δ-MnO₂–Mn₃O₄ Nanocomposite for Photochemical Water Oxidation: Active Structure Stabilized in the Interface

Pure phase manganese oxides have been widely studied as water oxidation catalysts, but further improvement of their activities is much challenging. Herein, we report an effective method to improve the water oxidation activity by fabricating a nanocomposite of Mn 3 O 4 and δ-MnO 2 with an active interface. The nanocomposite was achieved by a partial reduction approach which induced an in situ growth of Mn 3 O 4 nanoparticles from the surface of δ-MnO 2 nanosheets. The optimum composition was determined to be 38% Mn 3 O 4 and 62% δ-MnO 2 as confirmed by X-ray photoelectron spectra (XPS) and X-ray absorption spectra (XAS). The δ-MnO 2 –Mn 3 O 4 nanocomposite is a highly active water oxidation catalyst with a turnover frequency (TOF) of 0.93 s –1, which is much higher than the individual components of δ-MnO 2 and Mn 3 O 4 . We consider that the enhanced water oxidation activity could be explained by the active interface between two components. At the phase interface, weak Mn–O bonds are introduced by lattice disorder in the transition of hausmannite phase to birnessite phase, which provides active sites for water oxidation catalysis. Our study illustrates a new view to improve water oxidation activity of manganese oxides.