Electroreductive polymerization of trans-[RuCl2(vpy)4] on Nd-Fe-B magnets: electrochemical impedance spectroscopy interpretation, Raman spectroscopy, X-ray photoelectron spectroscopy and scanning electron microscopy analysis

摘要

The electropolymerization of trans-[RuCl_2(vpy)_4] (vpy=4-vinylpyridine) monomer on Nd-Fe-B magnets was studied by electrochemical impedance spectroscopy (EIS). Impedance diagrams obtained during the polymerization process were used to monitor film formation. The EIS results gave insight into the electrochemical phenomena occurring at the magnet surface as the polymerization process progressed. The film structure and morphology were also studied by X-ray photoelectron spectroscopy, scanning electron microscopy and Raman spectroscopy. The Raman spectroscopy results showed that the polymerization takes place at the vinyl groups of the monomer and also that the redox polymer structure is very similar to that of the monomer. The ratio of the intensity of the XPS peaks for fluorine (from the electrolyte PF_6~-) and ruthenium present in the film showed that the polymer on Nd-Fe-B contained an equal proportion of Ru~(2+) and Ru~(3+), indicating that part of the film is positively charged, i.e. {[RuCl_2(vpy)_4]~+}_n .