Mild In Situ Growth Strategy for Constructing High-Strength Zr-MOFs/PVDF Fabrics and Efficient Degradation of Chemical Warfare Agent Simulants

Zirconium-based metal organic frameworks (Zr-MOFs) exhibit rich porosity and superior catalytic activity, endowing them significant potential in the application of catalytic detoxification. Self-cleaning textiles developed by integrating Zr-MOFs into fibrous carriers represent an ideal form of protective material against chemical warfare agents (CWAs). Nanofibers have been extensively explored as substrates for flexible Zr-MOF textiles owing to their high specific surface areas and porosities. However, achieving a uniform and robust loading of Zr-MOFs onto nanofibers while maintaining their excellent mechanical properties remains challenging. In this study, we propose a methodology for preparing high-strength polyvinylidene fluoride (PVDF) nanofiber/Zr-MOFs flexible textiles. We introduce a mild in situ growth strategy that incorporates trisubstituted triazine (TTMA) as a cross-linking agent, successfully enabling the uniform growth of UiO-66-NH2 on PVDF nanofiber surfaces at 60 °C and ambient pressure. TTMA exhibited excellent dual-functional characteristics, promoting fiber cross-linking to enhance the mechanical strength of PVDF, while its abundant carbonyl groups served as active sites to induce rapid growth and secure attachment of UiO-66-NH2. The resulting UiO-66-NH2@PTH (nanofibers grew membranes with different TTMA contents) composite membranes exhibited outstanding flexibility and mechanical properties, with tensile strengths reaching up to 18.87 MPa. The uniformly and tightly loaded UiO-66-NH2 particles conferred exceptional catalytic degradation performance against CWA simulants, achieving degradation efficiencies of 99.15 and 99.24% for the CWA simulants 2-chloroethyl ethyl sulfide and dimethyl 4-nitrophenyl phosphate, respectively, with excellent stability and durability. Additionally, the UiO-66-NH2@PTH displays superior moisture vapor permeability, with a moisture vapor transmission rate of 5179.3 g/m2·24 h, ensuring a balance between protection and comfort. This simple and feasible strategy may also be applicable to other nanofiber/MOF combinations, offering insights and methods for developing high-performance protective materials against CWAs.