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.

BEAMS: a workforce development program to bridge the gap between biologists and material scientists.

To maximize innovation in materials science and synthetic biology, it is critical to master interdisciplinary understanding and communication within an organization. Programming aimed at this juncture has the potential to bring members of the workforce together to frame new networks and spark collaboration. In this article, we recognize the potential synergy between materials and synthetic biology research and describe our approach to this challenge as a case study.

High-Throughput Screening of MOFs for Breakdown of V-Series Nerve Agents.

Metal-organic frameworks (MOFs) have shown promise for the catalytic decomposition of chemical weapons. Finding the best materials for the degradation of nerve agents requires the ability to screen a high number of samples and elucidate the key parameters of effective catalysis. In this work, a high-throughput screening (HTS) method has been developed to evaluate MOFs as catalysts, specifically against the V-class of nerve agents.

Insights into the solvent-assisted degradation of organophosphorus compounds by a Zr-based metal-organic framework.

The degradation of a chemical warfare agent simulant using a catalytically active Zr-based metal-organic framework (MOF) as a function of different solvent systems was investigated. Complementary molecular modelling studies indicate that the differences in the degradation rates are related to the increasing size in the nucleophile, which hinders the rotation of the product molecule during degradation. Methanol was identified as an appropriate solvent for non-aqueous degradation applications and demonstrated to support the MOF-based destruction of both sarin and soman.

Metal Hydroxide/Polymer Textiles for Decontamination of Toxic Organophosphates: An Extensive Study of Wettability, Catalytic Activity, and the Effects of Aggregation.

Electrospun nanofibers (NFs) incorporated with catalytically active components have gained significant interest in chemical protective clothing. This is because of the desirable properties of the NFs combined with decontamination capability of the active component. Here, a series of metal hydroxide catalysts Ti(OH), Zr(OH), and Ce(OH) were incorporated into three different polymer NF systems.

Single-component frameworks for heterogeneous catalytic hydrolysis of organophosphorous compounds in pure water.

Amine modified Zr6-based metal-organic frameworks (MOFs) were synthesized through solvent-assisted linker incorporation (SALI) and utilized as single-component heterogeneous catalysts for the hydrolysis of organophosphorous compounds under solely aqueous conditions at room temperature. These materials display unprecidentedly fast catalytic hydrolysis for dimethyl p-nitrophenyl phosphate (DMNP) and nerve agent VX without the use of a buffered solution.

Solid-Phase Detoxification of Chemical Warfare Agents using Zirconium-Based Metal Organic Frameworks and the Moisture Effects: Analyze via Digestion.

Zirconium-based metal organic frameworks (Zr-MOFs) are highly chemically and thermally stable and have been of particular interest as reactive sorbents for chemical warfare agent (CWA) removal due to their fast and selective reactivity toward CWAs reported in buffer solutions. However, we find that decontamination of neat CWAs directly on Zr-MOFs, UiO-66, UiO-66-NH, and NU-1000 is rather slow, and the reactivity trend and products generated are very different from those in solution. Furthermore, we show that their decontamination rates are affected by the amount of moisture present in the MOFs.

Insight into organophosphate chemical warfare agent simulant hydrolysis in metal-organic frameworks.

Metal-organic frameworks (MOFs) are porous 3-dimensional crystalline structures that have shown promise for a variety of applications including adsorption, catalysis, and sensing. Modern warfare has placed chemical warfare agent (CWA) destruction at the forefront of chemical applications for MOFs. However, experiments involving CWAs can only be performed by a small number of highly trained individuals as they are extremely dangerous and available only to certain laboratories.

High-throughput screening of solid-state catalysts for nerve agent degradation.

A high-throughput screening (HTS) method was devised to increase the rate of discovery and evaluation of nerve agent degradation catalysts. Using this HTS method, >90 solid state materials, predominantly metal-organic frameworks (MOFs), were analyzed for their ability to hydrolyze the nerve agent simulant methyl paraoxon at two pH values (8.0 and 10.

Metal-Organic Framework Modified Glass Substrate for Analysis of Highly Volatile Chemical Warfare Agents by Paper Spray Mass Spectrometry.

Paper spray mass spectrometry has been shown to successfully analyze chemical warfare agent (CWA) simulants. However, due to the volatility differences between the simulants and real G-series (i.e.

Enhancing Van der Waals Interactions of Functionalized UiO-66 with Non-polar Adsorbates: The Unique Effect of para Hydroxyl Groups.

UiO-66 is a highly stable metal-organic framework (MOF) that has garnered interest for many adsorption applications. For small, nonpolar adsorbates, physisorption is dominated by weak Van der Waals interactions limiting the adsorption capacity. A common strategy to enhance the adsorption properties of isoreticular MOFs, such as UiO-66, is to add functional groups to the organic linker.

Chemical Warfare Agents Detoxification Properties of Zirconium Metal-Organic Frameworks by Synergistic Incorporation of Nucleophilic and Basic Sites.

The development of protective self-detoxifying materials is an important societal challenge to counteract risk of attacks employing highly toxic chemical warfare agents (CWAs). In this work, we have developed bifunctional zirconium metal-organic frameworks (MOFs) incorporating variable amounts of nucleophilic amino residues by means of formation of the mixed ligand [ZrO(OH)(bdc)(bdc-NH)] (UiO-66-xNH) and [ZrO(OH)(bpdc)(bpdc-(NH))] (UiO-67-x(NH)) systems where bdc = benzene-1,4-dicarboxylate; bdc-NH= benzene-2-amino-1,4-dicarboxylate; bpdc = 4,4'-biphenyldicarboxylate; bpdc-(NH) = 2,2'-diamino-4,4'-biphenyldicarboxylate and x = 0, 0.25, 0.

Tailoring the Adsorption and Reaction Chemistry of the Metal-Organic Frameworks UiO-66, UiO-66-NH, and HKUST-1 via the Incorporation of Molecular Guests.

Metal-organic frameworks (MOFs) are versatile materials highly regarded for their porous nature. Depending on the synthetic method, various guest molecules may remain in the pores or can be systematically loaded for various reasons. Herein, we present a study that explores the effect of guest molecules on the adsorption and reactivity of the MOF in both the gas phase and solution.

MOFabric: Electrospun Nanofiber Mats from PVDF/UiO-66-NH 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.

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

Chlorine (Cl) and hydrogen chloride (HCl) are heavily utilized industrial chemicals that present significant respiratory health risks. The metal-organic framework UiO-66-NH has shown an unprecedented ability in powder form to remove chlorine gas. Here, we engineered UiO-66-NH into 20×40 mesh granules and evaluated their ability to remove chlorine and hydrogen chloride gas challenges.

Postsynthetic Incorporation of a Singlet Oxygen Photosensitizer in a Metal-Organic Framework for Fast and Selective Oxidative Detoxification of Sulfur Mustard.

A fullerene-based photosensitizer is incorporated postsynthetically into a Zr -based MOF, NU-1000, for enhanced singlet oxygen production. The structural organic linkers in the MOF platform also act as photosensitizers which contribute to the overall generation of singlet oxygen from the material under UV irradiation. The singlet oxygen generated by the MOF/fullerene material is shown to oxidize sulfur mustard selectively to the less toxic bis(2-chloroethyl)sulfoxide with a half-life of only 11 min.

Enhanced aging properties of HKUST-1 in hydrophobic mixed-matrix membranes for ammonia adsorption.

Metal-organic frameworks (MOFs) in their free powder form have exhibited superior capacities for many gases when compared to other materials, due to their tailorable functionality and high surface areas. Specifically, the MOF HKUST-1 binds small Lewis bases, such as ammonia, with its coordinatively unsaturated copper sites. We describe here the use of HKUST-1 in mixed-matrix membranes (MMMs) prepared from polyvinylidene difluoride (PVDF) for the removal of ammonia gas.

Extraordinary NO2 Removal by the Metal-Organic Framework UiO-66-NH2.

Here we discuss the removal of nitrogen dioxide, an important toxic industrial chemical and pollutant, from air using the MOF UiO-66-NH2 . The amine group is found to substantially aid in the removal, resulting in unprecedented removal capacities upwards of 1.4 g of NO2  /g of MOF.

Efficient and selective oxidation of sulfur mustard using singlet oxygen generated by a pyrene-based metal-organic framework.

A pyrene-based metal-organic framework (MOF) NU-1000 was used as a heterogeneous photocatalyst for the degradation of a sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES). Using irradiation from a commercially available and inexpensive ultraviolet (UV) light-emitting diode (LED), singlet oxygen (O) is generated by NU-1000 and selectively oxidizes CEES to the nontoxic product 2-chloroethyl ethyl sulfoxide (CEESO). More importantly, this method was tested on the warfare agent sulfur mustard (HD) for the first time using O and a MOF catalyst, and this method proved to be effective in oxidizing sulfur mustard to nontoxic products without forming the toxic sulfone by-product.

Polymer-Metal-Organic Frameworks (polyMOFs) as Water Tolerant Materials for Selective Carbon Dioxide Separations.

Recently, polymer-metal-organic frameworks (polyMOFs) were reported as a new class of hybrid porous materials that combine advantages of both organic polymers and crystalline MOFs. Herein, we report a bridging coligand strategy to prepare new types of polyMOFs, demonstrating that polyMOFs are compatible with additional MOF architectures besides that of the earlier reported IRMOF-1 type polyMOF. Gas sorption studies revealed that these polyMOF materials exhibited relatively high CO2 sorption but very low N2 sorption, making them promising materials for CO2/N2 separations.

Effective, Facile, and Selective Hydrolysis of the Chemical Warfare Agent VX Using Zr6-Based Metal-Organic Frameworks.

The nerve agent VX is among the most toxic chemicals known to mankind, and robust solutions are needed to rapidly and selectively deactivate it. Herein, we demonstrate that three Zr6-based metal-organic frameworks (MOFs), namely, UiO-67, UiO-67-NH2, and UiO-67-N(Me)2, are selective and highly active catalysts for the hydrolysis of VX. Utilizing UiO-67, UiO-67-NH2, and UiO-67-N(Me)2 in a pH 10 buffered solution of N-ethylmorpholine, selective hydrolysis of the P-S bond in VX was observed.

Hierarchical Pore Development by Plasma Etching of Zr-Based Metal-Organic Frameworks.

The typically stable Zr-based metal-organic frameworks (MOFs) UiO-66 and UiO-66-NH2 were treated with tetrafluoromethane (CF4 ) and hexafluoroethane (C2 F6 ) plasmas. Through interactions between fluoride radicals from the perfluoroalkane plasma and the zirconium-oxygen bonds of the MOF, the resulting materials showed the development of mesoporosity, creating a hierarchical pore structure. It is anticipated that this strategy can be used as a post-synthetic technique for developing hierarchical networks in a variety of MOFs.

Tailoring the Pore Size and Functionality of UiO-Type Metal-Organic Frameworks for Optimal Nerve Agent Destruction.

Evaluation of UiO-66 and UiO-67 metal-organic framework derivatives as catalysts for the degradation of soman, a chemical warfare agent, showed the importance of both the linker size and functionality. The best catalysts yielded half-lives of less than 1 min. Further testing with a nerve agent simulant established that different rate-assessment techniques yield similar values for degradation half-lives.