Role of Nanoscale Inhomogeneities in Co₂FeO₄ Catalysts during the Oxygen Evolution Reaction

Abstract

Spinel-type catalysts are promising anode materials for the alkaline oxygen evolution reaction (OER), exhibiting low overpotentials and providing long-term stability. In this study, we compared two structurally equal Co₂FeO₄ spinels with nominally identical stoichiometry and substantially different OER activities. In particular, one of the samples, characterized by a metastable precatalyst state, was found to quickly achieve its steady-state optimum operation, while the other, which was initially closer to the ideal crystallographic spinel structure, never reached such a state and required 168 mV higher potential to achieve 1 mA/cm². In addition, the enhanced OER activity was accompanied by a larger resistance to corrosion. More specifically, using various <i>ex situ</i>, <i>quasi in situ</i>, and <i>operando</i> methods, we could identify a correlation between the catalytic activity and compositional inhomogeneities resulting in an X-ray amorphous Co²⁺-rich minority phase linking the crystalline spinel domains in the as-prepared state. <i>Operando</i> X-ray absorption spectroscopy revealed that these Co²⁺-rich domains transform during OER to structurally different Co³⁺-rich domains. These domains appear to be crucial for enhancing OER kinetics while exhibiting distinctly different redox properties. Our work emphasizes the necessity of the <i>operando</i> methodology to gain fundamental insight into the activity-determining properties of OER catalysts and presents a promising catalyst concept in which a stable, crystalline structure hosts the disordered and active catalyst phase.