PERGAMON Electrochimica Acta 44 (1999) 1733±1748

Electropolymerization of pyrrole and electrochemical

study of polypyrrole: 1. Evidence for structural
diversity of polypyrrole
Ming Zhou, JuÈrgen Heinze *
Institut fuÈr Physikalische Chemie, Albert-Ludwigs-UniversitaÈt Freiburg, Albertstrasse 21, D-79104 Freiburg, Germany

Received 6 April 1998; received in revised form 8 July 1998

Abstract

Conventional electropolymerization of pyrrole produces polypyrrole characterized voltammetrically by a single

oxidation wave (ca. 0.01 V vs. Ag/AgCl) followed by a broad plateau. This was considered to be an inherent
property of electrosynthesized polypyrrole, and intensive research based on such knowledge was carried out in the
past. The present studies of electrochemical properties of polypyrrole prepared at extremely low formation
potentials or currents reveal that polypyrrole may exhibit additional oxidation waves at potentials more negative
than those normally observed. A number of cyclic voltammograms manifest a great structural diversity in
polypyrrole doped by the same anion. The fact that the trace-crossing may not appear in some cases and, on the
other hand, may remain after the electrode has become polymer-coated in other cases leads to the conclusion that
the nucleation step is not the only factor responsible for the trace-crossing. # 1999 Elsevier Science Ltd. All rights
reserved.

Keywords: Pyrrole; Polypyrrole; Electropolymerization; Redox; Nucleation loop

1. Introduction One method of gaining more insight into CPs is to

Despite 20 years of studies on the basic aspects of
conducting polymers (CPs) [1±26], many issues, such
as the ®lm formation process, the charging/discharging
mechanism, and the interplay between structure, prop-
erties and synthesis conditions still remain controver-
sial. This is, of course, due to the complexity of the
electropolymerization mechanism and the lack of e€ec-
tive methods for the characterization of insoluble poly-
mers. Furthermore, the neglect of the experimental
conditions during the preparation of CPs is another
reason for many unresolved points in the debate. This
is particularly true for property studies and structural
characterization of polypyrrole (PPy).
* Corresponding author. Tel.: +49-761-203-622; Fax: +49-
761-203-6222; E-mail: heinze@sun2.ruf.uni-freiburg.de
extrapolate the properties from structurally well-
de®ned oligomers. This has proved to be largely suc-
cessful. Results obtained in recent years have greatly
contributed to a better understanding of charging/
discharging [22, 27], dimerization [21, 23, 28], chain
branching and cross-linking [25, 29] and
conductivity [30], etc. However, the knowledge of the
factors governing the electrochemical reactions and
the formation of polymer structures is still far from
complete. Almost no certain conclusions have been
drawn so far on how a single parameter in¯uences
the polymer's properties, or how interdependent the
experimental variables are. In previous work, atten-
tion was paid to the role of applied potentials in elec-
tropolymerization, and it was found that higher
potentials result in oligomeric radical cations with a
higher charge level, leading to longer chains in the
polymer structure [27].

0013-4686/99/$ - see front matter # 1999 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 1 3 - 4 6 8 6 ( 9 8 ) 0 0 2 9 3 - X
1734 M. Zhou, J. Heinze / Electrochimica Acta 44 (1999) 1733±1748

Fig. 1. Potential dependence of potentiodynamic growth of PPy ®lms. Nondegassed acetonitrile solution, 0.1 M pyrrole, 0.1 M
TBAPF6, 1 wt% water, temperature ÿ208C, scan rate 100 mV s ÿ 1. (a) ÿ1.12±1.13 V, 15 scans; (b) ÿ1.12±1.03 V, 12 scans; (c)
ÿ1.12±0.93 V, 20 scans; (d) ÿ1.12±0.88 V, 28 scans; (e) ÿ1.12±0.83 V, 40 scans, from 6th, every second scan recorded; (f) ÿ1.12±
0.83 V, 30 scans, partially recorded; scan range changed to ÿ1.12±0.78 V for another 28 scans, every third scan recorded.

Cyclic voltammetry is an essential method for the (CVs) has long been a subject of
characterization of the electrochemical properties of discussion [11, 13, 18, 22, 27, 31, 32], it is now accepted
CPs. Although the shape of cyclic voltammograms that the shape and position of CVs can re¯ect proper-
 M. Zhou, J. Heinze / Electrochimica Acta 44 (1999) 1733±1748
ties of polymer structure. In the case of pyrrole, typical
voltammograms of PPy electrosynthesized under mild
conditions (current density at the level of mA cm ÿ 2 in
the case of galvanostatic synthesis) show an oxidation
wave with a steep onset, followed by a broad plateau
and, on the reverse scan, a negatively shifted, weaker
reduction wave [13]. The shapes may vary, depending
on supporting electrolytes, solvents and other con-
ditions. Seeking to establish the relation between
applied potentials and voltammetric properties, we
conducted electrochemical polymerization experiments
with pyrrole in acetonitrile (0.1 M TBAPF6 and 1
wt% H2O) at potentials and/or currents, down to
levels that barely sustained ®lm formation. The study
not only results in the ®ndings of electrochemically
well-de®ned PPy, but also unequivocally demonstrates
that a small change in a single experimental variable
may in¯uence the properties of the resulting polymer
enormously, and that results obtained under widely
varying conditions cannot be uncritically used to draw
universal conclusions.
2. Experimental
Pyrrole (Aldrich) was previously distilled and stored
in the solid state in a freezer. Commercial HPLC grade
acetonitrile (Fisons Scienti®c Equipment) was used as
received. Added water (1.0 wt%) was deionized. The
supporting electrolytes, used always at 0.1 M in both
pyrrole-containing and pyrrole-free solutions, tetrabu-
tylammonium hexa¯uorophosphate (TBAPF6, Fluka,
electrochemical grade), tetrabutylammonium tri¯uoro-
methanesulfonate (TBACF3SO3, Fluka, electrochemi-
cal grade) and lithium perchlorate (LiClO4, Aldrich,
anhydrous, 99.98%), were vacuum dried in an air-tight
electrochemical cell immediately before use. Unless
otherwise indicated, TBAPF6 was used as standard
supporting electrolyte in the study. For the pyrrole-
and water-containing solutions, both nondegassing and
degassing protocols were adopted. In the degassing
protocol, pyrrole (twice distilled in argon), acetonitrile
and water were purged with argon for more than half
an hour and immediately introduced into the cell
under the protection of argon. Pyrrole- and water-free
solutions were passed through an alumina-®lled col-
umn (ICN alumina B-Super I, vacuum dried at 3008C
for 2 h immediately before use), till a good back-
ground in the required potential range was obtained.
All electrochemical experiments were performed at
ÿ208C and under argon protection. The prepared sol-
utions were normally used for a series of experiments,
and were also stored under argon in an air-tight cell
when not in use.
A Pt disk (diameter 1 mm, area 0.785 mm2) sealed
in a soft glass rod was used as working electrode; it
1735
was polished with diamond (0.25 mm) polishing paste
and then rinsed thoroughly with ethanol and acetone.
Pt and Ag wires were used as counter and quasirefer-
ence electrodes, respectively. Potentials versus the Ag
quasireference electrode were then rescaled by Ag/
AgCl, calibrated with the ferrocene/ferrocenium redox
couple (0.35 V vs. Ag/AgCl). An EG&G Potentiostat/
Galvanostat Model 273 and a Kipp and Zonen Delft
BV BD 92 recorder were used for electrochemical con-
trol and data recording. During electrochemical pro-
cess charges were read directly from the potentiostat/
galvanostat.
3. Results and discussions
3.1. The additional oxidation wave
Our initial ®ndings are illustrated in Fig. 1. The
potentiodynamic formation of PPy was studied in the
potential range between ÿ1.12 V and di€erent positive
switching potentials. As can be seen, when the switch-
ing potential shifted from 1.13 to 0.93 V, the cyclic
voltammograms change their shape from almost sym-
metrical anodic and cathodic waves (Fig. 1a) to waves
with a strong hysteresis between the anodic and the
cathodic scans (Fig. 1c). In addition to the normal
wave at E p00.01 V, a new sharp oxidation wave
emerged at potentials about ÿ0.23 V as the switching
potential was further lowered to 0.83 V (Fig. 1e). An
even stronger current response of the additional wave
could be observed when the scan was reversed at an
even lower potential in the course of potentiodynamic
polymerization (Fig. 1f).
Contrary to the well-resolved oxidation waves, the
reverse reduction half-cycle exhibited no additional
wave. However, there was a progressive negative shift
of the peak-like reduction wave when switching poten-
tials were lowered [E pc = ÿ 0.25 and ÿ0.33 V in
Fig. 1(b) and Fig. 1(f), respectively].
Results displayed in Fig. 1 were obtained with sol-
utions containing 0.1 M pyrrole at a temperature of
ÿ208C, but the same phenomena were observed over a
wide concentration range of pyrrole (Fig. 2), a tem-
perature range from ÿ40±208C and also with other
supporting electrolytes, such as TBACF3SO3 and
LiClO4 (Fig. 3).
In Fig. 2, using solutions containing 0.001, 0.01, 0.1
and 0.5 M pyrrole, the potential sweeps were made
with switching potentials adjusted as low as possible to
sustain a minimal rate of ®lm growth. It was found
that the new oxidation wave occurred over a concen-
tration range from 0.01±0.5 M pyrrole. Even when the
concentration was as low as 1  10 ÿ 3 M, the trace of
the new wave could be distinguished from the wide,
symmetrical and positively shifted redox wave (Fig. 2a).
1736 M. Zhou, J. Heinze / Electrochimica Acta 44 (1999) 1733±1748

Fig. 3. New oxidation wave of potentiodynamically grown

PPy doped by (a) CF3SO3ÿ , ÿ1.02±0.88 V, 18 scans; and (b)
ClO4ÿ , ÿ0.92±0.83 V, 38 scans, from the 5th, every third scan
recorded. Nondegassed acetonitrile solution, 0.1 M pyrrole,
0.1 M supporting electrolyte, 1 wt% water, temperature
ÿ208C, scan rate 100 mVs ÿ 1.

It should be pointed out that the switching potentials

required for the appearance of the additional wave
changed with the pyrrole concentration. The lower the
concentration of pyrrole, the higher the switching po-
tential required. This represents the interchangeability
between concentration and applied potential. When
TBACF3SO3 and LiClO4 are employed as supporting
electrolytes, the separation of the two anodic waves is

Fig. 2. Potentiodynamic growth of PPy ®lms at extremely low

formation potentials in solutions of di€erent pyrrole concen-
scan range ÿ1.03±0.87 V, 145 scans, from the 25th scan, every
tration. Degassed acetonitrile solutions, 0.1 M TBAPF6, 1
10th scan recorded; (c) 0.1 M pyrrole, scan range ÿ0.96±0.82
wt% water, temperature ÿ208C, scan rate 100 mVs ÿ 1. (a)
V, 75 scans, from the 5th scan, every 5th scan recorded; (d)
0.001 M pyrrole, scan range ÿ1.03±1.02 V, 130 scans, from
0.5 M pyrrole, scan range ÿ1.01±0.74 V, 80 scans, from the
the 10th scan, every 10th scan recorded; (b) 0.01 M pyrrole,
5th scan, every 5th scan recorded.
 M. Zhou, J. Heinze / Electrochimica Acta 44 (1999) 1733±1748 1737

smaller than in the case of TBAPF6 as supporting elec-

trolyte, but the ®ne structure is apparently distinguish-
able (Fig. 3).
The usually observed trace-crossing, the so-called
`nucleation loop' [6, 33±35] (visible in Fig. 1(a and b)),
did not occur in all cases of electropolymerization at
lower potentials (Fig. 1(c±f), Figs. 2 and 3). In a later
section of the paper, this type of trace-crossing will be
discussed in more detail.
The thickness of ®lms as measured approximately by
the peak current of the redox waves was di€erent: in
Fig. 1, from (a) to (e) the ®lms got gradually thinner.
This raises the question of whether ®lm thickness
played a crucial role. Both our subsequent results and
the quantitative comparison among the CVs in Fig. 1,
or better, between Fig. 1(c) and Fig. 4(b), indicate
that, though this new peak became indistinct when the
cyclic potential scan continued and the ®lm turned
thicker, the formation of the new peak was not the
consequence of a di€erence in ®lm thickness, but
instead, depended on the switching potential. However,
when the switching potential is set extremely low, the
mechanisms of polymerization and ®lm growth per-
haps change during the course of potential scan. Fig. 4
reveals that the change in CVs at low switching poten-
tial depends on the stage of the ®lm growth. While the
charging current of the polymer increased with the
number of scans, the position of the new peak shifted
gradually to a more positive potential (Fig. 4(a and
b)), leading eventually to an apparently wide wave
without observable ®ne structure (Fig. 4c).
It is also interesting to note that the position of the
switching potential at the end of the cathodic scan also
in¯uences the additional wave of the growing polymer
®lm. As shown in Fig. 4(a), each time the reverse scan
was switched at a more negative potential (initially at
ÿ0.64 V, then successively, ÿ0.94, ÿ1.34 and ÿ1.74 V),
the next oxidation scan gave rise to an immediate cur-
rent jump in the new peak. But no such e€ect was
found in the normal wave at 0.01 V. It is thus
suggested that the corresponding reduction of the poly-
mer with the additional oxidation peak must be com- Fig. 4. Potentiodynamic growth of PPy ®lm: in¯uence of dis-
charging extent and thickness. Nondegassed acetonitrile sol-
pleted at a more negative potential.
ution, 0.1 M pyrrole, 0.1 M TBAPF6, 1 wt% water,
temperature ÿ208C, scan rate 100 mVs ÿ 1, up-switching poten-
3.2. Properties of galvanostatically synthesized ®lms tial 0.86 V. (a) Discharging scan down to di€erent potentials
in the ®rst 46 scans; (b) 50±80th scans, every second scan
Thicker PPy ®lms with only one peak-like oxidation recorded; (c) 250th and 335th scans. Figures indicate the scan
wave at a potential less positive than normal can be number, dashed lines indicate the initial position of oxidation
synthesized galvanostatically at extremely low current waves.
densities, for example ca. 6 mA cm ÿ 2 (50 nA on our
electrode), which is about a few hundreds times lower CV (Fig. 5a). Upon repetitive cyclic potentiodynamic
than under conventional conditions [36±40]. In the scans between 0.75 and ÿ2.1 V, the peak at ÿ0.23 V
case of repetitive charging and discharging during a gradually grew and shifted positively little by little.
potentiodynamic multisweep in a monomer-free sol- Eventually, the structurally evolved polymer ®lm
ution, the initially synthesized PPy ®lm may be structu- showed completely reversible redox CVs, with a sharp
rally modi®ed, as evidenced by the evolution of the oxidation wave at ÿ0.09 V, followed by a very low pla-
1738 M. Zhou, J. Heinze / Electrochimica Acta 44 (1999) 1733±1748

Fig. 5. Evolution of voltammograms of PPy ®lms in monomer-free acetonitrile solution. 0.1 M TBAPF6, temperature ÿ208C, scan
rate 100 mV s ÿ 1, scan range 0.75± ÿ2.1 V. Film prepared in solution same as that in Fig. 1, galvanostatically at 50 nA, with charge
720.8 mC. Figures indicate the scan number.

teau, and very stable electrochemical properties
(Fig. 5b), with no more voltammetric changes during
subsequent hours of repetitive potential cycles. Note
also that the oxidation peak current was about four
times as high as that of the ®rst cycle. This implies
that the as-prepared ®lm was much less charged than
it could be. Such a dramatic evolution of the charging/
discharging properties re¯ected by the ®nal CV
(Fig. 5b), which reveals some structure-related reac-
tions in the solid state during the repetitive redox pro-
cess, has never been reported before.
The studies on the evolution of CVs from ®lms pre-
pared at di€erent currents clearly demonstrated a con-
tinuous change of voltammetric properties akin to the
situation in Fig. 1. These are illustrated in Figs. 6 and
7. The current used to produce the ®lm in Fig. 5 was
50 nA, i.e. ca. 6 mA cm ÿ 2. Increasing the current to
0.1 mA (i.e. 12.7 mA cm ÿ 2), the resulting polymer
exhibited an obviously composite oxidation wave, and
the more negative component became less dominant at
even higher currents (Fig. 6). In Fig. 6(b and c), the
composite feature of the oxidation wave is not so clear
as in Fig. 6a. However, upon a couple of cyclic poten-
tial scans in pyrrole free solution, the composite fea-
ture was disclosed by the decomposition of the
oxidation wave due to the di€erent evolution behaviors
of the two waves in monomer free solution. The results
in Figs. 5 and 6 convince us that the apparent oxi-
dation wave of PPy normally prepared at low current
densities, or low potentials (in controlled potential
mode) is a combination of oxidation processes of at
least two di€erent PPy variants. The evolution beha-
viors of these two variants are di€erent. In cyclic po-
tential scan the more negative wave tended to grow,
while the more positive wave tended to diminish, as
the arrows and the scan number in the ®gure indicate.
Fig. 6 shows the transition from the state displayed in
Fig. 5 to the normal voltammetric properties. As the
applied current further increased, another transition,
namely from peak-plateau form to symmetric form,
appeared. This is demonstrated in Fig. 7, where the
 M. Zhou, J. Heinze / Electrochimica Acta 44 (1999) 1733±1748 1739

current was increased from 50 to 100 mA [Fig. 7(a±d),
current density from ca. 6.4 to ca. 12.7 mA cm ÿ 1].
Since a higher current level corresponds to a higher
anodic potential, the tendency re¯ected in Figs. 5±7 is
in good agreement with that in the potentiodynamic
cases shown in Fig. 1(a±f).
In addition to the change in basic features of the
CVs, another two aspects should be mentioned.
First, the positions of the wave onset and the cur-
rent maximum shift negatively with decreasing syn-
thesis current. The shift can be clearly observed by
means of the dashed lines in Figs. 6 and 7. Second, in
Fig. 7, to keep peak current at the same level, less
charge was needed for the synthesis at a lower current.
At a higher current, more charge was needed to elevate
the plateau.
Our investigation of the structural evolution of PPy
in a monomer-free solution showed that electropoly-
merization is a very subtle process. A very small
change in conditions (e.g. 10% change of current

Fig. 6. Evolution of voltammograms of PPy ®lms in monomer-free acetonitrile solution. 0.1 M TBAPF6, temperature ÿ208C, scan
rate 100 mVs ÿ 1, scan range 0.75± ÿ2.1 V. Films prepared in solution same as that in Fig. 1, with current/charge (a) 0.1 mA/716.9
mC; (b) 0.2 mA/721.2 mC; (c) 0.4 mA/721.4 mC. Figures indicate the scan number.
1740 M. Zhou, J. Heinze / Electrochimica Acta 44 (1999) 1733±1748
Fig. 7. Voltammograms of PPy ®lms prepared at relatively
higher currents. 0.1 M TBAPF6, temperature ÿ208C, scan
rate 100 mV s ÿ 1, scan range 0.75± ÿ1.1 V. Films prepared in
solution same as that in Fig. 1, with current/charge (a) 50
mA/777.2 mC; (b) 70 mA/1.116 mC; (c) 80 mA/1.493 mC; (d)
100 mA/2.277 mC. Figures indicate the scan number.
intensity alone, as in Fig. 7, or a slight di€erence of
solution aging) could give rise to an observable discre-
pancy between CVs. Thus, the analysis and character-
ization of structure and properties of conducting
polymers, based on limited samples, may not be uni-
versally correct. At even lower current intensity, waves
appear at even more negative potentials (one pre-wave
in Fig. 5a, already present in the ®rst scans, sub-
sequently merges into the main peak-like wave), and
all these even more negative waves displayed instability
when the ®lms underwent repetitive potential scans in
monomer-free solution. It is worth noting that the
details of CVs are not always reproducible when extre-
mely low currents are employed. On the other hand,
this just re¯ects the susceptibility of the electropoly-
merization process to the conditions and the diversity
of the structures of the resulting polymer.
The change and evolution of CVs in monomer-free
solution might be the result of some solid-state reac-
tions and ion movement during charging and dischar-
ging. The relaxation e€ect [41, 42], as applied to
polythiophene for explaining CV change, is probably
too simple for our case.
At present, we are unable to interpret all the
phenomena reported above. In the following section
we shall try to explain only some of the observations.
3.3. The real factor
From the shape and separation of the two oxidation
waves in Fig. 1 and other features in Figs. 4±7, we
believe that the phenomenon related, should be attrib-
uted not to the stepwise electron transfer process, but
rather to the di€erent structural entities coexisting in
the polymer matrix.
Lei and Martin studied the reaction of pristine PPy
(i.e. in its neutral state) with oxygen [43]. The CVs
they obtained showed a negative shift of both the char-
ging and discharging waves from O-doped PPy. In our
®ndings, the additional wave also lies negative to the
normal charging wave (i.e. ÿ0.23 and 0.01 V, respect-
ively). Could the additional wave come from a species
of some state of O-doped PPy that might have been
formed in solution containing O2 when PPy was con-
stantly switched between the charging and discharging
states? Our experiments with solutions, well purged
with argon, indicated that this was not the case. The
additional wave can also appear in completely oxygen-
free solutions once the switching potentials have been
adjusted to very low levels in the potentiodynamic ex-
periments. As a matter of fact, the CVs in Fig. 2 were
all obtained from the solutions whose components
(acetonitrile, TBAPF6, pyrrole, and water) were inten-
sively degassed immediately before use. The compari-
son between Fig. 1(e) and Fig. 2(c) gives no support to
the assumption of a possible incorporation of oxygen.
The in¯uence of applied potential in the electropoly-
merization of conducting polymers is usually estimated
from the viewpoint of charging levels (i.e. monocation,
dication, etc.) and reactivity. The studies on oligomers
of thiophene, pyrrole and phenylene have already
demonstrated that the reactivity of oligomer cations
increases with a higher charging level and decreases
with increasing chain length [21, 22, 27, 44, 45]. This
was proved by the solid-state electropolymerization
experiments [27]. Another well-proved fact is that the
oxidation potentials of oligomers vary linearly with the
inverse of the number of repeating units. That is to
 M. Zhou, J. Heinze / Electrochimica Acta 44 (1999) 1733±1748
say, with a slight increase of the formation potential
(or current) in potentiodynamic (or galvanostatic) elec-
tropolymerization experiments, a negative shift of the
polymer oxidation wave should be expected, due to a
longer chain length. Surprisingly, our results from
both potentiodynamic and galvanostatic experiments
showed the opposite. At extremely low formation po-
tentials, the additional peak-like wave emerges at
ÿ0.23 V, which is more negative than those of `poly-
pyrrole' obtained electrochemically from pentapyrrole
and heptapyrrole [19], and those extrapolated values
from Zotti et al. [19] (ÿ0.59 V vs. Ag/0.1 M Ag + or
ÿ0.205 V vs. Ag/AgCl) and from Andrieux et al. [45]
(ÿ0.21 V vs. SCE, or ÿ0.165 V vs. Ag/AgCl) for the
`in®nite' oligomer pyrrole. It must be pointed out that
both values were extrapolated from measurements of
pyrrole oligomers in solution. In the case of solid state
experiments, a strong potential hysteresis e€ect was
normally observed for many conducting polymers, i.e.
the charging process always requires more energy than
is expected from extrapolation of solution data,
whereas the discharging process needs less energy than
extrapolation indicates. Since such a hysteresis e€ect
probably holds for polypyrrole, we should expect that
the oxidation potential for the in®nite oligomer pyrrole
(polypyrrole) to be more positive than ÿ0.205 or
ÿ0.165 V vs. Ag/AgCl. The deviation from our obser-
vation of ÿ0.23 V thus is even greater.
If we attribute the sharp wave at ÿ0.23 V to the
structural entity with longer chains, the inapplicability
of the potential/chain length relationship to this case
can be explained as follows. Because the potentials
required to charge the oligomer to di€erent levels are
discrete, changing potential between two neighboring
values cannot result in the more reactive species. In
our experiments, the change of potential (or current)
was probably not big enough to generate change in the
charging level of oligomer radical cations. Therefore,
the potential alone may not be a direct reason for the
appearance of the sharp wave at E pa = ÿ0.23 V.
Additional factors must be taken into account for this
process.
One should bear in mind that decreasing the switch-
ing potential in a potentiodynamic sweep, or current in
a galvanostatic experiment, can substantially decrease
the generation rate of monomer cations and hence
eventually lower the polymerization rate and ®lm
growth rate. As reported above, we focused on the po-
tential range from the oxidation onset to the peak po-
tential. A very important fact is that a slight shift in
the switching potential can cause a tremendous change
in the reaction rate.
Because monomer concentration, temperature and
potential can be used interchangeably to reach a
de®ned reaction rate, the potentials required to sustain
the minimal formation of polymer are not ®xed; higher
1741
potentials are needed for a lower monomer concen-
tration (see Fig. 2). Likewise, in experiments with vari-
able temperatures, a higher potential is needed for the
sustainable formation of polymer at lower tempera-
tures. With respect to the appearance of the additional
peak-like wave, it appears that the crucial factor was
none of these, but instead, the generation rate of rad-
ical cations, which was represented by the current level
of monomer oxidation.
Being a second-order reaction, the dimerization
coupling rate of radical cations depends strongly on
the concentration of the reactants, which are not the
neutral monomers, but rather, the radical cations gen-
erated in the ®rst electron transfer step. In this context,
it is apparent that the oxidation current, the reaction
rate and the generation rate of all charged species have
the same implications for our discussion of polymeriz-
ation rate.
According to the normally accepted polymerization
mechanism, the dimerization coupling is followed by
the elimination of two protons, which may change the
acidity within the di€usion layer as a function of the
reaction rate. If it is so high that proton generation is
faster than proton di€usion from the electrode to the
bulk solution, the reaction zone becomes rich in pro-
tons. If the reaction rate is extremely low, the relatively
faster di€usion of protons leads only to a minor pro-
ton gradient between the reaction zone and bulk sol-
ution. Thus, one of the signi®cant di€erences, caused
by varying the reaction rate, is the acidity of the actual
reaction environment. The in¯uences of pH on the pyr-
role electropolymerization process in aqueous solutions
and on the properties of the resulting polymer have
been discussed in the literature [46±48].
In addition to protons, other intermediates, originat-
ing from many possible reactions and changing with
the reaction rate, may also contribute to the reaction
environment.
As far as solid ®lms are concerned, the speci®c
nature of the solid state, such as the electrical resis-
tivity, capacitive e€ect, lattice relaxation, swelling
properties, and the related permeability to ions and
solvent, etc., must be taken into consideration in the
interpretation of the voltammetrical behavior of con-
ducting polymers [18]. These properties depend not
only on the polymeric chain structure (chain-length,
chain-branching, cross-linking), but also, to a great
extent, on the tertiary structure, namely, the stacking
mode of chains. The properties of polymers formed in
di€erent reaction environments may di€er from one
another. Such complications associated with the solid
state may constitute one of the reasons for the shift
and shape change of CVs.
From the viewpoint of deposition and crystalliza-
tion, a slow formation process favors a better crystalli-
nity, resulting in polymer deposition di€erent from
1742 M. Zhou, J. Heinze / Electrochimica Acta 44 (1999) 1733±1748

that at higher rates. Thus, our observation of the ad-

ditional wave (Fig. 1f) agrees with the fact that well-
crystallized electroactive substances show better-shaped
and sharp waves.
One of the referees of this paper proposes that the
wave at ÿ0.23 V may be due to a PPy with a higher
conjugation length, while the wave at 0.0 V should be
connected with the charging of a PPy matrix with a lot
of `defects', such as interchain cross linking. At this
level of discussion, such an explanation seems to be
very reliable. Anyway, the above hypotheses remain to
be proved and related phenomena deserve further in-
vestigation. Very recent studies have shown that upon
electropolymerization of pyrrole in the dependence on
experimental conditions di€erent types of PPy can be
generated. We will discuss in forthcoming papers [49]
the mechanistic pathways leading to these di€erent ma-
terials.
It should be noted that the negative shift of PPy was
also observed under other circumstances. Using 2,2 0 -
bipyrrole as starting substance, Zotti et al. [50] found
that anodic coupling in acetonitrile was in¯uenced by
the electron-donor properties of the anion of the sup-
porting electrolyte. Compared to electron-poor donor
anions (ClO4ÿ , PF6ÿ , BF4ÿ and CF3SO3ÿ ), electron-rich
donor anions (tosylate, benzenesulfonate, methanesul-
Fig. 8. Trace-crossing occurring on polymer-coated electrode.
fonate, camphorsulfonate, chloride, and nitrate) favor
Degassed acetonitrile solution, 0.1 M pyrrole, 0.1 M
polymerization, and lead to the resulting polymer
TBAPF6, 1 wt% water, temperature ÿ208C, scan rate 100 mV
showing a more negative redox pair. For example, the s ÿ 1. Scan range (a) ÿ0.96±0.99 V; (b) ÿ0.96±1.09 V; (c)
PPy doped by tosylate has a reversible oxidation pro- ÿ0.96±1.19 V. Figures indicate the scan number.
cess at E0 = ÿ 0.70 V (vs. Ag/0.1 M Ag + ), in com-
parison with ÿ0.45 V (vs. Ag/0.1 M Ag + ) for the PPy
doped by perchlorate. Furthermore, the UV-VIS spec- nucleation process also needs an overpotential, result-
trum and conductivity data indicate that tosylate ing in a higher current on the reverse scan in a certain
favors the deposition of a long-chain conjugated poly- potential range.
mer. This result supports the view that in some cases In most of our cases, in which the switching poten-
in addition to potential, other factors may play a cru- tials were set lower than the peak potential, no trace-
cial role in the formation of chain structure. What is crossing was observed [see Fig. 1(c±f), Figs. 2±4].
interesting is that the potential di€erence in the above However, the growth of polymer ®lms did occur.
example (0.25 V) is, coincidentally, almost the same as Although there is no doubt that the heterogeneous de-
the separation of the two waves in our case (0.24 V). position is initiated by the nucleation, the nucleation
process does not appear to be necessarily followed by
3.4. The `nucleation loop' the trace-crossing.
On the other hand, if the trace-crossing in the ®rst
In the voltammograms of conducting polymers, a cycle is attributed to the nucleation process, it should
frequently mentioned feature of the ®rst potential cycle not be observed in the second and the following cycles.
is the `nucleation loop' or `trace-crossing', which However, when switching potentials were set close to
appears when a freshly polished electrode is used and the peak potential, we observed the so-called `nuclea-
the scan is reversed at a potential close to the peak po- tion loops' even after several cycles, when the electrode
tential. Such behavior is similar in respect to the elec- was totally covered with polymer. As we can see in
trochemical deposition of metal on a foreign substrate, Fig. 1(a), the loop is still present in at least the second
in which an overpotential is required for nucleation cycle.
and then further growth of the metallic layer occurs at Besides, further experiments revealed that the trace-
the characteristic redox potential of the metal, leading crossing could return after disappearing. In Fig. 8 are
to a trace-crossing on the reverse sweep. It is proposed the results from the potential scans, carried out in-
that in the deposition of conducting polymers the itially between ÿ0.96±0.99 V (Fig. 8a). The trace-cross-
 M. Zhou, J. Heinze / Electrochimica Acta 44 (1999) 1733±1748 1743

Fig. 9. Trace-crossing in di€erent cases (®rst two scans). Degassed acetonitrile solutions, 0.1 M TBAPF6, 1 wt% water, temperature
ÿ208C. (a) 0.001 M pyrrole, 100 mVs ÿ 1, ÿ0.53±1.37 V; (b) 0.01 M pyrrole, 100 mV s ÿ 1, ÿ0.53±1.17 V; (c) 0.01 M pyrrole, 20
mVs ÿ 1, ÿ0.53±1.17 V; (d) 0.1 M pyrrole, 100 mVs ÿ 1, ÿ0.53±1.07 V; (e) 0.1 M pyrrole, 20 mVs ÿ 1, ÿ0.53±1.07 V; (f) 0.5 M pyrrole,
100 mV s ÿ 1, ÿ0.53±1.07 V; (g) 1.0 M pyrrole, 100 mV s ÿ 1, ÿ0.53±1.17 V.

ing occurred in the ®rst cycle, as it usually does.
Although the situation in the second cycle was equivocal
in this case Ð the forward trace and the backward trace
overlapped in the potential range of interest Ð from the
third cycle on, the trace-crossing was de®nitely absent.
After the sixth cycle, as the switching potential was
raised to 1.09 V in the seventh cycle, the trace-crossing
reappeared, as can be seen in Fig. 8(b). Moreover, when
the switching potential was further increased to 1.19 V
in the eighth cycle, the trace-crossing occurred once
again (Fig. 8c). It is of great interest that the electrode
was already completely coated with a polymer ®lm after
six potential cycles in the region of ÿ0.96±0.99 V.
The facts that polymer ®lm can grow without the in-
itial `nucleation loop', and that the `nucleation loop'
can emerge even after the electrode becomes comple-
tely polymer-coated, are inconsistent with the inter-
pretation based on the nucleation-and-growth
mechanism [33±35] of conducting polymers. Thus, the
nature of the trace-crossing is a matter that still needs
to be explained.
Further experiments indicated that the occurrence of
trace-crossing depends on several factors. The CVs in
Fig. 9 show the ®rst two cycles in solutions of di€erent
monomer concentrations. At an extremely low pyrrole
concentration (0.001 M), neither the ®rst nor the
1744 M. Zhou, J. Heinze / Electrochimica Acta 44 (1999) 1733±1748

Fig. 10. Repetitive sharp oxidation wave on the backward

scans. Degassed acetonitrile solution, 0.5 M pyrrole, 0.1 M
TBAPF6, 1 wt% water, temperature ÿ208C, scan rate 100 mV
s ÿ 1, ÿ1.01±1.09 V.

follow-up cycle gave rise to the trace-crossing (Fig. 9a).

What is more, the current levels of the second and the
follow-up scans were, at the switching potential, less
than that of the ®rst scan. At a higher pyrrole concen-
tration (0.01 M), we observed the normal behavior,
namely, the trace-crossing appeared in the ®rst for-
ward-reverse cycle, but disappeared in the second
cycle, when the scan rate was set at 100 mV s ÿ 1
(Fig. 9b). However, if the scan rate was changed from
100 to 20 mV s ÿ 1, the trace-crossing appeared in both
the ®rst and second cycles (Fig. 9c). There is no doubt
that more nucleation centers and deposit were formed
in the case of slower scan rate (Fig. 9c). When the pyr-
role concentration was even higher (0.1 M), trace-
crossing took place in the ®rst and second cycles at
Fig. 11. Studies of the oxidation wave on the backward scans
both scan rates of 100 and 20 mVs ÿ 1 (Fig. 9(d and Ð from solution or from newly formed polymer? Degassed
e)); and the lower scan rate resulted in the more acetonitrile solution, 0.1 M TBAPF6, temperature ÿ208C,
obvious crossing of traces (Fig. 9e). Our experiments scan rate 100 mV s ÿ 1. (a) and (c) 0.5 M pyrrole, 1 wt%
with a monomer concentration of 0.5 M enabled us to water, ÿ0.51±1.09 V. The scan stopped at the switching po-
gain more insight into the nature of the trace-crossing. tential 1.09 V on the third forward scan. (b) After (a), the
In Fig. 9(f), the CV is conspicuous by a strange peak- same electrolytic solution was shaken, 1.09± ÿ 0.51 V. (c)
like wave (indicated as P1) on the second reverse scan After (c), in pyrrole-free solution, 1.090ÿ0.51 V.
at about 0.96 V. It remained on the subsequent reverse
scans (Fig. 10). The nature of this peak is yet to be least one, if not the only, reason for the higher current
explained. Nevertheless, it leads us to believe that such on the reverse scan. Although the P1 can be more
a strong oxidation reaction on the reverse scan is at easily observed in solutions with a higher concentration
 M. Zhou, J. Heinze / Electrochimica Acta 44 (1999) 1733±1748
of monomers, increasing the monomer concentration
did not always make the phenomenon more obvious, as
shown in Fig. 9(g), where monomer concentration was
as high as 1.0 M.
Fig. 12. Studies of the oxidation wave on the backward scans:
potential scan starting from the positive side. Degassed aceto-
nitrile solution, 0.5 M pyrrole, 0.1 M TBAPF6, 1 wt% water,
temperature ÿ208C, scan rate 100 mV s ÿ 1. (a) 1.39± ÿ0.51±
1.09 V; (b) 1.29± ÿ0.51±1.09 V; (c) 1.19± ÿ0.51±1.09 V; (d)
1.09± ÿ0.51 V.
1745
Due to simultaneous polymer deposition on the
electrode, one may legitimately ask whether the P1 on
the reverse scan [Fig. 9(f) and Fig. 10] comes from
the oxidation of any species in the solution or from
the newly deposited polymer (or solid oligomer) on
the electrode.
The answer to this question was obtained from the
experiments in which the potential sweep was stopped
at the switching potential 1.09 V (Fig. 11(a and c)] on
the third forward scan, and then further investigations
were made in two protocols. In one protocol, the cell
was shaken for a while so that the reaction zone
around the electrode became the same as the bulk sol-
ution. Then, the potential scan was restarted from 1.09
V to the negative side. The P1 peak disappeared in this
case (Fig. 11b). This is solid support for assigning the
peak to the oxidation of species in the solution. In
another protocol, after the third potential scan was
stopped at 1.09 V (Fig. 11c), the electrolytic solution
in the cell was poured out. The cell was washed several
times with pure acetonitrile and 0.1 M TBAPF6 aceto-
nitrile solutions and then re®lled with the pyrrole-free
solution. In all the operation steps, the polymer-coated
electrode stayed in the Ar-protected cell without any
possible contact with atmosphere. The new potential
scan was then made in the pyrrole-free solution from
1.09 to ÿ0.51 V. The result shown in Fig. 11(d) indi-
cates again unequivocally that the strange peak in
question is not from the existing polymer.
Fig. 13. Studies of the oxidation wave on the backward scans:
the independence of the peak on the scan direction. Degassed
acetonitrile solution, 0.5 M pyrrole, 0.1 M TBAPF6, 1 wt%
water, temperature ÿ208C, scan rate 100 mV s ÿ 1. First two
scans: ÿ0.51±1.09 V; third scan: ÿ0.51±1.24 V.
1746 M. Zhou, J. Heinze / Electrochimica Acta 44 (1999) 1733±1748
More information pertaining to the P1 peak, was
found in the results shown in Fig. 12, in which the po-
tential sweep was initiated at potentials higher than 1.0
V. When the starting potentials were set at 1.39, 1.29
and 1.19 V, a small peak (P2) and a broad wave were
always observed after the initial quick drop of current
on the ®rst scan. Then, after the scan was switched at
1.09 V, the P1 peak appeared as it usually does. There
is no doubt that the initial quick current drop is due
to the depletion of monomer in the reaction zone. P2
and the accompanying broad wave are the conse-
quence of follow-up reactions. Since the P2 peak
appears after a short reaction period and has no de®ni-
tive peak potential value, we believe that P1 is identical
with P2 in nature. At a de®ned scan rate, once a cer-
tain amount of monomer is oxidized, the follow-up
electrochemical reactions will take place, showing the
P2 (or P1) peaks and the broad wave as well. In this
context, such a peak should also be observed on the
forward scan from lower potential to higher potential,
if the scan is not switched back too early. This is
proved by Fig. 13, in which the peak (indicated as P3)
on the third forward scan is actually the P1 on the sec-
ond backward scan.
The concentration of 0.5 M pyrrole provides a better
observation of the anodic current from the follow-up
reaction. Under other conditions, the follow-up reac-
tions in pyrrole polymerization process is also certain,
but whether a sharp peak, like P1, P2 and P3, and the
trace-crossing emerge depends on the conditions dis-
cussed in Fig. 9.
In conclusion, the electrochemical follow-up reac-
tions give rise to an additional anodic current. If the
scan is reversed in the time scale in which the follow-
up reactions occur, the current on the backward scan
will be possibly higher than the current on the former
immediate forward scan in certain potential range.
This is one of the reasons for the trace-crossing in
potentiodynamic electropolymerization, at least in the
case of pyrrole.
Early in 1970s, Feldberg [51] demonstrated theoreti-
cally the possibility of trace-crossing in certain ECE-
type reactions. Some experimental examples of trace-
crossing in the voltammograms of organic and organo-
metallic reactants can be found in the literature [52±
58]. In his review, Evans [59] also discussed in detail
trace-crossing in an ECE reaction scheme involving
electron-transfer reactions in solution. In all these
examples the trace-crossing has nothing to do with any
deposit on the electrode. Very recently, it was shown
that during the electropolymerization of
methylthiothiophenes trace crossing results from the
slow formation of a neutral tetramer in the di€usion
layer at the electrode and its subsequent oxidation to
its mono- and dication. Although the oxidation of the
monomeric starting species stops in the reverse scans,
the tetramer is still formed on account of the slow kin-
etics of the dimer-dimer coupling in front of the elec-
trode and, therefore, an anodic current, generated by
the mono- and dication formation of the tetramer, can
be observed at potentials negative to that of the
`monomer' oxidation [60].
While discussing trace-crossing, we should point out
another feature of CVs that many researchers of con-
ducting polymers tend to ignore. In the potentiody-
namic growth of conducting polymers, the current at a
certain oxidation potential increases from cycle to
cycle; in other words, the potential required to reach a
certain oxidation current decreases with each successive
scan. From general observations and experiments
using electrodes coated with di€erent thickness of the
same doped PPy ®lm, we established that the oxidation
current at a de®ned potential was dependent on the
amount of the existing polymer ®lm on the electrode.
The thicker the existing polymer deposition is, the lar-
ger the current of monomer oxidation. One subject of
speculation is the increase of the electrode surface
available for electron transfer. At the early stage of de-
position, the initial nuclei and the roughness of the
polymer formed, actually increase the electrode-sol-
ution interface available for electron transfer, and
hence contribute to the enhancement of monomer oxi-
dation. However, the nuclei and surface roughness is
signi®cant only in the ®rst few cycles. They do not
play any role once the electrode is completely covered
with polymer. Whatever deposition mechanism is con-
sidered, it is very dicult to imagine the electrode area
always on the increase.
Taking the already deposited polymer into consider-
ation, we propose a mechanism in which oxidation
takes place not only on the solution-electrode interface,
but also in the polymer matrix. There is evidence for
the swelling ability of PPy in acetonitrile [61] and the
swollen polypyrrole matrix may contain pyrrole mol-
ecules. Thus, the oxidation of pyrrole molecules in
polymer matrix is likely, especially on the newly
formed surface layer. In the potential scan exper-
iments, the contribution to the anodic current from
interface oxidation is almost constant after the elec-
trode is entirely polymer-coated and surface state no
longer changes, whereas the contribution to the anodic
current from matrix oxidation increases with depo-
sition. The thicker the polymer layere, the greater the
monomer amount in the polymer matrix, and the
stronger the total oxidation current, will be.
Accordingly, the current in the range of monomer oxi-
dation always increases with the number of scans.
However, due to the limits imposed by the swelling
pro®le and the increasing resistance of deposit, the
increment in the current at the switching potential,
after subtraction of the ever-growing current plateau,
becomes smaller and smaller.
 M. Zhou, J. Heinze / Electrochimica Acta 44 (1999) 1733±1748
The above two cases of monomer oxidation can also
be used to elucidate trace-crossing. As explained
above, monomer molecules di€use into the polymer
matrix due to the swollen structure of the polymer ®lm
produced on the forward scan. This enhances the
monomer oxidation on the reverse scan, producing a
current higher than that on the forward scan in the
same cycle. Because the relative increase in the amount
of polymer on the initial scans is bigger than that on
later scans, trace-crossing occurs in the ®rst cycles and
disappears in the later cycles.
The monomer oxidation in the polymer matrix can
explain why there is no trace-crossing when the switch-
ing potential or monomer concentration is very low,
and why, after disappearing, trace-crossing returns at
higher switching potentials (Fig. 8). If the relative
change in the amount of deposited polymer after each
scan is too small (as in the cases of low switching po-
tential and low monomer concentration, or when the
existing polymer ®lm is already thick), the monomer
oxidation in the matrix cannot make a substantial con-
tribution to the increase in total oxidation. Raising the
switching potential can generate a bigger relative
change in the amount of polymer and increase the con-
tribution of monomer oxidation in the polymer matrix,
leading to a higher current in the immediate reverse
scan.
The overall electrochemical polymerization of con-
ducting polymers comprises complex homogeneous
and heterogeneous reactions and processes, and a net
electrochemical response may be the result of many
factors. We do not rule out the nucleation-and-growth
mechanism as an explanation for trace-crossing.
However, it cannot explain all the facts described
above. Though we need further study, we feel that the
above suggestions, i.e. the possible oxidation of oligo-
mers to higher charging levels, the increase in the elec-
trode-solution interface at the initial stage of
deposition and the swollen structure of polymer ®lm,
can improve our understanding of trace-crossing.
4. Conclusion
Both the potentiodynamic and galvanostatic synth-
eses of polypyrrole at extremely low reaction rates
enable us to ®nd an additional oxidation wave at ca.
ÿ0.23 V, which is more negative than the normal oxi-
dation wave of polypyrrole. The well-de®ned polymer
showing only the sharp oxidation peak at ÿ0.23 V can
be galvanostatically synthesized at extremely low cur-
rent levels. Although the potential determines the char-
ging levels of oligomer radical cations and,
accordingly, in¯uences the chain-length of the resulting
polymer, it does not necessarily follow that changing
the potential in a certain range can always bring about
1747
the expected change in polymer structure. In some
cases, the change of chemical environment due to
di€erent reaction rates may have a more profound
impact on the properties of resulting polymers.
We have displayed many di€erent shapes of CVs of
PPy doped PF6ÿ . Hence, one point our experiments
unambiguously established is the structural diversity of
PPy. It must be emphasized that in the studies of con-
ducting polymers the results obtained under widely
varying conditions cannot be uncritically used to draw
universal conclusions, for a small change in a single ex-
perimental variable may greatly in¯uence the proper-
ties of the resulting polymer. We hope the opinions
stated here will shed some light on some controversial
issues.
The nucleation-growth mechanism can explain trace-
crossing in the ®rst potential cycle, but not all trace-
crossing phenomena. The follow-up reactions and the
swelling property of existing polymer should also be
taken into account in interpreting trace-crossing.
Acknowledgements
MZ is grateful to the Alexander von Humboldt
Foundation for an Alexander von Humboldt Research
Fellowship. The ®nancial support of the Fonds der
Chemischen Industrie is gratefully acknowledged.
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