Rapid room-temperature synthesis of nanocrystalline spinels as oxygen reduction and evolution electrocatalysts

Abstract

Spinels can serve as alternative low-cost bifunctional electrocatalysts for oxygen reduction/evolution reactions (ORR/OER), which are the key barriers in various electrochemical devices such as metal–air batteries, fuel cells and electrolysers. However, conventional ceramic synthesis of crystalline spinels requires an elevated temperature, complicated procedures and prolonged heating time, and the resulting product exhibits limited electrocatalytic performance. It has been challenging to develop energy-saving, facile and rapid synthetic methodologies for highly active spinels. In this Article, we report the synthesis of nanocrystalline M_xMn_3–xO₄ (M = divalent metals) spinels under ambient conditions and their electrocatalytic application. We show rapid and selective formation of tetragonal or cubic M_xMn_3–xO₄ from the reduction of amorphous MnO₂ in aqueous M²⁺ solution. The prepared Co_xMn_3–xO₄ nanoparticles manifest considerable catalytic activity towards the ORR/OER as a result of their high surface areas and abundant defects. The newly discovered phase-dependent electrocatalytic ORR/OER characteristics of Co–Mn–O spinels are also interpreted by experiment and first-principle theoretical studies.