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For the first time, creation of oxygen defects in the crystalline structure of WO3/SBA-15 catalysts and its correlation with Lewis acidity and catalytic activity in the oxidation of 4,6-dimethyl­dibenzothiophene (4,6-DMDBT) in a model diesel were reported. All the WO3/SBA-15 catalysts predominantly contained Lewis acid sites and some oxygen defects in the crystalline structure of WO3. The oxygen defect concentration increased from 1.67% to 16.66% per lattice cell unit, and the number of Lewis acid sites varied from 92 to 458 μmol/g as the WO3 content increased from 5 to 25 wt %. The 4,6-DMDBT conversion was almost proportional to both the number of Lewis acid sites and oxygen defects. Formic acid addition led to formation of peroxyformic acid which coordinated with surface W6+ to generate reactive oxygen species like peroxometallic complex, improving oxidant stability and 4,6-DMDBT oxidation efficiency. More than 99% of 4,6-DMDBT was removed with the best 25 wt % WO3/SBA-15 catalyst within 15 min of reaction under the optimal condition. A reaction mechanism involving peroxometallic complexes formation, 4,6-DMDBT molecules adsorption, and surface oxidation reaction on structural defects and vanadia nanoparticles was proposed. This biphasic reaction system consisting of a catalyst bearing Lewis acid site, a green oxidant, an oxidant promoter, and a polar solvent would simultaneously perform the oxidation and separation of polyaromatic sulfur compounds in one operation which was very practical for ultralow sulfur diesel production.

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In the present work, we study the phase composition of ZrO2-TiO2 system by means of XRD and Raman spectroscopy, using also TG-ATD, and N2 adsorption isotherms as complementary characterization techniques. TiO2-ZrO2 samples of selected compositions (0, 10, 90, 50 and 100% in weight of TiO2) were prepared by sol–gel method and annealed at three different temperatures (400, 600 and 800 °C). Structural characterization reveals that only the pure oxides are crystalline at 400 °C: TiO2 as anatasa with a minor brookite component, and ZrO2 as a mixture of tetragonal (majority) and monoclinic phases. Following the 600 °C calcination, the TiO2-ZrO2 50–50% sample forms the ZrTiO4 mixed oxide, although this materials remains partly amorphous. In contrast, samples with higher and lower TiO2 content form solid solutions with, respectively, anatasa and tetragonal ZrO2 structures. Zirconium incorporation into the TiO2 lattice leads to the expansion of the unit cell parameters, and it stabilizes the anatase phase, hindering its transformation into rutile. Similarly, dissolving titanium atoms into the ZrO2 structure delays the transformation from the tetragonal to the monoclinic polymorph.

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