A Bilayer Structure Composed of Mg|Co-MnO2 Deposited on a Co(OH)2 Film to Realize Selective Oxygen Evolution from Chloride-Containing Water.

Abstract

A fluorine-doped tin oxide-coated glass electrode modified with a bilayer film of underlying α-Co(OH)2 and overlying Mg-intercalated and Co-doped δ-type (layered) MnO2 (Mg|Co-MnO2) preferentially yielded oxygen with a Faradaic efficiency as high as 79% in the presence of chloride ions at high concentration (0.5 M). This noble metal-free electrode was fabricated by cathodic electrolysis of aqueous Co(NO3)2 followed by anodic electrolysis of a mixture of Mn2+, Co2+, and cetyltrimethylammonium (CTA+) ions in water. The CTA+ ions accommodated in the interlayer spaces of Co-doped δ-MnO2 were replaced with Mg2+ by ion exchange. The upper Mg|Co-MnO2 could effectively block the permeation of Cl- ions and allow only H2O and O2, while the under α-Co(OH)2 acted as an oxidation catalyst for the H2O penetrated through the upper coating. Thus, the oxygen evolution reaction (OER) was preferred to the chlorine evolution reaction (CER). In artificial seawater (pH 8.3), the blocking effect against Cl- decreased because of ion exchange of the intercalated Mg2+ ions with Na+ in solution, but the OER efficiency still remained at 57%, much higher than that (28%) without the upper Mg|Co-MnO2. This demonstrates that the interlayer spaces between MnO2 layers acted as pathways for H2O molecules to reach the active sites of the underlying Co(OH)2. Density functional theory (DFT) calculations revealed that the most stable structure of hydrated Mg2+ ion, in which a part of coordinated H2O molecules is hydrolyzed, has less affinity toward Cl- ion than that of hydrated Na+ ion.