Controllable Synthesis of Hierarchically Macro‐, Meso‐, and Microporous UiO‐66 for Efficient Catalysis

Abstract In recent years, the controllable synthesis of hierarchically porous metal–organic frameworks (HP‐MOFs) has received significant attention. However, most synthesized HP‐MOFs are primarily adjusted in terms of second‐order porosity, and the simultaneous control of mesopore and macropore sizes in HP‐MOFs remains difficult to attain. Herein, for the first time, HP‐UiO‐66‐NH 2 is successfully synthesized with simultaneously controllable macro‐, meso‐, and micropores (MMM‐UiO‐66‐NH 2 ) by combining the hard template methods and the water‐acid competitive nucleation strategy. Impressively, the innovative introduction of a water‐acid system can effectively slow down the dissolution of polystyrene (PS) microspheres, ultimately achieving simultaneous regulation of macropore sizes in the range of 160–400 nm and mesopore sizes in the range of 3.9–10.3 nm. Meanwhile, this method can be extended to other UiO‐66 series. The hierarchically macro‐, meso‐, and microporous structure provides sufficient accessibility to substrate molecules and enables rapid mass transfer, contributing to the highest Knoevenagel condensation reaction performance. Furthermore, the MMM‐UiO‐66‐NH 2 is used as an anchoring carrier to bind the bulky phosphomolybdic acid (PMA) through the strong host‐guest interaction, endowing it with excellent catalytic oxidative desulfurization (ODS) performance. This study has developed an effective synthetic strategy for preparing HP‐MOFs and further expanded the application of HP‐MOFs in macromolecular‐related catalysis.