Boosting Bifunctionality of SrCoO _3‐δ in Oxygen Electrocatalysis by Dual Doping of Bismuth and Phosphorous

Abstract Green hydrogen economy is the cornerstone of the energy landscape, defining the future of energy, which focuses on hydrogen production, storage, and efficient energy conversion. Efficiency of current electrochemical energy reactions such as, oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is primarily limited by the sluggish kinetics of OER/ORR. Pt‐group precious metal scarcity and restrictive cost of the benchmark catalysts restrict the mass adoption of electrochemical energy systems. A novel approach of dual doping of precious metal‐free and high valent metal and non‐metal cations in the A‐site and B‐site of the perovskite, SrCoO _3‐δ (SC) is used to enhance the oxygen electrocatalytic performance and stability of SC. Due to the high valency and acidity of Bi ³⁺ and P ⁵⁺ ions, Bi _0.05 Sr _0.95 Co _0.95 P _0.05 O _3‐δ (BSCP) exhibits enhanced conductivity, accessible active sites, activity, and stability in OER/ORR. The high‐valent dopants facilitate the steric stabilization of the highly symmetric cubic phase of SC in BSCP, promoting OER/ORR performance. The high Co ³⁺ /Co ⁴⁺ ratio with enhanced electron occupancy of the anti‐bonding eg orbital in the perovskite, a key descriptor for OER/ORR catalytic activity, and enriched oxygen vacancies in BSCP are due to Bi ³⁺ /P ⁵⁺ dual doping, promoting OER/ORR performance with a low bifunctional index (ΔE) of 0.79 V.