Abstract
Nickel-iron layered double hydroxides are known to be one of the most highly active catalysts for the oxygen evolution reaction in alkaline conditions. The high electrocatalytic activity of the material however cannot be sustained within the active voltage window on timescales consistent with commercial requirements. The goal of this work is to identify and prove the source of inherent catalyst instability by tracking changes in the material during OER activity. By combining in situ and ex situ Raman analyses we elucidate long-term effects on the catalyst performance from a changing crystallographic phase. In particular, we attribute electrochemically stimulated compositional degradation at active sites as the principal cause of the sharp loss of activity from NiFe LDHs shortly after the alkaline cell is turned on. EDX, XPS, and EELS analyses performed after OER also reveal noticeable leaching of Fe metals compared to Ni, principally from highly active edge sites. In addition, post-cycle analysis identified a ferrihydrite by-product formed from the leached Fe. Density functional theory calculations shed light on the thermodynamic driving force for the leaching of Fe metals and propose a dissolution pathway which involves [FeO(4)](2-) removal at relevant OER potentials.