Activatingthe Gate-Opening Effect in Multivariate MOFs by Defect Engineeringfor Oxidative Desulfurization

Abstract Metal–organic frameworks (MOFs) have shown great potential in catalytic oxidative desulfurization (ODS), yet their efficiency is often hampered by intrinsically inaccessible pore networks that impede the contact between active sites and reactants. To unlock the potential of these confined pores, we report a defect engineering strategy to construct multivariate MOFs by incorporating sulfonated linkers, which effectively induces linker vacancies to generate defect-fused pores (DFPs). These DFPs not only expand the pore aperture to 14.8 Å, leading to a 1.8-fold enhancement in dibenzothiophene adsorption capacity, but also modulate the electronic structure of Zr nodes, enhancing their electrophilicity. As a result, the optimized MTV-UiO-20 achieves an exceptional desulfurization efficiency of 99.9%, significantly outperforming pristine UiO-66 (58.3%) under identical conditions. Combined experimental and theoretical studies reveal that the gate-opening effect facilitated by DFPs promotes reactant accessibility to active sites, while hydroxyl radicals generated from H2O2 activation dominate the oxidation process. This work provides a rational design strategy for activating MOF catalysts through synergistic pore and defect engineering.