Oxygen reduction activity on perovskite oxide surfaces: a comparative first-principle study of LaMnO$_3$, LaFeO$_3$ and LaCrO$_3$

TL;DR

This study compares the oxygen reduction reaction activity on LaMnO3, LaFeO3, and LaCrO3 perovskite surfaces using various first-principles DFT methods, revealing the hybrid functional results align best with experimental data.

Contribution

It provides a comparative analysis of ORR mechanisms on LaBO3 surfaces using multiple DFT approaches, highlighting the accuracy of hybrid functionals.

Findings

Hybrid DFT suggests LaMnO3 has the highest ORR activity.

Results align with recent experimental findings.

GGA and GGA+U methods are less accurate than hybrid functionals.

Abstract

The understanding of oxygen reduction reaction (ORR) activity on perovskite oxide surfaces is essential for promising future fuel cell applications. We report a comparative study of ORR mechanisms on La$B$O$_3$ ($B$=Mn, Fe, Cr) surfaces by first-principles calculations based on density functional theory (DFT). Results obtained from varied DFT methods such as generalized gradient approximation(GGA), GGA+$U$ and the hybrid Hartree-Fock density functional method are reported for comparative purposes. We find that the results calculated from hybrid-functional method suggest that the order of ORR activity is LaMnO$_3$ $>$ LaCrO$_3$ $>$ LaFeO$_3$, which is in better agreement with recent experimental results (Suntivich \textit{et al.}, Nature Chemistry 3, 546 (2011)) than those using the GGA or GGA+$U$ method.