Hydrous oxide modified electrodes

for electrochemical water splitting

Mike Lyons
Trinity Electrochemical Energy Conversion & Electrocatalysis (TEECE) Group,
School of Chemistry & CRANN
Trinity College Dublin
Ireland
melyons@tcd.ie

Seminar, 24
th
July 2012,
Institute of Chemical Research of Catalonia (ICIQ),
Campus Universitari de Tarragona.



Trinity College
School of Chemistry
Lecture Outline
Electrochemical fundamentals: electrolysis cells and fuel cells
Hydrous oxide formation via Cyclic Potential Multicycling (CPM)
Redox Switching behaviour of hydrous Fe and Ni oxide modified
electrodes
Potential of Metal Oxide electrode as pH sensor
Kinetics and mechanism of anodic oxygen evolution reaction at
hydrous oxide coated Fe & Ni electrodes (subjected to CPM)
Electro-precipitated Nickel oxy-hydroxide thin films deposited on
Au support electrodes
Comparision with other metal oxide systems
Conclusions.


Electrode Electrolyte
Electronically conducting phase : metal,
semiconductor,
conducting polymer material etc.
Ionically conducting
medium : electrolyte
solution, molten salt,
solid electrolyte,
polymeric
electrolyte, etc.
Conduction
occurs via
migration of
electrons .
Solid state
Physics : energy
band theory.
Material transport occurs
via migration, diffusion
and convection
HIET
Electrochemical Science underpinned by interaction of electrons with
matter and electrochemical technologies based on consequences of
Heterogeneous interfacial electron transfer (HIET).
Electrochemical Science : the essentials
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.
( )
, e cell C A
E i E IR q q = + + +
Overpotential losses
increase
net electrical energy
needed as
input to drive reactions
at electrodes.
Electrolysis cell: electrochemical substance producer
Thermodynamics
(Nernst Potential)
Kinetics: Cathode reaction
Overpotential
Kinetics: Anodic reaction overpotential
Ohmic potential:
Cell design
Need to minimize
all overpotential
losses to make
applied potential
as close to Nernst
potential as possible.
Electrical energy produces chemicals.
Ballard PEM Fuel
Cell
Fuel Cell : Electrochemical
Energy Producer
( )
, e cell C A
E i E IR q q =
Overpotential losses reduce net
voltage output.
The bottom line
Water electrolysis device:
Very sluggish Oxygen Evolution
Reaction (OER) kinetics (v. high
overpotential) limit device
operational effectiveness (higher
electrical energy input required)
Fuel Cell:
Very sluggish Oxygen Reduction
Reaction (ORR) kinetics limit voltage
output of device
For both device types the cathodic
Hydrogen Evolution Reaction (HER)
or the anodic Hydrogen Oxidation
Reaction (HOR) are reasonable
kinetically facile.
Optimizing the kinetics of the
oxygen electrode and understanding
the mechanism of the oxygen
electrode reaction presents a grand
challenge and has direct implications
for photo-electrochemical splitting
of water.
Metal oxide materials exhibit useful
potential as catalysts for OER and ORR in
electrochemical energy conversion
devices.
Major aim of Science Foundation Ireland
(SFI) Principal Investigator Programme
Grant Number SFI/10/IN.1/I2969 is to
develop cheap and efficient oxide
electrode materials for use in water
electrolysis and fuel cells.
SFI Programme has major focus on:
Electrochemically generated
hydrous transition metal oxides
(TMO)
Electro-precipitated TMO
Thermally prepared TMO
Nanostructured TMO.
Examine demanding multistep,
multielectron transfer reactions such as:
Anodic oxygen evolution reaction
(OER)
Cathodic oxygen reduction reaction
(ORR)
Cathodic hydrogen evolution
reaction (HER)


Transition Metal Oxides
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
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 + 0.5 Na
+
+ 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.
2
A
''
2
C
'
2
C
''

o-Ni(OH)
2
|-Ni(OH)
2
|-NiOOH

Oxidation state
2.0 - 2.2
Oxidation state
2.0 - 2.2
Oxidation state
2.7 - 3.0
Oxidation state
3.5 - 3.67
o
x
i
d
a
t
i
o
n
r
e
d
u
c
t
i
o
n
Ageing
Charge
Charge
Discharge
Discharge
Overcharge
A
2

C
2

A
2
C
2

pH > 14
- NiOOH
Ni + OH
-
NiOH
(ads.)
+ e
-


NiOH
(ads.)
+ OH
-
Ni(OH)
2
+ e
-

A
1

Ni + 2.4 OH
-
[Ni(OH)
2.4
]
0.4


NiO + H
2
O + 2e
-
Ni + 2 OH
-
C
1

Ni(OH)
2
NiO + H
2
O
Peaks A
1
/C
1
observed only if upper limit
Of sweep does not exceed 0.20 V (Hg/HgO)
Uncycled Ni electrode 1M base, 50 mV/s
Multicycled (N=300)
Ni electrode, 1M
Base, 50 mV/s
|(II)/|(III) ; o(II)/o(III)
2
A
'
2
A
''
2
C
'
2
C
''
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
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.
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
R = 0.9935, R
2
= 0.9870
a = 0.0136 0.0003 C
b = 0.0156 0.0011 cycle
-1

Q=a(1-exp(-bN))
CPM methodology is
scalable.
Hydrous oxide growth
process does not depend on
electrode size.
Important for commercial
viability.
Potential (V)
-1.5 -1.0 -0.5 0.0 0.5 1.0
C
u
r
r
e
n
t

(
A
)
-0.006
-0.004
-0.002
0.000
0.002
0.004
0.006
0.008
0.010
0 cycles
75 cycles
150 cycles
R = 0.9869, R
2
= 0.9739
a = 0.00147.43x10
-5
C
b=0.0450.0004 cycle
-1

Hydrous oxide growth via CPM : Multicycled Ni electrode, 1.0 M NaOH.
N
0 100 200 300 400 500
Q
/
C
0.0000
0.0002
0.0004
0.0006
0.0008
0.0010
0.0012
0.0014
0.0016
Q versus N
Experimental data
95% Confidence Band
95% Prediction Band
Ni(II) Ni(III)
Ni(0) Ni(II)
Ni(III) Ni(II)
Q=a(1-exp(-bN))
Typical voltammetric response recorded for a
hydrous Ni(OH)
2
thin film growth on Ni support
electrode grown in aqueous 1.0 M NaOH for N =
30 cycles at 150 mV/s between limits -1.45-0.65
V vs Hg/HgO.
[Fe
2
(OH)
6
(OH
2
)
3
]
2-
+ 3OH
-

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

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.
Redox switching chemistry: hydrous oxide
Layer, Mixed conduction mechanism:
ion/electron transfer.
Fe(III) Oxidized form yellow-green
Fe(II) Reduced form transparent
Potential / V vs. Hg/HgO
-1.5 -1.0 -0.5 0.0 0.5 1.0
C
u
r
r
e
n
t

/

A
-0.004
-0.003
-0.002
-0.001
0.000
0.001
0.002
pH 14.0
pH 11.5
pH 9.0
O
2
evolution
A3
H
2
evolution
C2
C1
pH
8 9 10 11 12 13 14
P
e
a
k

P
o
t
e
n
t
i
a
l

/

V

v
s
.

H
g
/
H
g
O
-0.8
-0.6
-0.4
-0.2
0.0
0.2
Experiment 1 (120 cycles)
Experiment 2 (120 cycles)
Experiment 3 (120 cycles)
Slope = 0.10 V/pH unit
A
3
/C
2

2.303
( ) 0.059( ) /
dE RT
r q r q V pH
dpH F
= =
Variation of Ni oxide A
2
,C
2
and C
2

peak potentials with solution pH.

Potential / V
-1.5 -1.0 -0.5 0.0 0.5 1.0 1.5
C
u
r
r
e
n
t

\

A
-0.004
-0.002
0.000
0.002
0.004
0.006
0.008
pH 14.0
pH 13.0
pH 11.0
pH 9.0
pH
8 10 12 14
E
p
/
V
(
H
g
/
H
g
O
)
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
A
2

C
2

C
2

C
2

A
2

C
2

C
2

: dE/dpH = - 50 mV/dec
C
2
: dE/dpH = - 74 mV/dec
A
2
: dE/dpH = - 97 mV/dec
[Ni(OH)
3.5
(OH
2
)
n
]
0.5-
(Na
+
)
0.5
+e
-

Ni(OH)
2
(OH)
2
)
n
+ 0.5 Na
+
+ 1.5 OH
-

A
2
/C
2

(dE/dpH)
ave
= - 0.085 V
Both anions, electrons and cations are transported during redox switching.
M
O
-
OH
2
OH
O
-
HO
M
OH
2
OH
2
OH
O
-
M
O
OH
2
OH
O HO
M
OH
2
OH
2
OH
OH
H
H
+3nH
2
O, 2ne
-
-3nOH
-
3-
n
2-
n
M
2
O
3
(OH)
3
(OH
2
)
3
3-
n
M
2
(OH)
6
(OH
2
)
3
2-
n
[M
2
(OH)
6
(OH
2
)
3
]
n
2-
+ 3nOH
-

[M
2
O
3
(OH)
3
(OH
2
)
3
]
n
3-
+3nH
2
O + 2ne
-

M = Fe, Ni
Redox switching in hydrous oxide layer involves a rapid topotactic reaction
involving hydroxide ion ingress and solvent egress
at the oxide/solution interface, and electron injection at the
metal/oxide interface.
Also involves motion of charge compensating cations
through film.
M
II
(OH)
r
(r-3)-
+ e
-
M
III
(OH)
q
(q-2)-
+ (3/2) OH
-

r-q 1.5
dE/dpH = - 0.090 V = - 0.06 (r-q) V
Assume that oxidized form of hydrous metal oxide has same composition
as oxidized form of hydrous gold oxide.
OH
-

H
+

H
2
O
OH
-

H
+

H
2
O
Oxidation
Reduction
Electrode
Film
e
-

e
-

charge
2 2
discharge
( ) Ni OH OH NiOOH H O e

+ + +
Electro-precipitated Nickel
Oxyhydroxide :
Redox Switching
The redox switching reaction
(associated with the A
2
/C
2

voltammetric peaks) reflects the
change in oxidation state of the film
as a result of a potential perturbation.
Redox centres immediately adjacent
to the support electrode are directly
affected by the electrode potential,
whereas charge is further propagated
along the oxy-iron polymer strands in
the hydrous layer via a sequence of
electron self exchange reactions
between neighbouring oxy-metal sites.
This process is envisaged to be
analogous to redox conduction
exhibited by electroactive polymer
films. In the simplest terms this
electron hopping may be modelled in
terms of a diffusive process, and so
the charge percolation rate may be
quantified in terms of a charge
transport diffusion coefficient, D
CT
.
Diffusive time constant t
D
can be
extracted via Cyclic Voltammetry.
Redox switching involves both
Electron and ion transport.
Have Ni(II)/Ni(III) redox
Transition in ploymeric
Microdispersed hydrous
Oxide layer.
Oxide film is mixed conductor.
Can be modeled as dual rail
electrical transmission line.
[Ni
2
(OH)
6
(OH
2
)
3
]
n
2-
+ 3nOH
-

[Ni
2
O
3
(OH)
3
(OH
2
)
3
]
n
3-
+3nH
2
O + 2ne
-

Dual rail transmission line model for porous thin film
mixed electronic/ionic conductor. Note that _
1
and
_
2
corresponds to the specific conductivity of the
solid oxide phase and electrolyte solution
respectively and , represents the specific
polarization/charge transfer element at the
solid/solution interface.
(a) A.J. Terezo, J. Bisquert, E.C. Pereira,
G.Garcia-Belmonte, Separation of transport,
charge storage and reaction processes of porous
electrocatalytic IrO
2
and IrO
2
/Nb
2
O
5

electrodes. J. Electroanal. Chem., 508 (2001) 59-
69. (b) J. Bisquert, G. Garcia-Belmonte, F.
Fabregat Santiago, N.S. Ferriols, M. Yamashita,
E.C. Periera, Application of a distributed
impedance model in the analysis of conducting
polymer films. Electrochem. Commun., 2 (2000)
601-605.
22
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
Anion X
-
injection
Mixed conductivity:
Electron hopping coupled
with counterion transport.
log
-3.5 -3.0 -2.5 -2.0 -1.5 -1.0 -0.5 0.0 0.5
E
p

/

V
-0.2
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0 cycles
30 cycles
60 cycles
90 cycles
120 cycles
180 cycles
240 cycles
360 cycles
-3.5 -3.0 -2.5 -2.0 -1.5 -1.0 -0.5 0.0 0.5
0.0
0.2
0.4
0.6
0.8
Variation of voltammetric peak potential with log sweep rate for a series
of multicycled Ni electrodes in 1.0 M NaOH at 298 K.
Attention is focused on the main anodic and cathodic charge storage peaks
corresponding to the Ni(II)/Ni(III) redox transition located at potentials
prior to active oxygen evolution.
Quasi-reversible
Reversible
V s
-1
0.0 0.5 1.0 1.5 2.0
Q

(
C
)
0.000
0.005
0.010
0.015
0.020
0.025
0.030
0 cycles
30 cycles
60 cycles
90 cycles
120 cycles
180 cycles
240 cycles
360 cycles
Variation of voltammetric redox charge capacity Q
with analytical sweep rate for a series of Ni oxide
hydrous films grown under potential cycling
conditions for various number of cycles. Attention is
focused on the main anodic charge storage peak
corresponding to the Ni(II)/Ni(III) redox
transition located at potentials prior to active
oxygen evolution.
V s
-1
0.0 0.5 1.0 1.5 2.0
p
1
/
2
/

V
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0 cycles
30 cycles
60 cycles
90 cycles
120 cycles
180 cycles
240 cycles
360 cycles
Variation of peak width at half peak height
with sweep rate for a series of multicycled
nickel electrodes in 1.0 M NaOH.
( )
/ 2
2 3.53
ln 3 2 2
p
RT RT
E
nF nF
A = + =
Ideal Reversible behaviour
( / V s
-1
)
-1/2
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
I
p

/

A
0.000
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0 cycles
30 cycles
60 cycles
90 cycles
120 cycles
180 cycles
240 cycles
360 cycles
Typical Randles-Sevcik plots recorded for a series
of multicycled Ni electrodes in 1.0 M NaOH as a
function of number of oxide growth cycles.
1/ 2
1/ 2
2
0.4463
P
nF D
i nFA
RT L
u
| |
= I
|
\ .
Randles-Sevcik equation
2
D
D
L
t =
Can estimate diffusive time
constant t
D
from linear region
of plot.
RS data is non-linear however.
RS analysis assumes semi-infinite
Diffusion in layer.
Finite/bounded diffusion
more appropriate.
Quantifying redox switching in hydrous multicycled nickel oxyhydroxide thin films.
W
1/2
0 2 4 6
0.0
0.1
0.2
0.3
0.4
0.5
6.9
p
W i u >
1.3
p
W i u <
2
2
6.9
0.179
RT D
nF L
D
L
u
u
| |
>
|
\ .
| |
>
|
\ .
2
1.3
RT D
nF L
u
| |
<
|
\ .
2
0.034
D
L
u
| |
<
|
\ .
( )
| |
1/ 2
0.446tanh
P
i RT
nFA L nFDu

+ = = T
`
I
)
0.56 0.05 W W T = +
( )
1/ 2 1/ 2
tanh 0
D D D P
D
G i

t ot |t
t

= + =
`
)
( )
( )
3/ 2
1/ 2
1/ 2
0.446
0.56
0.05
nF
A
RT
nF
RT
nF
RT
o u
u
|
u

= I
=
| |
=
|
\ .
2
D
D L t =
2
2
D
nFL L
W
DRT X
u | |
= =
|
\ .
Aoki Equation
Finite diffusion in thin film
Solve Aoki equation numerically via
Bisection Algorithm
To get value of diffusive time constant.
Diffusive time constant.
No of Cycles
50 100 150 200 250 300 350 400
D
/
L
2


/

s
-
1
0.0
0.2
0.4
0.6
0.8
1.0
1.2
Randles-Sevcik Analysis
Aoki Analysis ( V s
-1
)
Variation of diffusive frequency characterizing
redox switching in multicycled hydrous oxide coated
Ni electrodes in 1.0 M NaOH with number of oxide
growth cycles.
Diffusive frequency : Hydrous Nickel oxyhydroxide thin films.
Potential / mV vs. SCE
-1000 -500 0 500 1000 1500
C
u
r
r
e
n
t

/

A
-4.0e-5
-2.0e-5
0.0
2.0e-5
4.0e-5
6.0e-5
8.0e-5
1.0e-4
Electro-precipitated Nickel Oxy-hydroxide films : Au support.
Electro-deposition solution: aqueous solution of 0.1 M NiSO
4
, 0.1 M sodium acetate, 1
mM KOH .
Electro-deposition method: Cyclic Potential Multicycling (CPM) ;Gold substrate, 30
cycles between -0.9 V & 1.2 V vs. SCE at 50 mV/s.
N
Au electrode
Pt electrode
GC electrode
Cyclic voltammogram recorded for a glassy carbon electrode
modified with a thin nickel hydroxide film (30 growth cycles)
in 1.0 M NaOH. Sweep rate, 40 mV/s. Potentials are quoted
with respect to Hg/HgO reference electrode (1 M OH
-
).
Cyclic voltammogram recorded for a Pt electrode modified
with a thin nickel hydroxide film (30 growth cycles) in 1.0 M
NaOH. Sweep rate, 40 mV/s. Potentials are quoted with
respect to Hg/HgO reference electrode (1 M OH
-
).
Au electrode
Cyclic voltammogram recorded for a polycrystalline gold electrode
modified with a thin nickel hydroxide film (30 growth cycles) in 1.0
M NaOH. Sweep rate, 40 mV/s. Potentials are quoted with respect
to Hg/HgO reference electrode (1 M OH
-
)
GC electrode
Pt electrode
Unmodified
Au
electrode
Au electrode
o-Ni(OH)
2
+ OH
-
- NiOOH + H
2
O + e
-

E
0
= 0.37 V, AE
p
= 74 mV
|-Ni(OH)
2
+ OH
-
|- NiOOH + H
2
O + e
-

E
0
= 0.496 V, AE
p
= 113 mV
o
| |
Bode Square Scheme
Electro-precipitated Ni(OH)
2

Potential / V vs. Hg/HgO
0 200 400 600 800
C
u
r
r
e
n
t

/

A
-0.0003
-0.0002
-0.0001
0.0000
0.0001
0.0002
0.0003
0.0004
0.0005
10 mV/s
20 mV/s
50 mV/s
Effect of growth scan rate: Each film was deposited
from the same solution , and using
the same number of growth cycles (30 cycles).
Typical voltammetric response recorded for an
electroprecipitated nickel oxide film deposited on a
polycrystalline gold substrate subjected to slow multicycling
(sweep rate 10 mV/s) between 0.1 and 0.7 V (vs Hg/HgO) in
5.0 M NaOH.
Initial Cycle
Final Cycle
N = 85
Typical voltammetric response recorded for an
electroprecipitated nickel oxide film deposited on a
polycrystalline gold substrate subjected to slow multicycling
(sweep rate 10 mV/s) between 0.1 and 0.7 V (vs Hg/HgO) in
5.0 M NaOH. The initial and final response profiles are
presented.
o
| |
Temporal effects on Nickel oxyhydroxide layer
redox chemistry.
1 mV/s 2 mV/s 5mV/s 10 mV/s
20 mV/s 100 mV/s
300 mV/s
50 mV/s 100 mV/s 200 mV/s
400 mV/s 500 mV/s 750 mV/s
1000 mV/s 1500 mV/s 2000 mV/s
Sweep rate :
CV response
CV in 1M NaOH at = 40mV s
-1
: Ni deposited on Au
electrode at -1.5V vs Ag/AgCl for 300s in 0.1 M
Ni(NO
3
)
2
/0.075M KNO
3

CV in 1M NaOH at = 40mV s
-1.
but after additional
multicycling for 30 cycles between -1.45 V to 0.65 V vs
Hg/HgO @ 150 mV s
-1


Deposition from Ni(NO
3
)
2
:

NO
3
-
+ 7H
2
0 + 8e
-
NH
3
+ 10 OH
-
(extra OH
-

generated from ammonia/ammonium ion
equilibrium, NH
3
+ H
2
O NH
4
+ + OH
-
)

Production of OH
-
increases the surface pH of
the electrode resulting in precipitation of
Ni(OH)
2


Ni
2+
+ 2 OH
-
Ni(OH)
2





Fine details of voltammetric response in aqueous
base depends on pretreatment history.
Note sharp onset of redox switching: Ni(II)/Ni(III).
Super-Nernstian pH shift signifies
possible development of more sensitive
and scalable metal oxide wire pH
sensors.
pH
E
Nernstian
Super-Nernstian
Enhanced sensitivity of sensor
to given pH change.
Sensor probe can be made very small
for biomedical applications.
Metal oxide wire pH sensor spinoff.
Open circuit potentials of electroprecipitated Ni on Au electrode versus log(time). Data from this graph
used to generated correlation graph. Faster film degradation in acidic pH.

Electrolyte: 1M NaOH Reference: Hg/HgO for pH 5 or greater. SCE for pH 4 and lower.
Timescale: 60,000 seconds.
Potential Response to pH
pH
0 2 4 6 8 10 12 14
P
o
t
e
n
t
i
a
l

v
s

(
H
g
/
H
g
O
)

/
V
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1,000 seconds
15,000 seconds
200 seconds
Plot 3 Regr
Open Circuit Potential versus pH for the electro-precipitated Ni oxyhydroxide films
on Au working electrode. Multiple times are shown and taken into account for linear
regression. Some scattering in pH 3 and lower data points. Slope used to calculate pH for
correlation graph.
Variation of OCP with changes in solution pH.
Calculated pH vs Measured pH
Measured pH
0 2 4 6 8 10 12 14 16
C
a
l
c
u
l
a
t
e
d

p
H
0
2
4
6
8
10
12
14
Measured pH vs Calculated pH
Plot 1 Regr
Intercept = -0.74
Slope = 1.01
r = 0.99
1.01 0.74
calc meas
pH pH =
Comparing pH calculated from
variation of OCP vs pH solution
plot (Super Nernstian) with pH
measured via
Glass electrode.
Typical electroprecipitation CV for Ni
on Au working electrode.
Rate: 20mV/s Limits: (-0.9 to 1.2)V
Reference: SCE Electrolyte: 1M NaOH, 30
cycles
Typical CV performed after 30 cycle
electrodeposition
of nickel oxyhydroxide on Au, (A) before
& (B) after titration experiment.
Sweep Rate: 40mV/s Limits: (-0.4 to 0.7)V
Reference: Hg/HgO Electrolyte: 1M NaOH
pH, Potential versus Volume of Sulphuric Acid Added
Volume Sulphuric Acid Added / cm^3
0 10 20 30 40 50
p
H
0
2
4
6
8
10
12
14
16
P
o
t
e
n
t
i
a
l

v
s

S
C
E

/
V
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
Volume acid added /cm^3 vs pH
Volume acid added /cm^3 vs OCP /V
A
Strong Acid (1.0 M H
2
SO
4
) vs Strong base (1.0 M NaOH)
Titration.
B
Well behaved titration
Au
ph, Potential versus Volume of Sulphuric Acid Added
Volume of 1M Sulphuric Acid Added /cm^3
0 10 20 30 40 50
p
H
0
2
4
6
8
10
12
14
P
o
t
e
n
t
i
a
l

v
s

S
C
E

/
V
0.2
0.4
0.6
0.8
Volume of 1M Sulphuric Acid Added vs pH
Volume of 1M Sulphuric Acid Added vs OCP /V
Misbehaved titrations
Strong Acid (1.0 M H
2
SO
4
) vs Strong base (1.0 M NaOH)
Titration.
pH, Potential versus Acid Added
Volume of Sulphuric Acid Added /cm^3
0 10 20 30 40 50
p
H
0
2
4
6
8
10
12
14
16
P
o
t
e
n
t
i
a
l

v
s

S
C
E

/
V
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
Volume Added /cm^3 vs pH
Volume Added /cm^3 vs OCP /V
Table 2. Kinetic parameters derived for 5 most common OER mechanisms [169].
Rate-determining step
Langmuir Temkin

v
b
0 1 0 1 NA
d
A
e
NA
d
A
e
condition
f

(I) Bockriss Oxide Path
1. M + OH

MOH + e

2. 2MOH MO + M + H2O

3. 2MO 2M + O2

4
2

1

2RT/F
RT/2F

RT/4F






1
2

4


0

0


2RT/F
RT/F


0.5
1


rOH ~ rO
rOH >> rO
K2 ~ 1
K2 << 1
RT/2F
RT/4F
RT/F
RT/3F
2
2
1
1
(II) Bockriss Electrochemical Path
1. M + OH

MOH + e

2. MOH + OH

MO + H2O + e

3. 2MO 2M + O2

2
2

1

2RT/F
2RT/3F

RT/4F


2RT/F



1
2

4


1

0


2RT/F
RT/F


1
1.5


rOH ~ rO
rOH >> rO
K2 ~ 1
K2 << 1
RT/2F
RT/4F
RT/F
RT/3F
2
4
1
3
(III) Krasilshchikovs Path
1. M + OH

MOH + e

2. MOH + OH

MO

+ H2O

3. MO

MO + e

4. 2MO 2M + O2

2
2

2

1

2RT/F
RT/F

2RT/3F

RT/4F




2RT/F



1
2

2

4


1

0

0



2RT/F
2RT/F
2RT/F


1
1.5
0
1


rOH ~ rO
rOH >> rO
K2 ~ 1
K2 << 1
K3 ~ 1
K3 << 1
RT/2F
RT/4F
RT/F
RT/3F
2
2
1
1
(IV) OGradys Path
1. M
z
+ OH

M
z
OH + e

2. M
z
OH M
z+1
OH + e

3. 2M
z+1
OH + 2OH

M
z
+ H2O + O2

2
2

1

2RT/F
2RT/3F

RT/4F


2RT/F



1
1

4


0

2


2RT/F
RT/F


0
0.5


r1 ~ r2
g

r1 >> r2
K2 ~ 1
K2 << 1
RT/2F
RT/4F
RT/F
RT/3F
4
4
3
3
(V) Kobussens Path
1. M + OH

MOH + e

2. MOH + OH

MO + H2O + e

3. MO + OH

MO2H

4. MO2H

+ OH

MO2

+ H2O + e

5. MO2

M + O2 + e

1
1

1

1

1

2RT/F
2RT/3F

RT/2F

2RT/5F

2RT/7F


2RT/3F



2RT/F



1
2

3

4

4


1

1

1

0


2RT/F
RT/F

RT/F
2RT/F
2RT/F


1
1.5
1
2
1
2


rOH ~ rO
rOH >> rO
K2

~ 1
K2 << 1
K3 ~ 1
K3 << 1
K4 ~ 1
K4 << 1
RT/F
RT/2F
2RT/F
2RT/3F
1
1
0.5
1.5
a
Symmetry factors, i.e. , , and , in all steps, were taken as .
b
Stoichiometric number.
c
is the potential difference between the
outer Helmholtz plane and the bulk of the solution.
d
Nonactivated desorption of O2.
e
Activated desorption of O2.
f
r is a coefficient
determining the variation of heat of adsorption of a particular species with coverage. Unless stated, r values for each species were
taken as equal. Ki is the equilibrium constant of the ith step.
g
r1 and r2 refer to r for M
z
OH and r for M
z+1
OH, respectively.

Kinetically limiting step in
water electrolysis cells and
PEM fuel cell.
Multistep multi-electron
transfer reaction involving
adsorbed intermediates.
Depending on RDS can explain
a variety of Tafel slopes.
Key mechanistic parameters
are : Tafel Slope, reaction
order wrt hydroxide ion
activity.
Overall reaction (alkaline
medium)
O
2
+ 2H
2
O + 4e
-
4OH
-
E
0
= 0.303 V (vs. Hg/HgO)
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)
S. Rebouillat, M.E.G. Lyons, M.P. Brandon, R.L. Doyle, Int. J. Electrochem. Sci., 6 (2011) 5830-5917.
Charge Q / C cm
-2
0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14
T
a
f
e
l

s
l
o
p
e

/

m
V

d
e
c
-
1
35
40
45
50
55
60
65
New Fe electrode
'Aged' Fe electrode
Charge Q / C cm
-2
0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09
C
u
r
r
e
n
t

D
e
n
s
i
t
y

i

/

A

c
m
-
2
0.060
0.065
0.070
0.075
0.080
0.085
0.090
0.85 V
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
Uncycled
30 cycles
60 cycles
120 cycles
180 cycles
240 cycles
300 cycles
Charge Q / C cm
-2
0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09
P
o
t
e
n
t
i
a
l

/

V

v
s
.

H
g
/
H
g
O
0.695
0.700
0.705
0.710
0.715
0.720
0.725
1 mA cm
-2
Anodic OER, Fe aqueous alkaline solution.
Tafel Plots
Hydrous Iron Oxide Electrodes.
OER Reaction Order Studies

Potential / V vs. Hg/HgO
0.5 0.6 0.7 0.8 0.9 1.0 1.1
L
o
g

(
i

/

A

c
m
-
2
)
-5
-4
-3
-2
-1
0
0.1 M
0.5 M
1.0 M
2.0 M
5.0 M
60 mV dec
-1
120 mV dec
-1
Log (a
OH-
)
-1.5 -1.0 -0.5 0.0 0.5 1.0
L
o
g

(
C
u
r
r
e
n
t

D
e
n
s
i
t
y

i

/

A

c
m
-
2
)
-4.0
-3.5
-3.0
-2.5
-2.0
-1.5
-1.0
-0.5
60 mV dec
-1
region
Slope = 0.87
120 mV dec
-1
region
Slope = 0.81
N = 120 cycles
Reaction order wrt OH
-
activity
ca. 0.9 (low TS region) and ca. 0.8
(high TS region).
Measure OER current density
at fixed overpotential from
analysis of Tafel Plots as function of
OH
-
ion activity.
E/V
0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1
l
o
g
(
I
/
A
)
-5
-4
-3
-2
-1
Tafel Plots for OER at Ni oxide layers grown via potential cycling
(N = 120 cycles) in 1.0 M NaOH recorded as function of base
concentration.
0.1M
0.25M
0.75M
1M
1.5M
2M
2.5M
3M
4M
5M
E/V
-0.6 -0.4 -0.2 0.0 0.2 0.4 0.6
I
/
A
-0.002
0.000
0.002
0.004
0.006
0.1M
0.25M
0.5M
0.75M
1M
1.5M
2M
2.5M
3M
4M
N = 120 cycles
N = 120 cycles
Low potential : TS = 60 mV/dec.
High potential : TS = 120 mV/dec
E=0.64V
= 0.337V
Regression
Confidence
c = -3.0513507838
m = 0.8526502073
r = 0.96614858
Ni oxide layer grown in 1.0 M
NaOH. N = 120 cycles.
Reaction order plot, low Tafel
Slope Region.
m
OH
-

= 0.85.
E=0.71V
= 0.407V
Regression
Confidence
c = -2.1450473735
m = 0.8182632348
r = 0.973540901
Ni oxide layer grown in 1.0 M
NaOH. N = 120 cycles.
Reaction order plot, high Tafel
Slope Region.
m
OH
-

= 0.82.
Voltammetric response of hydrous
Ni oxide film as function of base
Concentration.
Ni in aqueous base: redox activity
and OER behaviour.
Charge (C)
0.0000 0.0002 0.0004 0.0006 0.0008 0.0010 0.0012
T
a
f
e
l

S
l
o
p
e

(
V
)
0.055
0.060
0.065
0.070
0.075
0.080
0.085
Slope: 0.055041
Intercept 22.607
r : 0.92
Variation of low overpotential Tafel Slope for OER
at multicycled Ni oxide Electrode in 1.0 M NaOH
as a function of oxide charge capacity Q (thickness).
Tafel Plot OER as function of hydrous
layer thickness (# cycles).
Ni oxide electrode, 1M NaOH.
E/V
0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1
l
o
g
(
I
/
A
)
-5.0
-4.5
-4.0
-3.5
-3.0
-2.5
-2.0
-1.5
-1.0
Uncycled
30 Cycles
60 Cycles
120 Cycles
180 Cycles
240 Cycles
Low overpotential Tafel Slope
increases in a linear manner with increasing
hydrous oxide charge capacity.
Effect of oxide charge capacity Q
on OER catalytic efficiency: Ni in
aqueous base.
q=0.337V
q=0.347V
q=0.357V
Oxygen evolution rate at fixed potential at oxide coated Ni in 1.0 M
NaOH as function of redox charge storage capacity of hydrous layer.
(a) M.OBrien, L. Russell, I. Godwin, R.L. Doyle, and M.E.G. Lyons, Redox
switching and oxygen evolution at hydrous nickel oxide in aqueous
alkaline solution, Electrochemical Society Transactions, Spring
Meeting Seattle , USA, 2012, In press.
(b) M.E.G. Lyons, L. Russell, M. OBrien, R.L. Doyle, I. Godwin, M.P.
Brandon, Redox switching and oxygen evolution at hydrous
oxyhydroxide modified nickel electrodes in aqueous alkaline solution:
Effect of hydrous oxide thickness and base concentration. Int. J.
Electrochem. Sci., 7 (2012) 2710-2763.

Z' / O
0 100 200 300 400 500 600
Z
'
'

/

O
0
50
100
150
200
250
300
0.72 V
0.76 V
0.80 V
0.84 V
Circuit fit
Log (Freq / Hz)
-1 0 1 2 3 4 5
L
o
g

(
Z

/

O
)
1
2
3
0.72 V
0.76 V
0.80 V
0.84 V
Circuit fit
Log (Freq / Hz)
-1 0 1 2 3 4 5
P
h
a
s
e

a
n
g
l
e

/

d
e
g
0
10
20
30
40
50
60
0.72 V
0.76 V
0.80 V
0.84 V
Circuit fit
E / V R
O
/ O C
dl
/ F cm
-2
(o)
R
far
/ O C
film
/ F
cm
-2
(o)
R
film
/ O
0.70 5.1500 551 (0.78) 858.5 42.7 (0.90) 48.5
0.72 5.1340 560 (0.80) 516.1 45.4 (0.89) 35.6
0.74 5.0510 554 (0.83) 281.0 54.6 (0.86) 25.8
0.76 4.9600 567 (0.86) 143.4 66.8 (0.84) 18.2
0.78 4.8750 576 (0.87) 71.9 77.0 (0.82) 12.8
0.80 4.6430 536 (0.90) 36.8 112.0 (0.78) 9.6
0.82 4.1190 464 (0.93) 19.5 258.0 (0.69) 8.0
0.84 4.3430 419 (0.93) 12.0 97.7 (0.77) 5.3
0.86 4.5170 382 (0.94) 7.8 39.0 (0.84) 3.9
EIS Measurements : Hydrous iron oxide film
E/V(vs Hg/HgO)
0.68 0.70 0.72 0.74 0.76 0.78 0.80 0.82 0.84 0.86 0.88
R
f
ilm
/
0
10
20
30
40
50
60
EIS data
Metal oxide film becomes more conducting with increasing potential.
R.L. Doyle 2012, sub
At OER overpotentials where simple Tafel
behaviour prevails:



Differentiating gives:



Noting that di/d = di/dE = 1/R
far
:




EIS Tafel slope 66 mV dec
-1

Good agreement with steady-state polarisation
Tafel slope of 60 mV dec
-1
.
Potential / V vs. Hg/HgO
0.68 0.72 0.76 0.80 0.84 0.88
L
o
g

(
1
/
R
f
a
r
)
-3.5
-3.0
-2.5
-2.0
-1.5
-1.0
-0.5
0.0
66 mV dec
-1
Potential / V vs. Hg/HgO
0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.00 1.05
L
o
g

(
C
u
r
r
e
n
t

D
e
n
s
i
t
y

i

/

A

c
m
-
2
)
-4.0
-3.5
-3.0
-2.5
-2.0
-1.5
-1.0
-0.5
60 mV dec
-1
120 mV dec
-1
EIS Tafel Analysis
E/V (Hg/HgO)
0.68 0.70 0.72 0.74 0.76 0.78 0.80 0.82 0.84 0.86 0.88
R
f
a
r
a
d
a
i
c
/
0
200
400
600
800
1000
EIS data
Tafel Plots OER Multicycled Hydrous Oxide coated Ni and Fe
Electrodes (N = 120 cycles), 1.0 M Base, 298 K.
Ni has reduced overpotential for OER onset
compared with Fe.
Overpotential (
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
L
o
g

(
C
u
r
r
e
n
t

d
e
n
s
i
t
y

/

A

c
m
-
2
)
-5
-4
-3
-2
-1
0
Nickel (120 growth cycles)
Iron (120 growth cycles)
[OH
-
] = 1.0 M
q A
Overpotential q / mV
200 300 400 500 600 700
L
o
g

(
C
u
r
r
e
n
t

/

A
)
-6.0
-5.5
-5.0
-4.5
-4.0
-3.5
-3.0
-2.5
-2.0
0.1 M
0.5 M
1.0 M
5.0 M
Tafel Plots OER, alkaline solutions. Electro-precipitated Nickel
oxy-hydroxide thin films deposited via CPM on Au supports.
OER onset overpotential decreases with increasing base concentration.
c
OH
- / M
0 1 2 3 4 5 6
b
/

m
V

d
e
c
-
1
30
40
50
60
70
80
90
Run 1
Run 2
Run 3
N = 30 cycles SR = 50 mV s
-1
Plating medium: 0.1 M NiSO
4
, 0.1 M NaAc.3H
2
O, 0.001 M KOH
CPM : - 900, + 1200 mV (vs SCE), 50 mVs
-1
.
Low potential Tafel slope for OER at electro-precipitated nickel oxyhydroxide film
grown on Au support via CPM, as function of OH
-
concentration.
Limiting low potential
TS = 47 mV/ dec
c
OH
- /M
0 1 2 3 4 5 6
b
/

m
V

d
e
c
-
1
100
110
120
130
140
150
Run 1
Run 2
Run 3
High potential Tafel slope for OER at electro-precipitated nickel oxyhydroxide film
grown on Au support via CPM, as function of OH
-
concentration.
Log (a
OH-
)
-1.5 -1.0 -0.5 0.0 0.5 1.0
L
o
g

(
C
u
r
r
e
n
t

/

A
)
-6.5
-6.0
-5.5
-5.0
-4.5
-4.0
-3.5
-3.0
Run 1
Run 2
Run 3
Slope = 1.12
Reaction order plot. Electroprecipitated Nickel oxy-hydroxide thin films.
1.12
OH
m

=
E/mV(vs
Hg/HgO)
q/mV m
OH
-

Run 1
m
OH
-

Run 2

m
OH
-

Run 3

620 317 1.29 1.35 1.18
640 337 1.31 1.26 1.24
680 377 1.29 1.52 1.21
700 397 1.38 1.39 1.13
Run 1: Q
CV
= 8.23 x 10
-4
C
Run 2: Q
CV
= 7.06 x 10
-4
C
Run 3: Q
CV
= 9.51 x 10
-4
C
Reaction order for OER : electro-precipitated nickel oxide film, Au support.
Aqueous alkaline solution.
2 2
SOH OH SOH H O

+ +
SOH SOH e

+
2
SOH OH SO H O

+ +
SO SO e

+
SO OH SOOH e

+ +
2 2
SOOH OH SO H O e

+ + +
2 2
SO OH O SOH

+ +
OER Mechanism at Fe & Ni oxyhydroxide modified electrodes
S = surfaquo group attached to oxide lattice
via bridging oxygen ligands.
H
y
d
r
o
u
s

L
a
y
e
r
H
2
O
O
2
e
-
OH
-
e
-
e
-
OH
-
OH
-
OH
-
OH
-
H
2
O
e
-
, H
2
O
Low RDS:
T.S.=60 mV/dec
m
OH-
= 1
High RDS (1):
T.S.=120 mV/dec
m
OH-
= 1
SOH
2
SOH
-
SOH
SO
-
SOOH
SO
SO
2
OER mechanism involving surfaquo groups in the hydrous
oxy-metal hydroxide layer.
Octahedrally co-ordinated Ni(III)
Fast initial deprotonation
Metal oxide
Metal oxo
Low q RDS
TS = 40 mV/dec
m
OH
-
= 1
Metal peroxide
Low q RDS
TS = 40 mV/dec
m
OH
-
= 2
DFT calculations being initiated
to generate quantitative Energy
Landscape for OER Mechanism.
Mechanism valid for M = Fe & Ni.
Explains Tafel Slope & reaction order data.
Overpotential V
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
L
o
g

(
I
/
Q
)
-10
-8
-6
-4
-2
0
2
4
Electrodep Ni(OH)
2
on Pt
Electrodep Ni(OH)
2
on GC
Electrodep Ni(OH)
2
on Au
Electrodep aged Ni(OH) on Au
Hydrous Nickel Oxide 120 cycles
Hydrous Iron Oxide 120 cycles
Thermally prepared NiO on Ni Substrate
Thermally prepared RuO2 Ni substrate
Thermally prepared RuO2 on Ti substrate
Thermally prepared Rh2O3 on Ni substrate
Thermally prepared Rh2O3 on Ti substrate
An atlas of electrochemical reactivity for anodic OER
Electro-precipitated |-Ni(OH)
2
: The right type of oxide for OER
Current DSA
state of art
We have
succeeded in
preparing very
effective catalytic
electrodes for
anodic OER using
very cheap
Materials (nickel
oxide).
All currents (OER rate) scaled to
voltammetric charge
which is proportional to real surface
area.
Tafel Plots IR
Corrected.
Concluding Comments
Reproducible and scalable methodology developed for generation of hydrated Fe
& Ni metal oxide thin films and electroprecipitated nickel oxyhydroxide films on
Au, GC and Pt supports in aqueous base.
Duplex layer model proposed for structure of oxide/solution interface region.
Hydrous oxide thin films exhibit super-Nernstian shifts in redox potential with
respect to changes in solution pH value. Implying commercial spinoff potential
for new generation metal wire pH sensors for use in biomedical applications.
Dynamics of redox switching in hydrous oxide layer quantified via Aoki Model.
Electro-catalytic kinetics and mechanism with respect to anodic OER at Ni and
Fe electrodes in aqueous base evaluated and quantified.
Novel anodic water splitting OER mechanism proposed involving surfaquo groups
in hydrous oxide layer. OER onset potential depends on acid/base properties of
hydrous oxide layer.
Currently developing molecular scale model for detailed OER pathway in terms of
interlinked surfaquo group model.
Fe and Ni oxide materials are cheap and effective electrode materials for anodic
water splitting.
Next stage is to examine application of these oxide materials to Cathodic
Oxygen Reduction Reaction (ORR) and hydrogen evolution reaction (HER). The
latter topics are currently unexplored at hydrous oxide materials.
Extending analysis to metal oxide films prepared via thermal decomposition of
precursor & via sol/gel routes.

Main ideas developed in:
M.E.G. Lyons, L.D. Burke, J.
Electroanal. Chem., 170 (1984) 377-
381.
M.E.G. Lyons, L.D. Burke, J.
Electroanal. Chem., 198 (1986) 347-
368.
M.E.G. Lyons, M.P. Brandon,
International Journal of
Electrochemical Science, 3(12) (2008)
1386-1424.
M.E.G. Lyons, M.P. Brandon,
International Journal of
Electrochemical Science, 3(12) (2008)
1425-1462.
M.E.G. Lyons, M.P. Brandon, Int. J.
Electrochem. Sci., 3(12) (2008) 1463-
1503.
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) 62-70.
M.E.G. Lyons, M.P. Brandon, J.
Electroanal. Chem., 641 (2010) 119-
130.



Michael E.G. Lyons, Richard L. Doyle,
International Journal of
Electrochemical Science,6, 2011,
pp.5710-5730.
Michael E.G. Lyons, Serge Rebouillat,
Michael P. Brandon, Richard L. Doyle,
International Journal of
Electrochemical Science, 6, 2011, 5830-
5917.
Michael E.G. Lyons, Richard L. Doyle,
Michael P. Brandon, Physical Chemistry
Chemical Physics, 13, 2011, pp.21530-
21551.
Michael E.G. Lyons, Stephane Floquet,
Physical Chemistry Chemical Physics, 13,
2011, pp. 5314- 5335.
Michael E.G. Lyons, Lisa Russell, Maria O
Brien, Richard L Doyle, Michael P
Brandon, International Journal of
Electrochemical Science, 7, 2012, 2710-
2763.
M.OBrien, L. Russell, I. Godwin, R.L.
Doyle, M.E.G. Lyons, Transactions
Electrochemical Society, Spring Meeting
2012, Seattle, USA, in press.
R.L. Doyle, M.E.G. Lyons, Transactions
Electrochemical Society, Spring Meeting
2012, Seattle, USA, in press.

Trinity Electrochemical Energy Conversion &
Electrocatalysis (TEECE) Group
Current Group Personnel:
PI: Prof. Mike Lyons
PDRF: Dr Richard Doyle
PG: Mr Ian Godwin
UG PCAM Interns: Ms Maria OBrien, Ms Lisa Russell,
Patrick OBrien
Visiting Researcher: Ms Anja Cakala (TU Wien)
Group Alumni (Energy Conversion/storage):
Dr Gareth Keeley
Dr Michael Brandon
Collaborators:
Prof. Declan Burke, UCC (Passed away December
2011)
Dr Michael Brandon, QUB
Dr Serge Rebouillat, DuPont Geneva
Dr Chris Bell, IC London


TEECE Group funded by Science Foundation Ireland (SFI)
Principal Investigator Programme.
Grant Number SFI/10/IN.1/I2969.
Title: Redox and catalytic properties of hydrated metal oxide
electrodes for use in energy conversion and storage devices,
2011-2016.