Toxin‐Blocking Textiles: Rapid, Benign, Roll‐to‐Roll Production of Robust MOF‐Fabric Composites for Organophosphate Separation and Hydrolysis

Morgan, Sarah E.; Willis, Morgan L.; Dianat, Golnaz; Peterson, Gregory W.; Mahle, John J.; Parsons, Gregory N.

doi:10.1002/cssc.202201744

Cited by 9 publications

(20 citation statements)

References 41 publications

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“…It was hypothesized that CWA permeation time would increase with MOF loading. Based on previously published data, GD breaks through untreated PET instantaneously . For GD permeation tests, the time required to permeate through PET@UiO-66-NH 2 (x2) was greater than PET@UiO-66-NH 2 (x1).…”

Section: Resultsmentioning

confidence: 85%

“…Data points for StedCarb and untreated PET (0-PET) are reprinted from previous work. 17 GD hydrolysis was conducted by dosing the liquid agent directly to a MOF-fabric swatch without the use of buffer or solvent. Both untreated PET and StedCarb showed low reactivity.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Paraoxon-methyl (DMNP) hydrolysis tests were performed as previously described. ,, First, a stir bar, 14 mg of MOF-fabric, and 1 mL of 0.45 M aqueous N -ethylmorpholine (NEM, Fluka) were added to an Eppendorf tube and stirred for 15 min at ∼1100 RPM. Without contacting the NEM solution or MOF-fabric, 4 μL of DMNP (Pestanal) was added to the wall of the Eppendorf tube.…”

Section: Methodsmentioning

confidence: 99%

“…However, these composites were made using DMF, and GD permeation was not considered. There are very limited reports of UiO-66 fabric tested for the vapor permeation of GD. ,, Spandex@UiO-66-NH 2 and PET@UiO-66-NH 2 composites have been tested for GD hydrolysis and permeation, but no other CWAs were considered in these studies. , Not only is UiO-66-NH 2 effective toward neutralizing and delaying nerve agent permeation, but it has also been repeatedly shown to minimize permeation of 2-chloroethyl ethyl sulfide (CEES), a simulant for distilled mustard (HD). − Song et al tested a UiO-66-NH 2 graphene oxide/polytetrafluorethylene (ePTFE) membrane for both GD and HD permeation; however, that work did not test the composite for toxic chemical decontamination . Hence, UiO-66-NH 2 composites are an excellent candidate for dual agent protection applications, and more studies are needed to correlate both agent neutralization and permeation properties essential for effective personal protective equipment.…”

Section: Introductionmentioning

confidence: 99%

“…14,17,31 Spandex@UiO-66-NH 2 and PET@UiO-66-NH 2 composites have been tested for GD hydrolysis and permeation, but no other CWAs were considered in these studies. 14,17 Not only is UiO-66-NH 2 effective toward neutralizing and delaying nerve agent permeation, but it has also been repeatedly shown to minimize permeation of 2-chloroethyl ethyl sulfide (CEES), a simulant for distilled mustard (HD). 32−35 Song et al tested a UiO-66-NH 2 graphene oxide/polytetrafluorethylene (ePTFE) membrane for both GD and HD permeation; however, that work did not test the composite for toxic chemical decontamination.…”

Section: ■ Introductionmentioning

confidence: 99%

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Factors and Limitations of Green, Rapid Metal–Organic Framework-Fabric Synthesis and Effects on Dual Chemical Warfare Agent Protection

Morgan,

Rivera,

Willis

et al. 2023

Ind. Eng. Chem. Res.

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Metal−organic framework (MOF) fabric composites integrate important MOF chemistry with flexible, strong fabric substrates and are useful in many applications ranging from sensing, biomedical, and filtration to catalysis. Sorption-vapor synthesis (SVS) is a recently introduced method for MOF-fabric synthesis that allows high yields and rapid reactions and is scalable. However, little is known about the effects and limitations of process parameters on the final MOFfabric properties and performance. This work investigates process parameter−MOF property−MOF performance relationships for UiO-66-NH 2 fabric composites made using a rapid, benign SVS approach and is tested for toxic chemical vapor protection applications. Repeating SVS synthesis, ∼70 min per cycle, on the same fabric substrate led to an increase in MOF loading of 0.13 g MOF /g fiber per cycle and significant change in crystal morphology. It was determined that precursor concentrations >130 mM in the starting solution resulted in nonporous, amorphous MOF formation. The benign SVS method reported here achieved >95% heterogeneous MOF yield determined through scalability experiments. The MOF-fabrics were tested for organophosphate hydrolysis and permeation of both organophosphate and vesicant toxic vapors. It was found that the number of SVS cycles used to make a MOF-fabric significantly impacted performance, and despite having increased porous MOF loading, increasing over three SVS cycles led to reduced organophosphate hydrolysis rates and protection times. This work not only presents insights into the effect of synthesis process parameters on final MOF-fabric properties but also relates those changes to performance in dual toxic vapor protection applications.

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Section: Resultsmentioning

confidence: 85%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Factors and Limitations of Green, Rapid Metal–Organic Framework-Fabric Synthesis and Effects on Dual Chemical Warfare Agent Protection

Morgan,

Rivera,

Willis

et al. 2023

Ind. Eng. Chem. Res.

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Fibrous Material Structure Developments for Sustainable Heterogeneous Catalysis – An Overview

Loccufier,

Debecker,

D'hooge

et al. 2024

ChemCatChem

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The continuous development of advanced catalysts to increase process yield and selectivity is crucial. A high specific surface area and a good active phase dispersion are generally essential to create catalytic materials with a large number of active sites. Notably, materials with a fibrous morphology are appealing because of their large surface‐to‐volume ratio and flexibility. This contribution highlights the morphology of different types of fibrous structures currently under investigation, all the way from the nanoscale to the macroscale and back, where the distinction lies in the length and diameter of the fibers, as well as in the connection between the structures. Fibers with at least one nanoscale characteristic result in higher yield compared to macroscopic structures, but can display practical usability issues. Therefore, microfiber and fabric catalysts are more industrially relevant today. By combining different morphologies, the best of both nanomaterials and macroscopic integer materials can be combined into advanced catalytic materials. This overview showcases the large potential of these materials but makes clear that further research is needed to keep expanding the use and effectiveness of fibrous structures in catalysis.

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Toxin‐Blocking Textiles: Rapid, Benign, Roll‐to‐Roll Production of Robust MOF‐Fabric Composites for Organophosphate Separation and Hydrolysis

et al. 2022

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Current approaches to create zirconium‐based metal–organic framework (MOF) fabric composites for catalysis, water purification, wound healing, gas sorption, and other applications often rely on toxic solvents, long reaction/post processing times, and batch methods hindering process scalability. Here, a novel mechanism was reported for rapid UiO‐66‐NH2 synthesis in common low‐boiling‐point solvents (water, ethanol, and acetic acid) and revealed acid–base chemistry promoting full linker dissolution and vapor‐based crystallization. The mechanism enabled scalable roll‐to‐roll production of mechanically resilient UiO‐66‐NH2 fabrics with superior chemical protective capability. Solvent choice and segregated spray delivery of organic linker and metal salt MOF precursor solutions allowed for rapid MOF nucleation on the fiber surface and decreased the energy and time needed for post‐processing, producing an activated composite in less than 165 min, far outpacing conventional MOF‐fabric synthesis approaches. The MOF‐fabric hydrolyzed and blocked permeation of the chemical warfare agent soman, outperforming the protection‐standard activated carbon cloth. This work presents both chemical insights into Zr‐MOF powder and fabric composite formation by a rapid, industrially relevant approach and demonstrates its practicality and affordability for high‐performing personal protective equipment.

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Toxin‐Blocking Textiles: Rapid, Benign, Roll‐to‐Roll Production of Robust MOF‐Fabric Composites for Organophosphate Separation and Hydrolysis

Cited by 9 publications

References 41 publications

Factors and Limitations of Green, Rapid Metal–Organic Framework-Fabric Synthesis and Effects on Dual Chemical Warfare Agent Protection

Factors and Limitations of Green, Rapid Metal–Organic Framework-Fabric Synthesis and Effects on Dual Chemical Warfare Agent Protection

Fibrous Material Structure Developments for Sustainable Heterogeneous Catalysis – An Overview

Toxin‐Blocking Textiles: Rapid, Benign, Roll‐to‐Roll Production of Robust MOF‐Fabric Composites for Organophosphate Separation and Hydrolysis

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