A new synthesis method based on the
electrochemical reduction of
α,α,α′,α′-tetrabromo-p-xylene in the presence of single-walled carbon nanotubes
(SWNTs) is used to obtain composites of carbon nanotubes (CNTs) functionalized
with poly(para-phenylenevinylene) (PPV). To separate the effects of
metallic and semiconducting CNTs on their interaction with PPV, the
experiments are carried out with SWNTs enriched in semiconducting
(S, 99%) and metallic (M, 98%) tubes. Significant changes in the relative
intensity and shift of the radial breathing vibrational mode are reported
in the Raman spectra of the as-prepared SWNTs samples, i.e., as mixtures
of metallic (33%) and semiconducting (66%) entities and SWNTs enriched
in M tubes (98%) that result from the electrofunctionalization with
PPV. This different behavior originates in the noncovalent and covalent
functionalization of SWNTs enriched in M and S SWNTs tubes with PPV,
respectively. A gradual decrease in the absorption of the infrared
(IR) bands of PPV situated in the spectral range of 750–1000
cm–1 as a result of the increase of the polymer
weight on the blank Au support is reported. The electrofunctionalization
of the as-prepared SWNTs induces position changes of the PPV IR absorption
bands. In the presence of S-enriched SWNTs, a significant increase
in the absorbance of the two IR bands peaked at 1452 and 1471 cm–1, which are assigned to the vibrational modes of the
phenyl ring stretching and the quinoid structure of the PPV, respectively,
is reported. This results from the covalent bonding of the PPV macromolecular
chains onto the surface of the SWNTs enriched in S tubes. Our results
also demonstrate that the photoluminescence quenching effect reported
for the PPV/SWNTs composites is due to the metallic nanotubes.
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