Scalable Synthesis of Efficient Water Oxidation Catalysts: Insights into the Activity of Flame-Made Manganese Oxide Nanocrystals

Chemical energy storage by water splitting is a promising solution for the utilization of renewable energy in numerous currently impracticable needs, such as transportation and high temperature processing. Here, the synthesis of efficient ultrafine Mn3O4 water oxidation catalysts with tunable specific surface area is demonstrated by a scalable one-step flame-synthesis process. The water oxidation performance of these flame-made structures is compared with pure Mn2O3 and Mn5O8, obtained by post-calcination of as-prepared Mn3O4 (115 m(2) g(-1)), and commercial iso-structural polymorphs, probing the effect of the manganese oxidation state and synthetic route. The structural properties of the manganese oxide nanoparticles were investigated by XRD, FTIR, high-resolution TEM, and XPS. It is found that these flame-made nanostructures have substantially higher activity, reaching up to 350% higher surface-specific turnover frequency (0.07 mu mol(O2) m(-2) s(-1)) than commercial nanocrystals (0.02 mu mol(O2) m(-2) s(-1)), and production of up to 0.33 mmol(O2) mol(Mn)(-1) (s-1). Electrochemical characterization confirmed the high water oxidation activity of these catalysts with an initial current density of 10 mA cm(-2) achieved with overpotentials between 0.35 and 0.50 V in 1m NaOH electrolyte.