Mild In Situ Growth Strategy for Constructing High-Strength Zr-MOFs/PVDF Fabrics and Efficient Degradation of Chemical Warfare Agent Simulants
Pengju Han, Shiliang Sheng, Qin Qin, Xianglong Zheng, Shitao Wang, Xiang Li, Weili Shao, Fan Liu, Jianxin He, Xiaolong Hao, Rongwu Wang
Abstract
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-NH 2 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-NH 2 . The resulting UiO-66-NH 2 @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-NH 2 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-NH 2 @PTH displays superior moisture vapor permeability, with a moisture vapor transmission rate of 5179.3 g/m 2 ·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.