Encapsulating ZrW nanorods in hierarchical Zr-MOFs: Oxygen vacancy engineering for superior room-temperature oxidative desulfurization

A solvent-free strategy for the in situ implantation ZrW nanorods within Zr-FDCA was developed. • ZrW-Zr-FDCA retained hierarchical porosity, abundant oxygen vacancies and favorable oil-water wettability. • The optimized catalyst achieved complete oxidation of 1000 ppm sulfur to sulfone at 30 °C within 16 min. • The turnover frequency reaches 365.4 h −1 at 30 °C, which is 3653-fold higher than that of Zr-FDCA. • Tungsten active sites mediate H 2 O 2 activation to produce 1 O 2 as the primary reactive oxygen species. The rational design of highly effective desulfurization catalysts holds great promise for realizing exceptional synergistic catalytic activity toward the production of clean fuels. Herein, we provide a solvent-free strategy for the in situ implantation ZrW 2 O 7 (OH) 2 (H 2 O) 2 (ZrW) nanorods within a metal–organic framework (Zr-FDCA), using renewable organic linkers and Na 2 WO 4 ·2H 2 O as precursors. The resulting ZrW-Zr-FDCA composite retains hierarchical porosity, abundant oxygen vacancies and favorable oil-water wettability, which collectively promote interfacial contact and mass transfer in the biphasic system, thereby significantly enhancing oxidative desulfurization (ODS) performance at room temperature. The optimized catalyst achieves complete oxidation of 1000 ppm sulfur to sulfone at 30 °C within 16 min and maintains 96.7% sulfur removal efficiency over seven consecutive reaction cycles. Its turnover frequency reaches 365.4 h −1 at 30 °C, which is 3653-fold higher than that of Zr-FDCA. Quenching experiment and electron paramagnetic resonance spectroscopy identify W sites as the active centers responsible for H 2 O 2 activation, generating singlet oxygen as the dominant reactive oxygen species driving the ODS process. This work not only expands the one-pot solvent-free approach to encapsulate nanorods within MOFs but also provides an effective route for advancing low-temperature desulfurization. Download: Download high-res image (215KB) Download: Download full-size image