Iron and Nickel Substituted Perovskite Cobaltites for Sustainable Oxygen Evolving Anodes in Alkaline Environment

Abstract Perovskite oxides have great flexibility in their elemental composition, which is accompanied by large adjustability in their electronic properties. Herein, we synthesized twelve perovskite oxide‐based catalysts for the oxygen evolution reaction (OER) in alkaline media. The catalysts are based on the parent oxide perovskite Ba 0.5 Gd 0.8 La 0.7 Co 2 O 6‐δ (BGLC587) and are synthesized through the sol‐gel citrate synthesis route. To reduce the demand on cobalt (Co), but also increase the intrinsic catalytic activity of BGLC587 for the OER, we substitute Co on the B‐site with certain amounts of Fe and Ni, synthesizing catalysts of the general formula Ba 0.5 Gd 0.8 La 0.7 Co 2‐x‐y Fe x Ni y O 6‐δ . A plethora of physicochemical and electrochemical methods suggest that an Fe content between 30 % and 70 % increases the intrinsic catalytic activity of BGLC587, while Tafel slopes in combination with in‐situ Raman spectroscopy suggest the rate determining step is likely a proton‐exchange reaction, progressing possibly through the lattice oxygen mechanism (LOM). We apply one of the optimized, Co‐substituted perovskites in a monolithic, photovoltaic (PV)‐driven electrolysis cell and we achieve an initial solar‐to‐hydrogen (STH) conversion efficiency of 10.5 % under one sun solar simulated illumination.