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Mike Lyons

School of Chemistry
Trinity College Dublin 2
melyons@tcd.ie
Eirelec 11: Electrochemistry-The Future?
Dun Raven Arms, Adare, Limerick, 17 May 2011
Plus a change, plus c'est la mme chose.
Alphonse KARR, Les Gupes 1849.
(The more things change, the more they remain the
same. ...)
Hydrogen Economy
Transition Metal Oxides: compact and hydrous.
Preparation of Hydrous Oxide modified Fe
electrodes via Repetive Potential Cycling Method
(RPCM)
Duplex layer model of oxide/solution interface.
Acid/base behaviour of hydrous oxide film :
interconnected anionic surfaquo groups.
Redox switching behaviour of hydrous oxide film.
OER kinetics and mechanism of oxide modified Fe
electrodes in aqueous base.
Concluding comments.
The Hydrogen Economy:
Hydrogen as an energy carrier.
G.W. Crabtree, M.S. Dresselhaus, M.V.
Buchanan, The hydrogen Economy Physics
Today, Dec.2004, pp.39-45.
U. Bossel, Does a hydrogen economy make
sense? Proc. IEEE, 94 (10)(2006), pp.1826-
1836.
P.P. Edwards, V.L. Kuznetsov, W.I.F. David,
N. Brandon. Energy Policy 36(2008) 4356-4362.
2 types:
Compact anhydrous oxides,
e.g. rutile, perovskite, spinel.
Oxygen present only as bridging
species between two metal
cations and ideal crystals
constitute tightly packed giant
molecules.
Prepared via thermal techniques,
e.g decomposition of unstable
salt
Micro-dispersed hydrous
oxides
Oxygen is present not just as a
bridging species between metal
ions, but also as O
-
, OH and OH
2
species in coordinated terminal
group form.
Hydrous oxides in contact with
aqueous media contain large
quantities of loosely bound and
trapped water plus electrolyte
species.
Prepared via base precipitation,
electrochemical techniques.
Materials are prepared in
kinetically most accessible
rather than thermodynamically
most stable form.
Are often amorphous or only
poorly crystalline and prone to
rearrangement.
L. D. Burke, M.E.G. Lyons,
Modern Aspects Electrochemistry, 18 (1986)169-248.
Geothite
FeOOH
Cathodic Hydrogen Evolution Reaction (HER)
Acid: 2H
3
O
+
+ 2e
-
H
2
(g) +2 H
2
O
Base: 2H
2
O + 2e
-
H
2
(g) + 2 OH
-
Simplest (therefore most studied) representative electro-catalytic reaction.
Multistep process involving adsorbed intermediates.
Classical analysis assumes HER
Occurs on oxide free metal surface.
Volmer (V) : hydrogen adsorption or discharge step.
H
3
O
+
+ M + e
-
MH
ads
+ H
2
O
H
2
O + M + e
-
MH
ads
+ OH
-
Heyrovsky (H): Electrochemical Desorption step.
MH
ads
+ H
3
O
+
+ e
-
H
2
(g) + M + H
2
O
MH
ads
+ H
2
O + e
-
H
2
(g) + M + OH
-
Tafel (T) : Chemical Desorption step.
MH
ads
+ MH
ads
H
2
(g) + 2M
2 main mechanisms :
Volmer-Heyrovsky (VH)
Volmer-Tafel (VT).
Kinetically limiting step in water
electrolysis cells and PEM fuel cell.
Multistep multi-electron transfer reaction
involving adsorbed intermediates.
Overall reaction (alkaline medium)
O
2
+ 2H
2
O + 4e
-
4OH
-
E
0
= 0.303 V (vs. Hg/HgO)
Krasilshchikov (1963)
S + OH
-
SOH
ad
+ e
-
SOH
ad
+ OH
-
SO
-
ad
+ H
2
O
SO
-
ad
SO
ad
+ e
-
2SO
ad
2S + O
2
Bockris Electrochemical Oxide (1956)
S + OH
-
SOH
ad
+ e
-
SOH
ad
+ OH
-
SO + H
2
O + e
-
SO + SO 2S + O
2
Krasilshchikov/modification thereof, is
pathway most often proposed for OER on
metal / metal-oxide electrodes in alkaline
solution.
Depending on RDS can explain a variety of
Tafel slopes.
Modification permits concept of
formation/decomposition of higher oxide e.g.
for Ni
OH
-
OH
ad
+ e
-
OH
ad
+ OH
-
O
-
ad
+ H
2
O
2 -NiOOH + O
-
ad
2NiO
2
+ H
2
O + e
-
2NiO
2
+ H
2
O 2 -NiOOH + O
ad
O
ad
+ O
ad
O
2
OER at oxidized metal and metal oxide
electrodes involves active participation of
oxide.
Acid/base behaviour of oxide important
consideration .
Concept of active surface or surfaquo groups
important.
Anodic Oxygen Evolution Reaction (OER)
L.D. Burke, E.J.M. OSullivan J. Electroanal. Chem., 93 (1978) 11.
Rhodium redox chemistry: alkaline solution
L.D. Burke, E.J.M. OSullivan, J. Electroanal. Chem., 117(1981) 155.
Microdispersed hydrous oxide formed
via potential cycling technique (similar
to poly(aniline) deposition to form PME).
Duplex layer model: oxide/solution
interface.
OSullivan & Burke,
J. Electrochem. Soc.,
137 (1990) 466.
OER activity & mechanism
(shift in OER potential and
decrease in Tafel slope)
depends on charge capacity
(thickness) of hydrous
oxide layer.
Increasing oxide
thickness
OER at
multicycled
hydrous rhodium
oxide modified
electrodes.
Fe + OH
-
FeOH(ads.) + 2e
-
FeH(ads.) Fe + H
+
+ e
-
A
1
FeOH(ads.) + OH
-
Fe(OH)
2
+ e
-
FeOH(ads.) + OH
-
FeO + H
2
O + e
-
A
2
[Fe
2
(OH)
6
3H
2
O]
2-
+ 3OH
-
[Fe
2
(OH)
9
]
3-
+3H
2
O + 2e
-
A
3
/C
2
[Fe(OH)
3.5
nH
2
O]
0.5-
(Na
+
)
0.5
+ e
-
Fe(OH)
2
n H
2
O + 0.5Na
+
+ 1.5OH
-
FeO
.
FeOOH + H
2
O + 3e
-
Fe + FeO
2
2-
+ H
2
O + OH
-
C
1
A
0
: OER
C
0
: HER
Surface redox chemistry: Bright Fe electrode
3Fe(OH)
2
+ 2OH
-
Fe
3
O
4
+ 4H
2
O + 2e
-
3FeO + 2OH
-
Fe
3
O
4
+ H
2
O + 2e
-
A
4
In situ Raman
EQCM
RRDE
Greater fine structure
observed at low sweep
rate.
Hydrous Oxide Growth via Cyclic Potential Multicycling (CPM)
Procedure of Fe electrode in aqueous alkaline solution.
Layer growth parameters:
Upper, lower potential
sweep limits.
Solution temperature.
Solution pH.
Potential sweep rate.
Base concentration.
N
A
3
C
2
0.5 M NaOH
Lyons, Burke, J. Electroanal. Chem., 170 (1984) 377-381
Lyons, Burke, J. Electroanal. Chem., 198 (1986) 347-368
Lyons, Brandon Phys. Chem. Chem. Phys., 11 (2009) 2203-2217
N
0 200 400 600
Q
/

m
C

c
m
-
2
0
20
40
60
80
100
120
Q=a(1-exp(-bN))
R=0.9947, R
2
= 0.9895
a = 103.94 6.05 mC/cm
2
b = 0.0044 0.0006 cycle
-1
Hydrous oxide growth kinetics
Number of Growth Cycles
0 100 200 300 400 500
C
h
a
r
g
e

/

C
0.000
0.002
0.004
0.006
0.008
0.010
0.012
0.014
0.016
Murphy Ph.D Thesis UCC 1981
Fe wire electrode, 1.0 M NaOH
Inlaid Fe foil electrode, 0.5 M NaOH
Doyle, unpublished work, TCD 2011
RPS Methodology reproducible across space and time.
R = 0.9935, R
2
= 0.9870
a = 0.0136 0.0003 C
b = 0.0156 0.0011 cycle
-1
Hydrous oxide film regarded as a surface
bonded polynuclear species. Metal cations
in polymeric network held together by
sequence of oxy and hydroxy bridges.
Mixed conduction (electronic, ionic) behaviour
similar to that exhibited by
Polymer Modified Electrodes.
Can regard microdispersed hydrous oxide layer as
open porous mesh of interconnected surfaquo
metal oxy groups.
E
lower
/ V (vs Hg/HgO)
-1.7 -1.6 -1.5 -1.4 -1.3 -1.2 -1.1 -1.0 -0.9
Q

/
m
C
0
10
20
30
40
50
60
70
80
Upper Limit E = 0.324 V
Effect of lower potential limit E
LL
of growth sweep on development of hydrous
oxide charge capacity.
Q (proportional to oxide
layer thickness) identified as
anodic charge
capacity measured between
-1.226 and 0.324 V, at
33 mV/s after repetitive
triangular
sweep at 3.3 V/s for 5 min
between fixed UPL = 0.324V
and variable LPL as indicated.
E
LL, optimum
E
upper
/ V (vs Hg/HgO)
-1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
Q

/

m
C
0
10
20
30
40
50
60
70
80
Lower limit E = - 1.426 V
Effect of upper limit E
UL
of growth sweep on development of hydrous
oxide charge capacity.
Q (proportional to oxide
layer thickness) identified as
anodic charge
capacity measured between
-1.226 and 0.324 V, at
33 mV/s after repetitive
triangular
sweep at 3.3 V/s for 5 min
between fixed LPL = -1.426V
and variable UPL as indicated.
E
UL, optimum
Initial oxidation process involves
formation of OH and O radical species
which reversibly adsorb on metal
surface:
Fe + OH
-
FeOH
ads
+ e
-
With increasing degree of surface
coverage the adsorption takes on a
more irreversible character. A thin
largely anhydrous passivating phase
oxide is formed via a place exchange
mechanism:
FeOH
ads
HOFe (fast)
HOFe + OH
-
HOFeOH
ads
+ e
-
(rds)
HOFeOH
ads
Fe(OH)
2
FeO + H
2
O
In the anhydrous film ions are held in a
rigid manner in an extended network of
polar covalent bonds which drastically
reduce ion transport through (and
consequently extension of) the surface
layer.
The film thickening reaction (the
hydration process) is slow since it
involves rupture of primary
coordination M-O bonds. The
dependence of film growth on the
lower potential sweep limit E
LL
implies
that partial reduction of anhydrous
layer is important in generation of
thick microdispersed hydrous deposit.
On subsequent re-oxidation the
compact layer is restored but the outer
region of the film is present in a more
dispersed form. On further reduction
this latter material is incorporated into
the dispersed hydrated outer layer.
The hydrated layer formed in this way
exhibits an open, zeolite type
structure.
The optimum upper limit E
UL
corresponds to a potential which
represents the best compromise
between two opposing effects the
compact layer must attain a reasonable
thickness (hence the requirement of a
high anodic potential) but application of
too high an upper limit results in a very
unreactive layer
M/MO
x
/MO
a
(OH)
b
(OH
2
)
c
/aq phase
Hydration process promoted by increasing
adsorption of OH
-
ions as pH increases.
Hence adsorbed OH
-
species repel each other
and attract hydrated positive counter ions into
oxide matrix hence encouraging hydroxylation
processes.
[Fe
2
(OH)
6
(OH
2
)
3
]
2-

2Fe(OH)
2
+ 3H
2
O
2Fe(OH)
2
2FeO + 2H
2
O
Increased instability of hydrous
layer and more effective
passivation as solution
temperature increases.
A
4
A
3
C
2
E
P
A
2
C
1
A
1
: not determined. Peak ill-defined in pH range
Studied.
A
2
: Regular Nernstian shift. -0.06 V/dec (wrt SCE)
-2.303RT/F V/dec; zero shift wrt RHE.
A
3
: Super-Nernstian shift. 0.087 V/dec (wrt SCE) or
-0.028 V/dec (wrt RHE), i.e. - 3/2(2.303RT/F) V/dec
C
2
: Super-Nernstian shift. -0.092 V/dec (wrt SCE) or
0.033V/dec (wrt RHE), i.e. -3/2 (2.303RT/F) V/dec.
A
4
: Regular Nernstian shift. . -0.06 V/dec (wrt SCE)
-2.303RT/F V/dec; zero shift wrt RHE.
C
1
: + 0.044 V/dec (wrt RHE) or + 0.044 0.059 = -0.015 V/dec
wrt SCE.
E
P
passivation peak shows regular Nernstian behaviour.
A
1
Voltammetric response as function of solution pH
[Fe
2
(OH)
6
(OH
2
)
3
]
2-
+ 3OH
-

[Fe
2
O
3
(OH)
3
(OH
2
)
3
]
3-
+ 3H
2
O + 2e
-
[M
2
O
3
(OH)
3
(OH
2
)
3
]
n
3-
+ 3nOH
-

[MO
2
(OH)
2
(OH
2
)
2
]
2n
2-
+ 3nH
2
O + 2ne
-
M(IV)
M(III)
Fe(II)
Fe(III)
Redox switching involves topotactic charge
storage reactions in open hydrous oxide layer which
Behaves as ion exchange membrane.
Hydrated counter/co-ions (M
+
, H
+
, OH
-
assumed
present in pores and channels of film to balance
negative charge on polymer chain.
Equivalent circuit model: dual/multi- rail
Transmission Line as done for ECP films..
Super-Nernstian Redox Potential
vs pH shift related to hydrolysis
effects in hydrous layer yielding
anionic oxide structures.
L.D. Burke, M.E.G. Lyons, E.J.M.OSullivan,
D.P. Whelan J. Electroanal. Chem.,
122 (1981) 403.
M = Ir, Rh
dE/dpH = -3p/2
p= 2.303RT/F
p= -88.5 mV/dec
T = 298K
Rhodium oxide
Iron oxide
Redox switching chemistry: hydrous oxide
Layer, Mixed conduction mechanism:
ion/electron transfer.
Fe(III) Oxidized form yellow-green
Fe(II) Reduced form transparent
A
B A
B
A
B A
B
E
l
e
c
t
r
o
d
e
ne
-
Polymer layer Solution
Charge ejection/injection:
potential gradient driven
Charge ejection/injection:
potential gradient driven
Charge propagation:
concentration gradient driven
Charge propagation:
concentration gradient driven
D
E

o u = c k D
2
ex E
Mixed conductivity:
Electron hopping coupled
with counter ion transport.
Microdispersed hydrous
Oxide has many physical
characteristics similar to
those of electroactive
polymer material.
22
Migration/diffusion model for electron hopping.
)
`

c
o c
+
c
c
c
c
=
c
c

x c
ab
x
b
x
D
t
b
E
x
f
t
b
t
a
E
c
c
=
c
c
=
c
c
)
`

c
c
+
c
c
=

x c
ab
x
b
D f
E E
o
D-term M- term
Eqn. Of continuity
Steady state D/M flux
A
B A
B
A
B A
B
E
l
e
c
t
r
o
d
e
ne
-
Polymer layer Solution
Charge ejection/injection:
potential gradient driven
Charge ejection/injection:
potential gradient driven
Charge propagation:
concentration gradient driven
Charge propagation:
concentration gradient driven
D
E
| |
x x x
f k exp k k ~ o o =
- -
o o + =
x x
1 f
2
2
2
2
E
x c
b a
x x
b
c
b a
x
b
D
t
b
c
o c
+
c
o c
)
`

c
c
|
.
|

\
|

+
c
c
=
c
c

RT
FE
= o
Potential gradient
between sites
Nernst-Planck
equation.
macroscopic charge propagation through polymer
can be represented in terms of a diffusion-migration process
rate of electron hopping quantified via electron exchange
rate constant k
ex
or electron hopping diffusion coefficient D
E
local potential gradients between redox sites produce
a migration term in description of electron hopping flux
D
E
predicted to vary linearly with redox site concentration
electron hopping can be further described using the
Marcus theory of ET
mechanism of electron hopping dependent on degree of local
mobility of redox groups ; physical diffusion of redox groups also
may be important
electron hopping diffusion coefficients can be evaluated using
transient or steady state electrochemical techniques
Features of Redox Conduction.
Scan Rate / V s
-1
0.0 0.1 0.2 0.3 0.4 0.5
C
h
a
r
g
e

/

C
0.000
0.005
0.010
0.015
0.020
1 cycle
30 cycles
120 cycles
Variation of integrated voltammetric charge with
Sweep rate. Multicycled hydrous oxide coated Fe
electrodes, 0.5 M NaOH
More deeply buried Fe
sites accessed by EC
driving force at longer
Timescales.
Finite rate of electron
self exchange kinetics.
Thin films, 30 cycles
Thick films 240 cycles
Laviron Analysis
D
CT,ox
= 1.88 x10
-10
cm
2
s
-1
D
CT,red
=3.77 x10
-10
cm
2
s
-1
c

= p/M ; n = 2
Fe(II):
[Fe
2
(OH)
6
(OH
2
)
3
]
2-
M = 267 g mol
-1
p (Fe(OH)
2
=3.4 gcm
-3
Fe(III):
[Fe
2
O
3
(OH)
3
(OH
2
)
3
]
3-
M = 265 g mol
-1
p(Fe
2
O
3
.nH
2
O) 3 gcm
-3
Macroscopic average value.
Rate controlling transport
process during redox switching
probably ion diffusion.
Need EQCM analysis for
further confirmation.
26
Z
Y
X
Polymer
strand
Polymer strand/
pore solution
interface
Pore
electrolyte Support
electrode
Bulk electrolyte
solution
Z
Y
X
Polymer
strand
Polymer strand/
pore solution
interface
Pore
electrolyte Support
electrode
Bulk electrolyte
solution
General dual rail transmission line
model is used to reflect the coupled
processes of electronic and ionic
transport within a conducting
Polymer/metal oxide thin film.
Dual Rail Transmission Line Model
for Redox Switching in ECP/metal oxide films.
Two main approaches to TL analysis:
Assume ECP film is highly porous matrix.
Use porous electrode models
(de Levie, Bisquert, Paasch) to analyse
electrochemical response.
Polymer film assumed homogeneous
(Vorotyntsev, Buck, Albery).
Model diffusive (ambipolar) transport of
Polarons and counterions in terms of
characteristic resistances and
Nernst-Planck equations. Porosity
accounted for by associated distributed
capacitance.
Circuit Details.
.
Bisquert et al. J. Electroanal. Chem.
508 (2001) 59-69
The TL circuit consists of distributed
impedances corresponding to charge
transport along the polymer
strand (Z), ion transport within
the pore electrolyte (X) and an
impedance representing the interface
between the strand and the pore (Y).
At the simplest level Z corresponds
to the electronic resistance R
E
,
X to the ionic resistance R
I
, and
Y to a distributed capacitance C
E
.
Doyle, 2011, unpublished work
Hydrous Fe oxide
Layer,
30 cycles
Un-cycled Fe electrode
(vs Hg/HgO)
Layer growth parameters:
Upper, lower potential
sweep limits.
Solution temperature
Solution pH
Potential sweep rate.
Base concentration.
Hydrous Oxide Growth via potential multicycling
procedure in aqueous alkaline solution.
Lyons, Burke, J. Electroanal. Chem., 170 (1984) 377-381
Lyons, Burke, J. Electroanal. Chem., 198 (1986) 347-368
Lyons, Brandon Phys. Chem. Chem. Phys., 11 (2009) 2203-2217
Tafel slope
= 50 mV/dec
Tafel Slope
= 40 mV/dec
Tafel slope uncycled electrode = 50 mV/dec
Tafel slope for HO coated electrode ca. 40-45 mV/dec
independent of HO thickness.
Note: experiments performed in 0.5 M
NaOH on aged Fe electrodes.
Potential / V vs. Hg/HgO
0.6 0.7 0.8 0.9 1.0 1.1
L
o
g

(
C
u
r
r
e
n
t

/

A
)
-5.5
-5.0
-4.5
-4.0
-3.5
-3.0
-2.5
-2.0
-1.5
bare
30 cycles
60 cycles
120 cycles
180 cycles
240 cycles
300 cycles
Effect of potential cycling on Tafel Plot behaviour (iR
u
corrected)
recorded for hydrous oxide coated Fe electrodes in 0.5 M NaOH.
Potential span of Low Tafel Slope
region less for multi-cycled oxide
coated electrodes than for
uncycled electrode.
Tafel slope at low potential
independent of hydrous oxide
thickness once multicycling protocol
has begun (unlike rhodium oxide).
Tafel slope (iR corrected) for
Hydrous oxide coated Fe electrode
less than that recorded for
uncoated electrode.
Q /C
0.004 0.006 0.008 0.010 0.012 0.014 0.016 0.018 0.020 0.022
b
/
m
V

d
e
c
-
1
38
40
42
44
46
48
50
Tafel Slopes vary from ca. 50 mV/dec
for un-cycled Fe electrode to ca. 40 mV/dec
for Fe electrodes coated with thick
Hydrous oxide layers (0.1 M NaOH).
Hydrous Oxide: OER Kinetic parameters
Low overpotentials
b = 60 mV dec
-1
= 2.303(RT/F)
m
OH
-
= 3/2
High overpotentials
b = 120 mV dec
-1
= 2.303(2RT/F)
m
OH
-
= 1.0
Dual Tafel Slope behaviour not due to
change in RDS but arises due to potential
dependence of total fractional coverage u
E
of electrosorbed reaction intermediates.
Aged passive oxide
Coated Fe electrode
Aged electrode, severe cathodic
pre-treatment: OER Kinetic parameters
Low overpotentials
b = 60 mV dec
-1
= 2.303(RT/F)
m
OH
-
= 3/2
High overpotentials
b = 120 mV dec
-1
= 2.303(2RT/F)
m
OH
-
= 1.0
Pre-reduction at E = - 1.30V for t = 15 min, followed by 1 cycle between 1.175
And 0.625 V in 1.0 M NaOH at 40 mV/s.
S + OH
-
SOH + e
-
(AI)
SOH + OH
-
SO
-
+ H
2
O (AII)
SO
-
+ OH
-
SO
2
H
-
+ e
-
(AIII)
SO
2
H
-
+ OH
-
S + H
2
O + O
2
+ 2e
-
(AIV)
S = electrocatalytically active iron
surfaquo group = stabilized Fe(VI) moeity
QSSA, Langmuir Adsorption conditions:
| |
| |
OH
OH S
a k RT F k
RT F a a k Fk
i
2
0
1
2
2
0
1
) 1 ( exp
exp 4
+
=

n |
n |
{ } | | RT F k k a a Fk i
OH S
n exp 4
0
1
0
1
2
2
~
Step (AII) RDS
Low overpotential
| | RT F a a Fk i
OH S
n | exp 4
0
1
~
Step (AI)
RDS
High overpotential
Simple Kinetic analysis (Lyons 1984) predicts
Correct Tafel slopes over entire
n range, but predicts a reaction order m
OH
-
of 2 at low n (instead of 3/2) and 1 at high n.
OER Kinetic Analysis:
Model A
Lyons 1984
Dual Tafel Slope behaviour attributed
to change in RDS as potential increases.
S + OH
-
S-OH + e
-
(BI)
S-OH + OH
-
S-H
2
O
2
+ e
-
(BII)
S-H
2
O
2
+ OH
-
S-OH
2
-
+ H
2
O (BIII)
S-H
2
O
2
+ S-HO
2
-
O
2
+ H
2
O + OH
-
(BIV)
S-H
2
O
2
= physisorbed hydrogen peroxide
Assume intermediate surface coverage of S-OH species.
Pseudo equilibrium condition & Temkin adsorption isotherm
(interaction parameter g
j
) assumed.
OER Kinetic Analysis:
Model B
Lyons & Brandon 2009
Assume at low n step (BII) is rate limiting.
( )


~
E E
E
RT
F
RT
g g
a k f
O SH SOH
SOH OH
n |
u u
u exp
1
exp
2 2 0
2
2 / 1 1 1 0
8 . 0 0
~ = < <
< <
E
| |
u
( )


~
E
E
RT
F
RT
g
a k f
SOH
SOH OH
n | u
u exp
1
exp
0
2
2 2
O SH SOH
g g >>
Assume step (BI) is in pseudo-equilibrium.
( )
( ) ( )
{ } n u
n n u u
u
u
n | u
u
n | u
u
F Ka RT g
RT
F
Ka
RT
F
a
k
k
RT
g
RT
g
RT
F
RT
g
k f
RT
F
RT
g
a k f
f f
OH SOH
OH OH
SOH SOH
SOH
SOH
SOH
SOH
SOH
SOH OH
+ ~

)
`

=
=
E

E E
E

E

ln
exp exp exp exp
1
1
exp
1
exp
exp exp 1
0
1
0
1
0
1 1
0
1 1
1 1
( )

+
= ~

E
RT
F
a K k f f
OH SOH
n |
u

1
exp
2 1 0
2 2
( )
2 / 3 2
ln
ln
303 . 2
1
303 . 2
log
2 / 1
2 / 1
=
|
|
.
|

\
|
c
c
=

)
`

+
=
|
|
.
|

\
|
c
c
=
= E
= =
E

n
|

|
n
OH
OH
a
a
f
m
F
RT
F
RT
f
b
OH
At high n surface coverage conditions
change to where u
SOH
= u
E
1. Step (BII)
still rate determining.
Langmuir adsorption pertains. Also g
SOH
0.

~ ~
E
RT
F
a k f f
OH
n |
exp
0
2 2
0 . 1
2
303 . 2
=
)
`

=
OH
m
F
RT
b
Overpotential n / V
0.2 0.3 0.4 0.5 0.6 0.7
L
o
g

C
u
r
r
e
n
t

D
e
n
s
i
t
y

i

/

A
c
m
-
2
-6
-5
-4
-3
-2
-1
0
Fresh
Aged
b = 39.5 mVdec
-1
b = 44 mVdec
-1
OER Kinetics: Aged (EC polarization measurements) pre-reduced Fe
electrodes (not multicycled).
Overpotential n / V (Hg/HgO, 1 M)
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
L
o
g

C
u
r
r
e
n
t

D
e
n
s
i
t
y

i

/

A
c
m
-
2
-8
-7
-6
-5
-4
-3
-2
-1
0
1st forward
reverse
2nd forward
Slope of 40 mVdec
-1
Potential E / V (Hg/HgO, 1 M)
-1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8
C
u
r
r
e
n
t

D
e
n
s
i
t
y

i

/

A
c
m
-
2
-0.002
-0.001
0.000
0.001
LESS AGED
MORE AGED
Peak A
4
becomes more enhanced on aging.
Compact anhydrous oxide chemistry
Dominates interfacial EC behaviour.
Is associated with increase in low overpotential
Tafel slope from ca. 40 mV to ca. 45-47 mV.
Pre-treatment: cathodic polarization at E = - 1.10V
In 1.0 M NaOH, t = 5 min, followed by single
Cycle at 40 mV/s between limits 1.175 to 0.625 V.
Cyclic voltammograms (1.0 M NaOH, scan rate = 40
mV s
-1
) characterising an Fe electrode prior to its 1
st
,
5
th
and 16
th
utilisation in OER polarisation
experiments.
OER steady state polarisation curves for a pre-reduced
Fe electrode in various NaOH solutions. The trace
denoted as fresher 1.0 M was recorded for the same
electrode in an earlier experiment, before satisfactory
reproducibility with respect to Tafel slope had become
established.
Inset Reaction order plots constructed from the
reproducible polarisation data at a potential of E = 0.7
V.
[Fe(VI)O
m
(OH)
n
]
p-
+ OH
-
[Fe(VI)O
m+1
(OH)
n-1
]
p-
+ H
2
O + e
-
[Fe(VI)O
m+1
(OH)
n-1
]
p-
+ OH
-
[Fe(VI)O
m
OOH(OH)
n-1
]
p-
+ e
-
RDS
[Fe(VI)O
m
OOH(OH)
n-1
]
p-
+ OH
-
[Fe(VI)O
m
OO(OH)
n-1
]
p-
+ H
2
O + e
-
[Fe(VI)O
m
OO(OH)
n-1
]
p-
+ OH
-
[Fe(VI)O
m
(OH)
n
]
p-
+ O
2
+ e
-
p = 2m+n-6
Effect of oxide on OER Kinetics at oxidized aged Fe explained
in terms of Conway-Meyer dual barrier model.
b 2.3034RT/5F
m
OH
1
Physisorbed peroxide intermediate model assumed.
OER Kinetics: Aged pre-reduced Fe
electrodes (not multicycled).
Low overpotential
Conway-Meyer Dual Barrier Model
V
M
V
F
V
S
Barrier Oxide Film
Compact EDL
Solution
|
F
|
S
s i
F S
F
eff i
S F
S F
a
eff
i
m
is
m m
F
RT
F
RT
i
b
RT
F
a k f
S
S F
F
is
, ,
) (
303 . 2 303 . 2
log
exp ) (
| |
|
| |
| |
|
n
n |
| |
|
+
=
|
|
.
|

\
| +
=
|
|
.
|

\
|
=
|
|
.
|

\
|
c
c
=

~
E
E
+
E I
J.J. MacDonald, B.E. Conway,
Proc. Roy. Soc., Ser.A, 269 (1962) 419-440.
R.E. Meyer, J. Electrochem. Soc.,
107 (1960) 847-853.
Reaction order in absence of barrier
Effective reaction order
Effective symmetry
Factor |
E
= (|
F
/(|
F
+|
S
))|
S
Potential dependent field assisted charge
Transfer across a barrier oxide film
(process F) in series with interfacial
charge transfer reaction (process S).
Effective Symmetry factor (and hence
Tafel slope) and reaction order is
some fraction F(|) =|
F
/(|
F
+ |
S
)
of the true values.
( )
( )
( )
S i
S F
F
S i eff i
S eff
S
S F
F
S
m m F m
b F b
F
, , ,
1
|
|
.
|

\
|
+
= ~
~
|
|
.
|

\
|
+
= ~

E
| |
|
|
|
|
| |
|
| | |
S + OH
-
S-OH + e
-
(BI)
S-OH + OH
-
S-H
2
O
2
+ e
-
(BII)
S-H
2
O
2
+ OH
-
S-OH
2
-
+ H
2
O (BIII)
S-H
2
O
2
+ S-HO
2
-
O
2
+ H
2
O + OH
-
(BIV)
Assume step (BII) is rate determining (low n values), and that
dual barrier model pertains.
Analysis of barrier free situation suggests that b
S
= 40 mV/dec
(2.303(3RT/2F) and m
OH
= 2.
( )

+
~
E +
E
RT
F
Ka f
S F
F
OH
n |
| |
|
1
exp
2
( )
1
2
) (
/ 047 . 0
5
4
303 . 2
1
303 . 2
1
303 . 2
log
2 / 1
,
2 / 1

+
=
+
~
= |
.
|

\
|

|
|
|
|
|
.
|

\
|
|
|
.
|

\
|
+
+
=
|
|
.
|

\
|
+
=
|
|
.
|

\
|
c
c
~
= ~
= ~
E
S F
S F
OH
S F
F
OH
S F
F
eff OH
S F
S F a
eff
m m
dec V
F
RT
F
RT
F
RT
i
b
| |
| |
| |
|
| |
|
| |
| | |
n
( ) ( )
2 1
/ 235 . 0
4
303 . 2 303 . 2 303 . 2
exp
2 / 1 , 1
,
2 / 1

+
~
~ |
.
|

\
|

+
=
|
|
.
|

\
| +
~
|
|
.
|

\
|
~

~
= = =
= ~
E
E +
E
S F OH
S F
S F
F
m
OH
S F
F
eff OH
S
F
S F
S F
S F
eff
OH
m m
dec V
F
RT
b
F
RT
F
RT
b
RT
F
Ka f
| |
| |
| |
|
| |
|
|
| |
| |
| |
|
n |
Low overpotentials
Assume step (BI) is rate determining (high n values), and that dual barrier model pertains.
Analysis of barrier free situation suggests b
S
= 0.120V /dec (2.303(2RT/F) and m
OH
= 1.0.
Aged pre-reduced Fe
electrodes
OER Kinetic analysis
Incorporating DBM.
High overpotentials
Not easy to check this prediction at high n.
Bockris, Otagawa, J. Phys. Chem.,87 (1983 )2960
Bockris, Otagawa, J. Electrochem. Soc., 131 (1984) 290.
Hydrous Oxide
Layer
Compact Oxide
Layer
Lyons Brandon
Physisorbed peroxide
OER model incorporating
Dual Barrier concept.
Interlinked surfaquo
groups
Electrode
Experiment, b, m
OH
-
Dual
barrier
b, m
OH
for
analysis
Isotherm
L or T
Path-
way
Ni no-pre-treat
2RT/3F order not
measurable
No As listed left L, 0 C
Ni pre-reduced
2RT/3F, 1 No As listed left L, 0 C
Ni pre-oxidised
2RT/3F, 1 No As listed left L, 0 C
Co no-pre-treat 2RT/3F(5M)4RT/5F(1M) low [OH
-
]
----- ----- -----
Co pre-reduced
4RT/5F, 1 Yes 2RT/3F, 2 L, 0 E
Co aged low
RT/F, 3/2 No As listed left
T, r
I
>> r
II
E
Co aged high
2RT/F, 1 No As listed left L, 1 E
Fe no-pre-treat 2RT/3F(1M)4RT/5F(5M) high [OH
-
]
----- ----- -----
Fe pre-reduced
(fresh)
2RT/3F order not
measurable
No ----- ----- -----
Fe pre-reduced
(aged)
4RT/5F, 1 Yes 2RT/3F, 2 L, 0 E
Fe aged low
RT/F, 3/2 No As listed left T, r
I
>> r
II
E
Fe aged high
2RT/F, 1 No As listed left L, 1 E
OER Kinetics: Oxidized metal electrodes: Passive oxide films
M. Brandon, Ph.D Thesis University of Dublin, 2008
Hydrous microdispersed oxides readily prepared via repetitive cyclic potential sweep method
of parent metal (Fe, Co, Ni, Mn, Rh, Ir, Au, Pt, Pd) in aqueous alkaline solution. Method similar
to electropolymerization of ECP films.
Charge storage/charge percolation properties of hydrous oxide depend on electrochemical
and environmental variables such as: lower and upper potential sweep limits, potential sweep
rate, base concentration, solution temperature, solution pH.
Acid base behaviour of anodically formed transition metal oxides important when considering
mechanism of both redox switching & oxygen evolution
Hydrous oxide material is catalytically active wrt OER.
Hydrous oxides more difficult to reduce than less hydrated compact materials.
General mechanistic ideas : hydrous oxide akin to electroactive polymer . Hydrous oxide is
mixed ionic and electronic conductor. Hydrous oxide consists of an open structure derived
from extended linkages of active surfaquo groups which are involved in anodic OER process.
Full understanding of OER mechanism on passive oxide coated Fe and hydrous oxide coated Fe
electrodes in aqueous alkaline solution now obtained via SS Tafel Plot, open circuit potential
decay, complex impedance spectroscopy and reaction order measurements.
Main ideas developed in:
M.E.G. Lyons, M.P. Brandon, Phys. Chem. Chem. Phys., 11 (2009) 2203-2217.
M.E.G. Lyons, M.P. Brandon, J. Electroanal. Chem., 631 (2009) 62.
M.E.G. Lyons, M.P. Brandon, J. Electroanal. Chem., 641 (2010) 119.
M.E.G. Lyons, M.P. Brandon, Int. J. Electrochem. Sci., 3 (2008) 1463-1503.
M.E.G. Lyons, L.D. Burke, J. Electroanal. Chem., 198 (1986) 347-368.
M.E.G. Lyons, L.D. Burke, J. Electroanal. Chem., 170 (1984) 377-381
Dr Richard Doyle, TCD
Dr Michael Brandon, TCD
Prof. Declan Burke UCC
Acknowledgements: Funding
Science Foundation Ireland (SFI) Principal
Investigator Programme
Grant Number SFI/10/IN.1/I2969.
DuPont (Geneva)
Enterprise Ireland
IRCSET
Trinity College Dublin
EU ALFA Programme.
MEDIS
EU/LA
ALFA