Bioinspired Porphyrin-Based Catalysts From Temporospatial Confined Frameworks for Ultrafast Removal of Sulfaclozine

Inspired by natural photosynthetic systems, the rational design of artificial photocatalysts featuring asymmetrically coordinated dual-centers and a tailored microenvironment offers promising opportunities to overcome the intrinsic limitations in selective chemical reactions. Here, we present an asymmetric coordination catalyst by immobilizing porphyrins within a defect-engineered metal-organic framework. By leveraging the matched size of guest molecules in heterogeneous pores, the electron-hole recombination obstacle was significantly overcome. Across the library of multivariate zirconia metal-organic frameworks, the optimal member stands out for its photocatalytic properties, delivering an excellent apparent quantum yield (11.31%) for ultra-fast degradation of sulfaclozine (SCL) with a 10-minute reaction time. Consistent with the extended X-ray absorption fine structure (EXAFS) and theoretical calculations, the confined groups in microporous environments remarkably increased the charge separation ability of the Zr-O nano-capsules in biomimetic porous PSI and PSII systems. The turnover frequency is 32.1 and 36.9 times higher than that of the pristine framework and the commercial TiO₂ photocatalyst, respectively. This work establishes a broadly applicable strategy for multivariate zirconia metal-organic frameworks and provides a platform for tailoring active-site configuration for photocatalytic reactions.