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Outline
Electrocatalysis
Current state of theory of electrocatalysis
Oxygen evolution reaction
PEM
Alkaline
Synthesis of catalysts
Characterisation of catalysts
3
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-
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
6
c,a
s,a
E
IR
Er Vohm
IR
s,k
c,k
I
7
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)
8
log current
log exchange current
9
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
10
Example
electrocatalyst
reactant
product
adsorption
desorption
e- electron transfer
chemical bond
electrocatalyst
14
reactant
reactant
electrocatalyst
15
reactant
adsorption
chemical bond e-
electrocatalyst
16
optimal
Catalytic
activity
too too
weak strong
Binding energy
17
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
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
19
Particle size
and shape
Overlayer systems
or alloys: Ligand effects
(+ bifunctional)
- or both:
20
Alloys vs overlayers
H
E ~ 0.7 V
O .. CO2
H
e-
E ~ 0.5 V
H+ H+
23
(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
25
Analysis of
reaction
mechanisms
J. OM. Bockris, J. Chem. Phys. 24 (1956) 817
29
Lars-Erik~Owe, Mikhail~Tsypkin, Kia~Wallwork, Richard G. Haverkamp, Svein~Sunde, Electrochimica Acta, To be published (2012)
30
Adsorption is involved
Lars-Erik~Owe, Mikhail~Tsypkin, Kia~Wallwork, Richard G. Haverkamp, Svein~Sunde, Electrochimica Acta, To be published (2012)
31
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
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
I. A. Lervik, M. Tsypkin, L.-E. Owe, S. Sunde, J. Electroanal. Chem. 645 (2010) 135 - 142
40
Oxidation
potential
Ir-t2g: 6 5
IrO2: 9 + 2x6 = 21
valence electrons
O2-p: 16 16
41
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)
42
I. A. Lervik, M. Tsypkin, L.-E. Owe, S. Sunde, J. Electroanal. Chem. 645 (2010) 135 - 142
44
I. A. Lervik, M. Tsypkin, L.-E. Owe, S. Sunde, J. Electroanal. Chem. 645 (2010) 135 - 142
45
I. A. Lervik, M. Tsypkin, L.-E. Owe, S. Sunde, J. Electroanal. Chem. 645 (2010) 135 - 142
46
Lars-Erik~Owe, Mikhail~Tsypkin, Kia~Wallwork, Richard G. Haverkamp, Svein~Sunde, Electrochimica Acta, To be published (2012)
47
Lars-Erik~Owe, Mikhail~Tsypkin, Kia~Wallwork, Richard G. Haverkamp, Svein~Sunde, Electrochimica Acta, To be published (2012)
48
Lars-Erik~Owe, Mikhail~Tsypkin, Kia~Wallwork, Richard G. Haverkamp, Svein~Sunde, Electrochimica Acta, To be published (2012)
49
Lars-Erik~Owe, Mikhail~Tsypkin, Kia~Wallwork, Richard G. Haverkamp, Svein~Sunde, Electrochimica Acta, To be published (2012)
50
Ir oxide Ru oxide
electrode electrode
Lars-Erik~Owe, Mikhail~Tsypkin, Kia~Wallwork, Richard G. Haverkamp, Svein~Sunde, Electrochimica Acta, To be published (2012)
51
Significant surface
segregation!
Lars-Erik~Owe, Mikhail~Tsypkin, Kia~Wallwork, Richard G. Haverkamp, Svein~Sunde, Electrochimica Acta, To be published (2012)
52
Lars-Erik~Owe, Mikhail~Tsypkin, Kia~Wallwork, Richard G. Haverkamp, Svein~Sunde, Electrochimica Acta, To be published (2012)
53
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
54
Catalyst-electrolyte interaction:
Nafion vs H2SO4
L.-E. Owe, I. A. Lervik, M. Tsypkin, S. Sunde, J. Electrochem. Soc, 157 (2010) B1719 - B
55
Catalyst-electrolyte
interaction: H3PO4
IrO2 temperature
dependence
57
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
60
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
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
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)
63
olation
oxolation
solid
65
Nucleation
S<1 2 v
r*
G kT ln S
S c / cs
S>1
r*
Growth
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 (?)
69
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!