The Role of Alkali Metal Ions in Cooperative Electrocatalysis by Bifunctional Co−Mn‐Mixed Phosphates

Abstract Developing cost‐effective, non‐precious metal bifunctional electrocatalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is crucial for advancing sustainable energy storage and conversion technologies, including zinc‐air batteries, fuel cells, and water electrolyzers. This study presents a one‐pot synthesis of cobalt‐manganese mixed phosphates as effective bifunctional electrocatalysts for both ORR and OER. Among the catalysts tested, Na−Co−Mn−P NaCo 1.5 Mn 1.5 (HPO 4 ) 2 (PO 4 ) exhibited the highest catalytic activity, with a minimal ΔE of 0.86 V, indicating superior performance. The incorporation of alkali metals and the synergistic effects of metal and phosphate components enhance conductivity, electrochemical surface area, and mixed valency of transition metals, contributing to improved electrocatalytic activity. This work highlights a straightforward synthesis method and the beneficial role of metal‐phosphate synergy in oxygen electrocatalysis.