Formation of Ordered Honeycomb-like Structures of Manganese Oxide 2D Nanocrystals with the Birnessite-like Structure and Their Electrocatalytic Properties during Oxygen Evolution Reaction upon Water Splitting in an Alkaline Medium

Abstract

In this work, a chemical reaction between gaseous ozone and aqueous solution of Mn(CH₃COO)₂ in drops has been researched. It has been shown that the formation of H _x MnO₂·nH₂O nanocrystals with a morphology of nanosheets and a birnessite-like crystal structure with a thickness of 5-8 nm is observed on the surface of drops. These nanocrystals are oriented spontaneously to the solution-gas interface and constitute peculiar ribbons with a width of 1-2 μm, some of which form ordered honeycomb structures (OHS) with a 5-20 μm cell size. To explain the observed effect, the scheme of chemical reactions that take place at the interface between the surface of a drop and ozone has been modeled, and it can be described using a diffusion pattern model taking into account the action of "force fields" on the surface of a drop, which arise due to its curvature. After the drop is dried, these structures practically retain their morphology and form a fractal structure with a geometric area equal to the area of the drop base on the surface of the substrate. The study of the electrocatalytic properties of these structures revealed that they are active electrocatalysts in the oxygen evolution reaction (OER) during water electrolysis in alkaline medium. The most efficient of the obtained electrocatalysts are characterized by an overpotential value of 284 mV at a current of 10 mA/cm² and the Tafel coefficient of 37.7 mV/dec and are currently one of the best among pure manganese oxides. Finally, it has also been assumed that this effect is explained by the morphological features of the structures obtained, which contribute to the removal of oxygen bubbles from the electrode surface during electrolysis.