Nanostructured metaloxides forsolaror

photoelectrochemical watersplitting (PECWS)

Hydrogenisoneofthemostattractivefuelsduetoitshighenergycontentperunitmass
(about120kJ/g)andthedominant technology fordirecthydrogenproductionissteam
reformingthatinvolvesreactionsbetweensteamandhydrocarbonsmostlybasedonfossil
fuel

Photoelectrochemical (PEC)watersplittingisattractiveduetoitspotentialhighefficiency,
upto30%inprinciple

Pb:Storageofhydrogenwithhighmassorvolumedensityandatambienttemperatureand
pressurehasbeenextremely difficult.
So,besidesgeneration,storageandutilizationofhydrogenalsofacesomemajorchallenges
thatneedtobeovercomebeforeitcantrulybecomeaviablefuelforpracticalandlarge
scaleuse

References forPECWS,see e.g.:

Fujishima,Honda,Naturevol.238,p.37(1972)
Osterloh andParkinson,MRSBulletin vol.36,p.17(2011)
Zhang,MRSBulletin vol.36,p.48(2011)
Gratzel,Naturevol.414,p.339(2001)
VandeKroletal.,J.Mater.Chem.vol.18,p.2311(2008)

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 Fujishima andHondafirstpointedoutthe
applicationofthisconcepttowaterphotoelectrolysis
inaseriesofexperimentsthatusedanntyperutile
crystalaspartofaphotoelectrolysis cell.
TheinteractionoflightwithTiO2 produceselectron
holepairs,ofwhichtheholesoxidizewateratthe
TiO2 surfacetoformoxygen,andtheelectrons
migratetothePtcounterelectrodetoreducewater
toform hydrogen.

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 Photoanode:

Cathode:

energy cost;potential tobeovercome

4OH +4h+ 2H2O+O2

4H2O+4e 4OH +2H2

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 (redoxpotential:thetendencyofachemicalspeciestoacquire
electronsandtherebybereduced;themorepositivethepotential,the
greaterthespecies'affinityforelectronsandtendencytobereduced)
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 Photocatalytic watersplitting bydispersion ofsemiconductor nanoparticles insolution

Idealsemiconductor material

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 Photoelectrochemical watersplitting withasemiconductor photoanode

Required properties:

proper positioning ofVBandCB

largesurface area
low recombination rate(crystallinity,low defectivity)
good electrolyte infiltration
stability
spectral sensitivity ( doping,sensitization)
good andpreferential electrontransport
( vertical 1D,anisotropic orhierarchical structures)

6 P.Roy,S.Berger,P.Schmuki,Angew Chem Int.Ed50,2904(2011)

 Thephotoanode is typically asemiconductorthatabsorbslightandgeneratesexcitons or
electronholepairs
Theelectronsaretransportedtoametalcathode(e.g.,Pt),oftenaidedbyanexternalbiasthat
cancomefromasolarcellorfromtheelectricalgrid(alsoforTiO2,whenpotentiallossesare
considered)

Hydrogengenerationoccursatthecathodefromthereductionofprotonsbytheelectrons.
Onthephotoanode,theholesleftbehindoxidizewatermoleculesintooxygengasandprotons.

Efficiency,theratioofpoweremployedin
watersplittingtotheinputlightpower
(Vbias =appliedexternalpotential):

As usual,spectral quantumefficiency is
defined as:

Photocurrent,often taken as ameasure ofWSability

(together withdirect measurement ofH2 production,if
the2halfreactions occur inseparatehalfcells)

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 (1)lightabsorptionandchargecarriergenerationinthesolid
(2)chargeseparationandtransportinthesolidandatthesolidliquidinterface
(3)charge carrier extraction andelectrochemical productformationatthesolidliquidinterface
(4)managementoftheelectrochemicalproductsinsolution.

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 Comparedto0Dnanostructures(e.g.,sphericalNPs),1Dorquasi1Dnanostructures,suchas
nanorods andnanowires,areexpectedtoexhibitimprovedtransportpropertiesandthusreducethe
recombinationlossesatgrainboundariesduetodirectionalchargetransportalongthelongaxis
(but:relatively limited surface area hierarchical quasi1Dnanostructures?)

TiO2 nanotubes:
upon 320400nmillumination,hydrogen gaswas
generated at anoverallconversionefficiencyof67%

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 Most studied oxides:
TiO2,WO3,Fe2O3,ZnO

Visible lightharvesting?

Sensitization (e.g.CdSe QD)

QDs withsmaller bandgaps thantheMOcanbeconsideredas
sensitizers,similartodyemoleculesbutwiththeadvantagesof
potentiallyhigherstability andsizetunable absorption

Doping
Dopingcanbeaneffectivewaytoaltertheopticaland
electronicpropertiesofMOs:alargenumberofdopantshave
beenstudied,Fe,Cu,N,C.
decreasedeffectivebandgaporintrabandgapstatesthat
resultinvisiblelightabsorption;however,inmanycases,the
metalionsactasdefectslimitingtransport/separationof
photogenerated charges

TandemCells

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11
 Example:hierarchical treelike nanoparticle TiO2 assemblies byPLD

240 10
A B
220
200 650C
650C 8

Photoconversion efficiency
180
2
Current density, A/cm

160
140 6

120
100 4 500C
80
500C
60
2
40
20 800C 800C
0 0
-0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4
Potential, V Potential, V

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