Metal–Organic Frameworks (MOFs) as Artificial Phosphatases: From Biological Phosphate Ester Hydrolysis to Organophosphorus Chemical Warfare Agent Detoxification

Metal-organic frameworks (MOFs) have emerged as versatile artificial phosphatases capable of mimicking the Lewis acidic active sites of natural phosphoesterase enzymes. This review traces the development of MOF-based phosphatase catalysts from the fundamental principles of biological phosphate ester hydrolysis to their practical application in degrading organophosphorus pollutants and chemical warfare agents. The mechanistic challenges of activating the phosphorus center are discussed, with particular attention to the roles of metal ion Lewis acidity, coordination environment, and active-site architecture in governing catalytic activity. The structural advantages of MOFs are examined in the context of phosphate hydrolysis catalysis. Major MOF families and key structure-activity relationships, including node connectivity, defect engineering, and linker functionality, are discussed to provide mechanistic insight. The review further covers MOF phosphatase applications in detoxifying organophosphate pesticides and nerve agents, highlighting advances in solution-phase catalysis and solid-state decontamination. Special focus is given to deployable composites-MOF-coated textiles, membranes, hydrogels, and aerogels-designed to translate catalytic performance into practical protective systems. Finally, challenges limiting large-scale implementation are assessed, and future directions are outlined, including catalyst regeneration, hierarchical materials engineering, sustainable manufacturing, and the exploration of catalytic metal nodes beyond zirconium.