Near-instantaneous catalytic hydrolysis of organophosphorus nerve agents with zirconium-based MOF/hydrogel composites

Ma, Kaikai; Wasson, Megan C.; Wang, Xingjie; Zhang, Xuan; Idrees, Karam B.; Chen, Zhijie; Wu, Yüfang; Lee, Seung-Joon; Cao, Ran; Chen, Yongwei; Yang, Lifeng; Son, Florencia A.; İslamoğlu, Timur; Peterson, Gregory W.; Mahle, John J.; Farha, Omar K.

doi:10.1016/j.checat.2021.06.008

Cited by 61 publications

(78 citation statements)

References 51 publications

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“…The catalytic activity is very similar to that of the reaction in organic base solution, while the monolithic composite catalyst is practical as a mask filler against different nerve agent threats. MOF‐808/BC‐1 and BC‐1/BPEIH alone did not exhibit obvious conversion of DMNP, highlighting the resulting synergy of the composite (Figure S32, S33) [7c] . The MOF‐808/BC‐1/BPEIH composite was aged for 2 months in a sealed vial and fully converted DMNP within 10 min, consistent with the fresh sample (Figure 5d).…”

Section: Resultssupporting

confidence: 63%

“…The polymeric BPEIH acts as a nonvolatile base which supplies hydroxyl ions to regenerate the catalytic sites in MOF. Also, it supplies water to mediate the micro‐environment at the active site and to boost the catalytic hydrolysis of nerve agents and their simulants [7c] . At the same time, the hierarchical structure of the composite enables agent diffusion, with increased contact with the catalyst for faster hydrolysis.…”

Section: Resultsmentioning

confidence: 99%

“…To further improve the practicality of the composite used in protective gear, a crosslinked branched polyethyleneimine hydrogel (BPEIH) was introduced to the porous MOF‐808/BC‐1 composite (termed as MOF‐808/BC‐1/BPEIH, Figure 5a, b and Figure S30) [7c] . The polymeric BPEIH acts as a nonvolatile base which supplies hydroxyl ions to regenerate the catalytic sites in MOF.…”

Section: Resultsmentioning

confidence: 99%

“…At the same time, the hierarchical structure of the composite enables agent diffusion, with increased contact with the catalyst for faster hydrolysis. We carried out solid‐state hydrolysis of DMNP to probe the catalytic performance of this MOF‐808/BC‐1/BPEIH by adding 4 μL simulant on the composite's surface (0.7 cm×0.7 cm×0.015 cm, with 6 mol % catalyst, Figure S31) directly under ambient humidity (relative humidity=50 %) [7a,c] . The extent of the hydrolysis reaction was monitored by 31 P NMR following the digestion of the composite after a certain contact time.…”

Section: Resultsmentioning

confidence: 99%

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Environmentally Benign Biosynthesis of Hierarchical MOF/Bacterial Cellulose Composite Sponge for Nerve Agent Protection

Cheung

Wasson

et al. 2022

Angewandte Chemie

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The fabrication of MOF polymer composite materials enables the practical applications of MOF‐based technology, in particular for protective suits and masks. However, traditional production methods typically require organic solvent for processing which leads to environmental pollution, low‐loading efficiency, poor accessibility, and loss of functionality due to poor solvent resistance properties. For the first time, we have developed a microbial synthesis strategy to prepare a MOF/bacterial cellulose nanofiber composite sponge. The prepared sponge exhibited a hierarchically porous structure, high MOF loading (up to ≈90 %), good solvent resistance, and high catalytic activity for the liquid‐ and solid‐state hydrolysis of nerve agent simulants. Moreover, the MOF/ bacterial cellulose composite sponge reported here showed a nearly 8‐fold enhancement in the protection against an ultra‐toxic nerve agent (GD) in permeability studies as compared to a commercialized adsorptive carbon cloth. The results shown here present an essential step toward the practical application of MOF‐based protective gear against nerve agents.

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Section: Resultssupporting

confidence: 63%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Environmentally Benign Biosynthesis of Hierarchical MOF/Bacterial Cellulose Composite Sponge for Nerve Agent Protection

Cheung

Wasson

et al. 2022

Angewandte Chemie

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“…Metal–organic frameworks (MOFs), porous crystalline solids, composed of inorganic nodes and organic linkers, offer structural and chemical tunability amenable to a myriad of applications including toxic gas capture for air purification and the catalytic degradation of chemical warfare agents (CWAs). − Moreover, MOFs have been incorporated into a range of wearable textile fibers to form MOF-based fibrous composites for targeted applications. For example, along with others, we demonstrated the detoxification of CWAs using MOF/fiber composites which are paving the way for MOF-based protective suits and masks. − Specially, a porphyrin-based MOF was coated onto textile and showed good catalytic selective oxidation of mustard gas simulant . The use of UV light and solvent introduces challenges for the practical application.…”

Section: Introductionmentioning

confidence: 95%

Immobilized Regenerable Active Chlorine within a Zirconium-Based MOF Textile Composite to Eliminate Biological and Chemical Threats

Cheung

Leeuwen³

et al. 2021

J. Am. Chem. Soc.

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The most recent global health crisis caused by the SARS-CoV-2 outbreak and the alarming use of chemical warfare agents highlight the necessity to produce efficient protective clothing and masks against biohazard and chemical threats. However, the development of a multifunctional protective textile is still behind to supply adequate protection for the public. To tackle this challenge, we designed multifunctional and regenerable N-chlorine based biocidal and detoxifying textiles using a robust zirconium metal–organic framework (MOF), UiO-66-NH2, as a chlorine carrier which can be easily coated on textile fibers. A chlorine bleaching converted the amine groups located on the MOF linker to active N-chlorine structures. The fibrous composite exhibited rapid biocidal activity against both Gram-negative bacteria (E. coli) and Gram-positive bacteria (S. aureus) with up to a 7 log reduction within 5 min for each strain as well as a 5 log reduction of SARS-CoV-2 within 15 min. Moreover, the active chlorine loaded MOF/fiber composite selectively and rapidly degraded sulfur mustard and its chemical simulant 2-chloroethyl ethyl sulfide (CEES) with half-lives less than 3 minutes. The versatile MOF-based fibrous composite designed here has the potential to serve as protective cloth against both biological and chemical threats.

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Fibrous Zr‐MOF Nanozyme Aerogels with Macro‐Nanoporous Structure for Enhanced Catalytic Hydrolysis of Organophosphate Toxins

Ma,

Cheung,

Kirlikovali

et al. 2023

Advanced Materials

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Metal–organic frameworks (MOFs) with Lewis acid catalytic sites, such as zirconium‐based MOFs (Zr‐MOFs), comprise a growing class of phosphatase‐like nanozymes that can degrade toxic organophosphate pesticides and nerve agents. Rationally engineering and shaping MOFs from as‐synthesized powders into hierarchically porous monoliths is essential for their use in emerging applications, such as filters for air and water purification and personal protection gear. However, several challenges still limit the production of practical MOF composites, including the need for sophisticated reaction conditions, low MOF catalyst loadings in the resulting composites, and poor accessibility to MOF‐based active sites. To overcome these limitations, a rapid synthesis method is developed to introduce Zr‐MOF nanozyme coating into cellulose nanofibers, resulting in the formation of processable monolithic aerogel composites with high MOF loadings. These composites contain Zr‐MOF nanozymes embedded in the structure, and hierarchical macro‐micro porosity enables excellent accessibility to catalytic active sites. This multifaceted rational design strategy, including the selection of a MOF with many catalytic sites, fine‐tuning the coating morphology, and the fabrication of a hierarchically structured monolithic aerogel, renders synergistic effects toward the efficient continuous hydrolytic detoxification of organophosphorus‐based nerve agent simulants and pesticides from contaminated water.

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Near-instantaneous catalytic hydrolysis of organophosphorus nerve agents with zirconium-based MOF/hydrogel composites

Cited by 61 publications

References 51 publications

Environmentally Benign Biosynthesis of Hierarchical MOF/Bacterial Cellulose Composite Sponge for Nerve Agent Protection

Environmentally Benign Biosynthesis of Hierarchical MOF/Bacterial Cellulose Composite Sponge for Nerve Agent Protection

Immobilized Regenerable Active Chlorine within a Zirconium-Based MOF Textile Composite to Eliminate Biological and Chemical Threats

Fibrous Zr‐MOF Nanozyme Aerogels with Macro‐Nanoporous Structure for Enhanced Catalytic Hydrolysis of Organophosphate Toxins

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