Manganese oxides treated with organic compounds as catalysts for water oxidation reaction

Abstract

Manganese oxides of different crystalline structures: α-MnO2, δ-MnO2, α,γ-MnO2 and Mn2O3; were treated with the organic compounds picolinic acid, ethylenediamine and pyridine; and were applied as catalysts in the chemical water oxidation reaction using Ce(IV) ammonium nitrate as sacrificial oxidant. The treatment led to modifications in the oxides properties, such as reduction of the particle size, increase of surface area and partial reduction of Mn4+ to Mn3+ for the Mn(IV) oxides, or of Mn3+ to Mn2+ for Mn2O3, because of favored interactions of the organic molecules with the lattice planes with higher d spacing. Oxygen evolution reaction (OER) tests showed the superior catalytic activity of the treated Mn(IV) oxides, for instance α,γ-MnO2-en presented TOF five times higher than pure α,γ-MnO2. The increase in surface area as well as the higher Mn3+ content caused by the treatment of the Mn(IV) oxides were correlated with the improvement in the OER catalytic activity.