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

Selective adsorption of α,β-unsaturated aldehydes (α,β-UALs) is a prerequisite for the hydrogenation of α,β-UALs to high-value unsaturated alcohols, but a quantitative description of the interactions between the C═C/C═O bond of α,β-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 α,β-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 α,β-UALs.