The interplay between the suprafacial and intrafacial mechanisms for complete methane oxidation on substituted LaCoO3 perovskite oxides

•Catalytic behavior is altered by A/B-site substitutions in LaCoO3.•The O p-band relative to the B-site cation d-band center governs the catalytic performance.•A negative relative position valueindicates a suprafacial model-driven catalyst.•A positive relative position value indicates an intrafacial model-driven catalyst.•The as-revealed index can be applied for activity prediction in methane oxidation.