ELSEVIER

Synthetic

STUDIES

OF THE

Metals

84 (1997)

OVEROXIDATION

403-404

OF POLYPYRRQLE

3; W. Ix&;
G. G. Wallace1 , C. Y. Kim2, D. Y. Kim2,
of Chemistry, University of Wollongong, Northfields Avenue, WolIongong,
NSW, 2522,
AUSIRAUA
2Division of Polymer Science and Engineering, Korean Institute of Science and Technology, Seoul, SOUTH KOREA
________________________________________-----------------------------------------------------------------------Abstract:
Resistometry,
UV-Vis
and Raman Spectroscopy have been employed as in-situ methods for the
determination
of the overoxidation
potential of polypyrrole
(PPy). These methods all show that the onset of
overoxidation
begins at potentials as low as 0.65V v Ag/AgCl for unsubstituted PPy. They also show a strong
dependence of overoxidation potential on the pH of the supporting electrolyte, with an increase in stability at lower
pHs.
lIPRL,

Department

Keywords:
Polypyrrole and derivatives, Raman spectroscopy, UV-Vis absorption
_---------1------11--------------------------~~~~~~~~~-~----~----~-~--*------------------~~-~--~~---~---INlXODUCTION
A wide range of possible applications
have been
proposed
for conducting
electroactive
polymers
(CEPs,
eg polypyrroles,
polyanilines
and
polythiophenes).
These include sensors, electric-field
and radar shields, membranes, batteries, actuators and
anti-corrosion
films. However, in all but the most
inert of environments, one of the major limitations to
their widespread adoption is inherent lack of long term
stability.
Anodic overoxidation of CEPs is indicated by changes
in a number of measurable parameters, including
conductivity
(measurable
by in-situ resistometry),
topography
(measurable
by, for example, SEM or
AFM), loss of the normal redox behaviour (measurable
by cyclic voltammetry),
adhesion to a substrate
(measurable by in-situ Tensile Testing), a.s well as by
chemical changes in the polymer itself (measured by,
for example, UV/vis, IR/Raman and IR spectrometry).
To study this instability we have adapted a number of
these
techniques
including:
UVlvis
spectrophotometry,
IR/Raman spectrometry,
AFM,
resistometry
and cyclic voltammetry.
These allow
investigation
of the effects on oxidative degradation
of such fundamental chemical and physical variables
as the applied potential, the counterion (with varying
polarity,
electronegativity,
hydrophobicity,
size
etc.), the supporting
electrolyte
(with varying pH,
cation/anion charge, mobility, size), ring substituents
and substrate. These studies should provide further
insight into the mechanism
of the overoxidation
process and enable manipulation
and optimisation of
the overall stability of these polymers.
RESULTS AND DISCUSSION
To estimate the m
of overoxidation,
in-situ
resistometry and two in-situ spectrometric techniques
have been employed, namely UV/vis and Raman
spectrometry.
0379-6779/97/$17.00 0 1997 Elsevier Science S.A. All rights reserved
PII 80379-6779(96)03958-6

Simultaneous
resistometry
/ voltammetry
&eriments
were performed using a CSIRO,
Melbourne,
Australia, Resistometer connected in-line
to a BAS CV27 Potentiostat and a standard three
electrode cell. Data was collected by an ADI, Australia,
MacLab interface and an Apple Macintosh. By the
simultaneous use of resistometry and voltam.metry it is
possible to measure both conductivity and current flow
associated with overoxidation
during a single scan
(+400 to +12OOmV vs Ag/AgCl) at a low scan rate (0.5
to 5.0 mV/sec).
In a CV/CR experiment overoxidation of the polymer
by the increasing potential leads to a current peak,
which then decays to baseline, and an increase in
resistance, which plateaus after the initial slow rise. In
the case of PPyM03 in 1M NaNO3 (pH -6) the initial
increase in resistance begins at about +0.6OV vs
Ag/AgCl. Complete overoxidation
is deemed to have
occurred when the resistance has reached its plateau, in
the case of PPyM03
this corresponds to +0.86V vs
Ag/AgCl. (See Figure 1.) As the resistance plateau is
only reached when overoxidation is complete, and it is
very difficult to determine the point of initial increase
in resistance, the measured result is much higher than
the potential at which overoxidation
is initiated. It is
also interesting to note that the current rises before
any detectable increase in resistance, indicating that
chemical changes conunence before any change in
resistance is observed. This is to be expected since all
conducting pathways must be shut down conductivity
drops.
UV/vis experiments were performed on thin
ii.
polymer films grown on IndiumRin oxide (lT0) glass.
The spectra were collected from 300 to 820nm during
electrochemical measurements using a Hewlett Packard
8452A Diode Array Spectrophotometer.
Experiments
were run both with constant applied
potential
(800mV) at various supporting electrolyte pHs (~0.1,
1.43, 2.25, 6.24 and 11.05) and with constant
supporting electrolyte pH (2.25) at various applied
potentials (600, 700, 800, 900, 1000 and 1100mV).
The results clearly
indicate
the dependence
of
overoxidation
on both the applied potential and the

404

T.% Lewis

et al. /SyntheticMetals

pH of the supporting
electrolyte.
Figure 2 shows a
plot of absorbance
Cat SOOnm)
versus time for
polypyrrole/paratoluenesulphonate
(PPy/PTS)
in
NaClJHCl at pH 2.25 at various applied potentials.
From this, it can be seen that at pH 2.25
overoxidation
begins at between 750 and SOOmV.
Similar studies indicate that at pHcO.1, no detectable
overoxidation
occurs even after 60min at 8OOmV,
whereas at pH=l1.05,
overoxidation
is complete in a
matter of minutes at this potential.

84 (1997)
...

111.

IR&anntn

403-404

Similar
Spectroscopy.

experiments
were carried out using
These were also performed

in-situ , but employing a platinum substrate and a very

slow scan rate (O.ImV/sec).
Scans from 3500 to 500
wavenumbers
were collected every 50mV from 400 to
1100mV. Examination
of the spectra between 1700
and 1450 cm-l clearly shows chemical changes in the
polymer occurring
as low as 700mV for PPylPTS in
NaCWHCl (pH=2.25).

/I
.I
70

O&V

izure
1: Plot of Current
(PA),
Potential
(V v
Ag/AgCl)
and Resistance (a) versus Time (min) for
PPy/N03
(pH -6) obtained
from a simultaneous
resistometry/voltammetry
experiment.

*-I

-l-he

----o----

0.6%
0.7v

0.w

(tin)

F.36
u-2

E31

.--me-

-.-.

+.-.

0.9V

E33

l.OV

!34

l.lV

E3S

Eie2; Plot of absorbance (at 8OOnm) v time (min) for

PPy/PTS at various potentials
in NaCL/HCl (pH =
2.25)

u
Raman spectrum
of PPy/PTS
O.lmV/sec in NaCLHCl @H = 2.25).

scanned

at

CONCLUSION
A number of in-situ techniques have been developed to
monitor the onset of overoxidation
of polypyrrole
and
other CEPs. These techniques have indicated the onset
of overoxidation
at potentials as low as 0.65 to 0.7OV
(vAg/AgCl)
for PPy and the high dependence
of
stability on the pH of the supporting
electrolyte.
At
pHs approaching
0, the stability of PPy is increased
from minutes to hours over that measured at pH -6
when the polymer
is held at 0.8OV (v Ag/AgCl).
Neither the incorporated
counterion
nor substitution
on the pyrrole
ring, even at both the 3 and 4
positions,
generally
have significant
effect on the
overoxidation
potential of PPy. A possible means of
increasing
the overoxidation
potential
of this
polymer
is to increase
its hydrophobicity
by
substitution
of large organic molecules at the theree
position. In our experience
though, this leads to a
significant decrease in the inherent conductivity of the
film. Both the increase in hydrophobicity
and the
decrease in pH presumably
limit the effectiveness of
nucleophylic
attack by OH- , the most favoured
mechanism of overoxidation
of PPy.
References:
F. Beck, P. Braun, M. Oberst,
Chem 91 (1987) 967

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