Inorganic–organic dual modification for enhanced Ni–Mo synergy in efficient NiMoS hydrodesulfurization catalysts

NiMoS hydrodesulfurization (HDS) catalysts were synthesized through an inorganic–organic dual modification strategy with molybdenum‐based polyoxometalates (POMs) as precursors. Molybdenum metal powder partially reduced Mo(VI) to Mo(V) while preserving the Keggin framework, generating electron‐rich heteropoly blue species that strengthened electrostatic association with Ni 2+ . Simultaneously, citric acid (CA) coordinated Ni 2+ to regulate promoter dispersion and, upon sulfidation, formed carbonaceous species that may contribute to weaker active phase–support interactions. This dual regulation of the precursor electronic structure and coordination environment enhanced Mo sulfidation, Ni–Mo synergy, and the formation of NiMoS active sites with favorable MoS 2 morphology. The optimized S‐NiPMo 12 ‐CA‐red/Al 2 O 3 catalyst achieved 99.4% dibenzothiophene conversion at 300 °C and 5.5 MPa H 2 , with a k HDS value of 1.2 × 10 −6 mol DBT g cat. −1 s −1 and a turnover frequency of 2.4 × 10 −3 s −1 . This work establishes precursor‐level dual regulation as an effective route for designing advanced HDS catalysts.