Cr dopant regulating d-orbital electronic configuration of NiFe spinel oxide to improve oxygen evolution reaction in Zn-air battery.

Significant advancements towards enhancing the catalytic activity of spinel ferrites in oxygen evolution reaction (OER) have been achieved, however, further studies are required on this regard. In this study, Cr-doped spinel ferrite (NiFe 2 O 4) embedded in N-doped C (Cr-NiFe 2 O 4 @NC) was synthesized via a high-temperature treatment using an NiFe Prussian blue analog as a precursor and K 2 Cr 2 O 7 as a Cr source. Owing to the strong octahedral site preference energy, Cr3+ ions were successfully doped into octahedral sites and tailored the electronic configuration of NiFe 2 O 4 , as confirmed by XPS. The Cr-substituted Cr-NiFe 2 O 4 @NC exhibited the overpotential of 241 mV at 10 mA cm−2, which was smaller than that of NiFe 2 O 4 @NC (266 mV) at the same current density. Meanwhile, the Tafel slope of Cr-NiFe 2 O 4 @NC (65.32 mV dec−1) was also lower than that of NiFe 2 O 4 @NC (86.96 mV dec−1). Therefore, the Cr substitution can improve the electrocatalytic OER performance of NiFe 2 O 4 @NC. In particular, an assembled rechargeable Zn-air battery using Cr-NiFe 2 O 4 @NC as the cathode catalyst afforded a high power density (61.1 mA cm−2) together with a high specific capacity (740 mA g−1). Amazingly, it could power light-emitting diodes, demonstrating its real-world application. Density functional theory calculations revealed that Cr ion doping led to electron transfer in NiFe 2 O 4 , resulting in a density of electronic states close to the Fermi level, which probably regulated the adsorption/desorption behaviors of oxygenate intermediates (*O and *OOH), thus promoting the reaction kinetics of the OER. This study provides a helpful basis for the development of spinel oxides with high electrocatalytic OER activity and durability via cation doping. [Display omitted] • Cr-NiFe 2 O 4 @NC was prepared from NiFe Prussian blue analogue (NiFePBA). • The Cr dopant regulated d-band center position of NiFe2O4 for improving electrocatalytic OER activity. • The connection between Cr doping and OER activity was clarified by DFT. [ABSTRACT FROM AUTHOR]