Effective Heterogeneous Oxidative Desulfurization Catalyzed by H₃ PMo₉ W₃ O₄₀ @rht-MOF-1

With the increasingly strict standard for sulfur content in fuel, it is necessary to develop high-efficiency catalyst for extractive and catalytic oxidative desulfurization systems (ECODS). Herein, a series of three remarkable complexes H₃ PMo_(12-n) W_n O₄₀ @rht-MOF-1 (1 a, n=1; 2 a, n=2; 3 a, n=3) have been designed and prepared. Complexes 1 a, 2 a and 3 a were characterized by single-crystal X-ray diffraction and FT-IR, PXRD, SEM, N₂ adsorption-desorption isotherms, etc. Upon complex 3 a was applied as catalyst, it exhibited remarkably high catalytic activity in the ECODS reactions of aromatic sulfur compounds under optimal conditions. On the basis of its excellent heterogeneity, the catalyst could be recycled for nine consecutive cycles without significant losing of activity centers. Then, the reaction kinetics and mechanism were investigated and the activation energy have been calculated and discussed. Further, the complex 3 a is employed to catalyze the ODS of commercial diesel oil. As a result, the desulfurization efficiency reached 90%. These results provided important structure data for study the structure-property relationship and potential heterogeneous catalyst applied in ODS in industry.