Enhanced Activity of Gold-Supported Cobalt Oxide for the Electrochemical Evolution of Oxygen

TLDR

The study proposes and discusses a hypothesis that Co⁴⁺ cations enhance the oxygen evolution reaction on cobalt oxide films. The authors employed SEM, linear sweep voltammetry, chronoamperometry, and in situ surface‑enhanced Raman spectroscopy to probe OER on cobalt oxide films deposited on Au and other metals in 0.1 M KOH. Co oxide films of ~0.4 ML on Au exhibit OER turnover frequencies up to 40 × higher than bulk Co oxide and nearly 3 × higher than bulk Ir, with activity decreasing in the order Au > Pt > Pd > Cu > Co, and Raman indicates that the enhanced performance is due to a higher fraction of Co⁴⁺ sites formed as CoO(OH) under anodic potential.

Abstract

Scanning electron microscopy, linear sweep voltammetry, chronoamperometry, and in situ surface-enhanced Raman spectroscopy were used to investigate the electrochemical oxygen evolution reaction (OER) occurring on cobalt oxide films deposited on Au and other metal substrates. All experiments were carried out in 0.1 M KOH. A remarkable finding is that the turnover frequency for the OER exhibited by ∼0.4 ML of cobalt oxide deposited on Au is 40 times higher than that of bulk cobalt oxide. The activity of small amounts of cobalt oxide deposited on Pt, Pd, Cu, and Co decreased monotonically in the order Au > Pt > Pd > Cu > Co, paralleling the decreasing electronegativity of the substrate metal. Another notable finding is that the OER turnover frequency for ∼0.4 ML of cobalt oxide deposited on Au is nearly three times higher than that for bulk Ir. Raman spectroscopy revealed that the as-deposited cobalt oxide is present as Co3O4 but undergoes progressive oxidation to CoO(OH) with increasing anodic potential. The higher OER activity of cobalt oxide deposited on Au is attributed to an increase in fraction of the Co sites present as CoIV cations, a state of cobalt believed to be essential for OER to occur. A hypothesis for how CoIV cations contribute to OER is proposed and discussed.