Lattice Distortion‐Driven Metal Exsolution in Perovskite Oxides

ABSTRACT Metal‐exsolved materials have garnered significant attention in the field of heterogeneous catalysis for electrochemical and thermochemical energy conversions owing to their uniform nanoparticle dispersion and strong metal‐support socketing. Here, we propose a lattice‐engineering strategy that promotes metal exsolution by doping smaller cations into perovskite oxides, thereby inducing lattice distortion. According to computational simulations and experimental trends, lattice distortion destabilizes the perovskite lattice, lowers the energetic barrier for oxygen vacancy formation, and accelerates Ni segregation, enhancing exsolution of metallic nanoparticles. As a result, highly distorted perovskites exhibit enhanced reducibility, increased exsolved nanoparticle densities, and superior catalytic performance in electrochemical hydrogen oxidation and thermochemical dry reforming of CH ₄ and CO ₂ . Moreover, the socketed structure of nanoparticles and surface basicity of oxides suppresses agglomeration and undesirable side reactions, retaining their high activity. This work highlights lattice destabilization as a driving force for promoting metal exsolution, which enables highly active and durable catalysis.