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1158 J. Phys. Chem.

B 2006, 110, 1158-1165

Controllable Synthesis of Conducting Polypyrrole Nanostructures

Xuetong Zhang,*,†,‡ Jin Zhang,*,† Wenhui Song,‡ and Zhongfan Liu†


Key Laboratory for the Physics and Chemistry of NanodeVices, Centre for Nanoscale Science and Technology,
College of Chemistry and Molecular Engineering, Peking UniVersity, Beijing 100871, P.R. China, and
Wolfson Centre for Materials Processing, Brunel UniVersity, West London, UB8 3PH, United Kingdom
ReceiVed: August 4, 2005; In Final Form: October 7, 2005

Wire-, ribbon-, and sphere-like nanostructures of polypyrrole have been synthesized by solution chemistry
methods in the presence of various surfactants (anionic, cationic, or nonionic surfactant) with various oxidizing
agents [ammonium persulfate (APS) or ferric chloride (FeCl3), respectively]. The surfactants and oxidizing
agents used in this study have played a key role in tailoring the nanostructures of polypyrrole during the
polymerization. It is inferred that the lamellar structures of a mesophase are formed by self-assembly between
the cations of a long chain cationic surfactant [cetyltrimethylammonium bromide (CTAB) or dodeyltrimeth-
ylammonium bromide (DTAB)] and anions of oxidizing agent APS. These layered mesostructures are presumed
to act as templates for the formation of wire- and ribbon-like polypyrrole nanostructures. In contrast, if a
short chain cationic surfactant octyltrimethylammonium bromide (OTAB) or nonionic surfactant poly(ethylene
glycol) mono-p-nonylphenyl ether (Oπ-10) is used, sphere-like polypyrrole nanostructures are obtained,
whichever of the oxidizing agents mentioned above is used. In this case, micelles resulting from self-assembly
among surfactant molecules are envisaged to serve as the templates while the polymerization happens. It is
also noted that, if anionic surfactant sodium dodeyl surfate (SDS) is used, no characteristic nanostructures of
polypyrrole were observed. This may be attributed to the doping effect of anionic surfactants into the resulting
polypyrrole chains, and as a result, micelles self-assembled among surfactant molecules are broken down
during the polymerization. The effects of monomer concentration, surfactant concentration, and surfactant
chain length on the morphologies of the resulting polypyrrole have been investigated in detail. The molecular
structures, composition, and electrical properties of the nanostructured polypyrrole have also been investigated
in this study.

Introduction or molecule templates are often long range ordered structure


Micrometer- or nanometer-sized conducting polymers have self-assembled from certain surfactants or block copolymers,
attracted great attention mainly due to their potential applications etc., which provide well-defined rooms or channels for conduct-
in electronic circuits, chemical and electrochemical sensors, ing polymer chains to grow into micrometer-/nanometer-sized
photovoltaic cells, electrochromic devices, and field emission products.16-18 The advantage of using these soft-template
applications.1-5 One of the key strategies for synthesizing materials is that they are easy to remove after the synthesis,
conducting polymers with dimensions at such small scales is a and in the meantime, the micro-/nanostructures of the resulting
template-directed synthesis.6-12 Templates used in this route can polymers can remain. Recently some novel template molecules
be classified into two major categories, namely “hard” and “soft” including lipid9 and cyclodextrin19 have emerged. Moreover,
templates. Hard templates, pioneered by Wu6 and Martin,7 surface micelles,8,20 liquid-crystalline phases,21,22 and extraneous
include many kinds of conventional hard porous materials, such electrical fields22 have also been employed during the synthesis
as porous aluminosilicate MCM-416 and microporous polymeric of conducting polymers. Various micrometer-/nanometer-sized
filtration membranes.10 Recently hard templates have been conducting polymers have been synthesized with diverse
extended to carbon nanotubes,13 lipid tubule edges,14 and molecule assemblies as the templates. For example, submi-
electrospun polymer fibers15 for synthesizing micrometer-/ crometer-sized tube junctions and dendrites of polyaniline,23
nanometer-sized conducting polymers. However, to obtain helical poly(ethylenedioxythiophene),9 ribbon-like poly(p-phen-
appropriate hard-template materials, scientists have to purchase ylene vinylene),24 etc., have been synthesized successfully, and
or prepare appropriate porous materials before synthesizing the even conducting polymer microcontainers with bowl-, cup-, or
prospective materials. Moreover, to get pure conducting poly- bottle-like morphologies have been generated electrochemically
mers, the hard-template materials have to be removed after the by a so-called “soap bubble” technique.25,26
synthesis. This is very difficult in most cases, and may Out of the curiosity of the previous finding of polypyrrole
drastically alter or even destroy the resulting materials during nanowire/robbins in the system of pyrrole/CTAB/APS,27 herein
recovery from the templates. On the other hand, soft-templates we report a systematic study on the controllable synthesis of
conducting polypyrrole nanostructures by using a variety of self-
* Address correspondence to this author. Phone: 44-1895-267055. Fax: assembled surfactants as templates. Nanowire- and nanoribbon-
44-1895-269737. E-mail: xuetong.zhang@brunel.ac.uk (Dr. X. Zhang) and like polypyrrole can be synthesized in the presence of long chain
jinzhang@pku.edu.cn (Dr. J. Zhang).
† Peking University. cationic surfactants [cetyltrimethylammonium bromide (CTAB)
‡ Brunel University. or dodeyltrimethylammonium bromide (DTAB)] and anions of
10.1021/jp054335k CCC: $33.50 © 2006 American Chemical Society
Published on Web 12/24/2005
Synthesis of Conducting Polypyrrole Nanostructures J. Phys. Chem. B, Vol. 110, No. 3, 2006 1159

the oxidizing agent of ammonium persulfate (APS). In the case


of using the short chain cationic surfactant octyltrimethylam-
monium bromide (OTAB) or the nonionic surfactant poly(eth-
ylene glycol) mono-p-nonylphenyl ether (Oπ-10) instead,
regardless of the oxidizing agent used, nanosphere-like poly-
pyrrole can be formed. However when the anionic surfactant
sodium dodeyl sulfate (SDS) is used, no characteristic nanofea-
ture can be observed in the resulting products. The effects of
surfactant concentration, surfactant chain length, monomer
concentration, etc. on the morphologies of the resulting poly-
pyrrole have been investigated in detail. The mechanisms of
templates during the polymerization have been discussed. The
molecular structures, composition, and electrical properties of
the nanostructured polypyrrole have been investigated as well.

Experimental Section Figure 1. SEM images of polypyrrole nanostructures with different


The majority of the chemicals including pyrrole monomer, morphologies obtained by the different synthetic conditions (monomer
concentration 15 mM): (a) sphere-like polypyrrole by using CTAB
surfactants (CTAB, SDS, and Oπ-10), and oxidizing agents surfactant and FeCl3 oxidizing agent; (b) ribbon-like polypyrrole by
(APS and FeCl3) were purchased from Beijing Chemical using CTAB surfactant and APS oxidizing agent; (c) no polypyrrole
Reagents Company, with their purity in analytical grade except nanostructures were obtained by using SDS surfactant and APS
for Oπ-10 (average EO unit n ) 10, chemical grade). Other oxidizing agent; and (d) sphere-like polypyrrole by using poly(ethylene
surfactants, DTAB (=99%) and OTAB (g98%), were purchased glycol) mono-p-nonylphenyl ether (Oπ-10) surfactant and APS oxidiz-
from Sigma-Aldrich Company Ltd. Pyrrole monomer was ing agent.
purified by distillation before use. Other reagents were used as
received without further purification. TABLE 1: The Morphologies of the Resulting Polypyrrole
The polypyrole in the form of various nanostructures was Obtained in the Synthetic Conditions of Different
synthesized by the solution chemistry method. The synthetic Surfactants and Oxidizing Agents
process was as follows: pyrrole monomers with a definite polypyrrole
surfactants
volume were added into a quantitative cationic (CTAB, DTAB, nanostructures CTAB DTAB OTAB Oπ-10 SDS
OTAB), anionic (SDS), or nonionic surfactant (Oπ-10) aqueous
oxidizing agents
solution, respectively. Then an oxidizing agent (either APS or APS ribbon-like or sphere-like no geometrical
FeCl3) aqueous solution was added into the above mixture to wire-like nanofeature
initiate the polymerization. When using APS as oxidizing agent, FeCl3 sphere-like
the monomer and the oxidizing agent were kept equal (1:1);
however, when FeCl3 was used as the oxidizing agent, the mole
ratio of monomer to oxidizing agent was kept at 1:2. All SEM and TEM were prepared by placing a drop of an aqueous
solutions were precooled to 0-5 °C, and the polymerization in suspension of polypyrrole onto a silicon wafer and carbon-coated
the final mixture went on at 0-5 °C for 24 h. After reaction, copper grid, respectively. Infrared spectra were recorded with
the precipitates were filtrated and washed with deionized water a Magna-IR 750 system using powdered samples. XPS analysis
and ethanol alternately at least 3 times, then left to dry, resulting was performed with an Axis Ultra spectrometer (Kratos, UK)
in a black powder. using Monochromatic Al KR (1486.71 eV) radiation at 225 W
The concentrations of the surfactant aqueous solutions used power (15 mA, 15 kV). To compensate for surface charge
in the reaction systems were controlled in the ranges of micelle effects, binding energies were calibrated by using the C1s
aggregations according to the literature, with a maximum of hydrocarbon peak at 284.8 eV. Electrical conductivity was
12 cmc (critical micelle concentration) for the ionic surfactants. measured with an automatic computer controlled Keithley 220-
The cmc of CTAB is 0.87 mM in deionized water at room programmable current source and 181-nanovoltmeter. Samples
temperature and a transition from spherical to cylindrical used for DC electrical-conductivity measurements were in the
micelles occurs at a concentration of more than 12 cmc at room form of compressed pellets (12 mm in diameter and about 0.1
temperature.28,29 The cmcs for DTAB and OTAB are 14 mM mm in thickness) obtained by applying a hydraulic pressure of
and 0.9 M, respectively.30,31 The cmc for SDS is 8.2 mM in about 10 MPa.
deionized water at room temperature,32 and its phase diagram
was reported by Burducea.33 Nonionic surfactant Oπ-10 is a Results and Discussion
derivative of the well-studied Triton X-100 with the same Morphology of Polypyrrole. Table 1 summarizes the mor-
average number of EO and a slightly longer alkyl tail (three phologies of the resulting polypyrrole obtained respectively in
more CH2). Although the full information on the properties of the synthetic conditions of different surfactants and oxidizing
Oπ-10 aqueous solution is not available, it is certain that the agents. To compare the effects of surfactant and oxidizing agents
concentration range of micelle aggregation for Oπ-10 (5 wt % on the morphologies of the resulting polypyrrole nanostructures,
used in the work) should be more or less similar to that for the monomer concentrations were kept the same at 15 mM, and
Triton X-100 (with the oblate micelles existing up to the the resulting polypyrrole morphologies obtained in the synthetic
concentration of 15 wt %34). conditions of different surfactants and oxidization agents are
Scanning electron microscope (SEM) images were obtained shown in Figure 1. In the case of using CTAB as a surfactant
at 10 kV with an XL30S-FEG field-emission instrument. High- and keeping its concentration at 12 cmc, the different nano-
resolution transmission electron microscope (HRTEM) images structures of polypyrrole were obtained by using different
were recorded on a Tecnai F30 at 300 kV. Samples for both oxidizing agents (Figure 1a,b). If the oxidizing agent FeCl3 was
1160 J. Phys. Chem. B, Vol. 110, No. 3, 2006 Zhang et al.

used, polypyrrole nanoparticles were formed, showing uniform


sphere-like morphology with diameters in a narrow range
between 35 and 60 nm (Figure 1a). However, if the oxidizing
agent APS was used instead, the polypyrrole appeared to grow
in the shape of ribbon-like nanostructures with widths in the
range between 25 and 85 nm, heights in the range of several
nanometers, and lengths up to several micrometers (Figure 1b).
These indicate that the anions of the oxidizing agents may have
played a different role of counterions of altering ion pair
interaction and thus the CTAB packing parameter. In turn the
growth of polypyrrole nanostructures has been confined in
different ways during polymerization, providing a potential route
to control the morphology of the resulting polypyrrole. There
will be more discussions in the following sections.
The surfactant effects on the morphologies of the polypyrrole
were also investigated by using other surfactants. When nonionic
surfactant Oπ-10 (its concentration kept at 5 wt %) replaced Figure 2. Threshold pyrrole concentrations for the nanostructure of
the CTAB, whichever oxidizing agent (FeCl3 and APS) was resulting polypyrrole versus the surfactant concentration in the system
used, only nanosphere-like polypyrroles were obtained (Figure of pyrrole/CTAB/APS. In the area below Critical Line 1, ribbon-like
nanostructures would be synthesized, and in the area between Critical
1d shows an example of polypyrrole nanoparticles formed in Line 1 and 2, wire-like nanostructures would be formed. Above Critical
the presence of oxidizing agent APS). The diameters of the Line 2, highly entangled wire-like nanostructures and irregular structure
nanospheres were in the range between 45 and 70 nm. However of polypyrrole would appear.
when anionic surfactant SDS (its concentration kept at 12 cmc)
replaced the CTAB, in the presence of either oxidizing agent After adding ionic oxidizing agent into the solution, it
FeCl3 or APS, no regular nanostructure of polypyrrole was gradually diffused into the pyrrole reservoir and then oxopo-
observed (Figure 1c shows the morphology of polypyrrole lymerized the pyrrole monomers into polymers. Finally the
formed in the case of using SDS and APS). In contrast with sphere-like polypyrrole nanostructures were obtained as a
other surfactants, the surfactant SDS was difficult to remove consequence of spatially constraining the sphere-like micelles.
completely. In consequence, the morphology shown in Figure A similar self-assembly mechanism occurred when cationic
1c is actually the structure of the resulting polypyrrole mixed surfactant CTAB and oxidizing agent FeCl3 were used, and as
with SDS residue. These above observations indicate that, apart a consequence, polypyrrole nanoparticles were also made.
from the oxidizing agents, the surfactants can also have a However, the system of pyrrol/APS/CTAB in our previous
significant influence on the formation of the polypyrrole study27 suggested that a lamellar structure formed between the
morphology during polymerization. cations of the CTAB and the anions of the oxidizing agent APS
What is the mechanism for determining the morphology of in the aqueous solution, and was attributed to leading the growth
the polypyrrole behind the various and unpredictable factors in of ribbon-like polypyrrole. A similar mechanism occurs in the
the reactions, such as the chemical structures of oxidizing agents system of pyrrol/APS/DTAB (see below). Although the precise
and surfactants studied above, as well as the concentrations of mechanism of growth of polypyrrole nanorobbins/nanowires
monomer, oxidizing agents, and surfactants, etc.? Bearing this does not seem to be fully understood, it is almost certainly
question in mind, we have some clear clues from the review of related to the lamellar mesostructure of APS/CTAB and APS/
the fundamental knowledge, recent application of the self- DTAB supramolecular assemblies, which will be addressed in
assembly of surfactants,20-22 and our previous results.27 It is more detail in the following sections. Besides, anionic surfac-
well established that surfactants assemble into micelles, spheri- tants such as SDS did not serve as the templates to produce
cal, oblate, or cylindrical structures, due to their amphiphilic these polypyrrole nanostructures, probably because doped
nature in aqueous solution above a critical concentration. Further polypyrroles contained counterions in the polymer chains.
increases in the concentration result in the self-organization of Anionic surfactants would serve as counterions for the polymer
micelles into periodic hexagonal, cubic, or lamellar mesophases. chains, and thus permanently disrupt the structure of the sphere-
Recently, these self-assembly structures have been widely used like micelles.
as effective templates for synthesizing organic/inorganic/metal Effects of Monomer and Surfactant Concentrations. Pyrrole
nanomaterials.20-22,35-36 To be specific, when nonionic surfac- monomers are encapsulated into more or less uniform spherical
tant Oπ-10 was used, in the presence of either oxidizing agent micelles or between periodical lamellar structures driven by the
FeCl3 or APS, we supposed that amphiphilic macromolecular hydrophobic interaction. There should be a saturated monomer
chains of Oπ-10 (5 wt %) self-assembled into sphere-like concentration at which the micelles can accommodate the
micelles without interference from the ionic oxidizing agent. maximum number of monomers, because the total interior
The sphere-like micelles spatially separated and organized volume of micelles or lamellae is definite at an equilibrium state
hydrophobic pyrrole monomers into the micelles through once the surfactant concentration remains fixed. On the other
hydrophobic interaction. It should be pointed out that, even hand, it was obvious that the number of micelles, that is the
though pyrrole is soluble in water (0.9 M), it could easily enter interior volume of micelles, is a function of surfactant concen-
the interior of the micelles. Such “hydrophobic” behaviors of tration. Apparently, the morphology of the resulting polypyrrole
pyrrole molecules in the micelle aggregation have already been is bound to be dependent on both pyrrole monomer and
reported by others.8,20 Very recently, Manohar et al.37 has further surfactant concentrations. A plot as shown in Figure 2 demon-
characterized that there is a small increase of hydrodynamic strates a trend in that the polypyrrole nanostructure varies as a
radius of micelles and a decrease of cmc after adding the pyrrole function of both monomer and surfactant concentrations in the
into the CTAB/water system. system of pyrrole/CTAB/APS.
Synthesis of Conducting Polypyrrole Nanostructures J. Phys. Chem. B, Vol. 110, No. 3, 2006 1161

tures. Whereas the monomer concentration was increased to or


above the threshold 20 mM, wire-like nanostructures of the
resulting polypyrrole started to form. For example, when the
monomer concentration was kept at 20 mM, the resulting
polypyrrole nanostructures resulted in a mixture of the ribbon-
like and the wire-like (Figure 2e), which were proved by the
TEM observation in our previous work.27 With a further increase
in the monomer concentration from 25 to 45 mM, only wire-
like polypyrrole nanostructures were observed (Figure 2d-b).
Their diameters were in the range between 20 and 65 nm with
lengths up to several micrometers. It seemed that the diameters
of the resulting polypyrrole nanowires did not apparently vary,
but the nanowires seemed to become more entangled and shorter
with increasing monomer concentration. When the monomer
concentration was increased to 60 mM, as shown in Figure 2a,
some nanowires were entangled or twisted tightly, and some
even enclosed themselves into more or less ring-like structures.
Excess monomers may account for the above phenomenon. The
superfluous pyrrole could not enter into the hydrorphobic layers
of the self-assembled mesostructures and thus be oxopolymer-
ized at the exterior of the templates. Similar profiles have been
seen in another series of polymerizations as a function of the
monomer concentration at a consistent surfactant concentration
of 2 cmc, corresponding to the experimental points shown in
Figure 2. Therefore it is suggested that the monomer concentra-
tion would be controllable below the saturated value for
obtaining either nanoribbons or nanowires, otherwise polypyr-
role nanostructures would become less uniform or even non-
uniform after the reaction.
The formation of the wire-like polypyrrole nanostructure is
Figure 3. SEM images of polypyrrole nanostructures obtained at
different monomer concentrations (CTAB used as a surfactant and its
envisaged to be a result from rolling up the ribbon-like
concentration kept the same at 12 cmc, and APS was used as an polypyrrole, reminiscent of the mechanism reported in the
oxidizing agent): (a) 60, (b) 45, (c) 30, (d) 25, (e) 20, (f) 15, (g) 10, growth of other wire-like or tube-like nanomaterials.38-40 Apart
and (h) 5 mM. from the universal driving force by surface energy minimization,
First of all, the effect of the monomer concentration on the in our experiments, some specific factors may also be taken
polypyrrole nanostructure has been revealed and discussed. A into account for the occurrence of ribbon-like polypyrrole rolling
series of polymerizations were performed as a function of the up into the wire-like polypyrrole. Different from many inorganic
monomer concentration from 5 to 60 mM in the systems of nanomaterials that are crystals or single crystals, polypyrrole
CTAB used as a surfactant at a consistent concentration of 12 nanoribbons/nanowires are often amorphous.27 The polypyrrole
cmc and APS used as an oxidizing agent. The SEM images of long chains tend to entangle together due to the hydrogen
polypyrrole nanostructures are shown in Figure 3 and their bonding and π-π interaction among themselves. Another
corresponding points plotted in Figure 2. It is clearly seen from important aspect assumes that there would be an evolution of
these two figures that the morphologies of polypyrrole nano- self-assembly of templates during the polymerization of poly-
structures change in relation to the concentration of pyrrole pyrrole nanoribons/nanowires, from micelles to lamellar meso-
monomer. In the condition of the fixed surfactant concentration structure after oxidizing agent APS is added, simultaneously
of 12 cmc, the monomer concentration at 20 mM appeared to from lamellae back to micelles again as more APS molecules
be a threshold for determining the resulting polypyrrole nano- are further reduced. The late transition would assist the roll-up
structures, below that the polypyrroles were in the form of of the initially growing polypyrrole ribbons between the
nanoribbons (Figure 3e-h) and above that in the form of lamellae. In other words, the templates would take a more active
nanowires. The monomer concentration also has a profound role in the formation of polypyrrole ribbons and wires compared
influence on the uniformity of the polypyrrole nanostructures. with classic micelle templates. Above all, it is likely to determine
In the experiments, the concentration of 15 mM was also the final nanostructure of polypyrrole, either wire-like or ribbon-
apparent as an optimal monomer concentration for synthesizing like, by changing the monomer concentration within a certain
polypyrrole nanoribbons in terms of uniformity and yield range.
(Figures 1b and 3f). If the monomer concentration was below After continuing polymerization in different conditions, the
15 mM, the lower the monomer concentration, and the less the clear trend of the influence of the monomer concentration, as
resulting polypyrrole uniformity. With the monomer concentra- well as the surfactant concentration on the polypyrrole nano-
tion at 10 mM, the relatively uniform ribbonlike polypyrrole structure, emerges in the system of pyrrole/CTAB/APS, as
nanostructures were still visible (Figure 3g). A further decrease shown in Figure 2. The threshold of the pyrrole concentration
in the monomer concentration to 5 mM resulted in the for the formation of polypyrrole nanoribbons appears to increase
appearance of protrusions on the edges of polypyrrole nano- gradually from around 7.5 to 15 mM with increasing CTAB
structures although the overall morphology remained ribbon- concentration from 2 to 12 cmc, as illustrated in Critical Line
like (Figure 3h), which obviously is ascribed to the shortage of 1 in Figure 2. This implies a mild influence of surfactant
the monomers in some areas between the lamellar mesostruc- concentration on the growth of nanoribbon. In the region below
1162 J. Phys. Chem. B, Vol. 110, No. 3, 2006 Zhang et al.

are consistent with what we can anticipate from Figure 2. The


pyrrole concentration of 15 mM was found to be the threshold
for the growth of polypyrrole nanoribbons when the surfactant
concentration was 8 cmc, evidenced by the mixture of nano-
ribbons and nanowires in Figure 4c,d. In addition, the pyrrole
concentration of 15 mM is below Critical Line 2. Just as we
expected, when the surfactant was increased to 10 and 12 cmc,
more or less uniform ribbonlike polypyrrole nanostructures were
obtained (Figure 4a,b). On the other hand, when the surfactant
concentration is below 8 cmc while the pyrrole concentration
of 15 mM is within Critical Line 1 and Critical Line 2, the
resulting polypyrrole nanostructures grew into wire-like nano-
structures (Figure 4e,f).
As another example, if the monomer concentration is kept at
30 mM, and the surfactant concentration is varied form 12 to 2
cmc, according to Figure 2, we cannot observe the transforma-
tion form ribbon-like to wire-like polypyrrole, but we observe
the tendency from the uniform wire-like nanostructures of
polypyrrole to entangled and irregular structures of polypyrrole.
This interpretation is in good agreement with the experimental
observation shown in Figure 5.
In the experiments, it was noted that the sphere-like poly-
Figure 4. SEM images of polypyrrole nanostructures obtained at pyrrole nanostructures did not show the distinct dependence on
different surfactant concentrations (CTAB used as a surfactant and APS the monomer concentration, nor on the surfactant concentration
used as an oxidizing agent, monomer concentration was kept constant except for the small variations in their diameter when using
at 15 mM): (a) 12, (b) 10, (c and d) 8, (e) 4, and (f) 2 cmc. sphere-like micelles as templates. Being aware of the variation
Critical Line 1, polypyrrole nanoribbons are expected. Since of micelle size and volume with many parameters in the various
the pyrrol concentration in this region is far below the saturated surfactant systems, we suggest that a systematic study of the
concentration highlighted in Critical Line 2, the micelles would dependence of the size distribution of the polypyrrole nano-
be able to guarantee the uniform dispersion of a small amount spheres on the monomer and surfactant concentrations and
of pyrrol monomers, which should be a favored condition for compatibility between pyrrole monomer and surfactant micelle
the growth of the nanoribbons. This may help to interpret why would be worthwhile in the future.
the formation of the polypyrrole nanoribbons is more sensitive Surfactant Chain-Length Effect. The SEM images in Figure
to the monomer concentration as already demonstrated in Figure 6 show the resulting polypyrrole nanostructures obtained by
3, rather than the surfactant condition. However, the surfactant using different chain-length quaternary ammonium salts as
concentration is supposed to affect the efficiency and yield of surfactants. APS was used as oxidizing agent, the monomer
the polymerization, which is still unclear as well. Critical Line concentration was constant at 15 mM, and the surfactant
2 illustrates the profile of the saturated pyrrole concentration concentration was constant at 12 cmc. It was clearly seen that,
against the surfactant concentration. The saturated pyrrole in the system of either CTAB or DTAB used as surfactant,
concentration for the formation of well-defined polypyrrole ribbon-like polypyrrole was obtained (Figure 6a,b), whereas
nanowires increases more quickly with increasing surfactant OTAB as surfactant, sphere-like polypyrrole nanostructures was
concentration in comparison with the threshold concentration synthesized (Figure 6c). This indicates that the surfactant chain
in Critical Line 1. It is not surprising that the higher the length may affect the morphologies of the polypyrrole nano-
concentration of the surfactant, the more micelles, and thus the structures. As discussed above, the lamellar mesostructures self-
more pyrrole can be well dispersed, remembering that micelle assembled between the cations of the cationic surfactants and
molar concentration [Sm] in equilibrium is given by [Sm] ) the anions of the oxidizing agent APS would serve as the
Km[S]n, where Km is the corresponding equilibrium constant, templates for the formation of the ribbonlike polypyrrole
[S] is the molar concentration of the surfactant, and n is the nanostructures. However, the system of surfactant OTAB with
number of surfactant molecules in the micelle, the aggregation relatively short alkyl chain and oxidizing agent APS accordingly
number. In the region between Critical Line 1 and Critical Line did not provide the lamellar templates. In the previous study,27
2, well-defined polypyrrole nanowire can be synthesized, and we observed the white precipitate (lamellar mesostructure) when
moreover, more effective production is anticipated in the adding the APS aqueous solution into the CTAB aqueous
condition of higher surfactant and monomer concentrations. solution and the lamellar mesostructure was confirmed by XRD
Above Critical Line 2, the excess pyrrole outside the templates spectra. Similarly, the white precipitate was observed as well
is involved in the polymerization, and as a result, the morphol- when the APS aqueous solution was added into the DTAB
ogy of the resulting polypyrrole becomes less uniform and aqueous solution and the XRD spectra also proved the existence
undesirable. of its lamellar structure. However, when APS aqueous solution
Figure 2 provides a rough guide to the synthesis of polypyr- was added into the OTAB aqueous solution, no white precipitate
role with a desired nanostructure in the system of pyrrole/CTAB/ was observed, which implies that the cations of OTAB did not
APS. For example, when the monomer concentration remained interact with the anions of the oxidizing agent APS. In fact,
at 15 mM, the nanostructure of the resulting polypyrrole formed sphere-like micelles formed initially via self-assembly among
in a series of surfactant concentrations as shown in Figure 4, OTAB molecules themselves still remained, templating the
and the corresponding points are plotted in Figure 2. It is clearly formation of spherical polypyrrole. Similar trends in the phase
seen that the polypyrrole nanostructures obtained in Figure 4 behavior depending on the alkyl tail length have been reported
Synthesis of Conducting Polypyrrole Nanostructures J. Phys. Chem. B, Vol. 110, No. 3, 2006 1163

Figure 5. SEM images of polypyrrole nanostructures obtained at Figure 6. SEM images of polypyrrole nanostructures obtained by using
different surfactant concentrations (CTAB used as a surfactant and APS different chain-length quaternary ammonium salts as surfactants (used
used as an oxidizing agent, the monomer concentration was kept APS as an oxidizing agent, the monomer concentration was kept
constant at 30 mM): (a) 12, (b) 6, and (c) 2 cmc. constant at 15 mM and the surfactant concentration was kept constant
at 12 cmc): (a) CTAB, (b) DTAB, and (c) OTAB.
previously for the mixtures of the same series of cationic
surfactant with anionic surfactant.41,42 The reason for the spherical aggregates, between 1/3 and 1/2 rodlike micelles form,
different assembly behaviors between the long-chain quaternary and between 1/2 and 1 bilayers form, and close to 1 planar
ammonium salt surfactants, e.g. ,CTAB and DTAB, and the extended bilayer appears. The pairing of oppositely charged
short-chain quaternary ammonium salt surfactants, e.g., OTAB, counterions S2O82- from the oxidizing agent APS drastically
in the presence of APS is yet to be understood. Nevertheless, decreases the headgroup area A0, thereby increasing the packing
these observations indicated that the lamellar mesostructures parameter P. In fact, when the oxidizing agent was added to
might be assembled preferentially between the cations of the the CTAB or DTAB solution, the lamellar white precipitate
cationic surfactants with long alkyl chain and the anions of the (CTA)2S2O8 could be immediately obtained,27 from which we
APS as the templates for synthesis of polypyrrole nanostructures could deduce that the planar bilayer of the surfactant aggregates
with high aspect ratio. formed first, and then further congregated and deposited from
To rationalize these different assemblies, it is useful to the aqueous solution. So in such a case the electrostatic
consider the Israelachvilli’s packing parameter P ) V/A0lc, where interactions are strong, and in turn, the packing parameter P
V is the tail volume, lc the tail length, and A0 the area per would attain values close to 1. For comparison, when SO42-
headgroup.43 A packing parameter less than 1/3 will yield was added into the CTAB aqueous solution, we could not see
1164 J. Phys. Chem. B, Vol. 110, No. 3, 2006 Zhang et al.

Figure 8. Conductivity-temperature curve of the resulting wire-like


Figure 7. IR spectrum (bottom) and X-ray photoelectron spectrum polypyrrole.
(top) of the resulting wire-like polypyrrole nanostructures.
and oxidizing agent concentration were rather low, and (3) the
lamellar precipitates in the presence of SO42-, indicating the mole ratio of the oxidizing agent to monomer was not very high.
interactions are not strong enough to induce a bilayer structure Electrical Properties. Conductivities of the resulting wire-
or phase separation.27 Furthermore, for a given headgroup size, like polypyrrole nanostructures synthesized by using CTAB as
the ratio V/lc is almost unchanged between C8 and C16 chains; a surfactant and APS as an oxidizing agent were measured with
however, counterion binding increases with increasing chain the standard Van Der Pauw direct current (DC) four-probe
length, which results in the decrease of A0. This may be the method.50 Samples used for DC electrical-conductivity measure-
reason that increasing the number of carbons in the tails ments were in the form of compressed pellets according to the
enhances precipitation. procedure described in the Experimental Section. The polypyr-
So far, the synthesis methods and the influential parameters role nanostructures showed typical nonmetallic behavior51 with
have been systematically studied and discussed. In the following a conductivity of 7.3 × 10-3 S‚cm-1 at room temperature (25
paragraphs we will present the characterization and analysis of °C). The low room temperature conductivity of the polypyrrole
the resulting polypyrroles. The wire-like polypyrrole nanostruc- nanostructures was ascribed to the low doping level, which had
tures were chosen as an interesting example. been confirmed by the XPS analysis above. The overall pattern
Composition and Structure. Molecular structures of the of temperature-dependent conductivity of the polypyrrole nano-
resulting wire-like polypyrrole nanostructures obtained by using structures is well described by Mott’s law for quasi-one-
CTAB as a surfactant and APS as an oxidizing agent were dimensional variable-range hopping52 (Figure 8).
characterized by Fourier transform infrared spectroscopy (FTIR)
[Figure 7, bottom]. It was clearly seen that the characteristic Conclusions
polypyrrole peaks are located at 1560 and 1480 cm-1, due to Wire-, ribbon-, and sphere-like polypyrrole nanostructures
the symmetric and antisymmetric ring-stretching modes, re- have been synthesized by the solution chemistry method in the
spectively.44 Strong peaks near 1195 and 920 cm-1 indicated presence of various surfactants (anionic, cationic, or nonionic
the doping state of polypyrrole and a broad band at 3000-3500 surfactant) with various oxidizing agents (APS or FeCl3),
cm-1 was attributed to N-H and C-H stretching vibrations, respectively. Surfactants and oxidizing agents used in this study
respectively.45,46 Furthermore, the peaks at 1050 and 1315 cm-1 have played a key role in tailoring the resultant conducting
were attributed to C-H deformation vibrations and C-N polypyrrole nanostructures. The lamellar mesostructures would
stretching vibrations, respectively.45,46 The two very weak peaks be formed by self-assembly between the cations of long chain
around 2924 and 2854 cm-1 were attributed to the stretching cationic surfactant (CTAB or DTAB) and anions of the oxidizing
vibration mode of methylene, indicating that surfactants had agent of APS. These mesostructures have acted as templates
been almost completely eliminated from the polypyrrole nano- for the formation of wire- and ribbon-like polypyrrole nano-
structures. These demonstrated that the resulting polypyrrole structures. While the short chain cationic surfactant OTAB or
nanostructures were pure and in the doping states. nonionic surfactant Oπ-10 replaced the long chain cationic
The chemical composition of the wire-like polypyrrole surfactant, regardless of oxidizing agent used, sphere-like
nanostructures was further ascertained by X-ray photoelectron polypyrrole nanostructures are formed. The surfactants form
spectroscopy (XPS) [Figure 7, top]. Results indicated that micelles via self-assembly among surfactant molecules and then
polypyrrole nanostructures were composed of five elements serve as the templates. However, when anionic surfactant SDS
including hydrogen. The elementary composition (mass percent) is used, no polypyrrole nanostructures are obtained as the self-
was [C] 66.64, [N] 15.51, [O] 14.78, and [S] 3.08. The presence assembly of the surfactant molecules would break down due to
of a small amount sulfur indicated that some sulfate anions from the doping effect of anionic surfactants into the resulting
reduction of persulfate oxidant had been retained, almost polypyrrole chains. The morphologies of the resulting polypyr-
certainly doped into the polypyrrole polymers.47 The atomic ratio role nanostructures are greatly dependent on the monomer
of sulfur ([S]) to nitrogen ([N]) was ∼8.7%, suggesting the concentration, surfactant concentration, and surfactant chain
presence of one dopant molecule per twelve pyrrole rings. This length, which would provide the possibility of elaborate control
doping level is far lower than that of one dopant per three pyrrole of the morphologies of the resulting conducting polymers from
rings reported.47 In comparison with the other general synthe- the sphere-like, to the ribbon-like, to the wire-like. FTIR
sis,48,49 the reasons for such low doping levels are probably demonstrates that the resulting polypyrrole nanostructures are
ascribed to the following three points: (1) the synthesis occurred pure and in the doped states. XPS analysis suggests the presence
in the neutral aqueous solution, (2) the monomer concentration of one dopant molecule per twelve pyrrole rings. The overall
Synthesis of Conducting Polypyrrole Nanostructures J. Phys. Chem. B, Vol. 110, No. 3, 2006 1165

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