In situ confocal Raman micro-spectroscopy and electrochemical studies of mussel adhesive protein and ceria composite film on carbon steel in salt solutions

Abstract

Thin films composed of Mefp-1 and ceria nanoparticles have shown an increasing corrosion inhibition effect with time for carbon steel in acidic aqueous solutions containing phosphate, which motivates a detailed study of the inhibition mechanism by in situ confocal Raman micro-spectroscopy (CRM) and electrochemical impedance spectroscopy (EIS) measurements. The presence of both CeO2 and ferric oxides in the thin composite film was demonstrated by X-ray photoelectron spectroscopy analysis. The Raman spectra assisted by DFT calculations suggest that Mefp-1 forms tri-Fe3+/Mefp-1 complexes and binds to ceria nanoparticles in the composite film. The in situ CRM measurement allow us to follow the development of corrosion products. The measurements show a mixture of Fe oxides/oxyhydroxides, and also indicate that ferrous oxides may be further oxidized by the composite film. Moreover, phosphate ions react with the Fe ions released from the surface to form iron–phosphate deposits, which become incorporated into the corrosion product layer and the composite film. The EIS measurements suggest a layered surface structure formed by the initial Mefp-1/ceria composite layer and the corrosion products/iron–phosphate deposits. These measurements also demonstrate the greatly increased inhibition effect of the composite film in the presence of the phosphate ions. The consistent CRM and EIS results suggest that the iron–phosphate deposits heal defects in the composite film and corrosion product layer, which results in a significantly improved corrosion inhibition of the Mefp-1/ceria composite film during initial and long term exposure.