Fuels with extremely low sulfur content are highly desirable as a result of the growing environmental concerns. In this work, a simple and novel method to connect a ZrIV open site with polyoxometalates (POM) was introduced, which was used as an effective heterogeneous catalyst for oxidative desulfurization of fuel oil. ZrPTA X -BTC composites were synthesized conveniently and rapidly at room temperature and atmospheric pressure using pyromellitic acid (BTC) as a linker. The products were characterized by XRD, TGA, FT-IR, NMR, SEM, and N2 adsorption–desorption, which verified the successful preparation of ZrPTA X -BTC composite. ZrPTA X -BTC catalyst has high content of active components, and has excellent catalytic activity in oxidative desulfurization reaction. It achieves rapid and complete desulfurization under mild reaction conditions (T = 50 °C, O/S = 4, t = 30 min, DBT removal rate reaches 100%). Further studies show that the synergistic catalysis of a ZrIV open site and PTA molecule is the reason for its high catalytic activity, in which the ZrIV open site promotes the decomposition of H2O2 into O2·, PTA molecules combine with O2· to form peroxytungstate (W­(O2) n ), and the close distance between the ZrIV open site and PTA in ZrPTA X -BTC allows H2O2 to be efficiently utilized. In addition, ZrPTA X -BTC can be easily recovered and reused for at least five times, and only a slight decrease in catalytic activity has occurred. Therefore, ZrPTA X -BTC has high catalytic activity, high stability, and good reusability, which is a potential catalyst that can realize the application of fuel ultradeep desulfurization.

Deep desulfurization of fuel oil is always a highly challenging issue. In this work, Zr X PTA material was obtained by directly combining the ZrIV active site with PTA, and it was found that Zr X PTA has excellent catalytic activity in the oxidative desulfurization (ODS) process. Further, Zr X PTA was loaded on γ-Al2O3 by the two-step impregnation to obtain a granular Al2O3@Zr X PTA composite. The successful synthesis of the material was verified by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), scanning electron microscopy (SEM), energy-dispersive spectrometry (EDS), and N2 adsorption–desorption. The results show that Al2O3@Zr X PTA maintains the high ODS activity of Zr X PTA and realizes the rapid and complete removal of dibenzothiophene under mild reaction conditions (T = 40 °C, O/S = 4, t = 30 min). The mechanism study shows that the ODS activity of Al2O3@Zr X PTA is wholly derived from the counterpart of Zr X PTA, which benefits from the synergistic catalytic effect between the ZrIV active site and PTA. The direct binding of these two active sites makes the synergistic effect fully exerted. In addition, the recovery of Al2O3@Zr X PTA can be easily realized by simple filtration or decantation, and no significant activity loss was observed after five times recycling. Therefore, Al2O3@Zr X PTA has high ODS activity, high catalytic stability, and great potential as an ODS catalyst in practical applications.