An efficient and recyclable oxidative desulfurization process (ODS) to remove the most refractory sulfur-compounds (dibenzothiophene, 1-benzothiophene and 4,6-dimethyldibenzothiophene) from fuel is reported. The ODS process was catalyzed by terbium-polyoxometalate [Tb(PW11O39)(2)](11-) (Tb(PW11)(2)) and its composite Tb(PW11)(2)@MIL-101. The tetrabutylammonium (TBA) salt of Tb(PW11)(2) was prepared and further incorporated in the porous metal-organic framework MIL-101(Cr). The TBA compound and its composite were characterized by various techniques (powder X-ray diffraction, FT-IR, FT-Raman, SEM and elemental analysis), and their electrochemical behavior was investigated, indicating that the structure of the polyoxometalate anion must be retained after immobilization. The studied ODS process was based on a biphasic system formed by a model oil with various refractor sulfur-compounds and an extracting solvent using H2O2 as the oxidant. Two main steps in the process were carefully investigated: the initial extraction and the oxidative catalytic stage. The optimization of the ODS process was performed by the analysis of the most suitable extracting solvent and also comparing the desulfurization performance of the homogeneous Tb(PW11)(2) and the heterogeneous Tb(PW11)(2)@MIL-101 catalysts. Acetonitrile was selected as the best solvent because it allowed the highest desulfurization rate, conciliating good initial extraction and high catalytic performance. The presence of the porous catalyst Tb(PW11)(2)@MIL-101 seemed not to influence the initial extraction step; however, with this porous hybrid catalyst were obtained higher desulfurization rates during the catalytic stage. Remarkably, using Tb(PW11)(2)@MIL-101 and the oil-acetonitrile system complete desulfurization of oil was achieved only after 5 h. The recyclability of the solid catalyst was investigated for three consecutive ODS cycles and its stability was confirmed by several techniques
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.