datadirectspace

1ColloidalCu2-x(SySe1-y)AlloyNanocrystalswithControllableCrystalPhase:Synthesis,PlasmonicProperties,CationExchangeandElectro-chemicalLithiationEnricoDilenaa§,DirkDorfsa,b§,ChandramohanGeorgea§,KarolMisztaa,MauroPoviaa,AlessandroGenovesea,AlbertoCasua,MirkoPratoaandLiberatoMannaa*aIstitutoItalianodiTecnologia,ViaMorego30,16163Genova,Italy,tel.
+3901071781502;Email:liberato.
manna@iit.
itbInstitutfürPhysikalischeChemieundElektrochemie,LeibnizUniversittHannover,30167Hannover,Germany§Thesepeoplecontributedequallytothiswork.
CorrespondingAuthor*liberato.
manna@iit.
itSupportingInformation2TEManalysesCu-basedNCs.
NCsstructuraldata,obtainedfromHRTEMobservations,exhibitedlatticecellscompatiblewithcubicandhexagonalsymmetriesaccordingthesynthesisroute.
CubicNCsdisplayedberzelianite-likestructure,asconfirmedfromd-spacingmeasurementsandangularrelationshipsoflatticesetsindirectspaceandfromvec-torandangularrelationshipofdiffractionspotsinFourierspace(Figure1a).
ForwhatconcerntheNCswithhex-agonalsymmetryboththelatticesetsd-spacingmeasurementscarriedoutinthedirectspaceandthevectorandangularrelationshipsofdiffractionspotscarriedoutintheFourierspaceexhibitedchalcocite-likestructure(Fig-ure1b).
FigureS1.
a)HRTEMimagecubicCu-basedNCshowingthe(022)and(111)latticesetswithmeasuredd-spacingsof2.
00and3.
26,respectivelyanditscorresponding2D-FTpatternconsistentwithafccdiffractionpatternalong[01-1]zoneaxis.
b)HRTEMimageofhexagonalCu-basedNCdisplayingthe(1-101),(0002)and(2-200)latticesetswithd-spacingof3.
07,3.
41and1.
72,respectively;thecorresponding2D-FTpatternisconsistentwiththe[11-20]zoneaxisofchalcocite-likestructurewherethe[2-200]∧[1-101]angleis27°and[1-101]∧[0002]is63°.
3Cd-basedNCs.
ThetotalCd-exchangedNCsexhibitedthesamesymmetryofthecorrespondingpristineCu-basedNCs,i.
e.
cubicandhexagonal.
Figure2a,breporttworeferenceNCsderivingfromthecubicandhexagonalCu-basedNCsrespectively.
Alsohere,themeasurementsoflatticesetsd-spacinginthedirectspaceandthevec-torandangularrelationshipsofdiffractionspotsintheFourierspace,displayberzelianite-likeandchalcocite-likestructuresforcubicandhexagonalCd-basedalloys,respectively.
FigureS2.
a)HRTEMimageofcubicCd-exchangedNCshowingthe(220),(002)and(111)latticesetswithmeasuredd-spacingsof2.
09,3.
1and3.
45,respectivelyanditscorresponding2DFTconsistentwithafccdiffractioninthe[-110]zoneaxis.
b)HRTEMimageofhexagonalCd-exchangedNCshowingthe(-12-10),(-1100)and(01-10)latticesetswithmeasuredd-spacingof2.
09,3.
62and3.
65respectively;thecorrespond-ing2D-FTpatterniscomapatiblewitha[000-1]zoneaxisprojectionofachalcocite-likestructurewherethe[01-10]∧[-12-10]and[-1100]∧[-12-10]experimentalanglesareveryclosedto30°.
4FigureS3.
(a-b)HAADF-TEMandHRTEMofhexagonalCd(SySe1-y)NCsshowingtwophases:worm-likeCdSNCsandspherical-likeCd(SySe1-y)alloyedNCs.
FigureS4.
PlasmonpeaksuponoxidationovertheperiodoffourdaysintolueneofthehexagonalCu2-xS0.
48Se0.
52alloynanocrystals.
5FigureS5.
a)CVcyclesofCu2-x(SySe1-y)(S0.
5:Se0.
5)nanocrystalelectrodesat5mV/SVSLiFigureS6.
a)EISspectraofCu2-x(SySe1-y)(S0.
5:Se0.
5)depictingthelithitaionprocessfromlatercycles.
AdditionalReferences(1)Fultz,B.
;Howe,J.
M.
Transmissionelectronmicroscopyanddiffractometryofmaterials,2nded.
;Springer-Verlag:BerlinHeidelberg,2002.
(2)Egerton,R.
F.
Electronenergylossspectroscopyintheelectronmicroscope,2ndedition;PlenumPress:NewYork,1996.