Amorphous Cr₂WO₆-Modified WO₃ Nanowires with a Large Specific Surface Area and Rich Lewis Acid Sites: A Highly Efficient Catalyst for Oxidative Desulfurization

Abstract

The oxidative desulfurization (ODS) of fuel oils is of great significance for environmental protection, and the development of efficient ODS heterogeneous catalysts is highly desired. Herein, we have designed and synthesized a novel material of amorphous Cr₂WO₆-modified WO₃ (a-Cr₂WO₆/WO₃) nanowires (3-6 nm) with a large specific surface area of 289.5 m²·g^-1 and rich Lewis acid sites. The formation of such a unique nanowire is attributed to the adsorption of Cr³⁺ cations on non-(001) planes of WO₃. In the ODS process, the a-Cr₂WO₆/WO₃ nanowires can efficiently oxidize benzothiophene (BT), dibenzothiophene (DBT), and 4,6-dimethyldibenzothiophene (4,6-DMDBT) to their corresponding sulfones in a quasi-microemulsion reaction system and possess the highest activity (<i>E</i>_a = 55.4 kJ/mol) for DBT: 99.0% of 15,000 ppm DBT with 2600 ppm S can be removed (70 °C, H₂O₂ as the oxidant). The improvement in ODS activity from most of WO₃ catalysts is owing to the sufficient active sites and enhanced adsorption of DBT on the basis of structural features of a-Cr₂WO₆/WO₃ nanowires. Combined with free radical capture experiments, a possible ODS mechanism of W(O₂) peroxotungstate route based on surface -OH groups is reasonably proposed. Moreover, the a-Cr₂WO₆/WO₃ nanowires have good stability and can be synthesized on a large scale, suggesting its potential applications as an efficient heterogeneous catalyst.