Dual-functional metal-organic framework for chemisorption and colorimetric monitoring of cyanogen chloride.

Given the growing concern over the deployment of toxic chemicals in warfare, the rapid and accurate removal and detection of cyanogen chloride (CK) as a blood agent has become increasingly critical. However, conventional physisorbents and chemisorbents used in military respirators are insufficient for the effective removal of CK. In this study, we demonstrate the chemisorption and sensing abilities of Co2(m-DOBDC) (m-DOBDC4- = 4,6-dioxo-1,3-benzenedicarboxylate) for CK via electrophilic aromatic substitution (EAS) in humid environments. Unlike the chemisorption in triethylenediamine (TEDA) impregnated carbon materials, which generates by-products through hydrolysis, the electron-rich C5 sites in m-DOBDC4- ligands give rise to cyano substitution with CK. This leads to the formation of stable C-C bonds and chloride ions (Cl-) coordinating with open Co2+ sites. Such a mechanism prevents the generation of toxic by-products like cyanic acid and hydrochloric acid. Breakthrough experiments conducted in a packed-bed system conclusively demonstrated the superior CK removal capacity of Co2(m-DOBDC) (1662 min/g), compared to TEDA-impregnated activated carbon (323 min/g) under humid conditions. Considering that MOF-74 series, isostructural with Co2(m-DOBDC), barely adsorb CK under similar conditions, this finding marks a significant advancement in developing novel sorbents for CK removal. Moreover, this chemisorption not only exhibited rapid and highly efficient CK removal but also enabled colorimetric monitoring via the distinctive color change induced by the coordination of Cl- acting as σ donors. These findings facilitate the development of adsorption and sensing equipment to protect military personnel from toxic chemical threats.

Bayesian predictive modeling for gas purification using breakthrough curves.

This study proposes a predictive model for assessing adsorber performance in gas purification processes, specifically targeting the removal of chemical warfare agents (CWAs) using breakthrough curve analysis. Conventional parameter estimation methods, such as Brunauer-Emmett-Teller analysis, encounter challenges due to the limited availability of kinetic and equilibrium data for CWAs. To overcome these challenges, we implement a Bayesian parametric inference method, facilitating direct parameter estimation from breakthrough curves. The model's efficacy is confirmed by applying it to H2S purification in a fixed-bed setup, where predicted breakthrough curves aligned closely with previous experimental and numerical studies. Furthermore, the model is applied to sarin with ASZM-TEDA carbon, estimating key parameters that could not be assessed through conventional experimental techniques. The reconstructed breakthrough curves closely match actual measurements, highlighting the model's accuracy and robustness. This study not only enhances filter performance prediction for CWAs but also offers a streamlined approach for evaluating gas purification technologies under limited experimental data conditions.

Ultralight and Ultrathin Electrospun Membranes with Enhanced Air Permeability for Chemical and Biological Protection.

With the growing interest in chemical and biological warfare agents (CWAs/BWAs), the focus has shifted toward aerosol protection using protective clothing. However, compared to air-permeable membranes, those with water vapor permeability have been investigated more extensively. Filtering membranes without air permeability have limited practical usage in personal protective suits and masks. In this study, polyacrylonitrile membranes with tightly attached activated carbon and doped copper(II) oxide were prepared via electrospinning. The nanofibers with uniformly controlled diameters and smooth morphologies enable water/air breathability and protection against aerosol (100 nm polystyrene nanobeads similar to SARS-CoV-2) penetration. The uniformly distributed and tightly attached activated carbon and doped copper(II) oxide particles enhance the sorptive performance of the membranes by blocking gaseous CWAs, including soman, nerve chemical agents, and BWAs. Such dual-purpose membranes can be implemented in protective equipment owing to their high performance and easy processing.

Ag-exchanged mesoporous chromium terephthalate with sulfonate for removing radioactive methyl iodide at extremely low concentrations in humid environments.

The development of efficient adsorbents to remove radioactive methyl iodide (CH3I) in humid environments is crucial for air purification after pollution by nuclear power plant waste. In this work, we successfully prepared a post-synthetic covalent modified MIL-101 with a sulfonate group followed by the ion-exchange of Ag (I), which is well characterized by diffuse reflectance FT-IR spectroscopy, X-ray photoelectron spectroscopy (XPS) and the hydrophobic index (HI). After modification of the MOFs, we applied functionalized MIL-101 obtained by either one-pot synthesis (MIL-101-SO3Ag) or a post-synthetic modification process (MIL-101-RSO3Ag, R = NH(CH2)3) to remove the CH3I at an extremely low concentration (0.31 ppm) in an environment with very high relative humidity (RH 95%). Enhanced hydrophobicity of the surface-modified MIL-101 was evaluated by examining the HI with the competitive adsorption of water and cyclohexane vapor, with a high surface area maintained, as confirmed by Ar physisorption. Interestingly, the post-synthetically modified MIL-101-RSO3Ag showed exceptional adsorption performance as determined by its decontamination factor (DF = 195,350) at 303 K and RH 95%. This performance was in comparison to Ag (I)-exchanged 13X zeolite and MIL-101-SO3Ag, which include much higher amounts of Ag. Furthermore, MIL-101-RSO3Ag retained ~94-100% of its fresh adsorbent performance during five cycle repetitions.

Bi-MOF derived micro/meso-porous Bi@C nanoplates for high performance lithium-ion batteries.

Micro/meso-porous Bi@C nanoplates are synthesized by pyrolyzing Bi-based metal-organic frameworks (MOFs) prepared by a microwave-assisted hydrothermal method to overcome huge volume expansion and pulverization of anode materials during battery operation. The Bi@C nanoplates are composed of ∼10-50 nm Bi nanoparticles in an amorphous carbon shell. The material shows very high capacity (556 mA h g-1) after 100 cycles at 100 mA g-1 and good cycling performance. Moreover, the Bi@C nanoplates perform well at high current densities and have excellent cyclic stability; their capacity is 308 mA h g-1 after 50 cycles and 200 mA h g-1 after 1000 cycles at 3000 mA g-1. The outstanding performance of this anode is due to the nanosized Bi and amorphous carbon shell. The nanosized Bi reduces the diffusion length of Li ions, while the amorphous carbon shell improves the electrical conductivity of the anode and also restrains the pulverization and aggregation of the metal during cycling. The proposed hierarchical micro/meso-porous materials derived from MOFs are a new type of nanostructures that can aid the development of novel Bi-based anodes for LIBs.

Zr(OH)4/GO Nanocomposite for the Degradation of Nerve Agent Soman (GD) in High-Humidity Environments.

Zirconium hydroxide, Zr(OH)4 is known to be highly effective for the degradation of chemical nerve agents. Due to the strong interaction force between Zr(OH)4 and the adsorbed water, however, Zr(OH)4 rapidly loses its activity for nerve agents under high-humidity environments, limiting real-world applications. Here, we report a nanocomposite material of Zr(OH)4 and graphene oxide (GO) which showed enhanced stability in humid environments. Zr(OH)4/GO nanocomposite was prepared via a dropwise method, resulting in a well-dispersed and embedded GO in Zr(OH)4 nanocomposite. The nitrogen (N2) isotherm analysis showed that the pore structure of Zr(OH)4/GO nanocomposite is heterogeneous, and its meso-porosity increased from 0.050 to 0.251 cm3/g, compared with pristine Zr(OH)4 prepared. Notably, the composite material showed a better performance for nerve agent soman (GD) degradation hydrolysis under high-humidity air conditions (80% relative humidity) and even in aqueous solution. The soman (GD) degradation by the nanocomposite follows the catalytic reaction with a first-order half-life of 60 min. Water adsorption isotherm analysis and diffuse reflectance infrared Fourier transform (DRIFT) spectra provide direct evidence that the interaction between Zr(OH)4 and the adsorbed water is reduced in Zr(OH)4/GO nanocomposite, indicating that the active sites of Zr(OH)4 for the soman (GD) degradation, such as surface hydroxyl groups are almost available even in high-humidity environments.

Liquid-repellent textile surfaces using zirconium (Zr)-based porous materials and a polyhedral oligomeric silsesquioxane coating.

HYPOTHESIS: The development of clothing that protects soldiers in the battlefield against wetting and chemical/biological (CB) warfare agents is of utmost importance. There are many examples in nature where the structures of some surfaces render them resistant to particular liquids. Hence, it should be possible to prepare an omniphobic textile surface that repels both water and liquid chemical warfare agents by combining a zirconium (Zr)-based porous metal-organic framework (MOF) or metal oxide and a polyhedral oligomeric silsesquioxane (POSS) to control the surface structure. EXPERIMENTS: Hierarchical micro/nanostructures were generated on a textile surface by growing UiO-66-NH2 or Zr(OH)4 on cotton fabric. This was followed by a coating of a hydrophobic aminopropylisooctyl polyhedral oligomeric silsesquioxane (O-POSS) on the surface of the textile. FINDINGS: UiO-66-NH2 or Zr(OH)4 particles were well grown on the surface of the cotton fabric with micro/nano surface structures. Less than a monolayer coating of O-POSS preserved the surface feature of UiO-66-NH2 or Zr(OH)4. The O-POSS coated UiO-66-NH2 on cotton fabric thus formed exhibited resistance towards wetting with water and the chemical warfare agent, sulfur mustard (HD). The static contact angles are >150° for a 5 µL water droplet and 107° for a 3 µL HD droplet. The roll-off angle is 7° for a 50 µL water droplet. Thus, this method may provide fabric developers (military or ordinary) with strategies to design and fabricate better omniphobic fabrics with optimal liquid-repellent properties.

Magnesium Exchanged Zirconium Metal-Organic Frameworks with Improved Detoxification Properties of Nerve Agents.

UiO-66, MOF-808 and NU-1000 metal-organic frameworks exhibit a differentiated reactivity toward [Mg(OMe)2(MeOH)2]4 related to their pore accessibility. Microporous UiO-66 remains unchanged while mesoporous MOF-808 and hierarchical micro/mesoporous NU-1000 materials yield doped systems containing exposed MgZr5O2(OH)6 clusters in the mesoporous cavities. This modification is responsible for a remarkable enhancement of the catalytic activity toward the hydrolytic degradation of P-F and P-S bonds of toxic nerve agents, at room temperature, in unbuffered aqueous solutions.

Rapid Capture and Hydrolysis of a Sulfur Mustard Gas in Silver-Ion-Exchanged Zeolite Y.

Sulfur mustard gas, also called HD, is one of the main chemical warfare agents and has claimed thousands of lives and left many more contaminated. The development of functional materials to promptly capture and detoxify sulfur mustard within a few minutes is extremely important to save the lives of the affected people. This has motivated us to explore excellent detoxification systems that can be deployed in the field to rapidly capture and hydrolyze mustard gas in a short time. To that end, we present a silver-ion-exchanged zeolite Y [(Ag+) n@Y, n = 5, 13, 21, 32, 43, and 55] that can rapidly capture mustard gas and its simulant (2-chloroethyl ethyl sulfide, CEES) in ambient conditions to enable the prompt hydrolysis of the CEES captured in its nanopores. The capture and hydrolysis ability of Ag+@Y positively correlated with its number of Ag+ ions. In addition, 70% of CEES (2.5 µL in 1 mL) was captured by (Ag+)55@Y within 20 min at 25 °C in ambient conditions. Moreover, 100% CEES (2.5 µL in 1 mL aqueous ethanol cosolvent) was hydrolyzed in 1 min at 25 °C. The efficiency of Ag+@Y in capturing and hydrolyzing CEES as well as mustard gas is thus a system with high detoxification efficiency for this dangerous chemical warfare agent.

Degradation of chemical warfare agents over cotton fabric functionalized with UiO-66-NH2.

Herein, cotton fabric was treated with an alkaline solution to increase the content of surface hydroxyl groups and then functionalized with UiO-66-NH2, a nanoporous metal-organic framework. Instrumental analysis of the thus treated fabric revealed that its surface was covered with UiO-66-NH2 crystals in a uniform manner. The ability of the functionalized fabric to degrade two chemical warfare agents (soman and sulfur mustard) was probed by testing its permeability to these two agents (swatch testing), and the excellent degradation performance was concluded to be well suited for a broad range of filtration and decontamination applications.

Bismuth oxide as a high capacity anode material for sodium-ion batteries.

A bismuth oxide electrode, delivering high capacity, as an anode material for sodium-ion batteries was simply prepared. The electrochemical properties of bismuth oxide were studied by operando X-ray absorption near edge structure spectroscopy and ex situ X-ray diffraction methods. A bismuth oxide/carbon composite showed enhanced cycle stability at high current densities.

A simple L-cysteine-assisted method for the growth of MoS2 nanosheets on carbon nanotubes for high-performance lithium ion batteries.

We introduce a simple process to synthesize few-layered MoS(2) nanosheets supported on coaxial carbon nanotubes through an L-cysteine-assisted hydrothermal route, in which L-cysteine, a cheap and ordinary amino acid, plays a fundamental role in controlling the morphology of the hybrid material and the binder to help the growth of MoS(2) nanosheets on the surface of the carbon nanotubes. It is also demonstrated that the polypeptide formed by L-cysteine can be transformed into amorphous carbon by heat treatment under an inert atmosphere. The materials exhibit high capacity and excellent cycling performance when used as anode materials for lithium ion batteries. The specific capacity of a composite with 1 : 4 molar ratio of MoS(2) to carbon nanotubes is 736.5 mAh g(-1) after the first cycle, increased for several initial cycles, and remains at 823.4 mAh g(-1) even after 30 cycles, when cycled at a current density of 100 mA g(-1). At a very high current density of 1600 mA g(-1), the material shows a stable capacity of approximately 530 mAh g(-1) after 30 cycles. The noteworthy improvement in the electrochemical performance of the material can be attributed to their unique structure and the synergistic effects of amorphous carbon and few-layered MoS(2).