Defect-enriched UiO-66(Zr) synthesized via ball milling-assisted rapid crystallization for efficient oxidative desulfurization

The development of efficient oxidative desulfurization (ODS) catalysts is of great importance for clean energy. In this study, we report a method for the preparation of defect-enriched UiO-66(Zr) materials via a high-energy ball-milling pretreatment-assisted followed by rapid ethanol crystallization. This method significantly enhances ligand deficiency (46.1 %) and average pore diameter (4.1 nm) without using toxic solvents or pre-synthesized clusters, distinguishing it from conventional solvothermal and one-step mechanochemical approaches. Under the optimal parameters, the resulting UiO-66-BM catalyst exhibits excellent ODS performance, achieving full conversion of dibenzothiophene (DBT, 1000 ppm) within 6 min at 50 °C and 20 min at 30 °C using only 20 mg of catalyst and an O/S molar ratio of 5. The turnover frequency (19.85 h −1 ) and mass specific activity (53 mmol g −1  h −1 ) surpass those of most reported pristine MOFs-based catalysts. Moreover, the catalyst reaction activity maintains high activity over six consecutive cycles, showing excellent stability. The superior performance is attributed to the synergistic effect of ball milling and ethanol crystallization, which generates the enriched structural defects and enlarged mesopores, facilitating mass transfer and active site accessibility. This work presents an effective and eco-friendly strategy for the scalable synthesis of high-performance MOF catalysts for deep desulfurization.