  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.
