Synthetic Metals 150 (2005) 101–105

Oxidative electropolymerization of pyrrole

from neat monomer solution
Patricia Ann Mabrouk ∗
Department of Chemistry and Chemical Biology, Northeastern University, Boston, MA 02115, USA

Received 5 October 2004; received in revised form 27 January 2005; accepted 27 January 2005
Available online 3 March 2005

Abstract

Oxidative electrochemical polymerization of pyrrole at gold, indium doped tin oxide on glass, and stainless steel type 304 was accomplished
from neat monomer solution containing only supporting electrolyte (0.05–0.3 M n-tetrabutyl ammonium perchlorate, n-tetrabutyl ammonium
hexafluorophosphate, or n-tetrabutyl ammonium tetrafluoroborate) by multiple scan cyclic voltammetry. The results presented demonstrate
that thick (>1–14 ␮m), stable, highly conductive (up to 0.6 S/cm) polypyrrole films can be readily prepared on a wide range of electrode
substrates using this simple electrochemical method.
© 2005 Elsevier B.V. All rights reserved.

Keywords: Electrochemistry; Conducting polymer; Polypyrrole; Cyclic voltammetry

1. Introduction layer fluid properties. Subsequently, Murray and coworkers

Due to their light weight, high conductivity, good stabil-
ity and redox state-dependent physico-chemical properties
such as color and volume, intrinsically conducting polymers
(ICPs) such as polypyrrole (PPy), polyaniline, and polythio-
phene continue to be actively investigated [1,2]. Synthesis
of conducting polymers can be accomplished chemically or
electrochemically usually from dilute aqueous or nonaque-
ous solutions of the relevant monomer. Polypyrrole is one
of the most frequently investigated ICPs [3]. PPy is easy to
synthesize both chemically and electrochemically, exhibits
good electrical conductivity, and is relatively stability under
ambient conditions.
Several years ago, White and coworkers investigated the
electrochemistry of neat redox liquids in the absence of any
added inert solvent [4–7]. Electrochemistry in neat redox liq-
uids was shown to have several advantages, including a wide
voltage window when compared to water and other com-
monly used electrochemical solvents and unique transport
∗ Tel.: +1 617 373 2845; fax: +1 617 373 8795.
E-mail address: p.mabrouk@neu.edu.
[8] demonstrated that electropolymerization of aniline and
pyrrole could be accomplished from neat solutions. How-
ever, the authors did not characterize the resulting products
that they believed to be oligomers. In view of the growing
importance of ICPs, we wish to report the results of pre-
liminary studies demonstrating that thick, conductive, sta-
ble films of intrinsically conducting polymers, here, specifi-
cally, polypyrrole, can be readily synthesized electrochemi-
cally from neat monomer in the absence of an inert diluting
solvent.
2. Experimental
2.1. Reagents
Sodium perchlorate (Aldrich), n-tetrabutyl ammonium
perchlorate (TBAClO4 ; 99+%, Alfa Aesar), n-tetrabutyl am-
monium hexafluorophosphate (TBAPF6 , >99%, Sigma), and
n-tetrabutyl ammonium tetrafluoroborate (TBABF4 ; Alfa
Aesar) were purchased as A.C.S. analytical grade or better
and were used as received. Pyrrole (98%, Sigma) was distilled

0379-6779/$ – see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.synthmet.2005.01.011
102 P.A. Mabrouk / Synthetic Metals 150 (2005) 101–105
and stored in the dark under nitrogen at 5 ◦ C until use. Gold
foil (0.002 in thick, 99.95%, Alfa Aesar), stainless steel foil
(type 304, 0.001 in thick, Alfa Aesar) and indium tin oxide on
glass (Rs , 4–8
, Delta Technologies) were used to construct
the homemade working electrodes used in this study.
2.2. Electrodes
ITO/glass electrodes were prepared by wrapping a piece
of copper wire around the top of one side of a 5 mm × 5 mm
square of ITO/glass and then applying silver epoxy to estab-
lish good electrical contact between the surface of the ITO
and the copper wire touching it. The exposed copper wire
and silver epoxy were then coated with insulating epoxy to
ensure that only the exposed ITO surface would serve as the
electrode.
The Au and stainless steel type 304 (ss-304) working
electrodes were cleaned by gentle abrasion with alumina
and diamond polish. These electrodes were then rinsed with
distilled water, sonicated in a dilute solution of Alconox® ,
rinsed again with distilled water, and then briefly air-dried.
ITO/glass working electrodes were first rinsed with analyti-
cal grade methanol and acetone then sonicated in Alconox® ,
rinsed with distilled water and finally briefly air-dried. All
Au and ITO/glass working electrodes were characterized by
cyclic voltammetry (CV) at 100 mV/s using 2 mM potassium
ferricyanide in 1.0 M KNO3 prior to use. Ep was typically
<105 mV.
2.3. Electrochemical Instrumentation
Cyclic voltammetry experiments were conducted using a
Bioanalytical Systems (BAS) 100B electrochemical work-
station.
2.4. Electrochemical synthesis
Polypyrrole (PPy) films were electrochemically synthe-
sized by multiple scan cyclic voltammetry using 2 mL
aliquots of freshly distilled pyrrole containing the desired
electrolyte, either n-tetrabutyl ammonium perchlorate, n-
tetrabutyl ammonium hexafluorophosphate, or n-tetrabutyl
ammonium tetrafluoroborate. Three electrolyte concentra-
tions were investigated: 0.05, 0.15, or 0.30 M. A 10 mL
beaker served as the single compartment electrochemical
cell. Working electrodes were homemade from 5 mm × 5 mm
squares of gold foil, ITO/glass, or stainless steel foil, type
304. An Ag/AgCl (3 M NaCl; Bioanalytical Systems) elec-
trode served as the reference electrode and a homemade Pt
gauze flag (1 cm × 1 cm; 100 mesh, 99.9%, Aldrich) was used
as the counter electrode. The working electrodes were typi-
cally cycled for 40–120 cycles between 1000 and −1000 mV
versus Ag/AgCl (3 M NaCl; BAS) at 100 mV/s in order to af-
fect electropolymerization. All experiments were performed
at room temperature.
2.5. Electrochemical characterization
Once polymerization was accomplished the polypyrrole-
coated working electrode was removed from the electro-
chemical cell, rinsed generously with acetone, methanol, and
deionized water. The electrode was then characterized by
CV in the potential range from +1000 to −1000 mV versus
Ag/AgCl (3 M NaCl) at a scan rate of 100 mV/s in aqueous,
monomer-free 1.0 M potassium nitrate solution.
2.6. Electrical conductivity
The electrical conductivity of polypyrrole films prepared
using the above protocol was evaluated using the van der
Pauw method [9]. 5 mm × 5 mm squares of polypyrrole
films were lifted from the working electrode using Scotch®
heavy duty mounting tape. Colloidal silver liquid (Ted Pella)
was used to facilitate good electrical contact between four
0.005 in. diameter (99.99%, Alfa Aesar) gold wires and the
four corners of the polymer film. The gold wires were sol-
dered using indium metal (low melting) to four pins of a
14-pin low profile IC socket (Jameco Electronics). A con-
stant current of 8 ␮A was applied to two of the four pins and
the voltage across the remaining two pins was measured fol-
lowing the National Institute of Standards and Technology
protocol [9].
The average film thickness used in the calculation of the
electrical conductivity of the polypyrrole films was obtained
from the average of a minimum of three scans made at dif-
ferent positions on the polymer film (scan length: 2000 ␮m,
profile: hills, scan speed: medium, resolution: high, stylus
force: 10–30 mg) using a Dektak 3 ST profilometer equipped
with a 12.5 ␮m diameter stylus. The average variation in any
three thickness measurements for any one polymer film was
less than 22%.
2.7. Atomic force microscopy (AFM)
PPy film morphology was investigated ex situ using a Que-
sant Q-scope 350 atomic force microscope operating in tap-
ping mode. Noncontact NSC-16 silicon cantilever tips were
used. Micrographs were minimally processed using streak
removal when appropriate. Images were obtained by scan-
ning 22 ␮m × 22 ␮m regions at a scan rate of 1.5 Hz. Three
separate regions of each polymer film were characterized in
order to verify that the AFM images were representative of
that sample. All AFM images are shown in the 3D height
mode. Bright colors indicate higher regions on the sample
while darker colors indicate lower regions on the sample.
3. Results and discussion
Oxidative electrochemical polymerization of pyrrole at
gold, ITO/glass, and stainless steel type 304 (ss-304) has
been accomplished from neat monomer solution containing
 P.A. Mabrouk / Synthetic Metals 150 (2005) 101–105 103

Fig. 1. Electropolymerization of polypyrrole at Au from neat pyrrole containing 0.3 M TBAClO4 at 100 mV/s between 1.0 and −1.0 V vs. Ag/AgCl (3 M
NaCl). The first 10 cycles are shown.

only added electrolyte (0.05–0.30 M n-tetrabutyl ammonium
perchlorate, n-tetrabutyl ammonium hexafluorophosphate, or
n-tetrabutyl ammonium tetrafluoroborate) by multiple scan
cyclic voltammetry.
Representative data for the electropolymerization of pyr-
role containing 0.3 M TBAClO4 at Au are shown in Fig. 1.
On the first anodic scan, a single anodic wave was typically
observed at relatively high potential. This is consistent with
oxidation of pyrrole monomer to produce the radical cation.
Upon reduction, two cathodic waves were observed consis-
tent with reduction of the radical cation and the oxidized
polymer, respectively. On the second and all subsequent ox-
idative scans, a new anodic wave is observed that is consistent
with oxidation of the newly formed polymer. With each suc-
cessive scan, the peak current associated with both the anodic
and cathodic waves of the polymer increased consistent with
the growth of the polymer film. The growth rate of the poly-
mer was typically constant for about the first ten scans and
then was observed to decrease. Nonetheless, polymerization
as reflected by an increase in peak current persisted for at
least 120 scans. With repeated cycling, an increasingly thick,
dark film deposited on the working electrode. Films up to
14 ␮m thick were readily prepared after only 40 cycles.
PPy-coated electrodes prepared using the method de-
scribed above were then characterized by cyclic voltamme-
try in pyrrole-free aqueous solution containing 1 M potas-
sium nitrate. Fig. 2 shows a representative cyclic voltam-
mogram for the PPy film whose synthesis is depicted in
Fig. 1 after removing the electrode from the monomer solu-
tion and rinsing it with acetone, methanol, and deionized wa-
ter. Voltammograms for PPy films electropolymerized from
neat monomer solution exhibit fairly well-defined oxidation
and reduction waves. The peak current for both the anodic and
cathodic waves displays a linear dependence on the scan rate
(20–200 mV/s; r2 ≥ 0.99; not shown). This behavior is con-
sistent with a surface-confined redox process. Peak shapes

Fig. 2. Cyclic voltammogram showing the first two cycles obtained for the polypyrrole film polymerized in Fig. 1 which had been rinsed with acetone, methanol,
and deionized water, air-dried and subsequently placed in 1.0 M potassium nitrate solution. An Ag/AgCl (3 M NaCl) reference electrode and a Pt gauze counter
electrode were used. The scan rate is 100 mV/s.
104 P.A. Mabrouk / Synthetic Metals 150 (2005) 101–105

Fig. 3. Graph showing the dependence of the average PPy film conductivity as a function of the concentration of n-tetrabutylammonium perchlorate used in the
electropolymerization at ss-304 (squares), Au (circles), and ITO/glass (triangles). Each data point on the graph represents the average electrical conductivity
obtained in the study of a minimum of three independently prepared polypyrrole films.

and peak currents were not observed to change or dimin-
ish with repeated cycling – up to 1 h – of the PPy-coated
electrodes in aqueous electrolyte solution. This behavior is
consistent with a chemically reversible redox process.
3.1. Conductivity
The electrical conductivity of PPy films prepared on Au,
ss-304, and ITO/glass has been measured using the Van de
Pauw method [9]. Film conductivities typically ranged be-
tween 0.02 and 0.61 S/cm. The highest electrical conductiv-
ity was obtained for PPy/ss-304 films prepared using 0.05 M
TBAClO4 —on average 0.61 S/cm (n = 3).
As shown in Fig. 3, electrical conductivity was found
to be strongly dependent on the concentration of the elec-
trolyte used in the electrosynthesis and on the nature of
the electrode substrate. On the two metal electrode sub-
strates investigated (gold and stainless steel), a strong nega-
tive correlation was observed between the concentration of n-
tetrabutylammonium perchlorate used in the electrosynthesis
and the conductivity of the polypyrrole films produced. The
most conductive polypyrrole films were those that were pre-
pared using 0.05 M TBAClO4 . However, the concentration
of the electrolyte did not affect the electrical conductivity of
the polypyrrole films prepared on ITO/glass. The electrical
conductivity of the polypyrrole films did not appear to vary
with film thickness at least for films with an average thickness
between 1 and 14 ␮m.
The electrical conductivity of these films is a factor of 5–10
lower than that of polypyrrole synthesized electrochemically
from aqueous or nonaqueous solvents [3,10,11]. The sensi-
tivity of the resulting polymer conductivity to the nature of
the electrode substrate used in its preparation (metal oxide
as versus metal) is significant and suggests that the electrode
itself plays an important role in determining the mechanism
of electropolymerization.
The electrical conductivity of PPy films prepared using
this method is fairly stable under ambient conditions over a
period of several months. The stability of the electrical con-
ductivity of five polypyrrole films grown on ITO/glass or
stainless steel from pyrrole solutions containing TBAClO4
was investigated after approximately 3 months. On average
the electrical conductivity of these films decreased by 49%.
No significant difference was observed in the stability of
the films originally grown on ITO/glass as compared to that
grown on ss-304. The stability of the conductivity over this
time period for PPy films prepared using the solvent-free
method compares favorably with that of chemically synthe-
sized chloride-doped polypyrrole for which an 80% decrease
in electrical conductivity had been reported to occur over a
3-month period for polymer stored under ambient conditions
[12].

Fig. 4. AFM images showing the surface of Au (left), ITO/glass (middle), and stainless steel type 304 (right) substrates coated with electrosynthesized
polypyrrole. Scan rate 1.5 Hz. All three films were prepared voltammetrically at 100 mV/s from pyrrole containing 0.05 M TBAClO4 .
 P.A. Mabrouk / Synthetic Metals 150 (2005) 101–105
3.2. Film morphology
Polymer morphology was probed using tapping-mode
atomic force microscopy. As shown in Fig. 4, the morphology
of the relatively thick (>1 ␮m) polypyrrole films electrosyn-
thesized from monomer containing TBAClO4 was generally
globular (left and center) though some films (right) exhib-
ited the characteristic “cauliflower-like” morphology [13].
Surface features varied in size from 0.5 to 3 ␮m in diame-
ter between films. Neither the morphology nor the size of
the surface features appeared to correlate with the electrical
conductivity, thickness of the PPy films, or the nature of the
electrode substrate on which the films were electropolymer-
ized (Au, ITO/glass, or stainless steel type 304). The fact that
globular rather than cauliflower-like morphologies appear to
be favored may suggest that polymer growth is constrained
to certain preferred directions in neat monomer solution as
a consequence of the unique charge transport properties of
concentrated redox liquids [5].
4. Conclusion
In summary, we have demonstrated that thick, conduc-
tive films of polypyrrole can be readily electrosynthesized
from neat monomer solution on a wide range of electrode
substrates. The simplicity of the method, the potential cost
savings coupled with its environmentally friendly nature – the
approach eliminates the use of inert solvent – make further
research into this new method very attractive.
Acknowledgements
PAM gratefully acknowledges the assistance of Miss
Jamie Mayer and Miss Rachna Badlani in the early stages
105
of this project. She also wishes to recognize the support
of the Northeastern University Office of Technology Trans-
fer and to thank Dr. Sinan Muftu and Mr. Peter Ryan
of the Department of Mechanical Engineering at North-
eastern University for access to and assistance with the
profilometer and AFM instruments and Drs. Don Heiman
and Yajie Chen and Mr. Taiyang Chen of the Department
of Physics at Northeastern University for access to and
assistance in making the electrical conductivity measure-
ments.
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