Electrochemical Grafting of Reduced Graphene Oxide with Polydiphenylamine Doped with Heteropolyanions and Its Optical Properties

Electropolymerization of diphenylamine (DPA) onto a reduced graphene oxide (RGO) film was carried out to obtain a corresponding RGO/polydiphenylamie (PDPA) composite doped with phosphotungstic acid (H3PW12O40) heteropolyanions (PT). The synthesis was performed in the absence of light, since UVvis spectroscopy and photoluminescence (PL) studies on RGO/DPA blends irradiated by UV light revealed a partial transformation of the DPA monomer into oligomers of PDPA. Raman scattering demonstrates that the electropolymerization of DPA in the presence of H3PW12O40 (PTA) and RGO leads to the formation of PDPA covalently bonded to the RGO sheets (RGO/PDPA:PT). The presence of heteropolyanions in the PDPA matrix (PDPA:PT) is detected by FTIR spectroscopy. Comparing the PL excitation spectra of PDPA:PT and the RGO/PDPA:PT composite highlights an upshift of the band gap that is accompanied by a change in the composition of the PL spectrum in the spectral range of 2.253.54 eV. These changes originate in a charge transfer that takes place at the interface of nongrafted RGO and PDPA:PT. The gradual increase of the PL intensity of RGO covalently grafted with PDPA:PT reveals photochemical reactions under UV irradiation. These involve the CC stretching vibrational mode in the benzene ring of PDPA and indicate the transformation of an RGO/PDPA:PT composite containing HPW12O402 anions into an RGO/PDPA:PT composite stabilized by PW12O403 anions. These results not only provide important insights on the interactions between RGO, conjugated polymers, and stabilizing dopant ions but also impact on the synthesis conditions.