Enhanced C-H bond activation by tuning the local environment of surface lattice oxygen of MoO₃

The lattice oxygen on transition metal oxides serves as a critical active site in the dehydrogenation of alkanes, whose activity is determined by electronic properties and environmental structures. Hydrogen affinity has been used as a universal descriptor to predict C-H bond activation, while the understanding of the environmental structure is ambiguous due to its complexity. This paper describes a combined theoretical and experimental study to reveal the activity of lattice oxygen species with different local structures, taking Mo-based oxides and C-H bond activation of low-carbon alkanes as model catalytic systems. Our theoretical work suggests that oxygen species with convex curvature are more active than those with concave curvature. Theoretically, we propose an interpretative descriptor, the activation deformation energy, to quantify the surface reconstruction induced by adsorbates with various environmental structures. Experimentally, a Mo-based polyoxometalate with the convex curvature structure shows nearly five times the initial activity than single-crystal molybdenum oxide with the concave one. This work provides theoretical guidance for designing metal oxide catalysts with high activity.