Water Oxidation Catalysis by Birnessite@Iron Oxide Core-Shell Nanocomposites

In this work, magnetic nanocomposite particles were prepared for water oxidation reactions. The studied catalysts consist of maghemite (gamma-Fe2O3), magnetite (Fe3O4), and manganese ferrite (MnFe2O4) nanoparticles as cores coated in situ with birnessite-type manganese oxide shells and were characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, thermal, chemical, and surface analyses, and magnetic measurements. The particles were found to be of nearly spherical core-shell architectures with average diameter of 150 nm. Water oxidation catalysis was examined using Ce4+ as the sacrificial oxidant. All core-shell particles were found to be active water oxidation catalysts. However, the activity was found to depend on a variety of factors like the type of iron oxide core, the structure and composition of the shell, the coating characteristics, and the surface properties. Catalysts containing magnetite and manganese ferrite as core materials displayed higher catalytic activities per manganese ion (2650 or 3150 mmolO(2) mol(Mn)(-1) h(-1)) or per mass than nanoiron oxides (no activity) or birnessite alone (1850 mmolO(2) mol(Mn)(-1) h(-1)). This indicates synergistic effects between the MnOx shell and the FeOx core of the composites and proves the potential of the presented core-shell approach for further catalyst optimization. Additionally, the FeOx cores of the particles allow magnetic recovery of the catalyst and might also be beneficial for applications in water-oxidizing anodes because the incorporation of iron might enhance the overall conductivity of the material.