SEARCH FOR A VIABLE OXYGEN REDUCTION ELECTRODE

Ph. D., Seminar - 1

Ch. Venkateswara Rao

1
Contents

 Significance of oxygen reduction reaction in fuel cells

 Critical issues in oxygen reduction reaction

 Oxygen reduction electrocatalysts

- Noble metal based electrocatalysts
- Non-noble metal based electrocatalysts

 Pyrolyzed macrocycles (N4–metal chelates) as viable option

 Conclusions

2
Importance of electrochemical reduction of oxygen

 Fuel Cells

 Metal-Air batteries

 Industrial electrolytic processes

3
 Fuel Cells

Direct Energy Conversion Vs. Indirect Technology

ICE
Thermal Energy Mechanical Energy

Fuel Cell
Chemical Energy Electrical Energy

4
 Batteries/Internal Combustion Engines/Fuel Cells
Batteries
- Needs recharging
- Toxic chemicals
- Low energy density

Internal combustion engines

- Carnot limitations
- Moving parts and hence friction
- Noisy
Energy Conversion Efficiency (%)
(devise/fuel)
Fuel Cells
(H2/PEMFC) 50-60
Internal Combustion
Engine / Gasoline 20-25
C2H5OH
Diesel Engine / 25-30
Diesel 5
C. K. Dyer, J. Power Sources, 106 (2002) 245
 Fuel Cells – Advantages

 Efficiency

 Cleanliness

 Unique operating characteristics

 Planning flexibility

 Reliability

 Future development potential

6
Different Types
Fuel Cells
of
Fuel Cells
Low Temperature Medium Temperature High Temperature
Fuel Cells Fuel Cells Fuel Cells

PEMFC DMFC AFC PAFC SOFC MCFC

(Proton (Direct (Alkaline (Phosphoric (Solid Oxide Molten
Characteristic Exchange Methanol Fuel Acid Fuel Fuel Cells) Carbonate
Membrane Fuel Cells) Cells) Cells) Fuel Cells)
Fuel Cells)
Operating temp 60 – 80 60 – 80 100 –150 180 – 220 750 - 1050 650
(oC)
H2 (pure or CH3OH H2 H2 H2 and CO H2 and CO
Fuel reformed) (reformed) reformed & reformed
CH4 & CH4
Charge carrier H+ H+ OH- H+ CO32- O2-
in the
electrolyte
CO>10 Adsorbed CO, CO2 CO>1% H2S>1ppm H2S>0.5
Poison ppm intermediates H2S>50 ppm ppm
(CO)
Applications Transportation, Portable Space, Military Power generation,
Cogeneration 7
Chemical and Electrochemical data on various fuels

G0 E0theoretical E0max Energy density

FUEL kcal/mol (V) (V) (kWh/kg)

Hydrogen -56.69 1.23 1.15 32.67

Methanol -166.80 1.21 0.98 6.13
Ammonia -80.80 1.17 0.62 5.52
Hydrazine -143.90 1.56 1.28 5.22
Formaldehyde -124.70 1.35 1.15 4.82

Carbon monoxide -61.60 1.33 1.22 2.04

Formic acid -68.20 1.48 1.14 1.72

Methane -195.50 1.06 0.58 -
Propane -503.20 1.08 0.65 -

8
 Low Temperature Fuel Cells
PEMFC & DMFC

Anode Cathode

Fuel

O 2 + 4 H+ + 4 e-  2
PEMFC H2 0
2H2  4H+ +
4e-
DMFC Methanol
from Tank
CH3OH + H2O  CO2 + 6 H++ 6 e-

9
 PEMFC DMFC
H2  2 H+ + 2 e- ; Eo = 0.0 V (At Anode) CH3OH + H2O  CO2 + 6 H+ + 6 e-; Eo = 0.02 V
½ O2 + 2 H++ 2 e-  H2O; Eo = 1.23 V (At Cathode) 3/2 O2 + 6 H++ 6 e-  3 H2O ; Eo = 1.23 V
H2 + ½ O2  H2O; Eo = 1.23 V CH3OH + 3/2 O2  CO2 + 2 H2O; Eo = 1.21 V

Activation
losses
Ohmic losses
Concentration
losses

Performance losses in PEMFC & DMFC MEAs operating at 80 oC

10
T. R. Ralph and M. P. Hogarth, Platinum Met. Rev., 46 (2002) 146
Difficulties in PEMFC & DMFC

 Sluggish oxygen reduction kinetics

 Methanol crossover (in DMFC)

 Electrocatalysts

11
 Reaction pathways for oxygen reduction reaction

Path A – direct pathway, involves four-electron reduction

O2 + 4 H+ + 4 e-  2 H2O ; Eo = 1.229 V

Path B – indirect pathway, involves two-electron reduction

followed
by further two-electron reduction
O2 + 2 H+ + 2 e-  H2O2 ; Eo = 0.695 V
H2O2 + 2 H+ + 2 e-  2 H2O ; Eo = 1.77 V
Halina S. Wroblowa, Yen-Chi-Pan and Gerardo Razumney, J. Electroanal. Chem., 69 (1979)
12
195
Essential criteria for choosing an electrocatalyst for oxygen reduction

 High oxygen adsorption capacity

 Structural stability during oxygen adsorption and reduction

 Stability in electrolyte medium

 Ability to decompose H2O2

 High conductivity

 Tolerance to CH3OH (in DMFC)

 Low cost

13
Noble metal based electrocatalysts

 Pt

 Pt alloys
-- PtFe, PtCo, PtNi, PtCr

 Carbon supported Pt and its alloys

14
 Why Pt ?

 High work function ( 4.6 eV )

 Ability to catalyze the reduction of oxygen

 Good resistance to corrosion and dissolution

 High exchange current density

Oxygen reduction activity as a function

of the oxygen binding energy

J. J. Lingane, J. Electroanal. Chem., 2 (1961) 296 15

 Why carbon as an electrode support ?
Chemical properties
- Good corrosion resistance
- Available in high purity
- Forms intercalation compounds

Electrical Properties
- Good Conductivity

Mechanical Properties
- Dimensionally & Mechanically stable
- Low modulus of elasticity
- Light weight & adequate strength
- Availability in variety of physical Structures
- Easily fabricated into Composite Structures 16
  Most promising Electrocatalyst – 20 wt% Pt/C

Difficulties with Pt
 Slow ORR due to the formation of –OH species at +0.8 V

O2 + 2 Pt  Pt2O2

Pt2O2 + H+ + e-  Pt2-O2H
Pt2-O2H  Pt-OH + Pt-O
Pt-OH + Pt-O + H+ + e-  Pt-OH + Pt-OH
Pt-OH + Pt-OH + 2 H+ + 2 e-  2 Pt + 2 H2O
Cyclic voltammograms of the Pt electrode in
 Development of mixed potential (in DMFC) helium-deaerated () and O2 sat. (- - -) H2SO4

 Scarce and expensive

Charles C. Liang and Andre L. Juliard, J. Electroanal. Chem., 9 (1965) 390 17

 Why Pt alloys are more active for oxygen reduction ?

Kinetic current density (mA/cm2)

 Shortening of Pt-Pt interatomic distance
 Surface roughening
Increased d-band vacancies

Catalyst Pt-Pt Roughness

distance (Å) % Ni, Fe, Co atom%
Kinetically controlled current densities for the ORR at
Pt 2.77 5.8 0.76 V as a function of the composition of alloy catalysts
Pt53Ni47 2.64 8.3
Pt49Co51 2.69 12.5
Activity increases in the order:
Pt51Fe49 2.77 7.7 PtNi < PtCo < PtFe

S. Mukerjee, S. Srinivasan, M. P. Soriaga, and J. McBreen, J. Electrochem. Soc.,

142 (1995) 1409 18
 Proposed mechanism for oxygen reduction on Pt alloys

 Increase of 5d vacancies led to an increased 2 electron donation from O2 to

surface Pt and weaken the O-O bond

 As a result, scission of the bond must occur instantaneously as electrons are back
donated from 5d orbitals of Pt to 2* orbitals of the adsorbed O2

T. Toda, H. Igarashi, H. Uchida and M. Watanabe, J. Electrochem. Soc., 146 (1999) 3750
19
 PtCr/C
PtNi/C
PtCo/C
PtFe/C
Pt/C

Performance of DMFC MEAs operating at 80 oC Performance of PEMFC MEAs operating at 80 oC

 Pt alloys offer a performance gain of 25 mV compared to Pt/C

Difficulties
 Development of mixed potential (in DMFC)
 Expensive

T. R. Ralph and M. P. Hogarth, Platinum Met. Rev., 46 (2002) 3 20

Non-noble metal based electrocatalysts

 Transition metal oxides

 Transition metal carbides

 Transition metal chalcogenides

 Transition metal macrocycles

21
 Transition metal oxides

Perovskites
Ln 1-x SrxCoO3, Ln 1-x SrxMnO3 (Ln = La, Nd; x = 0 to 0.9), LaNiO3,
SrRuO3

Spinels
Co3O4, Mn3O4, Ni2CoO4, MnCo2O4, CdCo2O4

Pyrochlores

Pb2Ru2O7, Pb2Ru 1.95 Pb 0.05 O7-, Pb2Ru 1.95 Pb 0.05 O7-/C

Bi2Ru2O7, Pb2Ir2O7

22
Why Pb-Ru pyrochlores are preferred ? O'
Pb 
 stable in acid medium
 activity comparable to platinum

Ru 
O
Pb2Ru2O7  [Pb2O'. Ru2O6]
Active site
 alkaline medium – O' (bonded only to Pb cations)
 acid medium – O (bonded to Pb and Ru cations)

23
 Mechanism for oxygen reduction reaction

Pyrochlores (in acidic medium)

rds
Ru3+OH- + O2-  Ru3+O2- + OH-
Ru3+O2- + H2O + e-  Ru3+OOH- + OH-
Ru3+OOH- + H2O  Ru3+OH- + H2O2
Ru3+OOH- + H2O  Ru3+OH- + 2 OH-

Difficulty
- lower stability under fuel cell conditions

J. B. Goodenough, R. Manoharan and M. Paranthaman, J. Am. Chem. Soc., 112 (1990) 2076
24
 Transition metal carbides

WC, TaC, TiC, B4C

 Pt like behavior for the chemisorption of oxygen

 Lower activity compared to Pt

E, mV vs. NHE
Difficulties I (mA/cm2)
Cathodic polarization curves for
O2 reduction on various carbides
- Synthesis is expensive
- Low corrosion resistance under acidic conditions

F. Mazza and S. Trassatti, J. Electrochem. Soc., 110 (1963) 847 25

 Transition metal chalcogenides
 Chevrel phase compounds
- general formula, M6X8
MoxRuySz, RhxRuySz, RexRuySz, MoxRuySez , Ru

MoxRhySz, MoxOsySz, WxRuySz

RuxSy, RuxSey, RuxTey

Carbon supported catalysts

Characteristic features
 Metal cluster - reservoir of electronic charge carriers

 Capacity to provide neighbouring binding sites for reactants and intermediates

 Volume and bond distances are flexible

 High conductivity 26
 Mechanism for oxygen reduction reaction
• Ru
O X = S, Se, Te

O2 + 4 H++ 4 e-  2 H2O

e
Crystal structure of RuxXy catalysts

Schematic representation of molecular oxygen reduction on the Ru xXy catalysts

 Cleavage of O-O bond occurs due to the large interatomic distance (2.7 Å)
and leads to the formation of H2O
N. Alonso Vante, W. Jaegerman, H. Tributsch, W. Honle and K. Yvon,
J. Am. Chem. Soc., 109 (1987) 3251 27
 Effect of Chalcogens on the activity of Ru clusters to catalyze ORR
EXAFS results for the Ru K-edge spectrum of samples in oxygen atm. under potential variation
Sample Element Parameter Electrode potential (V) Vs. NHE
Forward scan Backward scan
0.08 0.33 0.53 0.78 0.53 0.33 0.08

O R (Å) 2.13 2.13 2.09 2.01 2.12 2.12 2.17

CN 0.9 0.7 0.5 0.6 0.3 0.3 0.4
R (Å) 2.37 2.37 2.37 2.39 2.35 2.34 2.33
RuxSey Se
CN 0.8 0.8 0.8 0.9 0.6 0.3 0.2
R (Å) 2.65 2.65 2.64 2.66 2.64 2.64 2.64
Ru CN 5.9 5.5 5.4 4.8 6.0 6.1 6.4

O R (Å) 2.05 2.04 2.04 2.07 2.01 2.02 2.04

CN 1.5 1.5 1.9 2.8 2.7 1.9 0.5
R (Å) -- -- -- -- -- -- --
RuxTez Te CN 0.1 0.2 0.3 0.4 0.4 0.4 0.5
R (Å) 2.63 2.63 2.65 2.68 2.65 2.65 2.64
Ru CN 3.1 3.3 3.2 1.7 2.4 2.9 3.8

O R (Å) 2.18 2.18 2.18 2.18 2.19 2.18 2.18

CN 1.9 1.6 1.9 2.3 1.9 2.0 1.8
R (Å) 2.38 2.39 2.39 2.39 2.39 2.37 2.38
RuxSy S CN 2.4 2.4 2.3 2.3 2.2 2.3 2.4
R (Å) 2.72 2.73 2.73 2.74 2.72 2.71 2.71
Ru CN 0.7 0.6 0.6 0.6 0.6 0.7 0.7 28
 Influence of selenium

 High current densities

 Inhibition of formation of Ru oxides

 Lower amount of H2O2 production (< 3 vol%) Tafel plots for the ORR, as obtained from RDE
experiments in O2 saturated 0.5 M H2SO4

 Enhanced stability towards electrochemical

oxidation Tafel slopes and over potentials for Ru-based
cluster catalysts with different Se contents

A: 0 Mol% Se Ru Mol% Tafel slope Overpotential //

B: 10.01 Mol% Se
C: 14.3 Mol% Se Se /mV dec-1 mV at 10 A cm-2
RuOx A: 14.3 mol% Se
B: 5.27 mol% Se
C: 0 mol% Se
14.3 96.6 330.0
D: metallic Ru
10.0 101.5 322.5
5.3 120.0 317.5
1.8 128.4 327.0
0 146.2 342.5
XRD-spectra of catalysts prepared with
Potential dependent hydrogen peroxide production of Ru
different amounts of selenium
based cluster catalysts with different selenium content

M. Bron, P. Bogdanoff, S. Fiechter, I. Dorbandt, M. Hilgendorff, H. Schulenburg and 29

H. Tributch, J. Electroanal. Chem., 500 (2001) 510
 Transition metal macrocycles

 Square planar complexes with the central

metal atom symmetrically surrounded by
four nitrogen atoms

 Structural analogues of metabolic systems

 Delocalization of ‘’ electrons

– high conductivity

 Stability in both acidic and basic media

-linked face-to-face metal porphyrin 30

Why Fe- and Co- containing macrocycles appear to be the best for
oxygen reduction ?
Oxygen reduction activities
Volcano plot of various catalysts
Mass activity at

. ..
catalyst 0.7 V vs. NHE
CoOEP
ORR activity (V vs. SCE)

CoTPP
FeTPP (mA/mg)
FeTPP 0.06
CoTPP 0.08
FePc 0.07
CoPc 0.05
RuPc 0.04
RuTPP 0.02
MnTPP 0.01
Redox potential (V vs. SCE) OsTPP 0.007
CrTPP 0.007
CoTAA 0.005

Jose H. Zagal, Coord. Chem. Rev., 119 (1992) 89 31

Adverse effect of H2O2 on catalytic activity

x x
+ H2O2, + O2
M M M
-x -M
x x

Mechanism of the disintegration of metal macrocycle

K. Weisener, Electrochimica Acta, 31 (1986) 1073 32

 How to increase the oxygen reduction activity ?

 Pyrolysis of the carbon supported metal macrocycles

Remarkable oxygen reduction activities of pyrolyzed Fe- and Co- based catalysts
Metal loading ORR activity at 0.7 V vs.
catalyst (wt%) NHE
(mA/cm )
2
(mA/mg)
FeTPP/Vulcan XC72R heat treated at 600 oC 2.0 3.9 102 (0.06)#
CoTPP/Vulcan XC72R heat treated at 600 oC 2.0 3.1 98 (0.08)
FePc/Vulcan XC72R heat treated at 500oC 2.0 4.0 78 (0.07)
CoPc/Vulcan XC72R heat treated at 600oC 1.9 3.1 58 (0.05)
FeTMPP-Cl/BP heat treated at 800oC 2.0 5.1 127 (0.11)
FeTPP/CoTPP heat treated at 600oC 2.0 3.0 69 (----)
# The values shown in bracket are the activities of non-heat treated catalysts
* The catalytic activity was determined by taking the difference between the current
measured at 0.7 V vs. NHE when the electrode is rotating at 1500 rpm and when it is
stationary.
33
 Effect of heat-treatment
 Improving the dispersion of supported macrocycle

 Formation of a highly active carbon, which modify the electronic structure

of the central metal

 Retention of metal-N4 coordinate

Visualization of the reaction of the porphyrin with the carbon during heat treatment

Active species for oxygen reduction --- MN4Cx (M = Fe, Co)

34
Methods of preparation

 Heat-treatment of metal porphyrins and phthalocyanines adsorbed on

carbon supports (scheme – 1)

 Pretreatment of carbon with nitrogen containing media and exploiting

these materials as supports for metal salts followed by heat treatment
(scheme – 2)

 Heat-treatment of metal included nitrogen containing polymers, which

was adsorbed on carbon (scheme – 3)

35
 Scheme - 1
General procedure for the preparation of metal porphyrins (ii) Adsorption of metal complex on
phthalocyanines carbon and thermal treatment

Metal complex + Solvent

Carbon support

Metal porphyrin
refluxing under Ar

filtration and wash

with H2O

drying at 75 C

complex/carbon

heat-treatment under
Ar

MN4Cx

    G. Faubert, G. Lalande, R. Cote, D. Guay, J. P. Dodelet, L.T. Weng, P. Bertrand

and G. Denes, Electrochimica Acta 41 (1996) 1689 36
 Scheme - 2
(i) Modification of carbon support (ii) Addition of ‘M’ ions

HNO3 treatment Modified carbon + Metal salt solution

Carbon black + X wt% HNO3
ultrasonication for 1 hr
refluxing
drying at 75 oC
filtration and wash
with H2O M-based catalyst
drying at 75 oC heat-treatment under
Ar
HNO3 treated carbon
MN4Cx
NH3 treatment
NH3
Carbon black NH3 treated carbon

H. Wang, R. Cote, G. Faubert, D. Guay and J. P. Dodelet, J. Phys. Chem. B 103 (1999) 2042
37
 Scheme - 3

Solution of polymer and metal salt

e.g., polyacrylonitrile and cobalt acetate in DMF

carbon support

evaporation under Ar to remove solvent

solid

heat-treatment under Ar

MN4Cx

    S. Lj. Gojkovic, S. Gupta and R. F. Savinell, J. Electrochem. Soc. 145 (1998) 3493
38
 Evidence for the formation of CoN4

A CoN4
B Co-Co

Co-N

Co K edge (A) XANES and (B) EXAFS spectra of (a) cobalt phthalocyanine (PcCo), (b-e) PcCo on
Vulcan XC-72 [(b) untreated sample; (c-e) sample heated to (c) 700 °C, (d) 800 °C, and (e) 1000 °C],
and (f) Co metal

M. C. Martins Alves, J. P. Dodelet, D. Guay, M. T. Ladouceur and G. Tourillon,

J. Phy. Chem. 96 (1992) 10898 39
 Evidence for the formation of FeN4

FeN4

Fe-N

Fe-O

FT EXAFS spectra of heat-treated

Fe K-edge XANES spectra of neat FePc (A), neat (FePc)2O (B), (FePc)2O/KB at 600 °C
nonheat-treated (FePc)2O/KB (C), and heat-treated samples at
500 (D), 600 (E), 700 (F), 800 (G), 900 (H), and 1000 °C (I)
Curve J is of Fe2O3 for comparison purpose

H. J. Choi, G. Kwag and S. Kim, J. Electroanal. Chem., 535 (2002) 113 40

Can the pyrolyzed macrocycles be a viable option for the
oxygen reduction in PEMFC & DMFC ?

Comparable activity with platinum

Structural stability during oxygen adsorption and reduction

 H2O2 decomposition

 Methanol insensitivity

 Low cost

41
 Oxygen reduction activity
ToF-SIMS measurements
FeN4Cx+
FeN2Cx+
FeN3Cx+
FeN1Cx+

Polarization curves obtained Relative intensities of various FeNxCy+ ions as a

at 80 °C in H2/O2 fuel cell function of the pyrolysis temperature for FeTMPP/C

 Even with 40% active sites (FeN4Cx), this heat-treated catalyst

exhibited comparable activity with commercial Pt catalyst

 Is there any scope to increase the activity of Macrocyclic complexes ?

M. Lefevre, P. Bertrand and J. P. Dodelet, J. Phy. Chem. B 104 (2000) 11238 42

Number of electrons transferred (n) and vol% H2O2 released in ORR
at the maximum activity for Fe-based catalysts

Precursor Carbon Heat-treatment n % H2 O2

support (oC)

Fe acetate Pyrrole black 800 3.90 5

FeTMPP R B carbon 800 3.96 2
FeTMPyP Vulcan XC72R 800 2.7 15
FeTPPS Vulcan XC72R 800 2.7 15
FeNPc Printex XE2 500 3.5 25
FeTMPP-Cl Black Pearls 200-1000 3.45 - 4.0 28 – 0
Fe(phen)3 Vulcan XC72R 800 3.7 15
FeTPP/CoTPP No support 600 4.0 0
CoTMPP Vulcan XC72R 800 4.0 0

20% Pt/C (commercial catalyst) 3.9 <5

M. Lefevre and J. P. Dodelet, Electrochimica Acta, 48 (2003) 2749 43

Comparison between Pt-based catalysts, RuxSey and Fe- based catalysts

Current (Amp)

Fe-TMPP/C at 800 oC

RuxSey/C

Potential (V vs. NHE)

Cyclic voltammograms in O2 -saturated aq. H2SO4
44
A. K. Shukla and R. K. Raman, Annu. Rev. Mater. Res., 33 (2003) 155
 Conclusions

 Though oxygen reduction reaction is quite often exploited in many fold,

the mechanism remained less understood

 There are several intricacies involved in bringing out the processes with the
very many existing electrocatalysts

 There is an abrupt need for the transition to non-noble metal electrodes

 Pyrolyzed macrocyclic systems (N4 – metal chelates) appears to be a viable

option as cathode electrocatalyst materials for oxygen reduction

45
46