Rational Integration of Amino Functionalization and Catalytic Site Modulation in Zr‐MOFs for Synergistic Enhanced Photocatalysis

Abstract The modular nature endows metal–organic frameworks (MOFs) with structural precision and functional programmability. However, the predefined structural constraints of precursors and confined post‐synthetic environments pose significant challenges for achieving cooperative regulation of dual modules toward unified functionality. Herein, a versatile platform enabling precise modulation of the primary building blocks (PBBs) and secondary building blocks (SBBs) was constructed. The synergistic effect between the amino functionalization of the PBBs and the regulation of catalytic sites focusing on SBBs significantly enhances the efficiency of photocatalytic processes. The photocatalytic H 2 evolution rate of NKM‐818‐BDBPt can reach 871 µmol g −1 h −1 , which is 10.62 times higher than that of NKM‐818@Pt. This work establishes a new paradigm for exploring synergistic interactions among modular components in MOFs, and contributes to the further development of coordination‐engineering‐driven single‐site photocatalysts with excellent activity.