructure!
CarefulanalysisofXRDdatamayshedlightonspecificdefects(likedisorderorstrain)
whichcanberelevantforcatalyticactivity.
- Catalyticreactionsusuallyoccuratthesurfaceofa
heterogeneouscatalyst.
- Activesitesoftendifferfromaveragestructure.
- ThecatalyticallyactivephasemaybeXRD
amorphous.
73
Xraydiffraction
Complementarymethods
- Likeallotheranalyticalmethods,XRDhasbothstrengthsandlimitations.
- Itisgenerallyagoodideatocombineanumberofcharacterizationtechniquesinorderto
answerspecificscientificquestions.
- SometechniquesareparticularlywellsuitedtocomplementXRD.
74
Xraydiffraction
Complementarymethods:XraydiffractionandEXAFS(extendedXrayabsorptionfine
structure)
XRD
Analysisoflongrangeorder.
Limitedtocrystallinematerials.
Notelementspecific.
Distinguishesdifferentcrystallographicsites.
Averagesoverdifferentelementsonthe
samecrystallographicsite.
Distinguishesdifferent(crystalline)phases.
75
EXAFSwillbecoveredinmoredetailbyProf.vanBokhovenonthe17
th
and22
nd
ofNovember.
EXAFS
Analysisofshortrangeorder.
Coversbothcrystallineandamorphous
materials.
Elementspecific.
Averagesoverdifferentsites(forthesame
element).
Distinguishesdifferentelementsonthe
samecrystallographicsite.
Averagesoverdifferentphases(containing
thesameelement).
Xraydiffraction
Complementarymethods:Xrayandelectrondiffraction(transmissionelectron
microscopy)
XRD
Averagingoverthewholesample.
Limitedtolargercrystallites (reflection
broadening).
Amorphousmaterialinvisible.
3Ddistributionofdspacings.
Usuallynobeamdamage.
76
ElectronmicroscopywillbecoveredinmoredetailbyDr.Krumeichonthe1
st
and6
th
of
December.
TEM
Relatively local.
Limitedtosmallercrystallites(>30)
beamtransparencyrequired!
Amorphousmaterialvisible.
2Dprojectionofdspacings (butcollapsed
into1D).
Beamdamagequitepossible.
TakecarewhencomparingparticlesizesestimatedbyTEMandPXRD.
Xraydiffraction
Complementarymethods:Xrayandneutrondiffraction?
Xrays
Electromagnetic wave
Nomass,spin1,nomagneticdipole
moment
Xrayphotonsinteractwiththeelectrons
Scatteringpowerfallsofwith2.
77
Neutrons
Particlewave
Mass, spin,magneticdipolemoment.
Neutronsinteractwiththenucleus.
Scattering powerindependentof2.
Whataretheconsequencesondiffraction?
Xraydiffraction
Essentialsofneutrondiffraction
78
Neutronsgeneratedfromatomicnuclei.
Twomethods:
1) Fissionreactor
2) Spallation source:Proton
bombardmentofleadnuclei,releasing
spallation neutrons.
Waveparticledualism
(=h/mv,deBroglie).
Similar andpenetrationtoXrays
Spectraldistributionofneutronsfromfission
reactor.Neutronenergies1MeVveryhigh
sloweddownforpracticaluse.
Xraydiffraction
Essentialsofneutrondiffraction
79
Nodirectrelationshipbetweenscatteringfactorandatomicweight.
Lighterelementsvisible.
Candistinguishbetweenelementsofsimilaratomicweighte.g.SiandAl.
Possibletodetectisotopicsubstitution.
Xraydiffraction
Essentialsofneutrondiffraction
80
ReflectionsinsamepositionifneutronsandXrayshavethesamewavelength.
DifferentreflectionintensitieswithXray/neutrondiffraction.
Xraydiffraction
Complementarymethods:Xrayandneutrondiffraction
XRD
Interactionwithelectronshell.
Atomicorderonly.
Scatteringpowerdependsonatomicnumber.
Cannotdistinguishisotopesorneighboring
elementsinPSE.
Lightelementshardtolocalize(hydrogen
almostinvisible).
81
Neutrondiffraction
Interactionwithnucleus.
Atomicandmagneticorder.
Scatteringpowerdependsonnucleus
structure.
Distinguishesisotopesandneighboring
elementsinPSE.
Noproblemwithlightelements(vanadium
almostinvisible).
Clarification
TwoXrayemissions(K
1
andK
2
)resultfrom
relaxationofelectronsfromsecond(L)tofirst(K)
quantumshell.
Bothoriginatefrom2porbitals.Thedifferencein
energyarisesfromdifferencesinthespinorbit
interaction(high/lowspinstate).
Mostmonochromatorscantseparatethese
wavelengthsdoubletsinXRDpattern.
Occursatalldiffractionanglesbutdifferenceis
morenoticeableathigher2u duetogreater
multiplication(Braggslawn=2dsinu).
Photoemissionwillbefurther
studiedinXrayphotoelectron
spectroscopy(XPS)byProf.van
Bokhoven on29
th
November.
Extension of basic crystallographic concepts
Threedimensionalcrystalstructure
constructedbystackingofunitcell.
Crystalstructuresgroupedaccording
tothesymmetryoftheirunitcell
7crystalsystems.
Bravaisdemonstratedthatforathree
dimensionallatticethereare14
possiblelatticetypesbasedon
translationalsymmetry.
Symmetry=Patternedselfsimmilaritye.g.throughgeometricsymmetryoperatorssuchas
translation,rotation,inversionetc.
Areothersymmetriespossible?
84
Mirrorsymmetry
3foldRotationalsymmetry
Extension of basic crystallographic concepts
Escherfamiliartoallcrystallographers.
Exploredsymmetryoperationssuchas
reflection,rotation,inversionthroughart.
Pointgroupsymmetrydescribesymmetry
operationswhichdonotinvolvetranslation.
Thecombinationofallavailablesymmetry
operators(32pointgroups),withtranslational
symmetryandthe14availablelattices230
SpaceGroups.
Describetheonlywaysinwhichidentical
objectscanbearrangedinaninfinitelattice.
85
Extension of basic crystallographic concepts
Certainspacegroupsareimmediately
identifiablebytheobservationofsystematic
absencesinthediffractionpattern.
SymmetryElement Absenceconditions
AcenteredLattice(A) k+l =2n+1
BcenteredLattice(B) h+l =2n+1
CcenteredLattice(C) h+k =2n+1
facecenteredLattice(F) h+k =2n+1
h+l =2n+1
k+l =2n+1
BodycenteredLattice(I) h+k+l =2n+1
Commonsystematicabsencesrelatedto
crystalstructure
Helpfulforcrystalstructuredetermination