Facile electrochemical co-deposition of a graphene–cobalt nanocomposite for highly efficient water oxidation in alkaline media: direct detection of underlying electron transfer reactions under catalytic turnover conditions

Abstract

A facile electrochemical co-deposition method has been developed for the fabrication of graphene–cobalt nanocomposite modified electrodes that achieve exceptionally efficient water oxidation in highly alkaline media. In the method reported, a graphene–cobalt nanocomposite film was deposited electrochemically from a medium containing 1 mg ml⁻¹ graphene oxide, 0.8 mM cobalt nitrate and 0.05 M phytic acid (pH 7). The formation of the nanocomposite film was confirmed using electrochemical, Raman spectroscopic and scanning electron microscopic techniques. The nanocomposite film exhibits excellent activity and stability towards water oxidation to generate oxygen in 1 M NaOH aqueous electrolyte media. A turn over frequency of 34 s⁻¹ at an overpotential of 0.59 V and a faradaic efficiency of 97.7% were deduced from analysis of data obtained by rotating ring disk electrode voltammetry. Controlled potential electrolysis data suggests that the graphene supported catalyst exhibits excellent stability under these harsh conditions. Phytate anion acts as stabilizer for the electrochemical formation of cobalt nanoparticles. Fourier transformed ac voltammetry allowed the redox chemistry associated with catalysis to be detected directly under catalytic turnover conditions. Estimates of formal reversible potentials obtained from this method and derived from the overall reactions 3Co(OH)₂ + 2OH⁻ ⇌ Co₃O₄ + 4H₂O + 2e⁻, Co₃O₄ + OH⁻ ⇌ 3CoOOH + e⁻ and CoOOH + OH⁻ ⇌ CoO₂ + H₂O + e⁻ are 0.10, 0.44 and 0.59 V vs. Ag/AgCl, respectively.