A transformative route to nanoporous manganese oxides of controlled oxidation states with identical textural properties

Abstract

Nanoporous nanocrystalline metal oxides with tunable oxidation states are crucial for controlling their catalytic, electronic, and optical properties. However, previous approaches to modulate oxidation states in nanoporous metal oxides commonly lead to the breakdown of the nanoporous structure as well as involve concomitant changes in their morphology, pore size, surface area, and nanocrystalline size. Herein, we present a transformative route to nanoporous metal oxides with various oxidation states using manganese oxides as model systems. Thermal conversion of Mn-based metal–organic frameworks (Mn-MOFs) at controlled temperature and atmosphere yielded a series of nanoporous manganese oxides with continuously tuned oxidation states: MnO, Mn₃O₄, Mn₅O₈, and Mn₂O₃. This transformation enabled the preparation of low-oxidation phase MnO and metastable intermediate phase Mn₅O₈ with nanoporous architectures, which were previously rarely accessible. Significantly, nanoporous MnO, Mn₃O₄, and Mn₅O₈ had a very similar morphology, surface area, and crystalline size. We investigated the electrocatalytic activity of nanoporous manganese oxides for oxygen reduction reaction (ORR) to identify the role of oxidation states, and observed oxidation state-dependent activity and kinetics for the ORR.