Electronic Structure Descriptors for CO${}_2$ Conversion Activity in Perovskite Oxides

Abstract

Electronic structure descriptors have been widely used to rationalize catalytic activity, but their application to CO${}_2$-to-CH${}_4$ conversion in perovskite oxides remains relatively limited. Here, we investigate six electronic structure descriptors related to band centers and bandwidths. We find that the unoccupied transition-metal (TM) $3d$-band center, charge-transfer energy, and the ratio of the unoccupied TM $3d$ to occupied O $2p$ bandwidths, $W_{3d}/W_{2p}$, exhibit negative correlations with CH${}_4$ activity. These qualitative trends are further quantified using a parametric brute-force searching (BFS) approach to obtain explicit fitting equations. Notably, the selected equations depend only on $W_{3d}/W_{2p}$, providing an electronic structure perspective on the enhanced activity in double perovskites. We apply the selected equation to screen 24 La-based double perovskites. This screening suggests that La${}_2$CoGaO${}_6$, La${}_2$CoAlO${}_6$, and Ti-containing compositions are promising candidates. The present approach can help identify descriptor-activity relationships and guide materials screening in perovskite oxides.