Assessing correlations of perovskite catalytic performance with electronic structure descriptors

TL;DR

This study evaluates how well the oxygen p-band center, calculated via various density functional theory methods, predicts catalytic performance in perovskite oxides, finding strong correlations especially at the PBE level.

Contribution

It systematically assesses the predictive power of the oxygen p-band center across multiple functionals and catalytic measures, establishing a reliable computational descriptor for catalyst development.

Findings

Strong linear correlations (R2 = 0.81-0.87) between p-band center and catalytic activity.

PBE-level calculations provide the best correlation with experimental data.

The bulk oxygen p-band center is a useful descriptor for guiding perovskite catalyst design.

Abstract

Electronic structure descriptors are computationally efficient quantities used to construct qualitative correlations for a variety of properties. In particular, the oxygen p-band center has been used to guide material discovery and fundamental understanding of an array of perovskite compounds for use in catalyzing the oxygen reduction and evolution reactions. However, an assessment of the effectiveness of the oxygen p-band center at predicting key measures of perovskite catalytic activity has not been made, and would be highly beneficial to guide future predictions and codify best practices. Here, we have used Density Functional Theory at the PBE, PBEsol, PBE+U, SCAN and HSE06 levels to assess the correlations of numerous measures of catalytic performance for a series of technologically relevant perovskite oxides, using the bulk oxygen p-band center as an electronic structure descriptor. We have analyzed correlations of the calculated oxygen p-band center for all considered functionals with the experimentally measured X-ray emission spectroscopy oxygen p-band center and multiple measures of catalytic activity, including high temperature oxygen reduction surface exchange rates, aqueous oxygen evolution current densities, and binding energies of oxygen evolution intermediate species. Our results show that the best correlations for all measures of catalytic activity considered here are made with PBE-level calculations, with strong observed linear correlations with the bulk oxygen p-band center (R2 = 0.81-0.87). This study shows that strong linear correlations between numerous important measures of catalytic activity and the oxygen p-band bulk descriptor can be obtained under a consistent computational framework, and these correlations can serve as a guide for future experiments and simulations for development of perovskite and related oxide catalysts.