Defect-rich bimetallic UiO-66(Hf-Zr): Solvent-free rapid synthesis and robust ambient-temperature oxidative desulfurization performance

Desulfurization of fuel oil is an indispensable step to obtain clean energy source. Design of bimetallic metal-organic frameworks (MOFs) with plentiful defects and highly dispersion active species, opens a new door to boost the catalytic activity for targeted reactions. In this work, we demonstrate a rapid green approach for fabricating bimetallic UiO-66(Hf-Zr) with highly dispersion of Hf/Zr-OH defect sites under solvent-free condition. UiO-66(0.13Hf-Zr) exhibited superior activity for oxidating sulfur compounds (1000 ppm S) of fuel oil at room temperature within 15 min. The turnover frequency (TOF) number reach 129.5 h-1 at 30 °C, which is 32.2 times higher than pristine UiO-66(Zr). Theoretical results reveal that the exposed Hf-OH sites readily react with H2O2 to produce Hf-OOH intermediates which manipulate the reaction performance. Our work not only proposes a green solvent-free avenue for rapid preparation of defective bimetallic MOFs but also extends the application of bimetallic MOFs in the field of desulfurization.