Surfactant‐Mediated Crystalline Structure Evolution Enabling the Ultrafast Green Synthesis of Bismuth‐MOF in Aqueous Condition

Green synthesis of stable metal‐organic frameworks (MOFs) with permanent and highly ordered porosity at room temperature without needing toxic and harmful solvents and long‐term high‐temperature reactions is crucial for sustainable production. Herein, a rapid and environmentally friendly synthesis strategy is reported to synthesize the complex topological bismuth‐based‐MOFs (Bi‐MOFs), [Bi 9 (C 9 H 3 O 6 ) 9 (H 2 O) 9 ] (denoted CAU‐17), in water under ambient conditions by surfactant‐mediated sonochemical approach, which could also be applicable to other MOFs. This strategy explores using cetyltrimethylammonium bromide (CTAB) amphiphilic molecules as structure‐inducing agents to control the removal of non‐coordinated water (dehydration) and enhance the degree of deprotonation of the ligands, thereby regulating the coordination and crystallization in aqueous solutions. In addition, another two new strategies for synthesizing CAU‐17 by crystal reconstruction and one‐step synthesis in binary solvents are provided, and the solvent‐induced synthesis mechanism of CAU‐17 is studied. The as‐prepared CAU‐17 presents a competitive iodine capture capability and effective delivery of the antiarrhythmic drug procainamide (PA) for enteropatia due to the broad pH tolerance and the unique phosphate‐responsive destruction in the intestine. The findings will provide valuable ideas for the follow‐up study of surfactant‐assisted aqueous synthesis of MOFs and their potential applications.