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.