Interaction of poly(4-vinylpyridine) with copper surfaces: electrochemical, thermal and spectroscopic studies

the interaction of poly(4-vinylpyridine) (p4vp) and thiocyanate ions with copper in acid solutions was studied by cyclic voltammetry, thermogravimetry, elemental analysis and infrared spectroscopy. it is shown that at ca. -0.45 v/sce the electrogenerated cu(i) ions at the surface of a copper electrode induce a complexing reaction with p4vp and scn- both present in solution. the resulting electroactive polymer-complex grows onto the electrode surface as a film, and the metallic center is further oxidized to cu(ii) in a subsequent step at ca. -0.23 v/sce. according to thermogravimetric results, the polymer-complex is less thermally-stable than p4vp as evidenced by the lowering in the initial temperature of degradation from ca. 400 oc (p4vp) to ca. 200 oc (complex). the elemental analysis revealed a chemical composition of 2:1:2 for p4vp:cu:scn, and the infrared spectra indicated that the complex comprises a copper metallic center coordinated with nitrogen pyridinic rings (p4vp) and thiocyanate ions.