Vacancy Clusters Enable Configurational Matching for Selective Olefin C─H Activation Through Orbital Coupling

ABSTRACT Selective oxidation of olefins offers an attractive route for upgrading light olefins into value‐added chemicals, yet achieving high selectivity requires precise control over both orbital interactions and adsorption configurations at catalyst surfaces. Here, oxidative dehydrogenation (ODH) of 1‐butene is employed as a model reaction to demonstrate that coupled bismuth–oxygen vacancy clusters on Bi 2 WO 6 regulate the orbital coupling between surface Bi 6p states and the olefin π orbital, thereby reconstructing the adsorption configuration. In situ spectroscopic measurements combined with density functional theory calculations reveal that pristine Bi 2 WO 6 favors a flat π adsorption mode dominated by C═C interaction, leaving the reactive C─H bond poorly aligned with neighboring W─O lattice oxygen sites. Vacancy clusters induce a tilted π adsorption configuration that spatially aligns the target C─H bond with the dehydrogenation site. This orbital‐guided configurational matching promotes selective C─H activation while suppressing competing oxidation pathways. These findings establish orbital‐regulated adsorption reorientation through vacancy‐cluster engineering as a strategy for controlling selective olefin oxidation.