Assessing Correlations of Perovskite Catalytic Performance with Electronic Structure Descriptors

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 Perdew–Burke–Ernzerhof
(PBE), PBEsol, PBE + U, strongly constrained and
appropriately normed functional, and Heyd–Scuseria–Ernzerhof
(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.