Hybrid organic–inorganic materials based on poly(o-phenylenediamine) and polyoxometallate functionalized carbon nanotubes

The chemical polymerization of o-phenylenediamine (OPD) on single-walled carbon nanotubes (SWCNTs) in the presence of phosphomolybdic acid (H3PMo12O40 xH2O) has been studied by surface enhanced resonant Raman scattering (SERRS) spectroscopy. One demonstrates that an organic–inorganic hybrid composite of the type poly(o-phenylenediamine)/polyoxometallate-functionalized SWCNTs is produced by the chemical interaction between polyoxometallate-functionalized SWCNTs and poly(o-phenylenediamine) (POPD) doped with [H2PMo12O40]− ions. According to TEM investigations, a result of the chemical interaction of SWCNT with H3PMo12O40 xH2O is the formation into the composite mass of tube fragments of shorter length, which behave like closed shell fullerenes since Raman fingerprint is given by lines situated at 240–275 and 1450–1472 cm−1. The chemical polymerization of OPD on SWCNTs achieved in the absence of H3PMo12O40 xH2O leads to a covalent functionalization of the wall side of the tubes, which is revealed in Raman spectra, recorded at the excitation wavelength of 514 nm, by an enhancement of the lines associated with the tangential vibrational modes of SWCNTs. Using FTIR spectroscopy, significant hindrance steric effects are evidenced in the POPD/polyoxometallate-functionalized SWCNT composite.