Peripheral Coordination-Dependent Descriptor for Selective Interactions between Near-Frontier Molecular Orbitals and Single-Atom Catalysts

Selective adsorption of alpha,beta-unsaturated aldehydes (alpha,beta-UALs) is a prerequisite for the hydrogenation of alpha,beta-UALs to high-value unsaturated alcohols, but a quantitative description of the interactions between the C=C/C=O bond of alpha,beta-UALs and the catalysts is still lacking. Herein, based on comprehensive density functional theory calculations, we developed a descriptor that combines the near-frontier molecular orbitals of the C=C/C=O bonds of alpha,beta-UALs with the fundamental physical properties of single-atom catalysts (SACs) and considers the inner/outer coordination environment. All of the parameters used in this descriptor are easily accessible and interpretable, enabling an efficient assessment of the selectivity of SACs for the C=C/C=O bonds of alpha,beta-UALs.