Heterogeneous Peracid Catalysis over Sulfonated Porous Aromatic Frameworks for Ultradeep Oxidative Desulfurization of Straight-Run Gasoline

Liquid-phase acidic systems efficiently promote oxidative desulfurization (ODS) of real fuels but suffer from corrosion, fuel contamination, and difficult separation. Herein, sulfonated porous aromatic frameworks (PAF-30-SO 3 H) are demonstrated as heterogeneous analogues of peracid systems for ultradeep ODS of a real straight-run gasoline fraction. Using hydrogen peroxide as an oxidant, sulfur content was reduced from 880 to 7 ppm in 20 min at an H 2 O 2:S molar ratio of 4:1. Catalytic activity correlated with sulfo group density rather than surface area. Mechanistic experiments with preactivated catalysts confirmed in situ formation of surface-bound peracid intermediates, enabling truly heterogeneous oxidation. Sulfone removal was optimized using acetonitrile–water (3:2 vol.) extractants, achieving efficient separation with minimal fuel losses. GC–MS and FTIR analyses confirmed preservation of the hydrocarbon matrix, and the catalyst retained activity over five regeneration cycles. This metal-free, corrosion-free system provides a practical platform for ultradeep desulfurization of real gasoline fractions.