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 metalorganic 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 degrees 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.

Automated summary

This work demonstrates a green approach for rapid preparation of defective bimetallic MOFs with enhanced catalytic activity, showcasing the fabrication of UiO-66(Hf-Zr) with plentiful defect sites under solvent-free condition. The bimetallic UiO-66(0.13Hf-Zr) exhibits superior desulfurization activity for fuel oil, with a turnover frequency significantly higher than pristine UiO-66(Zr).