PPy Synthesis 2
PPy Synthesis 2
PPy Synthesis 2
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.
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.
profile of temperature-dependent conductivity of the polypyrrole (23) Wei, Z. X.; Zhang, L. J.; Yu, M.; Yang, Y. S.; Wan, M. X. AdV.
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