GLOBAL CLIMATE AND ENERGY PROJECT

STANFORD UNIVERSITY

Energy Tutorial:
Electrocatalysis 101

G C E P R E S E A R C H S Y M P O S I U M 2 01 2 | S T A N F O R D , C A

Thomas Jaramillo
Assistant Professor Department of Chemical Engineering Stanford University
GCEP Research Theme Leader Electrochemical Energy Conversion and Storage
Stanford University

O C T O B E R 11 , 2 012

GLOBAL CHALLENGES GLOBAL SOLUTIONS GLOBAL OPPORTUNITIES

 Outlineforthistutorial
Introduction
Fundamentalsofelectrochemistry&electrocatalysis
Thermodynamics
Kinetics
Methodsinelectrocatalysis research
Figuresofmeritforelectrocatalyst development
Applications twoexamples
Thehydrogenevolutionreaction(HER)
Thecarbondioxidereductionreaction(CO2RR)

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 Whatisacatalyst?
catalyst noun \ka-t-lst\
1: a substance that enables a chemical reaction to proceed at a usually
faster rate or under different conditions (as at a lower temperature) than
otherwise possible.

2: an agent that provokes or speeds significant change or action.

Elementarychemicalreaction:
A+B AB A+B

www.mw.com AB
www.newworldencyclopedia.org
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 Fivebroadclassesofcatalysisresearch

Conventional Ultrahigh
Homogeneous Heterogeneous Vacuum(UHV)
Biocatalysts Catalysts Electrocatalysts Catalysts SurfaceScience
e.g.enzymes e.g.transitionmetal e.g.Pt nanoparticles e.g.Rhnanoparticles e.g.Ru(109)
complexes
Fundamentalstudies
H2Ooxidationin Finechemicals FuelCells Catalyticconverters Adsorption,
photosynthesis Olefinmetathesis Waterelectrolysis NH3 synthesis desorption,reaction

H+ ande transfers H+/e,thermochemical H+/e,thermochemical Thermochemical Thermochemical

AmbientTemp LowIntermediateTs WiderangeofTemps WiderangeofTemps WiderangeofTemps
AmbientPressure WiderangePs WiderangePs WiderangeofPs VerylowP(vacuum)
Liquid(aqueous) Liquid(aq.ornonaq.) Liquid(aq.ornonaq.) Gasorliquidphase Gasonsurface

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 Electrocatalysis comesindifferentforms
Photocatalysts SolutionphaseElectrocatalysts

H.I.Karunadasa et.al.Science (2012)

Surface
Electrocatalysts

Y.Huet.al.NatureMaterials (2011) K.P.Kuhl et.al.Energy&EnvironmentalScience (2012)

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Threekeyenergyconversionreactions
inneedofimprovedelectrocatalysts

FuelProduction

2H+ + 2e- H2

CO2 + nH+ + ne- CxHy + CaHbOcH + mH2O

2H2O O2 + 4H+ + 4e-

FuelConsumption

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 Keytermsinelectrochemistry
Whatisoxidation?Whatisreduction?
LosingElectronsisOxidation.
GainingElectronsisReduction.

Justremember:LEO theliongoesGERRRR.

Whatisacathode?Whatisananode?
ReductionhappensattheCathode.
OxidationhappensattheAnode.

JustremembertothinkofaRedCat.

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 Chemistry Electrochemistry
EquilibriumThermodynamics
A+B AB A A+ +e (oxidation) E 1
B+A+ +e AB(reduction) E 2
G=100kJ/mol
A+B AB

G =100kJ/mol =nFEcell

Where: n=#ofelectronstransferred(overallrxn)
F=Faradaysconstant=96,485C/mol
Ecell =Ecanbeconfusing!

Seenextslidesonhowtousetablesofstandard
electrochemicalpotentialstocalculatethis.

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EquilibriumPotentials
Mainlythestudyofhalf
reactions

Thermodynamicsofhalf
reactionsdefinedonan
absolutepotential (E0)scale,
G0=nFE0

Potentialscalecanbeshifted
forconvenience
e.g.Evac =ESHE 4.44V

Cellvoltages (E0 a.k.a.cell

potentialE0cell)aredifferences
inpotentialfromtwohalf
reactionsthatmakeupa
completereaction.
http://hsc.csu.edu.au

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CalculatingCellPotentials:
TheStatueofLiberty
Important:Weareusingastandardreduction tablefromtheprecedingslide.
Step1:Identifytherelevantredoxreactions.Inthisexample,therelevant
reactionsareredoxreactionsinvolvingFeandCu:
Rxn 1: Fe3+ +3e Fe0(s) E1 =0.02V 1886 2012
Rxn 2: Cu2+ +2e Cu0(s) E2 =+0.34V
Step2:Chooseonereactiontobetheoxidation,andonetobethereduction(an
arbitrarydecision).Forthisexample,letschooseRxn 1tobetheoxidationrxn.

Step3:Ecell =Ecathode Eanode.Theminussignarisesbecauseweareusingtabulated

datafromreduction tables.Andsinceoxidationiswhatoccursattheanode,thesign
mustbereversedsincethereactionrunsinthereversedirection.
Ecell =E2 E1 =+0.34V (0.02V)=+0.36V.

Step4:Balancetheoverallequation(cathoderxn +anoderxn)andthencalculateG.
(3/2)Cu2+ +Fe0(s) (3/2)Cu0(s)+Fe3+ n=3e transferred
G =(3)(96,485C/mol)(+0.36V)=104,204J/mol =104.2kJ/mol.
Keyresult:G isnegative sotheoverallrxn isspontaneousaswritten.

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 Thermodynamicconsiderationsfor
electrocatalytic conversionsrelatedtoenergy
Y.Hori,ElectrochemicalCO2 reductiononmetalelectrodesModernAspectsof
Electrochemistry,Number42,editedbyC.Vayenas et.al.,Springer,NY(2008) E0 vs.RHE
2H+ +2e H2 0.00V

CO2 +2H+ +2e CO+H2O 0.11V

CO2 +6H+ +6e CH3OH+H2O +0.02V Allvalues

arecloseto
CO2 +8H+ +8e CH4 +2H2O +0.16V theH2
evolution
2CO2 +12H+ +12e C2H4 +4H2O +0.07V potential
(0.00V).
2CO2 +12H+ +12e C2H5OH+3H2O +0.08V

3CO2 +18H+ +18e C3H7OH+5H2O +0.09V

O2 +4H+ +4e 2H2O +1.23V

i (mA/cm2)
EH+/H2 EO2/H2O

ECO2/fuel E(Vvs.RHE)

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 ReactionkineticsinvolvingH2OH2O2

M.T.M.Koper,H.A.Heering,inFuelCellScience,Eds.A.Wieckowski,J.K.Nrskov,Wiley(2010),p.71110

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 ReactionkineticsinvolvingfuelsCO2

M.T.M.Koper,H.A.Heering,inFuelCellScience,Eds.A.Wieckowski,J.K.Nrskov,Wiley(2010),p.71110

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 Electrochemicalmethods(3electrodecell)
Working
Electrode(WE)
Counter
Electrode(CE)

Potentiostat
Reference
Gasbubbler Electrode(RE):
Ag/AgCl
RHE
Saturated
calomel(SCE)
achema.sg

Hydrodynamicmethods(e.g.rotatingdiskelectrode)are
particularlyusefulforcaseswheremasstransferisbeing
studiedand/ormaybeproblematic(e.g.lowconcentrationof
dissolvedgasesorgasbubbleformationonthe www.pineinst.com
electrocatalyst surface). www.cheng.cam.ac.uk

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Threeprimaryfiguresofmeritforcatalysts

Activity

Stability Selectivity

Q:Whichoftheseismostcriticallyneededincatalystdevelopment?
A:Allthree!Buteveryreactionhasdifferentneedsforcatalystdevelopment.

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 Electrochemicalreactionkinetics
Thebigquestion:HowmuchcurrentdoIachievefortheamountofoverpotential thatIapply?

Dependsontwomajorfactors(aswithanychemicalreaction):
(1) Theinherentkineticsofthereaction.
(2) Effectsofmasstransfer.
TheButlerVolmer Equation

exp exp i =currentdensity

io =exchangecurrentdensity
n=#ofelectronstransferred
=transfercoefficient(anodicorcathodic)
anodicterm cathodic term F=Faradaysconstant:96,485C/mol
+ =(E Eequil )=overpotential
R=gasconstant
Assumesonlyonestepisratedetermining T=temperature
Ifnearequilibrium,bothtermsareimportant.
Iffartherfromequilibrium,onetermdominatescanusetheTafel Equation!
exp
whereb=Tafel slope
exp

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 Electrocatalyst activity:Figuresofmerit
Fourprimaryfiguresofmeritforelectrocatalyst activity: ButlerVolmer

Exchangecurrentdensity,io (mA/cm2) exp

Tafel slope,b(mV/decade)
Currentdensityatagivenoverpotential:
iE(Vvs.RHE)(mA/cm2)
Overpotential neededtoreachagivencurrentdensity:
i=10mA/cm^2(mV)
exp

Threewaystoreportcurrentdensities:
Easy/Practical
Pergeometricarea(cm2geo)
Persurfacearea(cm2real)
Perelectrochemicallyactivesurfacearea(cm2ECSA)
ClosesttoatrueTurnoverFrequency(TOF)
Difficult/Useful Tafel

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 Recappingthefundamentals
Thermodynamics
Kinetics
Methodsinelectrocatalysis research
Figuresofmeritforelectrocatalyst development

Fourprimaryfiguresofmeritforelectrocatalyst activity:
Exchangecurrentdensity,io (mA/cm2)
Tafel slope,b(mV/decade)
Currentdensityatagivenoverpotential:
iE(Vvs.RHE)(mA/cm2)
Overpotential neededtoreachagivencurrentdensity:
i=10mA/cm^2(mV) 10mA/cm2

Threewaystoreportcurrentdensities:
Pergeometricarea(cm2geo)
Persurfacearea(cm2real)
Relevantmetric
Perelectrochemicallyactivesurfacearea(cm2ECSA) forsolarfuels
ThisistheclosesttoprovidingatrueTurnoverFrequency(TOF)

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Nowthatwehavecoveredthefundamentals,
letusexaminesomeexamplesof
electrocatalyst development.
H2 evolution
CO2 reductiontofuelsandchemicals

19
 Thehydrogenevolutionreaction(HER):
Experimentalmethodology

RotatingDiskElectrode(RDE)
Standard3electrode
Electrochemicalcell

3electrodeElectrochemical
Compressioncell

20
 Tafel PlotsforvariousHERcatalysts

10mA/cm2
Chen Z, Jaramillo T.F., et al. NanoLetters 11, 10 (2011)

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Amolecularscaleview:H2 evolutionmechanisms

OverallRxn:2H+ +2e H2
VolmerTafel VolmerHeyrovsky
(i.e.LangmuirHinshelwood) (i.e.toEleyRideal)

[Volmer] {H++e H*}x2 [Volmer] H++e H*

[Tafel] 2H* H2 [Heyrovsky]H+ +H*+e H2
+
H
+ + +
H H H
+
H
+

H H H

e e e

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Towardsquantitativedescriptorsforcatalysis
PaulSabatier(1911): Anoptimalcatalystwillbindreactionintermediatesmoderately onitssurface;
nottoostronglynortooweakly.
RogerParsons(1957): Thefirstqualitativevolcanoinelectrocatalysis,indicatingthatthebestHER
catalystsshouldexhibitGH 0eV.
Measuredcatalyticactivity

calculatedbyDFT
J.Greeley,T.F.Jaramillo,J.Bonde,I.Chorkendorff,J.K.Nrskov,NatureMaterials5(2006)909913.

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 Abioinspiredapproach

MoS2 edge:
GH=+0.08eV

GH=0.06eV GH=0.07eV
B.Hinnemann andJ.KNrskov,
J.Am.Chem.Soc. 126,3920(2004)

P.Siegbahn,Adv.Inorg.Chem. 56,101(2004)

B.Hinnemann,P.G.Moses,J.Bonde,K.P.Jrgensen,J.H.Nielsen,S.Horch, T.F.Jaramillo,K.P.Jrgensen,J.Bonde,J.H.Nielsen,
I.Chorkendorff,J.K.Nrskov,J.Amer.Chem.Soc.127(2005)53085309. S.Horch,I.Chorkendorff;Science 317(2007)100.

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AfamilyofnanostructuredMoS2 catalysts
fortheHER
Coreshell
MoO3MoS2
nanowires
Z.Chen,D.Cummins,B.N.Reinecke,E.Clark,M.K.Sunkara,T.F.Jaramillo,NanoLetters, v11(2011)41684175.

Doublegyroid
MoS2 thinfilms

J.Kibsgaard,Z.Chen,B.N.Reinecke,T.F.Jaramillo,NatureMaterials
[advanceonlinepublicationOct7,2012,DOI:10.1038/NMAT3439].

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CurrentstateofcatalystdevelopmentforH2 evolution
Catalyst Advantages
Precious metals (Pt, Pd) Best known catalysts.
Common metals (Al, V) Inexpensive.
Nickel alloys (NiMo, NiAl) Inexpensive,
stable in base, very active.
Molybdenum sulfides (MoS2) Inexpensive,
stable in acid, very active.
Disadvantages
Expensive ($65/gram for Pt).
Poor activity.
Lower activity than precious metals,
unstable in acidic electrolyte.
Lower activity than precious metals,
unstable in base.
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 AmolecularscaleviewofCO2 reduction
Y.Hori,ElectrochemicalCO2 reductiononmetalelectrodes E0 vs.RHE
2H+ +2e H2 0.00V

CO2 +2H+ +2e CO+H2O 0.11V

Allvalues
CO2 +8H+ +8e CH4 +2H2O arecloseto
+0.16V
theH2
2CO2 +12H+ +12e C2H4 +4H2O evolution
+0.07V
potential
2CO2 +12H+ +12e C2H5OH+3H2O (0.00V).
+0.08V
A.Peterson,F.AbildPederson,F.Studt,J.Rossmeisl,
3CO2 +18H+ +18e C3H7OH+5H2O +0.09V J.K.Nrskov,Energy&EnvironmentalScience
v3(2010)13111315.

+H+ +e +H+ +e +H+ +e +H+ +e +H+ +e +H+ +e +H+ +e +H+ +e

27
CO2 electroreductiononcopper

K.P.Kuhl,E.Cave,D.N.Abram,&T.F.Jaramillo,
Energy&EnvironmentalScience,
Vol.5,pp.70507059,2012.
 Summary
Introduction
Theroleofelectrocatalysis andhowitrelatestoenergyconversion
Electrochemistryfundamentals
Anodes,cathodes,redoxchemistry
Thermodynamics
Equilibriumpotentialsandreactionenergetics
Kinetics
Keyequations:ButlerVolmer andTafel
Primaryfiguresofmeritindeterminingelectrocatalyst activity
Methodsinelectrocatalysis research
3electrodeelectrochemicalcellsandtherotatingdiskelectrode(RDE)
Figuresofmeritforelectrocatalyst evaluationanddevelopment
Applications&examples:Amolecularscaleviewofelectrocatalysis
Thehydrogenevolutionreaction(HER)
Thecarbondioxidereductionreaction(CO2RR)
References
A.J.Bard&L.Faulkner,ElectrochemicalMethods:FundamentalsandApplications,Wiley,2000.
J.OM.Bockris &S.U.M.Khan,SurfaceElectrochemistry:AMolecularLevelApproach,Springer,1993.
J.Newman&K.E.ThomasAlyea,ElectrochemicalSystems,Wiley,2004.

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