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. 400degreesC (P4VP) to ca. 200degreesC (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.