METALLIC NANOPARTICLES

DRAGOMIRMIRELA
UNIVERSITYOFNOVAGORICA
DOCTORALSTUDY,PROGRAMMEPHYSICS
1

INTRODUCTIONTOTHENANOWORLD
WHATISNANO?
Theprefixnano isvariouslysaidtoderivefromthe
Greekwordo ortheLatinwordnannus,both
meaningdwarf.ItwasadoptedasanofficialSIprefix,
meaning109 ofanSIbaseunit,atthe11th
ConfrenceGnraledesPoidsetMesures(CGPM)
in1960(althoughithadinformalstatusbeforethat).

Nanoscience
thestudyofthephenomenaat1100nm
Nanomaterials
thosewhichhavestructuredcomponents
withatleastonedimensionlessthan100nm
ZeroDimensionalNanostructuresNanoparticles
OneDimensionalNanostructuresNanowiresandNanorods
TwoDimensionalNanostructuresThinFilms
Nanoparticles arenanosized structuresinwhichatleastoneof
itsphaseshasoneormoredimensions(length,widthor
thickness)inthenanometersizerange(1to100nm)as
depictedinfigure1.

Figure1.Depictionofthesizeregimeofnanoparticles relatedto
commonnano scaleobjects;Aprokaryoticcell,Bultraviolet
wave,Cvirus,Denzyme.Bluespheresrepresenta50nmmetal
nanoparticle [RobinJ.WhiteChem.Soc.Rev,2009,38].

2.METALLICNANOPARTICLES

Thetermmetalnanoparticle isusedtodescribednanosized metalswith

dimensions(length,widthorthickness)withinthesizerange1100nm.

Theexistenceofmetallicnanoparticles insolutionwasfirstrecognizedbyFaraday
in1857andaquantitativeexplanationoftheircolour wasgivenbyMiein1908.

Figure2. Thegrowthofnumberofpublications
dealingwithmetal nanoparticles [JuanM.Campelo
ChemSusChem2009,2]

Figure3.Interestinspecificelementsinthe
preparationofnanoparticles overthepast17years
[J RobinJ.WhiteChem.Soc.Rev,2009,38]

ThemaincharacteristicsofMNPs
largesurfaceareatovolumeratioascomparedtothebulk
equivalents;
largesurfaceenergies
thetransitionbetweenmolecularandmetallicstates
providingspecificelectronicstructure(localdensityofstates
LDOS);
plasmonexcitation;
quantumconfinement;
shortrangeordering;
increasednumberofkinks;
alargenumberoflowcoordinationsitessuchascornersand
edges,havingalargenumberofdangling bondsand
consequentlyspecificandchemicalpropertiesandtheability
6
tostoreexcesselectrons.

DensityofStates
Figure4.Relationshipbetweennanoparticle size,energyandtheprincipleofenergy
ofstates[RobinJ.WhiteChem.Soc.Rev,2009,38].

SurfacePlasmonResonance
Figure5.Oscillationofametallicnanoparticles electroncloud(red)relativetothe
metalcore(blue)inresponsetotheelectromagneticfield;thebasisforthesurface
plasmon resonanceeffectobservedinnanoparticles [RobinJ.WhiteChem.Soc.
Rev,2009,38].

Localfield factor

TheSPRcan be simply formalized,inafirstapproach,bysolving Laplaces

equation inthecaseofasingleconducting sphere surrounded bya
homogeneous transparentmedium,with theappropiate continuity relationsat
themetaldielectric interfaceandassuming that thesphere radiusis much
lower than thewavelength (quasistatic approximation).Thehomogeneous
localelectric field inside theparticle,El :

Eq.1:
where:
E0 is theapplied field
m =dielectric function ofmetal
d =dielectric function ofthehostmedium

Thelocalfield factoris defined astheratioofthelocalfield totheapplied one:

Eq.2:

f =El/E0
9

SYNTHESISMETHODS
A. CHEMICALMETHODS
A.1.Chemicalreductionofmetalsalts
A.1.1.Thealcoholreductionprocess
A.1.2.Thepolyolprocess

A.2.Microemulsions
A.3.Thermaldecompositionofmetalsalts
A.4.Electrochemicalsynthesis
10

B.PHYSICALMETHODS
B.1.Explodingwiretechnique
B.2.Plasma
B.3.Chemicalvapourdeposition
B.4.Microwaveirradiation
B.5.Pulsedlaserablation
B.6.Supercriticalfluids
B.6.Sonochemicalreduction
B.7.Gammaradiation
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Goals and Problems in

MetallicNanoparticlesSynthesis
Ideally, metallicnanoparticlesshouldbepreparedbyamethodwhich:
isreproducible
maycontroltheshapeoftheparticles
yieldsmonodispersemetallicnanoparticles
iseasy,cheap
uselesstoxisprecursors:inwaterormoreenvironmentallybenignsolvents(e.g.
ethanol)
use theleastnumberofreagents
usea reactiontemperatureclosetoroomtemperature
withasfewsyntheticstepsaspossible(onepotreaction)
minimizingthequantitiesofgeneratedbyproductsandwaste.
12

A.1. Chemical reduction of metal salts

In1857MichaelFaraday
reportedasystematicstudyof
thesynthesisandcolorsof
colloidalgold.
In1951,J.Turkevichreproduced
standardprotocolsforthe
preparationofmetalcolloids
(wasrefinedin1970byG.
Frens)

Figure 6.The formation ofmetalcolloids

bythesaltreductionmethod [Helmut Boennemann
Eur.J.Inorg.Chem, 2001].

13

NucleationandGrowth(LaMer)
1. Nucleation
takesplacebecausethesupersaturatedsolutionisthermodynamically
unstable.Forthenucleationprocesstooccur,thesolutionmustbesupersaturatedinorder
togenerateanextremelysmallsizesolparticle.

Figure 7. The concept of monodisperse colloid growth of la Merr model (A) and typically synthetic apparatus (B)
[JohnA.Blackman Metallicnanoparticles,Elsevier,2009].

14

NucleationandGrowth(LaMer)
2.Growth
Afterthenucleiareformedfromthesolution,
theygrowviadepositionofthesolublespeciesontothesolid
surface(molecularaddition).

Therelativeratesofgrowthofsmallandlargeparticlesare
differentwhenthereactantsaredepletedduetoparticlegrowth.
Secondary growth

thegrowthofparticlesbyaggregation
isfasterthanthatbymolecularaddition
itoccursbystableparticlescombining
withsmallerunstablenuclei

15

StabilizingMetallicNanoparticles
by placing them in an inert environment
by adding surface-protecting reagents

an inorganic matrix or

polymer
organic ligands figure 9
inorganic capping materials figure 8

Figure 9 . Steric stabilization of

nanostructured metal colloids
[Helmut Boennemann
Eur.J.Inorg.Chem.2001]
Figure 8. Electrostatic stabilization of metal colloid particles. Attractive van
der Waals forces are outweighed by repulsive electrostatic forces between
adsorbed ions and associated counterions at moderate interparticle separation
[GunterSchmid ClustersandColloids,VCH,1994]

16

A.1.Chemicalreductionofmetalsalts

Table1.Summaryof
precursors,reductionagents
andpolymeratabilizers
[GuozongChao
NANOSTRUCTURESAND
NANOMATERIALS,Imperial
CollegePress,2004]

17

Au
nanoparticles

Influencesofreducingreagents
Table2.ComparisonofaveragesizesofAunanoparticles synthesizedusingvarious reduction
[GuozongChaoNANOSTRUCTURESANDNANOMATERIALS,ImperialCollegePress,2004]

18

Au
nanoparticles

Influencesofreducingreagents

Figure10.SEMmicrographsofgoldnanoparticles preparedwithsodiumcitrate(a)and citricacid(b)as

reductionreagents,respectively,underotherwisesimilarsynthesisconditions.
[W.O.Miligan andR.H.Morriss,J.Am.Chem.SOC.86,3461(1964).]

19

Influencesofreducingreagents
InthecaseofPd

Figure 11.TheparticlesizeofPdcolloidsasafunctionofpeakpotentialsof reduction reagent,

carboxylates,inwhichsmallerpeakpotentialsmean strongerreductionreagents.
[M.T.Reetz andM.Maase,Adv.Muter.11,773(1999)]
20

Au
nanoparticles

InfluencesofpH

Figure 12.Transmissionelectronmicrographsofgoldnanoparticles obtainedbycitrate

reductionatthefollowingpHvalues:(a)4.0,(b)4.5,(c)5.0,(d)5.5,(e)6.0,and (f)6.5
[W.Patungwasa,J.H.Hodak ,MaterialsChemistryandPhysics108(2008)]
21

Pt nanoparticles

lnfluencesofpolymerstabilizer
Influenceof
sodium
polyacrylate
onthe
shape
ofPtNPs
Figure13.Ptnanoparticles synthesizedincolloidalsolutionandhavingdifferentshapes (11
nmcubesontheleftand~7nmtetrahedronsontheright)
[T.S.Ahmadi,Z.L.Wang,T.C.Green,A.Henglein,M.A.ElSayed,Science272,1924(1996).]

22

A.1.1.Thealcoholreductionprocess

Figure 14. Preparation of polymer-capped metal nanoparticle by alcohol reduction [Marcel Dekker,
DekkerEncyclopediaofNanoscience andNanotechnology,NewYork,2004]

23

A.2.Microemulsions
Theformationofreversemicelleswasconfirmedtobeaninterestingand
environmentallyfriendlyalternativetothepreparationofmetalnanoparticles.
Reversemicelles

Normalmicelles

Figure15.Reversemicelleandnormalmicellestructures[Burdaetal.,Chem.Rev, 2005,105].

Also,byturningthereactionparameters,differentnanoparticleshapescanbeproduced
24

A.2.Microemulsions
Nanosized Agparticleswithauniformsizedistribution havebeenpreparedusinga reverse
micelleprocess

Figure 16.TEMmicrographsoftheAgpowderssynthesizedbyareversemicelleprocess withdifferent

water/surfactantratio: (a)R=4,(b)R=6,and(c)R=8
[DongSikBaeetal.,MetalsandMaterialsInt.,11,4,2005]
25

A.3.Thermaldecompositionofmetalsalts

Figure 17. Apparatus used to make metal nanoparticles by thermally decomposing solids
consisting of metal cations and molecular anions, or metal organic solids
[Charles P. Poole, Jr. Frank J. Owens, Introduction to nanotechnology, John Wiley & Sons, Inc., 2003].

26

A.4.Electrochemicalsynthesis
Theoverallprocessofelectrochemicalsynthesis
(equation)canbedividedintosixelementarysteps:
1.OxidativedissolutionofthesacrificialMbulk
anode.
2.MigrationofMn+ ionstothecathode.
3.Reductiveformationofzerovalentmetalatoms
atthecathode.
4.Formationofmetalparticlesbynucleationand
growth.
5.Arrestofthegrowthprocessandstabilizationof
theparticlesbycolloidalprotectiveagents(e.g.
tetraalkylammoniumions).
6.Precipitationofthenanostructuredmetal
colloids.

Figure 18. Electrochemical formation of NR4+Cl- stabilized nanometal

27
[Helmut Boennemann Eur.J.Inorg.Chem.2001]

B.PHYSICALMETHODS
B.2.Plasma
Anovelplasmareductionmethodatroomtemperaturehasbeenusedto
preparesupportedmetalnanoparticles.
Legrandetal.employedadihydrogenmicrowaveplasmatoreducevarious
metalsolutions(Au,PtandPtAu)onzeolites.
Thistechniqueisaverypromisingandstraightforwardwaytoprepare
metalnanoparticlesasitis:
anenvironmentallyfriendly,
fastand
simplemethodologyandalsoapromisingalternativetohydrogen
reductionathightemperatures.
However,thespecialisedequipmentneededmakesdifficultits
widespreaduse.
28

B.5.Pulsedlaserablation
Thelaserapproachinvolves:
thevaporisationofmetalsemployingapulsedlaser(e.g.NdYAG)and
subsequentcontrolleddepositiononthesurfaceofthesupportunderwelldefinedconditionsof
temperatureandpressureorpulsedlaserablationoftargetsinliquidenvironment(insolution)

AdvantagesofPLAinsolution:
alesserneedtoaddsurfactantforcappingofcolloidalparticlessomorepureparticles
canbeachieved
nanoparticlescanbeproducedinarbitrarysolution changingthenatureoftheliquid
environmentcancontrolthesizedistributionandstabilityofmetallicNPs
Someparametersthatinfluenceablation,nucleation,growthandaggregation
mechanismsare:
Laserwavelength:thediameterofNPsdecreasedwithanincreaseofphoton
energyorlaserlight
Pulseenergy:thediameterofNPsdecreasedwithanincreaseofpulsenumber
Pulseduration,
Repetitionrate
Liquidenvironment

29

Figure19.TypicalTEMimageofsilvernanoparticles inethanolanditssizedistribution
[Tilaki etal.Appl.Phys.A,84,2006]

30

Figure 20. TypicalTEMimageofsilvernanoparticles inwateranditssize

distribution [Tilaki etal.Appl.Phys.A,84,2006]
31

Characterization

Figure21.CommonmethodsavailableforthecharacterizationofmatallicNPs
[J.D.AikenIII,JournalofMolecularCatalysisA:Chemical145(1999)]
32

PROPERTIES
Physicalproperties
Effectofsizeonmeltingtemperature

Themeltingtemperaturedecreaseswiththe
dimensionsofmetallicNPs

Themanysurfaceatoms,
beinglessrestrictedin
theirthermalmotions,
willfluctuatemoreeasily
spatially,thereby
loweringthemelting
temperature

Figure 22. Size dependence of the melting temperature of gold [J.C.Bertolini,Nanomaterialsand

Nanochemistry,Springer,Berlin,2008]

33

Opticalproperties

Figure 23.Schematicdrawingoftheinteractionofanelectromagneticradiationwitha
metalnanosphere.Adipoleisinduced,whichoscillatesinphasewiththeelectricfieldof
theincominglight.[LuisM.LizMarzn Nanometals:formationandcolor,Elsevier,2004]

Figure24.Left:TransmissionelectronmicrographsofAunanospheres
andnanorods (a,b)andAgnanoprisms (c,mostlytruncatedtriangles)
formedusingcitratereduction,seededgrowth,and DMFreduction,
respectively.
Right:PhotographsofcolloidaldispersionsofAuAg alloynanoparticles
withincreasingAuconcentration(d),Aunanorods ofincreasingaspect
ratio(e),and
Agnanoprisms withincreasinglateralsize(f)
[LuisM.LizMarzn Nanometals:formationandcolor,Elsevier,2004]

34

Applications
InCatalysis:
CatalystsbasedonmetalNPsare:
9 Highlyactive

conventional
metalcatalyst

metalnanoparticles
cappedbypolymers

9 Selective
9 Exhibitlonglifetimefor
severalkindofreactions
Figure25.Schematicillustrationofthestructuresof(a)conventional
metalcatalystand(b)metalnanoparticlescappedbypolymers
[Marcel Dekker, DekkerEncyclopediaofNanoscience and
Nanotechnology,NewYork,2004]

heterogenouscatalysts immobilizedoninnorganicsupports(figure25 a)
homogenouscatalysts metalNPssurroundedwithstabilizers(figure25 b)
35

Table3. Applications
ofvarioussupported
Aumetal
nanoparticlesin
catalysis
[JuanM.Campelo,
ChemSusChem
2009,2]

36

Applicationsofhomogenouscatalysts:
Olefinhydrogenation
Nitrilehydrogenation
Photoinducedelectrontransfer

Applicationsofheterogeneouscatalysts:
Oxidationreactions
Hydrogenation
Hydrodechlorination
SynthesisofH2O2
Water gasshift
37

ApplicationinFuelCellCatalysts
Thefuellcelltechnology allowsthedirectconversionof
chemicalenergyintoelectricity
HydrogenfuelcellcatalystsrelyonpurePt
Ptalloyelectrocatalystsareemployedfortheconversionofreformergas
intoelectricity
Examples
ColloidalPt/Rucatalystsareusedin
directmethanolfuelcells DMFCs
InPEMFCs

PotentialApplicationsinMaterialsScience
Planararraysofuniformmetalnanoparticleswouldalowthe

designofnewsupercomputershavingasuperiordatastorage
capacity
NickelNPsareusedasmagneticrecordingmedium,electrical
conductivepastes,batterymaterials,etc.

38

BiologicalApplications
AuNPs1.4nmwerefoundtoarrangethemselves
intoalinearrowwhenattachedtosingle
strandedDNAolinucleotides
Magneticnanoparticles(withinorganicshells)
havebeenstudiedforbilogicalapplicationsuch
as:
ForbindingBSA
Fordrugdelivery
Forbiosensing
Forbioseparations
39

Sensors
1.Electrochemicalsensors theintroductionofmetal
NPs(mostlysupported)ontheelectrodecan:
decreasetheoverpotentialsofmanyelectrochemical
reactions
turnintoreversiblesomeredoxreactionsthatarenormally
irreversibleinconventionalunmodifiedelectrodes
Examples:sensitiveNO,H2O2 andsugarandaminosacidsensors

2.Biosensors:
canenhancetheelectrontransferbetweenbiomolecules
AgNPssupportedonglass usedasselectivebiosensorsfor
thebiotinstreptavidinsystem
40

Silvernanoparticles
isbecominganincreasinglyimportantmaterialinmanytechnologies

AgNPs

exhibitsthehighestefficiencyofplasmon excitation

is the only material whose plasmon resonance can be tuned to any wavelength
in the visible spectrum

41

AgNPs

SYNTHESISMETHODS

1.Traditional methods

Aqueous solutionreduction

2.Nontraditional methods
Microemulsion techniques
Hightemperaturereductioninporoussolidmatrices
Vaporphasecondensationofametaltargetontoasolidsupport
Laser ablationofametaltargetintoasuspendingliquid
Gamma radiationinducedmethods
Photoreduction ofAgions

42

AgNPs

Goals andproblems regardingthe

synthesisofAgNPs

Withthetraditionalmethods,themajorproblemisoftenalimited
flexibilityinthesizeofparticlesthatcanbeproducedandsuch
methodsareusuallysoldontheirabilitytomake<10nm
themajorproblemsforthenontraditionalmethodsareoftena
widesizedistribution,lackofparticlecrystallinity,andthecostand
scalabilityoftheproduction
synthesizinguniformandstablesilvernanoparticles witha
controllablesizeisdifficult
theoptimumsyntheticmethodshouldaddressalloftheabove
problemsandadditionallyyieldparticleswithnoextraneous
chemicalsthatcanpotentiallyaltertheparticlesopticalproperties
andsurfacechemistry
43

OpticalpropertiesofAgNPs
AgNPsshowremarkablephysicalandchemicalproperties
zhataresizeandshapedependent.

Themainfactorsthatcancontroletheoptical
propertiesofAgNpsare:
nanoparticlemorphology sizeandshape
therefractiveindexofthesurroundingmedium
adsorptionphenomenaatthesolidsolutioninterface
thedistancebetweentheparticles

44

InfluenceoftheparticlemorphologyontheSPR
ofAgNPS

inthecaseofasphere,asinglepeakintheopticalabsorptionspectrawasfound
for20and100nmnanospheres,SPRpeaksareatabout370and600nm,respectively
whenananoparticlebecomestruncated,themainresonanceisblueshifted
theresonancesvanishasthenumberoffacesincreases,orwhenthesymmetryofthe
nanoparticleislarger

Figure26.DeviationsfromsphericalgeometrystronglyaffecttheopticalpropertiesofAg NPs
45
[JuanM.Campelo ChemSusChem2009,2]

Influenceofthesurroundingmedium
Thelocationofthesurfaceplasmonresonancesissensitivetothedielectric
environment,andastherefractionindexincreases,theSPABisshiftedtolonger
wavelengths

Figure27.(A)ResonantRayleighscatteringspectraofanindividualAgNPinvariousdielectricenvironments
(N2,methanol,1propanol,chloroform,andbenzene).(B)Aplotdepictingthelinearrelationshipbetween
thesolventrefactiveindexandtheNPsmax.
[ChristyL.Haynes,NanoparticleswithtunablelocalizedSPR,TopicsinFluorescenceSpectroscopy,Volume8:
Radiative DecayEngineering,NewYork,2005]

46

ApplicationsofAgNPs
1.Catalysis
SupportedAgareimportantin:
theselectiveoxidationofalcohols,alkanesandalkenes
forthesynthesisofindustriallyinterestingproductsincludingepoxides andaldehydes

2.Photocatalysis:
watersplitting
degradationoforganicpollutants

3.BiologyandMedicine: Agisahighlyantimicrobialmaterialusedin:

waterpurification
woundcare
medicaldevices
drogdelivery

4.Optics:Optoelectronicdevices activewaveguidesinopticaldevices(amplifiers)
5.Electronics:electronicallyconductiveadhesives(ECAs)
47

CONCLUSIONS
The21stcenturyhasbroughtagreatinterestand
expansionofthenanomaterialsduetouniquesproperties
thatexistatthenanometricscales.
Recentadvancesinthedesignandpreparationofmetallic
NPshaveprovedthatanumerousvarietyofMNPscan
nowadaysbesynthesisedthroughdifferentpreparation
routes.
SynthesisofMNPsisimportantbecauseoftheirnovel
electrical,optical,magneticalandchemicalproperties.
AgNPsareofstrongresearchfocusbecauseoftheirunique
functionalpropertieswhichleadtovariedapplications.

48

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THANK YOU FOR YOUR TIME!