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Preparation and characterization of poly(o-phenylenediamine)

microrods using ferric chloride as an oxidant


Xiaofeng Lu
a
, Hui Mao
a
, Danming Chao
a
, Xiaogang Zhao
a
, Wanjin Zhang
a,

, Yen Wei
b
a
Alan G. MacDiarmid Institute, Jilin University, Changchun 130012, P. R. China
b
Department of Chemistry, Drexel University, Philadelphia, PA 19104, USA
Received 4 April 2006; accepted 13 July 2006
Available online 1 August 2006
Abstract
Microrods of poly(o-phenylenediamine) (PoPD) were synthesized by a templateless method using ferric chloride as an oxidant. The microrod
morphologies of the resulting PoPD were confirmed by scanning electron microscopic (SEM) and transmission electron microscopic (TEM)
images. When the concentration of o-phenylenediamine (oPD) was 0.03 M, the microrods of PoPD had a diameter in the range of 0.52 m and a
length from 2 m to 20 m. It was found that the concentration of oPD monomer had much influence on the morphology of the obtained PoPD.
When the concentration of oPD was lower than 0.03 M, long microrods could be observed. However, when the concentration of oPD monomer
was higher than 0.12 M, the length of the microrods became very short and the diameter became bigger. Fourier transform infrared spectroscopy
(FTIR), UVvis absorption spectra and X-ray diffraction (XRD) were used to characterize the structure of the obtained PoPD microrods.
2006 Elsevier B.V. All rights reserved.
Keywords: Poly(o-phenylenediamine); Microrods; Ferric chloride
1. Introduction
In the past decades, conducting polymers have become well-
known because of its useful electronic, photonic, and electrolu-
minescence properties, as well as potential applications in elec-
trode materials, microelectronics, electrochromic materials and
antisepsis [13]. In recent years, one-dimensional nanostructures
including nanofibers, nanotubes, nanorods and nanobelts of
conducting polymers have been studied extensively. These 1D
nanostructured materials have distinctive geometries, and novel
physical and chemical properties, which are probably applicable
in nanodevices [4]. There are many methods to be developed for
synthesizing 1D conducting polymers. For example, a hard-tem-
plate based method to prepare 1D conducting polymers was first
investigated [57]. Micelles, surfactants, liquid crystals, thiolated
cyclodextrins and polyacids were also used as a soft-template to
prepare nanofibers and nanotubes of conducting polymers [8
14]. Recently, interfacial polymerization, dilute polymerization
and fiber seeding methods were developed to prepare PANI
nanofibers [1517]. However, the major disadvantage of PANI is
its insolubility in common organic solvents and its infusibility
because of its stiffness of the PANI backbone and the hydrogen-
bonding interactions between the amine moieties of adjacent
chains. Therefore, polymers based on aniline derivatives have
also been extensively investigated.
Poly(o-phenylenediamine), PoPD, is a polyaniline derivative
which can be achieved through substituting hydrogens by an
amino group in an aniline nucleus. Compared with PANI, the
oxidative polymer of oPDhas apparently shown different charac-
teristics of molecular structure and properties. It has been used as
an electrochemical reduction catalyst for dioxygen, anticorrosion
coatings for metals, sensors for some chemical species and im-
munosorbent assays [1821]. PoPD is usually prepared by
electrochemical polymerization. In this polymerization method,
the obtained PoPDusually has an irregular morphology. Recently,
Sun et al. prepared 1Dnanostructures of PoPDby directly mixing
HAuCl
4
and oPD aqueous solutions at room temperature without
using any template or surfactant [22]. However, the resulting
precipitates are not pure, and there are some Au nanoparticles in
the final product.
Materials Letters 61 (2007) 14001403
www.elsevier.com/locate/matlet

Corresponding author. Tel./fax: +86 431 5168924.


E-mail address: wjzhang@jlu.edu.cn (W. Zhang).
0167-577X/$ - see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2006.07.040
In this article, we describe the preparation of PoPD microrods
with different lengths using ferric chloride as an oxidant. In this
method, ferric chloride is reduced to FeCl
2
which can be easily
removed by washing with water. Therefore, the obtained PoPD is
pure. Moreover, TEM image shows that the resulting 1D
structures with high ratio of length to diameter are not solid and
are composed of many thin fibers.
2. Experimental
2.1. Materials
All the reagents including oPD, ferric chloride and ammonium
peroxydisulfate were of analytical grade (AR), and used without
further purification.
2.2. Preparation of PoPD microrods using ferric chloride as
an oxidant
PoPDmicrorods were synthesized by chemical oxidationusing
ferric chloride as an oxidant. In a typical procedure, different
content of oPD monomer was dissolved in 30 mL de-ionized
water at roomtemperature. Then 10 mL aqueous solution of ferric
chloride (the molar ratio of ferric chloride to oPDis 1:1) was added
to the above mixture under vigorous stirring at room temperature
for 5 h. The resulting precipitate was washed with water twice.
Finally, the product was dried in vacuum at 50 C for 24 h.
2.3. Characterization
Scanning electron microscopy (SEM) measurements were
performed on a SHIMADZU SSX-550 microscope. Transmis-
sion electron microscopy (TEM) experiments were performed
on a Hitachi H-8100 electron microscope with an acceleration
voltage of 200 kV. Gel permeation chromatography (GPC)
instrument was equipped with a Shimadzu GPC-802D gel
column and SPD-M10AVP detector and with N,N-dimethyl-
formamide as an eluent at a flow rate of 1 mL min
1
. FTIR
Spectra of KBr powder-pressed pellets were recorded on a
BRUKER VECTOR22 Spectrometer. UVvis absorption
spectra of PoPD microrods were recorded on a Shimadzu UV-
2501 PC Spectrometer. X-ray diffraction patterns (XRD) were
obtained with a Siemens D5005 diffractometer using Cu K
radiation.
3. Results and discussion
In the conventional preparation of polyaniline and its derivative by
chemical oxidation polymerization, ammonium peroxydisulfate and
ferric chloride were usually used as common oxidants. In this experiment,
we polymerized oPDusing the above two oxidants. Fig. 1a and b presents
SEM images of the PoPD samples synthesized under 0.03 M oPD
monomer using ferric chloride and ammonium peroxydisulfate as oxi-
dants, respectively. It reveals that the sample synthesized using ferric
chloride as an oxidant has rod-like morphology, while no one-dimen-
sional morphology of PoPDcan be found by ammoniumperoxydisulfate
as an oxidant. The diameters of the microrods are in the range of 0.5 mto
2 m and the length is about several to tens of micrometers. A typical
TEM image of the as-synthesized PoPDmicrorods is shown in Fig. 1c. It
is found that the PoPD microrods seem to be composed of many thin
fibers. The influence of the concentration of oPD on the morphologies of
PoPD is studied. SEM images of PoPD microrods synthesized with
different concentrations of oPD are shown in Fig. 2. It is found that when
the concentration of oPD is lower than 0.03 M, the morphology is
dominated by the microrods with a high ratio of length to diameter.
However, when the concentration is higher than 0.12 M, the length of
PoPD microrods is reduced below 5 m, while the diameters of most
Fig. 1. SEM images of PoPD microrods by chemical oxidation polymerization
using (a) ferric chloride and (b) ammonium peroxydisulfate as an oxidant under
the concentrations of oPD=0.03 M. (c) TEM image of PoPD microrods using
ferric chloride as an oxidant under the concentrations of oPD=0.03 M.
1401 X. Lu et al. / Materials Letters 61 (2007) 14001403
PoPD microrods increased to more than 2 m. The formation of PoPD
microrods is probably related to the self-assembly of PoPD through
intermolecular interactions and electrostatic repulsion interactions,
which is similar to a previous report [23].
The molecular weight and polydispersity of the resulting PoPD
determined by gel permeation chromatography (GPC) with uniform
polystyrene standards are ca. 2308 and 1.002, respectively. This result
demonstrated that the obtained PoPD has about 22 units of oPD
monomer, which is a little higher than that synthesized by AgNO
3
as
oxidant [23]. Fig. 3a gives typical FTIR spectra of PoPD microrods.
The bands at 3382 and 3306 cm
1
are due to the characteristic NH
stretching vibrations of the NH group. The broad peak at around
3194 cm
1
can be assigned to the NH stretching vibration of the
NH
2
group. The two bands at around 1525 and 1648 cm
1
are assigned
to the stretching vibration of the C_C and C_N in the phenazine ring,
respectively. The presence of the bands appearing at 758 and 586 cm
1
is characteristic of the CH out-of-plane bending vibrations of benzene
nuclei in the phenazine skeleton. The peaks at 1237 and 1363 cm
1
are
associated with the CN stretching in the benzenoid and quinoid imine
units, respectively. All of these data are similar to a previous report,
which confirm that the obtained microrod sample is PoPD [24].
Fig. 3b presents the UVvisible spectra of the PoPD microrods
dispersed in water solution. The major peaks at about 258 and 437 nm
are observed. The band near 437 nm is assigned to transition
associated with the phenazine ring conjugated to the two lone pairs of
nitrogen of the NH
2
groups. The other peak at about 258 nm is mainly
assigned to the transitions of the benzenoid and quinoid
structures. The X-ray diffraction pattern of the PoPD microrods is
shown in Fig. 3c. From it we can find that a series of sharp lines
between 5 and 40 are observed, which indicates that the obtained
sample has good crystallinity and long range ordering.
4. Conclusions
In summary, microrods of PoPD have been synthesized
using ferric chloride as the oxidant. It is found that the
concentration of oPD has much influence on the morphologies
of PoPD. We think that the mechanism of microrods formation
may be related to the self-assembly of PoPD through
intermolecular interactions and electrostatic repulsion
interactions. FTIR, UVvis absorption spectra and XRD are
used to characterize the structure of microrods of PoPD, which
indicate that the obtained microrod sample is indeed PoPD.
Acknowledgements
The financial support from the Major International Collab-
orative Project of National Natural Science Foundation of China
(Grant 20320120169), the National Major Project for Funda-
mental Research of China (National 973 Program No.
Fig. 2. SEMimages of PoPDmicrorods using ferric chloride as an oxidant under different concentrations of oPD. (a) [oPD]=0.0075 M; (b) [oPD]=0.03 M; (c) [oPD] =0.12 M;
and (d) [oPD] =0.48 M.
1402 X. Lu et al. / Materials Letters 61 (2007) 14001403
001CB610505 and No. 2003CB615604) and the National
Nature Science Foundation of China (No. 50473007) is greatly
appreciated.
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Fig. 3. (a) FTIR spectrum and (b) UVvis absorption spectrum of PoPD
microrods using ferric chloride as an oxidant. (c) XRD diffraction pattern of
PoPD microrods using ferric chloride as an oxidant.
1403 X. Lu et al. / Materials Letters 61 (2007) 14001403