Tuning Pore Geometry of Zirconium Metal–Organic Frameworks via Bent Ligands for Enhanced Sulfide Oxidation Catalysis

Pore engineering represents a powerful strategy to tailor the physicochemical properties of metal–organic frameworks (MOFs), yet the structure‐activity relationship linking pore geometry to catalytic performance remains poorly understood for zirconium‐based MOFs (Zr‐MOFs). Herein, we report a new Zr‐MOF (PCN‐1010), featuring a scu topology with channel‐type porosity via ligand conformational bending. Distinct from the ftw ‐topology Zr‐MOF with cage‐type porosity constructed from a straight tetra‐topic ligand, PCN‐1010 contains 8‐connected Zr 6 clusters with more accessible catalytic sites and open one‐dimensional (1D) channels. The bent conformation of the linker creates alternating concave and convex surfaces along the c ‐axis, facilitating the accessibility of the active sites. In addition, PCN‐1010 exhibits high chemical stability in various organic solvents owing to the robust zirconium‐oxo coordination. As a catalytic platform for sulfide oxidation, PCN‐1010, integrated with 12‐tungstophosphoric acid, delivers high‐selectivity sulfone production with a yield of 97% instead of sulfoxide at room temperature, alongside good recyclability and broad substrate compatibility. The enhanced catalytic performance of PCN‐1010 relative to its cage‐type ftw counterpart demonstrates that rational pore geometry regulation via ligand bending is an effective route to optimize mass transport and active‐site accessibility.