Redox-Inert Fe Ions in Octahedral Sites of Co-Fe Spinel Oxides with Enhanced Oxygen Catalytic Activity for Rechargeable Zinc-Air Batteries.

Bimetallic cobalt-based spinel is sparking much interest, most notably for its excellent bifunctional performance. However, the effect of Fe doping in Co O spinel remains poorly understood, mainly because the surface state of a catalyst is difficult to characterize. Herein, a bifunctional oxygen electrode composed of spinel Co FeO /(Co Fe ) (Co Fe ) O nanoparticles grown on N-doped carbon nanotubes (NCNTs) is designed, which exhibits superior performance to state-of-the-art noble metal catalysts. Theoretical calculations and magnetic measurements reveal that the introduction of Fe ions into the Co O network causes delocalization of the Co 3d electrons and spin-state transition. Fe ions can effectively activate adjacent Co ions under the action of both spin and charge effect, resulting in the enhanced intrinsic oxygen catalytic activity of the hybrid spinel Co FeO . This work provides not only a promising bifunctional electrode for zinc-air batteries, but also offers a new insight to understand the Co-Fe spinel oxides for oxygen electrocatalysis.