Electrocatalysis of Oxygen on Bifunctional Nickel‐Cobaltite Spinel

Transition‐metal‐based materials are among the most active and durable catalysts for the effective electrocatalysis of oxygen‐related reactions. Herein, we present a study on bifunctional catalysts as air electrodes aimed at metal‐air batteries based on nickel and cobalt spinel (NiCo2O4) supported on electrospun carbon nanofibers. The physicochemical features of these transition‐metal‐based catalysts are essential for the understanding of their electrochemical activity. Results show that the major presence of oxidized Ni and Co species (Ni3+ and Co3+) produces higher activity for the oxygen evolution reaction (OER), whereas lower oxidation states of the metals (Ni2+, Co2+, Ni0 and Co0) together with the presence of N‐doped carbon lead to enhanced oxygen reduction reaction (ORR) performance. This study highlights the importance of designing catalysts in terms of crystallographic structure and proper oxidation states of the elements for maximizing their performance. Spin me round: Transition‐metal‐based materials are among the most active and durable catalysts for the effective electrocatalysis of oxygen‐related reactions. NiCo2O4 spinel supported on electrospun carbon nanofibers presents good performance and bifunctionality for both the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Oxidized species (Ni3+ and Co3+) enhance OER, whereas lower oxidation states (Ni2+, Co2+, Ni0 and Co0) enhance ORR.