1

Norges teknisk-naturvitenskapelige universitet

Catalysts for alkaline and

PEM water electrolysis
Svein Sunde
NTNU, Department of Materials Science
Sem Slands vei 6, N-7491 Trondheim
SUSHGEN Spring School
Fuel Cells and Hydrogen Technology
University of Newcastle, Newcastle upon Tyne, March 21, 2012

Sunde: Water electrolysis

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Outline
Electrocatalysis
Current state of theory of electrocatalysis
Oxygen evolution reaction
PEM
Alkaline
Synthesis of catalysts
Characterisation of catalysts
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What is electrocatalysis?
Redox or outer-sphere reactions: Current at a certain
overpotential only weakly dependent on the electrode material
(typically within a factor of 2 3):
Example: Fe(CN)63- + e- Fe(CN)64-

Reactions involving bond formation between reactants,

intermediates, or products and the electrode: Huge variations
from material to material (orders of magnitude): Electrocatalytic
reactions
Example: H2 2H+ + 2e-
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Electrocatalysis and energy

Water electrolysis: Fuel cells:

Oxygen evolution Oxygen reduction
Hydrogen evolution Hydrogen oxidation
Oxidation of small organic
molecules and CO
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Electrochemical splitting of
water
Electrical energy (DG ) Heat (Qs )

H2
H2O Breakdown of H2O
O2
Cathode: 4H+ + 4e- 2H2
Anode: 2H2O O2 + 4H+ + 4e-
Total: 2H2O O2 + 2H2
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Components of cell voltage

E = E + hs ,a + hs ,c + IR + hc ,a + hc ,c
r

c,a

s,a
E
IR

Er Vohm

IR
s,k

c,k

I
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Components of cell voltage

Surface, or activation overpotential

RT i
h s , a = 2.303 lo g = a + b log i
aa F i0

E = E r + h s , a + h s , c + IR + h c , a + h c , c

a H 2 (a O 2 )
1 2
RT
E r (T , P ) = E r (T , P = 1) + ln
nF a H 2O

(Nernst equation)
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Activation overpotential the

voltage-dependent part of the
activation energy
potential
solid solution

Tafel slope b (mV/dec)

e-

log current
log exchange current
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Technological Importance of
Reaction Mechanism
The overpotential is
dependent on the rate of
low jo
exchange of electrons at high jo
the interface under Jo(1) Jo(2)
Erev
reversible conditions j0
and: on the Tafel slope b low b
which is dependent on the E/V
mechanism
high b

= b log (j/jo)

log(j)
Here j is the net current
density
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The Tafel slope and exchange current density contain

mechanistic information Hydrogen Evolution Reaction
(HER)
I. H++e-+MM-H (A)
2M-H 2M + H2 (B)
II. H++e-+M M-H (A)
M-H+H++e- M + H2 (C)
Mechanism RDS Overpotential Tafel slope Reaction
range order
(H+)
I or II A All (120 mV)-1 1

I B Low (30 mV)-1 2

II C Low (40 mV)-1 2

High (120 mV)-1 1
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Example

B. V. Tilak, P. W. T. Lu, J. E. Colman, and S. Srinivasan, Electrolytic production of

Hydrogen, in J. OM. Bockris, B. E. Conway, E. Yeager, and R. E. White, Comprehensive
Treatment of Electrochemistry, Vol. 2, Plenum Press, New York (1981)
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Adsorption and volcano curves

The rates of some electrochemical

reactions depend on the electrode
material: Electrocatalytic reactions

electrocatalyst

Transition metals: d-band energy critical

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Electrochemical processes and electrocatalysis

reactant

product

adsorption
desorption

e- electron transfer
chemical bond

electrocatalyst
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Reactant interacting too weakly with the

catalyst: No adsorption and no current

reactant

reactant

electrocatalyst
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Product interacting too strongly with the

catalyst: No desorption, blocking and eventually
no current

reactant

adsorption

chemical bond e-

electrocatalyst
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Volcano curves, Sabatier principle

optimal

Catalytic
activity

too too
weak strong

Binding energy
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The d-band position and the binding energy:
The ligand effect

electrocatalyst antibonding

bonding

adsorbed atom
atom
A.~Christensen, A.~V. Ruban, P.~Stolze, K.~W. Jacobsen, H.~L. Skriver, J.~K. N{\o}rskov, Phys. Rev. B: Condens.
Matter Mater. Phys. 56 (1997) 5822--5834.
A.~Ruban, B.~Hammer, P.~Stolze, H.~L. Skriver, J.~K. N{\o}rskov, J. Mol. Catal. A: Chem. 115 (1997) 421--429.
B.~Hammer, Top. Catal. 37 (2006) 3--16.
18

d-bands and ORR

Y. Xu, M. Shao, M. Mavrikakis, and R. R. Adzic, Recent developments in the Electrocatalysis of the O2 Reduction Reaction,
in M. T. M. Koper, Fuel Cell Catalysis. A Surface Science Approach, John Wiley & Sons, Hoboken,
New Jersey (2009) pp. 271 - 315
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How to change the d-band energy?

Particle size
and shape

Support (carbon, nano-carbon, oxides)

Overlayer systems
or alloys: Ligand effects
(+ bifunctional)

- or both:
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How to shift the d-band:

compression
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Bifunctional mechanism for reactions involving

two adsorbates

Optimum for adsorbate A Optimum for adsorbate B

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Alloys vs overlayers
H
E ~ 0.7 V
O .. CO2
H
e-

Bifunctional mechanism: Ligand effect:

H+
H
O .. CO2
H
e- e-

E ~ 0.5 V
H+ H+
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Noble metal oxides as anode

materials
OER the most sluggish of the electrochemical reactions by far!
Pt inadequate as an OER catalyst: formation of insulating oxide
Carbon cannot be used as a support due to carbon corrosion
After Henry B.Beers patent in 1969 [1] TiO2-based RuO2 DSA
electrodes has taken over the anode technology for the chlorine
evolution.
IrO2 is used as active material for oxygen evolution since RuO2
becomes unstable at high potentials due to formation of higher valent
Ru oxides
The corrosion rate of RuO2 decreases considerably at X IrO2> 0.2
Active catalysts are stabilized by non-noble metal oxides like TiO2,
SnO2, Ta2O5, Nb2O5
Mixtures of RuO2 and IrO2 were found most promising as anode
catalysts by Ktz and Stucki [2] in their pioneering work on SPE
electrolysis
In our studies we have chosen IrO2 as the base material with additions
of RuO2 for increased activity and SnO2, and to a certain degree Ta2O5
and TiO2, for increased stability
Ref.:
(1) Henry B.Beer, British Patent 1969
(2) R. Ktz and S. Stucki, E.Acta 31, 1311 (1986)
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Conductivity: The rutile band structure

J. B. Goodenough, Progress in Solid State Chemistry, Vol. 5, Pergamon,
Oxford (1971) 145

(6)

p p (2)
s s
eg (4) RhO2, IrO2
d RuO2
MnO2
t2g (6) t CrO2,MoO2,WO2 ,VO2,NbO2

TiO2 p
s
(4)
(8)

(4)
metal atoms CF bands oxygens
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The Oxygen Evolution Reaction

(OER) at oxides

(One) proposed mechanism:

1. S + H2O -> S-OH + H+ + e- I EC

2. S-OH -> S-O + H+ + e- II EC

3. 2 S-O -> O2 + 2S III C

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Example of Tafel slope estimate

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Analysis of
reaction
mechanisms
J. OM. Bockris, J. Chem. Phys. 24 (1956) 817
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Tafel slopes and the OER

Lars-Erik~Owe, Mikhail~Tsypkin, Kia~Wallwork, Richard G. Haverkamp, Svein~Sunde, Electrochimica Acta, To be published (2012)
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Tafel slopes and the OER

Tafel slope < 60 mV/dec
as expected for a 2-electron
outer-sphere transfer:

Adsorption is involved

Lars-Erik~Owe, Mikhail~Tsypkin, Kia~Wallwork, Richard G. Haverkamp, Svein~Sunde, Electrochimica Acta, To be published (2012)
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Correlation: OH-surface bond

Paul Retschi, Paul Delahay, J. Chem. Phys. 23 (1955) 556

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Point of zero charge (pzc)/ isoelectric point (IEP)

Acid-base properties of
oxide assumed to reflect the
oxygen binding
Acid-base strength depend
on electronegativity of metal
cation: Basis for catalyst
selection
Pcz and electrocatalytic
properties frequently found
to correlate with pzc
Intensive parameter

S. Trasatti, Materials Chemistry and Physics,16 (1987) 157

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Pzc v Tafel slope II

S. Trasatti, Croatica Chemica Acta, 63 (1990) 313

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Another perspective on OER at oxides:

oxidation-reduction switching of the oxide
Minimum potential for OER correlates with potential of lower oxide/higher
oxide couple (P. Rasiyah and A. C. C. Tseung, J. Electrochem. Soc. 131
(1984) 803)
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Trasatti model: Adsorption is analogous to switching from an oxide in which the metal is
in a lower oxidation state to one that it is in a higher oxidation state

Vulcano plot: vs. - H

The enthalphy of formation of higher valent from
lower valent oxide should be average, not too high,
not too low
RuO2 and IrO2 on top

S. Trasatti, J. Electroanalytical Chem., 111 (1980) 125

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Density Functional Theory calculations: O, OH,

and OOH intermediates

J. Rossmeisl, Z.-W. Qu, H. Zhu, G.-J. Kroes, and J. K. Nrskov,

J. Electroanal. Chem, 607 (2007) 83 - 89
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Density Functional Theory

calculations: Activity

No simple rationalisation as in metals (d-band theory)

J. Rossmeisl, Z.-W. Qu, H. Zhu, G.-J. Kroes, and J. K. Nrskov,

J. Electroanal. Chem, 607 (2007) 83 - 89
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Mixed oxides: Synergism?

E. Kotz, H. Neff, Surf. Sci. 160 (1985) 517530

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Mixed oxides, synergism, electronic

structure, and IrO2

AIROF in hexacyanoferrate solution, high pH AIROF in hexacyanoferrate solution, low pH

I. A. Lervik, M. Tsypkin, L.-E. Owe, S. Sunde, J. Electroanal. Chem. 645 (2010) 135 - 142
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Band structure of IrO2

Ir-eg: 4

Oxidation
potential
Ir-t2g: 6 5

IrO2: 9 + 2x6 = 21
valence electrons

O2-p: 16 16
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Electrochemical reduction of
IrO2
IrO2:
eg Electronically conducting
Coloured (optical absorption
in the visible, intraband
H+ H+ H+ H+ H+ H+ absorption)

e- e- e- e- e- e- HIrO2:
Electronically
semiconducting
t2g Transparent in the visible
(optical absorption across
bandgap)
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E. R. Ktz and H. Neff, Surface Science 160 (1985) 517,

L. F. Mattheiss, Phys. Rev. B 13 (1976) 2433
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AIROF and hexacyanoferrates

I. A. Lervik, M. Tsypkin, L.-E. Owe, S. Sunde, J. Electroanal. Chem. 645 (2010) 135 - 142
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IrO2 powders synthesised by

hudrolysis are different

h-IrO2 in hexacyanoferrate solution, high pH h-IrO2 in hexacyanoferrate solution, low pH

I. A. Lervik, M. Tsypkin, L.-E. Owe, S. Sunde, J. Electroanal. Chem. 645 (2010) 135 - 142
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but the activity is the same!

I. A. Lervik, M. Tsypkin, L.-E. Owe, S. Sunde, J. Electroanal. Chem. 645 (2010) 135 - 142
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Ir1-xRuxO2 mixed oxides

Lars-Erik~Owe, Mikhail~Tsypkin, Kia~Wallwork, Richard G. Haverkamp, Svein~Sunde, Electrochimica Acta, To be published (2012)
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Ir1-xRuxO2 mixed oxides

Lars-Erik~Owe, Mikhail~Tsypkin, Kia~Wallwork, Richard G. Haverkamp, Svein~Sunde, Electrochimica Acta, To be published (2012)
48

Ir1-xRuxO2 mixed oxides

Lars-Erik~Owe, Mikhail~Tsypkin, Kia~Wallwork, Richard G. Haverkamp, Svein~Sunde, Electrochimica Acta, To be published (2012)
49

Ir1-xRuxO2 mixed oxides

Lars-Erik~Owe, Mikhail~Tsypkin, Kia~Wallwork, Richard G. Haverkamp, Svein~Sunde, Electrochimica Acta, To be published (2012)
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Ir1-xRuxO2 mixed oxides

Ir oxide Ru oxide

Atomically mixed oxide

Physically mixed oxide

electrode electrode

Lars-Erik~Owe, Mikhail~Tsypkin, Kia~Wallwork, Richard G. Haverkamp, Svein~Sunde, Electrochimica Acta, To be published (2012)
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Ir1-xRuxO2 mixed oxides

Atomically mixed oxide Physically mixed oxide

Significant surface
segregation!

Lars-Erik~Owe, Mikhail~Tsypkin, Kia~Wallwork, Richard G. Haverkamp, Svein~Sunde, Electrochimica Acta, To be published (2012)
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Ir1-xRuxO2 mixed oxides

Lars-Erik~Owe, Mikhail~Tsypkin, Kia~Wallwork, Richard G. Haverkamp, Svein~Sunde, Electrochimica Acta, To be published (2012)
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Getting the catalyst in the right

place? good

cheap

See also I.~C. Man, Theoretical study of electro-catalysts for oxygen evolution, Ph.D. thesis,
Technical University of Denmark (2011). http://orbit.dtu.dk/getResource?recordId=275298\&objectId=2\&versionId=1
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Catalyst-electrolyte interaction:
Nafion vs H2SO4

L.-E. Owe, I. A. Lervik, M. Tsypkin, S. Sunde, J. Electrochem. Soc, 157 (2010) B1719 - B
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Catalyst-electrolyte
interaction: H3PO4

L.-E. Owe, M. Tsypkin, S. Sunde, Electrochimica Acta, 58 (2011) 231 -237

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IrO2 temperature
dependence
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Catalysts for alkaline WE

Metals, usually Ni-based
Ni-plated steel
Porosity increased by leaching of alloying component
(Raney nickel) or sulfur (Norsk Hydro patent)
Usually not stable with time
Re-generation of electrodes after 3 or more years
usual
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Catalysts for alkaline WE: oxides

Perovskites
Pzc and binding energy (OH) correlations

John OM. Bockris, Takaaki Otagawa, J. Electrochem. Soc. 131 (1984) 290
59

Optimum perovskite

Jin Sunitivich, Kevin J. May, Hubert A. Gasteiger, John B. Goodenough, Yang Shao-Horn, Science, 331 (2011) 1381
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Preparation of Electrocatalyst
Modified polyol: Precursor reduction by EG +
annealing
Pyrolysis method using nitrate melt (Adams fusion)
Freeze frying of metal salt solutions
Hydrolysis
Solid-state reaction
Pechini
Thermal oxidation (DSA)
Sol-gel
Electrochemical from solution precursors
Sputtering
Electrochemical oxidation of base metal
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Example: Hydrolysis
Step I: hydrolysis
z z h
M OH 2 N hH 2O M OH h OH 2 N h hH aq
h = hydrolysis ratio
z z 1 z 2
M OH 2 M OH H aq M O 2H

H 0 75.2 9.6 z kJmol 1

O2-
S 0 148.4 73.1z Jmol 1
G298
0
119.5 31.35 z kJmol 1
HO-

Z=4: No pure aquo complexes at RT

Forced hydrolysis at elevated T
H2O

J.-P. Jolivet, Metal Oxide Chemistry and Synthesis, Wiley (2000)

C. J. Brinker and G. W. Scherer, Sol-Gel Science, Academic Press (1990)
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Hydrolysis
Step II: condensation

Nucleophilic substitution
Prerequisite I: Presence of a nucleophilic ligand
Prerequisite II: The presence of a leaving group
Hydroxyl ligands are good nucleophiles
Aquo ligand has no nucleophilic character, but good leaving group
Zero-charge complexes neccessary to sustain polymerisation
Anion may influence resulting structure
Relevant quantities may be calculated from available electronegativites

Olation (fast): M OH M OH 2 M OH M H 2O

Oxolation (slow): M OH M OH M OH M OH M O M H 2O

Partial charge model:

OH 0; M 0.3
J.-P. Jolivet, Metal Oxide Chemistry and Synthesis, Wiley (2000)
C. J. Brinker and G. W. Scherer, Sol-Gel Science, Academic Press (1990)
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Prediction of reaction mechanism

olation

oxolation

J.-P. Jolivet, Metal Oxide Chemistry and Synthesis, Wiley (2000)

C. J. Brinker and G. W. Scherer, Sol-Gel Science, Academic Press (1990)
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Nucleation, growth, ageing

(i) Formation of zero-charge precursors
(ii) Creation of nuclei
(iii) Growth of nuclei
(iv) Ageing in suspension
riii >> rii: Narrow size distribution
Simultaneous nucleation and growth: Wide size distribution
Supersaturation due to surface tension. Critical radius r*
liquid
liquid
solid

solid
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Nucleation

S<1 2 v
r*
G kT ln S
S c / cs

S>1

r*

Subsequent growth: Diffusion-limited growth implies narrower size

distribution than kinetically limitid growth
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Quick reaction burst =

narrow size distribution

G. Cao, Nanostructures & Nanomaterials. Synthesis, Properties & Applications,

Imperial College Press, London (2004)
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Growth

G. Cao, Nanostructures & Nanomaterials. Synthesis, Properties & Applications,

Imperial College Press, London (2004)
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Iridium oxide
H2Ir(Cl)6
NaOH, 80 oC, 1h
HNO3, pH approx 8
Precipitate
Centrifuging, washing
Annealing (400 600 oC)
X-talline (T > 450 oC), black powder, particle size a few hundred nm,
crystallite size 10 - 20 nm
Large surface area
Mixed oxides: Aqueous solvents appear to promote atomic mixing (?)
Mixed oxides: Organic solvents appear to promote segregation (?)
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Conclusions
Little interaction apparent in mixed, nanostructured
oxides
Getting the elements in the right place
Surface segregation important depends on
synthesis method
The volcano-curve is still on!
In practical applications: Be ware of the electrolyte!