Synergistic Deep Extractive Oxidative Desulfurization of Fuel Over PW 11 Mn@MOF‐525

Deep desulfurization of fuels is critical for environmental protection and clean energy production. Herein, a novel composite catalyst, PW 11 Mn@MOF‐525, was synthesized by in situ encapsulation of a manganese‐substituted Keggin‐type polyoxometalate PW 11 Mn within a zirconium‐based metal–organic framework (MOF‐525). The catalyst was thoroughly characterized by various methods, confirming uniform dispersion of PW 11 Mn within the MOF pores without framework collapse. The PW 11 Mn@MOF‐525 composite was applied for extractive catalytic oxidative desulfurization (ECODS) of dibenzothiophene (DBT) using H 2 O 2 as oxidant and acetonitrile as extractant. Under optimized conditions, the composite achieved 99.2% DBT removal within 80 min, owing to synergistic H 2 O 2 activation by the Lewis acidic Zr‐oxo clusters and redox‐active PW 11 Mn clusters. Kinetic analysis revealed pseudo‐first‐order behavior with an activation energy of 57.66 kJ·mol −1 . Radical trapping experiments identified hydroxyl radicals (·OH) as the dominant active species. The catalyst exhibited excellent recyclability, maintaining 94.9% DBT removal after five cycles with negligible leaching. This work demonstrates that encapsulation of polyoxometalates within MOF‐525 is a promising strategy for efficient and stable deep oxidative desulfurization.