Robust Functionalized Cotton Fabrics with Zr-Based Tetrahedral Cages for Degrading a Chemical Warfare Agent Simulant

The resurgence of chemical warfare agents (CWAs) in recent decades underscores the urgent need for efficient and durable personal protective equipment (PPE). Conventional systems employing zeolites or activated carbons provide only passive protection via adsorption and suffer from limited porosity, low catalytic activity, and weak adhesion to textile substrates. To address these challenges, metal-organic cages (MOCs) offer a promising alternative to metal-organic frameworks (MOFs) due to their solubility, molecular nature, and tunable surface reactivity. In this study, we report the deposition of zirconium-based MOCs (ZrMOCs) onto cotton fabrics using impregnation and in situ growth techniques to develop catalytically active and mechanically robust composites. The resulting MOC-cotton materials were characterized for deposition uniformity and durability under abrasion and aging tests. Their catalytic performance was evaluated toward the hydrolytic degradation of dimethyl 4-nitrophenyl phosphate (DMNP), a nerve-agent simulant. The in situ growth method yielded homogeneous coverage and strong interfacial bonding between the ZrMOCs and cellulose fibers, resulting in enhanced resistance to mechanical stress and artificial aging, while retaining excellent breathability. Despite a moderate loading (6 wt %), the composite exhibited rapid DMNP decomposition (t1/2 < 25 min) and maintained activity after the abrasion normed test. Although catalytic efficiency decreased after aging, it remained superior to that of MOF-based cotton composites (UiO-66-NH₂). These results demonstrate the potential of ZrMOC-functionalized textiles as active protective materials for next-generation PPE for CWA decontamination, offering a promising route toward durable and multifunctional fabrics.