Dislocation Engineering Steers Reaction‐Induced Reconstruction of Vanadium Oxides for Selective Oxidation of Ethane

ABSTRACT Catalytic active sites or centers could evolve from their initial form under realistic reaction conditions due to the autonomous behaviors of the constituent atoms to adapt to the surrounding environment. Controlling such adaptability of metal‐oxide‐based catalysts is crucial yet challenging for understanding catalyst dynamics and enabling rational catalyst design. Here, we report a dislocation‐mediated strategy to steer the dynamic evolution of vanadium oxides by systematically tuning the lattice dislocation density of TiO 2 supports. A combination of in situ Raman and DRIFTS reveals that in response to reaction conditions, dislocations of TiO 2 enable the depolymerization of crystalline V 2 O 5 into polymeric VO x species while simultaneously inducing charge redistribution through strong V─O─Ti interfacial polarization. Those polymeric, electrophilic VO x centers exhibit enhanced C─H activation ability, boosting selective oxidation of ethane to acetic acid via the Mars–van Krevelen mechanism. These findings provide a conceptual framework linking dislocation‐induced lattice dynamics to catalytic function and highlight the potential of dislocation engineering as a feasible strategy for designing adaptive catalytic systems with tunable redox properties and structural resilience under operating conditions.