Mechanistic insights into oxygen reduction reaction on metal/perovskite catalysts: Interfacial interactions and reaction pathways

The oxygen reduction reaction (ORR) is a critical process in energy conversion systems, influencing the efficiency and performance of various devices such as fuel cells, batteries , and electrolyzers. Perovskite-supported metal materials (metal/perovskite) offer several advantages as ORR electrocatalysts , including strong metal-support interactions, oxygen vacancy formation in the perovskite lattice, and synergistic triple-phase boundary (TPB) activity at the interface. Despite their significance, the mechanistic understanding of ORR on metal/perovskite catalysts remains incomplete, particularly at metal/perovskite interfaces. This study investigates ORR on BaZrO 3 (BZO) perovskite-supported metal clusters (Pt or Ag) using density functional theory (DFT) to unravel critical insights into charge redistribution at the metal/BZO interface. Energy profiles for elemental steps along two different ORR pathways—oxygen adsorption on the metal cluster surface and direct oxygen adsorption at the TPB—were calculated to explore the effects of different active sites. The results provide a deeper understanding of ORR on metal/perovskite catalysts, emphasizing the role of interfacial interactions and pathway-dependent reaction mechanisms. This work paves the way for guiding the design of high-performance electrocatalysts for ORR in terms of composition , interface design, and local environment modification for a broad range of energy applications. • Mechanistic insights into ORR on perovskite-supported metal clusters using DFT. • Comparative study of TPB and metal cluster pathways for Pt/BZO and Ag/BZO systems. • Charge redistribution impacts surface diffusion and reaction profiles. • Ag/BZO exhibits superior ORR kinetics associated with surface diffusion process.