A Universal Approach for High-Yield Synthesis of Single-Crystalline Ordered Macro-Microporous Metal–Organic Frameworks

Despite the excellent properties of single-crystalline ordered macro-microporous MOFs (SOM-MOFs) compared to conventional MOFs, their further development has been hindered by the lack of versatile and high-yielding preparation protocols. This study introduces an innovative universal fabrication method that can easily solve the two major challenges of precursor stabilization and crystallization modulation, enabling the efficient synthesis of various SOM-MOFs with high yields. Notably, our approach has successfully yielded SOM-MIL-88A, a novel MOF showcasing exceptional stability in both water and acidic solutions, a remarkable achievement unprecedented in prior SOM-MOF research. SOM-MIL-88A has demonstrated exponentially improved performance over conventional MIL-88A in adsorption, catalysis, immobilized enzymes, and composite biosensing. Furthermore, our versatile protocol has been successfully applied to synthesize SOM-HKUST-1 and SOM-ZIF-8, resulting in significantly improved yields (increase by about 10-fold and 2-fold, respectively, compared to the previously reported protocol). This groundbreaking achievement marks a pivotal advancement in the preparation of diverse SOM-MOFs with tailored properties, presenting exciting prospects for future research on MOFs.