Electrocatalytic activity and surface oxide reconstruction of bimetallic iron-cobalt nanocarbide electrocatalysts for...

For renewable energy technology to become ubiquitous, it is imperative to develop efficient oxygen evolution reaction (OER) electrocatalysts, which is challenging due to the kinetically and thermodynamically unfavorable OER mechanism. Transition metal carbides (TMCs) have recently been investigated as desirable OER pre-catalysts, but the ability to tune electrocatalytic performance of bimetallic catalysts and understand their transformation under electrochemical oxidation requires further study. In an effort to understand the tunable TMC material properties for enhancing electrocatalytic activity, we synthesized bimetallic FeCo nanocarbides with a complex mixture of FeCo carbide crystal phases. The synthesized FeCo nanocarbides were tuned by percent proportion Fe (i.e. % Fe), and analysis revealed a non-linear dependence of OER electrocatalytic activity on % Fe, with a minimum overpotential of 0.42 V (15-20% Fe) in alkaline conditions. In an effort to understand the effects of Fe composition on electrocatalytic performance of FeCo nanocarbides, we assessed the structural phase and electronic state of the carbides. Although we did not identify a single activity descriptor for tuning activity for FeCo nanocarbides, we found that surface reconstruction of the carbide surface to oxide during water oxidation plays a pivotal role in defining electrocatalytic activity over time. We observed that a rapid increase of the (Fe_xCo_1-x)₂O₄ phase on the carbide surface correlated with lower electrocatalytic activity (i.e. higher overpotential). We have demonstrated that the electrochemical performance of carbides under harsh alkaline conditions has the potential to be fine-tuned via Fe incorporation and with control, or suppression, of the growth of the oxide phase.