Tunable Photocatalytic Singlet Oxygen Generation by Metal-Organic Frameworks via Functionalization of Pyrene-Containing Linkers.

Metal-organic frameworks (MOFs) are highly versatile materials that have shown great promise in chemical warfare agent (CWA) adsorption and decontamination. Sulfur mustard has been one of the most prominently used CWAs over the last century; therefore, the development of effective detoxification strategies is of utmost importance. However, typical routes of detoxification are slow and/or result in the production of harmful byproducts. NU-1000 has previously shown promise as a "soft" oxidizer that can readily detoxify sulfur mustard and its simulant 2-chloroethyl ethyl sulfide (2-CEES) through the generation of singlet oxygen in the presence of either UV (396 nm) or blue (465 nm) light. Several variants of NU-1000 were synthesized (MOF-R, R = -Cl, -NO2, -CH3) with functional groups positioned either ortho or meta to the carboxylic acid on the linker. NU-1000-o-(Cl)4 and NU-1000-m-(Cl)4 showed significant enhancement of photooxidation of 2-CEES due to spin-orbit coupling, enhancing the intersystem crossing into the MOF triplet (T1) state. Furthermore, substitution of MOF linkers led to pyrene-phenyl rotation. Linkers with substituents in the ortho-position were shown to have smaller pyrene-phenyl torsion angles, leading to enhanced conjugation between the rings and a subsequent red shift in the absorption spectra. This red shift leads to enhanced reactivity of NU-1000-o-(Cl)4 under blue light conditions and gives perspective on making materials with enhanced reactivity utilizing visible light.

Laponite-Incorporated UiO-66-NH2-Polyethylene Oxide Composite Membranes for Protection against Chemical Warfare Agent Simulants.

A strategy is developed to enhance the barrier protection of polyethylene oxide (PEO)-metal-organic framework (MOF) composite films against chemical warfare agent simulants. To achieve enhanced protection, an impermeable high-aspect-ratio filler in the form of Laponite RD (LRD) clay platelets was incorporated into a composite PEO film containing MOF UiO-66-NH2. The inclusion of the platelets aids in mitigating permeation of inert hydrocarbons (octane) and toxic chemicals (2-chloroethyl ethyl sulfide, 2-CEES) of dimensions/chemistry similar to prominent vesicant threats while still maintaining high water vapor transport rates (WVTR). By utilizing small-angle neutron scattering, small-angle X-ray scattering, and wide-angle X-ray scattering, the LRD platelet alignment of the films was determined, and the structure of the films was correlated with performance as a barrier material. Performance of the membranes against toxic chemical threats was assessed using permeation testing of octane and 2-CEES, a common simulant for the vesicant mustard gas, and breathability of the membranes was assessed using WVTR measurements. To assess their robustness, chemical exposure (in situ diffuse reflectance infrared Fourier transform spectroscopy) and mechanical (tensile strength) measurements were also performed. It was demonstrated that the barrier performance of the film upon inclusion of the LRD platelets exceeds that of other MOF-polymer composites found in the literature and that this approach establishes a new path for improving permselective materials for chemical protection applications.

Conducting an evaluation of CBRN canister protection capabilities against emerging chemical and radiological hazards.

In the event of a chemical, biological, radiological, or nuclear (CBRN) hazard release, emergency responders rely on respiratory protection to prevent inhalation of these hazards. The National Institute for Occupational Safety and Health's (NIOSH) CBRN Statement of Standard calls for CBRN respirator canisters to be challenged with 11 different chemical test representative agents (TRAs) during certification testing, which represent hazards from 7 distinct Chemical Families; these 11 TRAs were identified during the original 2001 CBRN hazard assessment. CBRN hazards are constantly evolving in type, intent of use, and ways of dissemination. Thus, new and emerging hazards must be identified to ensure CBRN canisters continue to provide protection to emergency responders against all hazards that would most likely be used in an intentional or unintentional event. The objectives are to: (1) update the CBRN list of hazards to ensure NIOSH-approved CBRN canisters continue to provide adequate protection capabilities from newly emerging chemical and radiological hazards and (2) identify the need to update NIOSH TRAs to ensure testing conditions represent relevant hazards. These objectives were accomplished by reviewing recent hazard assessments to identify a list of chemical and radiological respiratory hazards, evaluate chemical/physical properties and filtration behavior for these hazards, group the hazards based on NIOSH's current Chemical Families, and finally compare the hazards to the current TRAs based on anticipated filtration behavior, among other criteria. Upon completion of the evaluation process, 237 hazards were identified and compared to NIOSH's current CBRN TRAs. Of these 237 hazards, 203 were able to be categorized into one of NIOSH's current seven Chemical Families. Five were identified for further evaluation. Based on reviewing key chemical/physical properties of each hazard, NIOSH's current 11 TRAs remain representative of the identified respiratory CBRN hazards to emergency responders and should continue to be used during NIOSH certification testing. Thus, NIOSH's CBRN Statement of Standard remains unchanged. The process developed standardizes a methodology for future hazard evaluations.

Flexible SIS/HKUST-1 Mixed Matrix Composites as Protective Barriers against Chemical Warfare Agent Simulants.

We fabricated and demonstrated, for the first time, metal-organic framework (MOF), polymer mixed-matrix composites (MMCs) as effective, low burden barriers against chemical warfare agent (CWA) simulants. We incorporated the MOF HKUST-1 into elastomeric triblock copolymers of polystyrene- block-polyisoprene- block-polystyrene (SIS) for use as semipermeable barrier against the CWA simulant 2-chloroethyl ethyl sulfide (CEES). MMCs containing up to 50 wt % HKUST-1 were cast and evaluated for CEES permeation, moisture vapor transport rate (MVTR), and mechanical properties, such as elastic modulus and percent elongation. Increasing the MOF content resulted in longer protection against CEES with breakthrough times ranging from immediate breakthrough for the baseline SIS to over 4000 min for the best-performing MMC. MVTRs of high-MOF-content MMCs were approximately 5-10 times higher than either SIS or typical laboratory gloves made from nitrile and latex. The elastic moduli increased with increased MOF content corresponding to a reduction in percent elongation. The triblock copolymer also was found to protect the MOF crystal structure after exposure to CEES and liquid water, which may lead to longer usage time and shelf life. The ability to resist degradation due to moisture shows the potential utility of these composites when exposed to rain, sweat, or other moisture-rich environments. Finally, the MOF-containing composites functioned as robust colorimetric indicators of CEES exposure. Thus, these MMC materials present a potential route toward next-generation personal protective equipment with a combination of detoxification, sensing, environmental stability, and thermal/user-comfort properties not present in current materials solutions.

MOFwich: Sandwiched Metal-Organic Framework-Containing Mixed Matrix Composites for Chemical Warfare Agent Removal.

This work describes a new strategy for fabricating mixed matrix composites containing layered metal-organic framework (MOF)/polymer films as functional barriers for chemical warfare agent protection. Through the use of mechanically robust polymers as the top and bottom encasing layers, a high-MOF-loading, high-performance-core layer can be sandwiched within. We term this multifunctional composite "MOFwich". We found that the use of elastomeric encasing layers enabled core layer reformation after breakage, an important feature for composites and membranes alike. The incorporation of MOFs into the core layer led to enhanced removal of chemical warfare agents while simultaneously promoting moisture vapor transport through the composite, showcasing the promise of these composites for protection applications.

MOFabric: Electrospun Nanofiber Mats from PVDF/UiO-66-NH2 for Chemical Protection and Decontamination.

Textiles capable of capture and detoxification of toxic chemicals, such as chemical-warfare agents (CWAs), are of high interest. Some metal-organic frameworks (MOFs) exhibit superior reactivity toward CWAs. However, it remains a challenge to integrate powder MOFs into engineered materials like textiles, while retaining functionalities like crystallinity, adsorptivity, and reactivity. Here, we present a simple method of electrospinning UiO-66-NH2, a zirconium MOF, with polyvinylidene fluoride (PVDF). The electrospun composite, which we refer to as "MOFabric", exhibits comparable crystal patterns, surface area, chlorine uptake, and simulant hydrolysis to powder UiO-66-NH2. The MOFabric is also capable of breaking down GD (O-pinacolyl methylphosphonofluoridae) faster than powder UiO-66-NH2. Half-life of GD monitored by solid-state NMR for MOFabric is 131 min versus 315 min on powder UiO-66-NH2.

Filtration of chlorine and hydrogen chloride gas by engineered UiO-66-NH2 metal-organic framework.

Chlorine (Cl2) and hydrogen chloride (HCl) are heavily utilized industrial chemicals that present significant respiratory health risks. The metal-organic framework UiO-66-NH2 has shown an unprecedented ability in powder form to remove chlorine gas. Here, we engineered UiO-66-NH2 into 20×40 mesh granules and evaluated their ability to remove chlorine and hydrogen chloride gas challenges. The exposed materials were characterized with nitrogen isotherms, powder X-ray diffraction, and attenuated total reflectance - Fourier transform infrared spectroscopy. Breakthrough results revealed that UiO-66-NH2 sorption of chlorine and hydrogen chloride met or exceeded sorption of state-of-the-art metal-impregnated activated carbon materials on a mass and volume basis in engineered form.

Removal of chlorine gas by an amine functionalized metal-organic framework via electrophilic aromatic substitution.

Here we report the removal of chlorine gas from air via a reaction with an amine functionalized metal-organic framework (MOF). It is found that UiO-66-NH2 has the ability to remove 1.24 g of Cl2 per g of MOF via an electrophilic aromatic substitution reaction producing HCl, which is subsequently neutralized by the MOF.

Removal of airborne toxic chemicals by porous organic polymers containing metal-catecholates.

Porous organic polymers bearing metal-catecholate groups were evaluated for their ability to remove airborne ammonia, cyanogen chloride, sulphur dioxide, and octane by micro-breakthrough analysis. For ammonia, the metal-catecholate materials showed remarkable uptake under humid conditions.

Adsorption of ammonia by sulfuric acid treated zirconium hydroxide.

The adsorption of ammonia on Zr(OH)(4), as well as Zr(OH)(4) treated with sulfuric acid, were examined. The results show that treating Zr(OH)(4) with sulfuric acid leads to the formation of a sulfate on the surface of the material, and that the sulfate contributes to the ammonia adsorption capacity through the formation of an ammonium sulfates species. Calcination of Zr(OH)(4) decreases the ammonia adsorption capacity of the material and limits the formation of sulfate species. NMR and FTIR spectroscopy results are presented that show the presence of two distinct ammonium species on the surface of the material. The adsorption capacity of the materials is shown to be a complex phenomenon that is impacted by the surface area, the sulfur content, and the pH of the material. The results illustrate that Zr(OH)(4), which is known to adsorb acidic gases, can be modified and used to adsorb basic gases.