Advances in Ma terials Physics and Che mist ry, 2012, 2, 89-91
doi:10.4236/ampc.2012.24B024 Published Online December 2012 (htt p://www.SciRP.org/journal/ampc)
Polypyrrole Micro/Nanostructure Prepared Using Azo Dyes
wit h D i f fe rent Substit uents
Dusan Kopecky, Jitka Skodova, Martin Vrnata, Premysl Fitl
Department of Physics an d Mea sur ements, Institute of Chemical Technology, Prague, Czech Repub l ic
Received 2012
ABSTRACT
This contribution deals with simple way of polypyrrole structure modification. Using azo dyes in polymerization reaction as
soft-template with similar molecular structure but different type and distribution of substitution groups lead to formation of
one-dimensional and newly also three-dimension al p ol ypyrrole micro /n anost ru ctures. These str uct ur es are ch aract eri stic with geome-
trical symmetry and uniformity. Geometry of prepared structures was studied by scanning electron microscopy (SEM) and by me-
thods of image analysis; nanotubes are hundreds of nm in diameter and units of µm in length, new tree-dimensional structures have
units of µm in diameter. Infrared spectra (ATR-FTIR) confirmed that azo dyes work only as intermediate supporting structures
without reaction with polypyrrole.
Keywords: Polypyrrole; Nanostructure; Azo Dye; Soft-template
1. Introduction
Conducting polymers (CP) are popular organic semiconducting
materials which have been attracting attention since discovery
of their electrical conductivity in the 1970s. Usually the con-
ductivity of CP is around tenths or units of S·cm-1 [1] and
charge transfer is predominantly directed by variable range
hopping mechanism due to highly disordered physical structure
with predispositions to slowly self-degradation of conjugation
by atmospheric oxygen or water vapors. For some application
as plasti c electronic, sensors or actuato rs there should be better
to dominate intrinsic band conductivity with long term stability
[2] .
Last decade of intensive research showed some remarkable
properties of CP – namely their ability to organize themself
under certain conditions into highly ordered systems. CP are
able to create uniform structured shapes with micrometric or
even nan ometric sizes (nanostructures), for example nanotubes,
nanowires, nanorods [3] . This could be the potential future
solution of their designated disadvantages and further, there is
possibility to obtain material with higher specific surface.
These known shapes are often collectively called 1-D struc-
tures of conducting polymers. The description is based on a
widely used simplification which assumes that structural prop-
erties of 1-D polymer structure are predominantly determined
by its longest dimension (which is always orders of magnitude
larger than the other two).
1-D structured CP could be synthesized using either template
or special template free procedures. There are two means of
template synthesis, the so-called hard and soft template method.
The hard template method uses zeolites and membranes as a
hard template, but the necessity of template removing after
synthesis is very limiting.
On the other side the so called soft-template synthesis, using
intermediate supporting structures of auxiliary substances (mi-
cellar systems, surfactants etc.), brings many advantages: (i)
change in temperature synthesis, time synthesis or molar ration
of reactants can influence the geometric dimension of the pre-
pared 1-D structures, (ii) it is effective, cheap and simple me-
thod, (iii) template autonomously degrades after the reaction is
over and therefore it is easily removed from solution without
damaging of prepared polymer nanostructure [4].
Soft-template method presented here is based on supposed
reaction of azo dye and oxidant which create temporary sup-
porting structure. After addition of the monomer (in our case
pyrrole), polymer (polypyrrole) forms on its surface resulting in
less or more ordered systems. Some of them should be consi-
dered as 3-D structures thanks to their spatial symmetry. All
uses only two basic types of azo dye molecular structures as a
soft-template; substantial difference is in the type of azo dye
substituents and their position on the skeleton of molecule.
The molecular structure of azo dyes significantly affects the
structure of prepared structured polymer. Therefore it must be
reflect strength, number and distance of ligands in a molecule
of azo dye, acid obasic p roperties, degree o f molecule pl anarity,
etc.
2. Experimental
Pyrrole, ferric chloride (FeCl3), Methyl Orange, Methyl Red,
Congo Red, Acid RED 1, Orange G, Sunset Yellow FCF and
Tropaeolin O Sodium Salt (all purchased from Sigma-Aldrich)
were used as received without further modifications. The mo-
lecular s tructures of azo dyes are shown in Figure 1.
The s ynthesis process of the structured PPY was as follows:
ferric chloride (oxidant) was dissolved in 200 ml of 5 mM solu-
tion of azo dye and deionized water. Then 700 µl pyrrole mo-
nomer was added dropwise in the first two hours of synthesis to
the solution. Molar ratio of reactive monomer : oxidant : azo
dye was 10:10:1 for all synthesis. The solution was tempered at

D. KOPECKY ET AL.
90
5°C and stirred during synthesis at constant speed. Due to com-
plex structure of prepared PPY, remnants of a template must be
removed by Soxhlet extraction. The prepared PPY was ex-
tracted with ethanol until extraction reagent was colorless (up
to one week). The prepared structures of PPY were dried at
45°C in vacuum drier.
For comparison unstructured PPY was also synthesized.
Molar ration of reactants (oxidant: monomer) was 1:1 in
aqueous environment.
The structures of prepared PPY were observed by Scanning
Electron Microscope (SEM) JEOL model JSM-7500F. Struc-
ture of prepared PPY was confirmed by Attenuated Total Ref-
lection Fourier Transform Infrared spectroscopy (ATR-FTIR)
BRUKER IFS 66v with diamond ATR attachment.
3. Results and Discussion
Characteristic shape of unstructured PPY is shown on SEM
image Figure 2(a). This sample was synthesized by standard
chemical p olymerization with out presence of azo dye. As seen,
unstructured PPY has characteristic fruticose formations that
create highly disor dered arr angement.
Figure 2 (b)-(h) show SEM images of structured PPY pre-
pared by the soft-template method using different azo dyes. It is
apparent that azo dyes, as an auxiliary substance, significantly
affect the structure of prepared PPY. The most evident is this
capabi lit y in th e case of Met h yl Oran ge, Acid Red 1 and Sun set
Yellow. In all these cases there are created symmetrical mi-
cro/nanostructures. Methyl Orange and Acid Red 1 contribute
to the formation of 1-D PPY structure. Di mension o f these PPY
nanotubes are approximately 80 nanometers in diameter and
Figure 1. Chemical structures of used azo dyes: a) Methyl Orange,
b) Methyl Red, c) Congo Red, d) Acid RED 1, e) Orange G, f) Sun-
set Yellow FCF, g) Tropaeolin O Sodium Salt.
Figure 2. Structures of PPY prepared by: a) without azo dye, b)
Methyl Orange, c) Methyl Red, d) Congo Red, e) Acid RED 1, f)
Orange G, g) Sunset Yellow FCF, h) Tropaeoli n O Sodium Salt.
hundreds of nanometers in length. Dimension of PPY nano-
tubes prepared from Acid RED 1 are approximately 340 nano-
meters in diameter and units of microns in length.
PPY synthesized in presence of Sunset Yellow FCF creates
brand new type of formations. There are o bserved symmet rical
3-D structures. Probably, the Sunset Yellow FCF molecule
allows creating more spatially-oriented complex of supporting
structure in polar solvent, due to suppressing of hydrophilic and
hydrophobic molecule polarization by SO3- polar groups.
Other azo dyes with the same molecular structure – Orange
G, Tropaeolin O – are more polarized due to spreading out of
polar substitution groups on and in polar solvent they are prob-
ably forced to create poorly soluble phase which suppress sup-
porting structure formation. In this case PPY has the same
structure as unst ructured sample. Last sa mple p repared in C on-
go Red is comprised from “crushed stone” like formations.
Further important observation concerns degree of structure
spreading in the whole volume of native liquor. Methyl Orange
is the only (from all tested azo-dyes) soft-template which
creates micro/nanostructures in the entire volume and also at
different molar ratios (10:10:1, 10:10:0,5, 10:10:0,1). On the
other side Acid RED 1 and Sunset Yellow FCF create nano-
structures in insulated spatially distributed domains at higher
molar ratio only (10:10:1). This is probably connected with the
molecular structure of azo dye which affect still poorly under-
stand mechanism of supporting structure creation.
The main tas k of ATR-F TIR measu rement s was to veri fy the
chemical structure of prepared PPY and to detect potential re-
sidue of azo dye used during synthesis. Interpretation of the
spectra was focused on the region 1800 - 600 cm-1, the so called
“finger print area”. Interpretation of PPY spectra could be dif-
ficult because of variable degree of conjugation of PPY back-
bone and a large number of different types of disturbances
(non-linear shape of the polymer chain, oxidation by air oxygen,
etc.). Nevertheless, in all cases it was confirmed PP Y as a basic

D. KOPECKY ET AL.
91
Figure 3. Overview of ATR-FTIR spectra of PPY prepared in the
presence of: a) Methyl Orange, b) Methyl Red, c) Congo Red, d)
Acid Red 1, e) Orange G, f) Sunset Yellow FCF, g) Tropaeolin O
Sodium Salt.
unit of all formations (Figure 3). The unstructured PPY spec-
trum contains following characteristic peaks: 1527 cm-1 (C-C,
C=C stretching), 1427 cm-1 (C=C, C-N stretching), 1270 cm-1
(C-H, C-N in plane deformation), 1129 cm-1 (breathing vibra-
tion of the PY ring), 1086 cm-1 (C-H, N-H in plane deforma-
tion), 997 cm-1 (C-H in plane deformation), 956 cm-1 (C-C out
of plane deformation), 849 cm-1 and 727 cm-1 (C-H, N-H out of
plane deformation), 646 cm-1 (C-C out of plane deformation).
These peaks are evident in presented spectra of structured PPY.
Slight shifts in spectra cannot be attributed to direct chemical
reaction between pyrrole and azo dye, but only to changes in
degree of conjugation of polypyrrole chains. It is apparent that
used azo dye acts only as a supporting structure for forming
polymer structure and after polymerization it self-degrades.
4. Conclusion
This contribution deals with preparation of PPY micro/nanos-
tructures by soft-template method. As a soft-template seven
different azo dyes were used. Using Methyl Orange and Acid
RED 1 lead to formation of 1-D structures. New type (3-D
structure) of PPY structure was observed for Sunset Yellow as
soft-template.
5. Acknowledgements
This work was supported by Grant Agency of the Czech Re-
public (GAČR) projects No. P108/11/1298 and P108/12/P802
and also financial support from specific university research
(MSMT No. 21/2012).
REFERENCES
[1] N. V. Blinova, J. Stejskal, M. Trhová, J. Prokeš, M. Omastová,
“Polyaniline and polypyrrole: A comparative study of the prepa-
ration”, Eur. Polym. J., vol. 43, pp. 2331-2341, 2007.
[2] U. Lange, N. V. Roznyatovskaya, V. M. Mirsky, “Conducting
polymers in chemical sensors and arrays”, Anal. Chimica Acta,
vol. 614, pp. 1-26, 2008.
[3] X. Yang, Z. Zhu, T. Dai, Y. Lu, “Nanotubes via a reactive
self-degraded template”, Macromol. Rapid Commun.vol. 26, pp.
1736-1740, 2005.
[4] D. Zhang, Y. Wang, “Synthesis and applications of
one-dimensional nano-structured polyaniline: An overview”,
Mater. Sci. Eng., B, vol. 134, pp. 9-19, 2006.