Electrochemical polymerization and characterization of a poly(azulene)-TiO2 nanoparticle composite film

Abstract

A poly(azulene)-TiO 2 composite film (PAz-TiO 2 ) was synthesized electrochemically by oxidation of azulene in an electrolyte medium containing TiO 2 nanoparticles. Polymerization was performed under magnetic stirring in an acetonitrile solution containing tetrabutylammonium hexafluorophosphate as the electrolyte salt. Influence of the concentration of TiO 2 in the reaction suspension on the electrochemical and optical properties and on the structure of the composite films was studied by cyclic voltammetry, ex situ Raman and FTIR reflection spectroscopy and in situ UV-vis and FTIR spectroelectrochemical techniques. Morphology of the composite films was studied by Scanning Electron Microscopy and the amount and distribution of the TiO 2 nanoparticles within the polymeric matrix by Inductively Coupled Plasma Mass Spectrometry with laser ablation. Addition of TiO 2 in the reaction suspension had a small catalytic activity for the polymerization of Az. Inclusion of TiO 2 nanoparticles in PAz did not affect the voltammetric behavior or the chemical structure of the formed polymer films. However, a different chain conformation and morphology of the film was formed when synthesized in presence of TiO 2 compared to the plain PAz film. It was also found that the film morphology was more homogeneous when the concentration of TiO 2 was C10 mM in the polymerization solution than films polymerized without any TiO 2 .

Electrochemical preparation of oligo(azulene) on nanoporous TiO2 and characterization of the composite layer

“…This may be due to the electron withdrawing effect of TiO 2 that accelerates oxidation of the monomer. The same kind of catalytic activity of TiO 2 has also been observed in electropolymerization of pyrrole [43] and Az [44] in solutions containing TiO 2 nanoparticles. The charging-discharging reaction of the nanoporous OAz-TiO 2 composite layer made as in Fig.…”

“…, at 1475 cm -1 [54, Table 11.1], and at 1395 cm -1 [26,56] in both spectra are assigned to aromatic C=C ring stretching vibrations. PAz [28] and the OAz-TiO 2 [44] composite layer show intense infrared active vibration bands in the wavenumber region around 1500 cm -1 . The intensity of the band at 1475 cm -1 in the spectrum of PAz (almost invisible in the spectrum of OAz-TiO 2 composite) may indicate that PAz on ITO is in more conductive state than the composite layer.…”

“…The strong band at 839 cm -1 in the spectrum of PAz is due to the vibration originating from the doping anion PF 6 -[54, Table 22.1]. The band from the doping anion in the spectrum of the composite may have a lower intensity than in the PAz spectrum and be located under the broader band between 830 and 900 cm -1 which is assigned to a doping-induced band [28,44].…”

The role of (photo)electrochemistry in the rational design of hybrid conducting polymer/semiconductor assemblies: From fundamental concepts to practical applications

“…[31] Polyazulene potentiodynamic The influence of TiO 2 concentration on the incorporated amount was shown. [33] galvanostatic The crucial role of different anions, potentially adsorbed on the NP surface, was demonstrated. [22] galvanostatic Oxalic acid was used as electrolyte during the deposition.…”

Application of cobalt oxide nanoparticles as an electron transfer facilitator in direct electron transfer and biocatalytic reactivity of cytochrome c

“…Oxide semiconductor nanoparticles have received considerable attention in many fields [1][2][3]. They are suitable substrates for biomolecule immobilization due to their good biocompatibility and easy preparation.…”