The Roles of Composition and Mesostructure of Cobalt-Based Spinel Catalysts in Oxygen Evolution Reactions

By using the crystalline precursor decomposition approach and direct co-precipitation the composition and mesostructure of cobalt-based spinels can be controlled. A systematic substitution of cobalt with redox-active iron and redox-inactive magnesium and aluminum in a cobalt spinel with anisotropic particle morphology with a preferred 111 surface termination is presented, resulting in a substitution series including Co₃ O₄ , MgCo₂ O₄ , Co₂ FeO₄ , Co₂ AlO₄ and CoFe₂ O₄ . The role of redox pairs in the spinels is investigated in chemical water oxidation by using ceric ammonium nitrate (CAN test), electrochemical oxygen evolution reaction (OER) and H₂ O₂ decomposition. Studying the effect of dominant surface termination, isotropic Co₃ O₄ and CoFe₂ O₄ catalysts with more or less spherical particles are compared to their anisotropic analogues. For CAN-test and OER, Co³⁺ plays the major role for high activity. In H₂ O₂ decomposition, Co²⁺ reveals itself to be of major importance. Redox active cations in the structure enhance the catalytic activity in all reactions. A benefit of a predominant 111 surface termination depends on the cobalt oxidation state in the as-prepared catalysts and the investigated reaction.