Dual-Function Detoxifying Nanofabrics against Nerve Agent and Blistering Agent Simulants

Abstract

The development of functional materials that can detoxify multiple chemical warfare agents (CWAs) at the same time is of great significance to cope with the uncertainty of CWA use in real-world situations. Although many catalysts capable of detoxifying CWAs have been reported, there is still a lack of effective means to integrate these catalytic-active materials on practical fibers/fabrics to achieve effective protection against coexistence of a variety of CWAs. In this work, by a combination of electrospinning and in situ solvothermal reaction, PAN@Zr(OH)4@MOF-808 nanofiber membranes were prepared for detoxification of both nerve agent and blistering agent simulants dimethyl 4-nitrophenyl phosphate (DMNP) and 2-chloroethyl ethyl sulfide (CEES). Under the catalytic effect of the MOF-808 component, DMNP hydrolysis with a half-life as short as 1.19 min was achieved. Meanwhile, an 89.3% CEES removal rate was obtained within 12 h by adsorption and catalysis of MOF-808 and Zr(OH)4 components at ambient conditions, respectively. PAN@Zr(OH)4@MOF-808 nanofiber membranes also showed a superior blocking effect on CEES compared to bare PAN and PAN@Zr(OH)4 nanofiber membranes. Simultaneous protection against DMNP and CEES showed effective inhibition of both simulants for at least 2 h. The preparation method also imparted intrinsically good interfacial adhesion between the components, contributing to the excellent recycling stability of PAN@Zr(OH)4@MOF-808 nanofiber membranes. Therefore, the prepared composite nanofabrics have great application potential, which provides a new idea for the construction of broad-spectrum protective detoxification materials.

Self-Assembled MOF-on-MOF Nanofabrics for Synergistic Detoxification of Chemical Warfare Agent Simulants

“…Therefore, PAN/UiO-66-NH 2 /MIL-101(Cr) nanofabrics were further explored to capture and remove the sulfur mustard simulant CEES. It is known that oxidation and hydrolysis are two general pathways for sulfur mustard detoxification. , Here, experiments for CEES removal were carried out at 25 °C and a 50% RH in the air, without the use of LED irradiation and concentrated oxygen, avoiding the risk of excessive oxidation. The slow hydrolysis of CEES under such natural conditions using a UiO-66-NH 2 catalyst could be supplemented by the reaction with the amino group and the adsorption in giant cages of MIL-101(Cr).…”

“…Metal–organic framework (MOF) materials, a class of porous crystalline materials assembled from metal nodes and organic linkers, have received tremendous research attention in both capture and detoxification of many types of CWAs due to their exceptionally high surface areas and high tunability, chemical versatility, and abundant catalytic sites. − Among the MOFs being studied (e.g., MOF-5, Cu-BTC, and MIL-101), Zr-based MOFs have shown great promise for the detoxification of CWAs for their high density of accessible strong Lewis acidic sites, exceptional thermal and chemical stability, and Zr 6 cluster nodes with varying degrees of connectivity. − However, MOFs tend to form nano-to-micro-sized particles during typical synthesis, making them inconvenient to process and deploy in protective gears. The integration of MOFs with support materials such as flexible textile fibers improves processability and is ideal for the realization of personal textiles. ,− Over the past decade, many strategies have been developed for the fabrication of composite MOF fabrics for CWA protection, − but several limitations still exist that ultimately hinder their widespread adoption. Depending on whether the catalytic MOFs are presynthesized or not, the composite fabric fabrication strategies can be broadly divided into two types.…”

“…Depending on whether the catalytic MOFs are presynthesized or not, the composite fabric fabrication strategies can be broadly divided into two types. The first one, and also the most reported at present, is to deposit catalytic MOFs on modified or unmodified fibrous substrates through in situ growth. − For instance, Zr-MOF nanofiber kebabs were prepared by a solvothermal reaction using atomic layer deposition (ALD)-modified nanofibers, which showed ultrafast detoxification of nerve agents . Direct growth of Zr-MOFs on pristine textiles has also been achieved by regulating the solvothermal reaction conditions, which greatly simplifies the procedures. − While in situ growth can effectively adjust the uniformity and morphology of the composite fibers, the harsh conditions under which an MOF forms including solvents and high temperatures greatly limit the choice of synthetic polymeric fibers .…”

Metal–organic frameworks on versatile substrates

“…Other self-designed substrate, like carbon substrate, 170 in situ annealing of plants, 171 nitrogen templates, and sulfur templates, 172 can also be used as matrices. Besides, some organic conducting polymers, such as polyacrylonitrile (PAN), [172][173][174][175][176][177][178][179][180][181][182][183][184][185] polyaniline (PANI), [186][187][188][189] and polypyrrole 190 have also been investigated. The fabrication of MOF lms on conducting substrates has shown great potential in the applications of electronic conduction and sensing.…”

Boosted ability of ZIF-8 for early-stage adsorption and degradation of chemical warfare agent simulants

“…Metal–organic frameworks (MOFs) are an interesting class of porous materials that have garnered considerable attention owing to their unique properties and applications in various fields. 1–28 These materials comprise metal ions or clusters linked by organic ligands, resulting in highly porous structures with large surface areas and tunable pore sizes. MOFs have a wide range of applications in gas storage, catalysis, sensing, adsorption, and separation.…”