Cation Acidity‐Driven Superior Catalytic Activity Enhancement in Perovskite Cobaltate Cathodes for Reversible Solid Oxide Cells

Developing high-performance and durable cathodes is crucial for efficient reversible solid oxide cells (R-SOCs). While A-site cation effects on perovskite cathodes are well-established, the mechanistic role of B-site cation acidity in regulating oxygen reduction reaction (ORR) and CO₂ reduction reaction (CO₂RR) remains inadequately understood. This study systematically investigates the influence of B-site cation acidity in BaCo_0.8M_0.2O_{3- δ} (M = Fe, Nb, and Ta) on electrochemical performance. Our findings reveal a direct correlation between dopant acidity and enhanced performance. Specifically, Fe doping (BCFO) leads to significant structural evolution with suppressed Jahn-Teller distortion, resulting in a lower Co⁴⁺/Co³⁺ ratio and increased oxygen vacancy concentration that promotes oxygen ion diffusion. At 800°C, BCFO achieves the highest peak power density in fuel cell mode (1520 mW·cm^-2) and superior CO₂ electrolysis current density (2.60 A·cm^-2 at 1.3 V). Notably, a clear trend of performance enhancement with increasing dopant acidity is observed (BCFO > BCNO > BCTO). The superior performance of BCFO is attributed to its optimal metal-oxygen bond energy, balancing facile bond dissociation and formation. This work establishes B-site cation acidity as a predictive descriptor for the rational design of highly active and stable perovskite cathodes for advanced solid oxide fuel cells and electrolysis cells.