UiO-66-NH₂ Fabrics: Role of Trifluoroacetic Acid as a Modulator on MOF Uniform Coating on Electrospun Nanofibers and Efficient Decontamination of Chemical Warfare Agent Simulants

Abstract

Protective fabrics with air-permeable and flexible features are crucial for practical application in the detoxification of chemical warfare agents (CWAs). Zr-based metal−organic frameworks (Zr-MOFs) are desirable to exhibit outstanding degradation toward CWAs. However, generally, MOFs with powders cannot afford the utilization as a protective layer directly; meanwhile, it is still a puzzling challenge to integrate MOFs with textiles efficiently. Herein, we develop a scalable and controllable strategy to fabricate UiO-66-NH 2 on electrospun polyacrylonitrile nanofibers (UiO-66-NH 2 fabrics) firmly and uniformly to capture and catalyze 2chloroethyl ethyl sulfide (CEES) effectively for self-detoxification. The obtained UiO-66-NH 2 fabrics are greatly capable of specific surface area, ample porosity, excellent crystallinity, and abundant catalytic active sites. Consequently, CEES can be removed efficiently up to 97.7% after 48 h by reaction and adsorption. The degradation products mainly including ethyl-2-hydroxyethyl sulfide, ether, bis [2-(ethylthio)ethyl], and 2-(2-(ethylthio)ethylamino) terephthalic acid are detected. Moreover, the obtained nanofibrous fabrics possess air-permeable, washable, and flexible as well as lightweight merits, totally ensuring their promising engineering applications for protective clothing.

Ultrafast Degradation and High Adsorption Capability of a Sulfur Mustard Simulant under Ambient Conditions Using Granular UiO-66-NH2 Metal–Organic Gels

“…As shown in Figure S17, there were neither an obvious peak of the hydrolyzed product, 2-HEES, and nor peaks of other substances, and 2-CEES was quantified to be 23.4 mg in total, which is almost equal to the value evaluated by weight. This indicates that the MOG hardly reacts with 2-CEES after adsorption of 2-CEES vapor, which is not consistent with the situation of UiO-66-NH 2 powders or fabrics …”

“…Similar results are also observed by other researchers in several studies. 20,42,43 Unfortunately, the amount of the hydrolysis product is extremely low. In addition to the hydrolysis product, the residual 2-CEES amount (with m/z values at 124, 109, 89, 75, and 47) is more.…”

“…Zirconium-based metal–organic frameworks (Zr-MOFs) are foreseen as promising materials for the degradation of CWAs due to their ease and plentiful synthesis methods and exceptional thermal, chemical, and mechanical stability. − UiO-66-NH 2 is a representative type of Zr-MOF that is assembled by Zr 6 (μ 3 -O) 4 (μ 3 -OH) 4 clusters with 2-aminoterephthalic acid through coordination bonds. It exhibits excellent activity on actual nerve agents and their simulants but lower efficacy against the detoxification of blistering agents and their simulants. − Furthermore, the crystallization of UiO-66-NH 2 tends to form microcrystalline powders. The practicability of powdered MOFs is greatly restricted due to its particle aggregation, poor processability, mass-transfer limitations, high air resistance, and difficult recycle. − On the other hand, adsorption performance is another important capability for defense against CWAs.…”

Washable and Reusable Zr-Metal–Organic Framework Nanostructure/Polyacrylonitrile Fibrous Mats for Catalytic Degradation of Real Chemical Warfare Agents

“…Compared to previous papers reported on the same topic, ,,, the novelty of our study lies in the unprecedented fabrication of well-defined fibrous mats incorporating a very high MOF NP loading that exhibit excellent catalytic CWA degradation. This is a key achievement since these fibrous mats were obtained by a simple mixing dispersion of known MOF NPs in PAN, that paves the way toward a fast and simple large-scale production for a further promotion at the market.…”

A continuous flow generator of organic hypochlorites for the neutralization of chemical warfare agent simulants

“…The development of new neutralization protocols on chemical warfare agent (CWA) simulants (as well as on actual CWAs with military clearance) has attracted increasing attention from the Chemical and Chemical Engineering communities, as evidenced by an increasing number of reviews and original articles over the past 10 years. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18] This is somehow paradoxical, yet easily justifiable with the current background threat of terror attacks, as well as alleged reports of the use of CWA targeting both entire populations or individuals. The Chemical Weapons Convention (CWC) bans since 1993 the possession, manufacture, and use of CWAs and all their precursors.…”