Sulfur Mustard Research Articles

A new kinetic model on hydrolysis of sulfur mustard non-dissolved and dissolved in aqueous solution

This paper aims to establish a hydrolysis extent equation and rate dependence of initial and boundary conditions for sulfur mustard (HD) non-dissolved and dissolved in water by the following work. Firstly, non-homogeneous hydrolysis extent was found to be accurately described by a product of logistic with exponential convex growth function because of slow collision-complex formation between activated H2O and HD molecule to non-linearly couple with transition state decay, while the homogeneous has grown up only in an exponential convex function because of fast collision-complex formation to make its initial extent ratio extremely quickly close to unity. Secondly, initial non-temperature effects from (ethanol, acid, base) additives, HD concentration and droplet size, and rotation speed on hydrolysis rate could be summarized into a Boltzmann function of rate constant with initial molar free energy because of a thermal equilibrium distribution of internal quantum state at a given energy for bi-molecular structures before and after complexing. The results from 5 mL solution under vortex was nearly similar to the stirring 100 mL solution and would helpfully clarify the detoxification kinetics to establish a standard method for evaluating reactivity of aqueous decontaminants against chemical warfare agents at necessarily specified conditions.

Development of a Multiparticulate Metal-Organic Framework/Textile Fiber Swatch.

The versatility of metal-organic frameworks (MOFs) has led to groundbreaking applications in a wide variety of fields, especially in the areas of energy, environment, and sustainability. For example, MOFs can be designed for high uptake of toxic gases and pollutants, such as CO2, NH3, and SO2, but designing a single MOF that shows tangible uptake for all of these gases is challenging due to the differences in the chemical and physical properties of these molecules. To this end, integrating multiple MOFs onto textile fibers and crafting various structures have emerged as pivotal developments, enhancing framework durability and usability. MOF composites prepared on readily available textile fibers offer the flexibility essential for critical applications, including heterogeneous catalysis, chemical sensing, toxic gas adsorption, and drug delivery, while preserving the unique characteristics of MOFs. This study introduces a scalable and adaptable method for seamlessly embedding multiple high-performing MOFs onto a single textile fiber using a dip-coating method. We explored the uptake capacity of these multi-MOF composites for CO2, NH3, and SO2 and observed a performance similar to that of traditional powdered materials. Along with harmful gas adsorption, we also have evaluated the permeation and reactivity of these MOF/textile composites toward chemical warfare agents (CWAs) like GD (soman), HD (mustard gas), and VX. In combination, these results demonstrate a fundamental advancement toward establishing a consistent strategy for the hydrolysis of nerve agents in real-world scenarios. This approach can substantially increase the protection toward CWAs and enhance the effectiveness of protective equipment such as fabrics for protective garments. This dip-coating method for the integration of multiple MOFs on a single textile fiber unlocks a wealth of possibilities and paves the way for future innovations in the deployment of MOF-based composites.

Effect of wavelength and liquid on formation of Ag, Au, Ag/Au nanoparticles via picosecond laser ablation and SERS-based detection of DMMP.

The present study investigates the effects of input wavelength (1064, 532, and 355 nm) and surrounding liquid environment (distilled water and aqueous NaCl solution) on the picosecond laser ablation on silver (Ag), gold (Au), and Ag/Au alloy targets. The efficacy of the laser ablation technique was meticulously evaluated by analyzing the ablation rates, surface plasmon resonance peak positions, and particle size distributions of the obtained colloids. The nanoparticles (NPs) were characterized using the techniques of UV-visible absorption, transmission electron microscopy, and energy-dispersive X-ray spectroscopy. Furthermore, NPs of various sizes ranging from 6 to 35 nm were loaded onto a filter paper by a simple and effective drop-casting approach to achieve flexible surface-enhanced Raman spectroscopy (SERS) substrates/sensors. These substrates were tested using a simple, portable Raman device to identify various hazardous chemicals (malachite green, methyl salicylate, and thiram). The stability of the substrates was also systematically investigated by determining the decay percentages in the SERS signals over 60 days. The optimized SERS substrate was subsequently employed to detect chemical warfare agent (CWA) simulants such as methyl salicylate (a CWA simulant for sulfur mustard) and dimethyl methyl phosphonate (has some structural similarities to the G-series nerve agents) at different laser excitations (325, 532, and 633 nm). A notably higher SERS efficiency for CWA simulants was observed at a 325 nm Raman excitation. Our findings reveal that a higher ablation yield was observed at IR irradiation than those obtained at the other wavelengths. A size decrease of the NPs was noticed by changing the liquid environment to an electrolyte. These findings have significant implications for developing more efficient and stable SERS substrates for chemical detection applications.

A Pillar[5]arene-Containing Metal-Organic Framework for Rapid and Highly Capable Adsorption of a Mustard Gas Simulant.

Mustard gas causes irreversible damage upon inhalation or contact with the human body. Consequently, the development of adsorbents for effective interception of mustard gas at low concentrations and high flow rates is an urgent necessity. Here we report a stable porous pillar[5]arene-containing metal-organic framework (MOF) based on zirconium (EtP5-Zr-scu), demonstrating that embedding pillar[5]arene units in MOFs can provide specific binding sites for efficient adsorption of a mustard gas simulant, 2-chloroethyl ethyl sulfide (CEES). EtP5-Zr-scu achieves a higher capacity and more rapid adsorption compared to its counterpart without embedded pillar[5]arene units (H4tcpt-Zr-scu) and perethylated pillar[5]arene (EtP5) alone. Single crystal X-ray diffraction and solid-state nuclear magnetic resonance reveal that the enhanced performance of EtP5-Zr-scu is derived from the host-guest complexation between CEES and pillar[5]arene moieties. Moreover, breakthrough experiments confirmed that the interception performance of EtP5-Zr-scu against CEES (800 ppm, 120 mL/min) was significantly improved (566 min/g) compared with H4tcpt-Zr-scu (353 min/g) and EtP5 (0.873 min/g), attributed to the integration of open channels with specific recognition sites. This work marks a significant advancement in the development of macrocycle-incorporated crystalline framework materials with recognition sites for the efficient capture of guest molecules.

Investigating the Role of Sulfur Mustard in Triggering Molecular Inflammatory Mechanisms

Sulfur mustard, a chemical warfare agent, that has been used in the Iraq-Iran conflict, exerts its devastating effects through multifaceted biochemical pathways. Its primary mode of action involves the alkylation of cellular macromolecules, particularly DNA and proteins, leading to cellular dysfunction and damage. DNA alkylation by sulfur mustard results in the formation of adducts, causing genetic mutations, chromosomal aberrations and ultimately cell death or malignant transformation. Similarly, protein alkylation disrupts cellular signaling pathways and homeostasis, contributing to tissue damage and dysfunction. Additionally, sulfur mustard exposure induces the generation of reactive oxygen species, exacerbating cellular damage, inflammation, and oxidative stress. This triggers the activation of inflammatory pathways, including NF-κB, MAPK, JAK/STAT and inflammasome activation, leading to the production of cytokines, adhesion molecules, chemokines, activator protein-1 (AP-1), and other inflammatory mediators. The inflammatory cascade initiated by sulfur mustard exposure perpetuates tissue damage, immune cell recruitment and systemic effects, enhancing acute symptoms and potential long-term health complications.

Artificial intelligence, adversarial attacks, and ocular warfare

PurposeWe explore the potential misuse of artificial intelligence (AI), specifically large language models (LLMs), in generating harmful content related to ocular warfare. By examining the vulnerabilities of AI systems to adversarial attacks, we aim to highlight the urgent need for robust safety measures, enforceable regulation, and proactive ethics. DesignA viewpoint paper discussing the ethical challenges posed by AI, using ophthalmology as a case study. It examines the susceptibility of AI systems to adversarial attacks and the potential for their misuse in creating harmful content. MethodsThe study involved crafting adversarial prompts to test the safeguards of a well-known LLM, OpenAI's ChatGPT-4.0. The focus was on evaluating the model's responses to hypothetical scenarios aimed at causing ocular damage through biological, chemical, and physical means. ResultsThe AI provided detailed responses on using Onchocerca volvulus for mass infection, methanol for optic nerve damage, mustard gas for severe eye injuries, and high-powered lasers for inducing blindness. Despite significant safeguards, the study revealed that with enough effort, it was possible to bypass these constraints and obtain harmful information, underscoring the vulnerabilities in AI systems. ConclusionAI holds the potential for both positive transformative change and malevolent exploitation. The susceptibility of LLMs to adversarial attacks and the possibility of purposefully trained unethical AI systems present significant risks. This paper calls for improved robustness of AI systems, global legal and ethical frameworks, and proactive measures to ensure AI technologies benefit humanity and do not pose threats.

Bacterial microcompartment-mimicking Pickering emulsion droplets for detoxification of chemical threats under sweet conditions

Chemical warfare agents represent a severe threat to mankind and their efficient decontamination is a global necessity. However, traditional disposal strategies have limitations, including high energy consumption, use of aggressive reagents and generation of toxic byproducts. Here, inspired by the compartmentalized architecture and detoxification mechanism of bacterial micro-compartments, we constructed oil-in-water Pickering emulsion droplets stabilized by hydrogen-bonded organic framework immobilized cascade enzymes for decontaminating mustard gas simulant (2-chloroethyl ethyl sulfide, CEES) under sweet conditions. Two exemplified droplet systems were developed with two-enzyme (glucose oxidase/chloroperoxidase) and three-enzyme (invertase/glucose oxidase/chloroperoxidase) cascades, both achieving over 6-fold enhancement in decontamination efficiency compared with free enzymes and >99% selectivity towards non-toxic sulfoxide. We found that the favored mass transfer of sugars and CEES from their respective phases to approach the cascade enzymes located at the droplet surface and the facilitated substrate channeling between proximally immobilized enzymes were key factors in augmenting the decontamination efficacy. More importantly, the robustness of immobilized enzymes enabled easy reproduction of both the droplet formation and detoxification performance over 10 cycles, following long-term storage and in far-field locations.

An experimental and mechanism study on the pyrolysis of sulfur mustard

Experimental studies on the pyrolysis of sulfur mustard (HD) were conducted from 673 to 1473 K using Py-GC/MS combined with two separate columns. The HD pyrolysis rate exceeded 99 % at a pyrolysis time of approximately 2 seconds above 1073 K. The pyrolysis products of HD mainly include ethylene, vinyl chloride, carbon disulfide, thiophene, hydrogen chloride and hydrogen sulfide. The main reaction mechanism of HD pyrolysis was investigated using quantum chemistry methods combined with the TST/VTST theory. At 673 K, the initial reaction pathway of HD primarily involves an intramolecular HCl elimination and the cleavage of the C-S bond. The radical reactions will dominate the pyrolysis of HD once radical pool is formed. The reaction pathways of the important radical intermediates were analyzed, and the formation mechanisms of the main pyrolysis products were investigated. Theoretically, the high-pressure limit rate constants for the major reactions were calculated. This study contributes to a deeper understanding of the HD pyrolysis mechanism and provides a theoretical and data foundation for the destruction of HD.

Reliable Detection of Chemical Warfare Agents Using High Kinetic Energy Ion Mobility Spectrometry.

High Kinetic Energy Ion Mobility Spectrometers (HiKE-IMS) ionize and separate ions at reduced pressures of 10-40 mbar and over a wide range of reduced electric field strengths E/N of up to 120 Td. Their reduced operating pressure is distinct from that of conventional drift tube ion mobility spectrometers that operate at ambient pressure for trace compound detection. High E/N can lead to a field-induced fragmentation pattern that provides more specific structural information about the analytes. In addition, operation at high E/N values adds the field dependence of ion mobility as an additional separation dimension to low-field ion mobility, making interfering compounds less likely to cause a false positive alarm. In this work, we study the chemical warfare agents tabun (GA), sarin (GB), soman (GD), cyclosarin (GF) and sulfur mustard (HD) in a HiKE-IMS at variable E/N in both the reaction and the drift region. The results show that varying E/N can lead to specific fragmentation patterns at high E/N values combined with molecular signals at low E/N. Compared to the operation at a single E/N value in the drift region, the variation of E/N in the drift region also provides the analyte-specific field dependence of ion mobility as additional information. The accumulated data establish a unique fingerprint for each analyte that allows for reliable detection of chemical warfare agents even in the presence of interfering compounds with similar low-field ion mobilities, thus reducing false positives.

Confining polyoxometalates in porphyrin-based porous cationic polymer toward boosting visible-light-driven synthesis of sulfoxides and detoxification of mustard gas simulants

Visible-light-driven oxidation of sulfides has attracted the profound attention to synthesize sulfoxides and purify mustard gas simulant. In this work, a series of visible-light-responsive polyoxometalate-based porous cationic polymers, i.e. SiW12-PCP 1, PW12-PCP 2, SiW11-PCP 3, SiW10-PCP 4, SiW9-PCP 5 (PCP = porphyrin-based porous cationic polymer), were synthesized by ion exchange process. These POM-PCPs exhibit excellent ability of trapping visible light due to their built-in porphyrin units, which can rapidly oxidize sulfides and degrade 2-chloroethyl ethyl sulfide (CEES) in the presence of a 10 W white LED light and O2. Benefiting from the synergistic effect between [SiW12] and PCP, hybrid 1 has the highest photocatalytic efficiency, attaining 99 % conversion of sulfides within 16 min and 99 % CEES purification in 8 min, much higher than PCP precursor. The reaction mechanism reveals that both O2•− and 1O2 are involved in the photocatalytic process. What's more, hybrid 1 has remarkable applicability to numerous sulfides and robust six-round recycling with no reduction in catalytic efficiency.

Chromo-fluorogenic detection of Sarin, Tabun, and mustard gas mimics triggering the ring-opening reaction in a spirolactam-based probe

Nerve agents are becoming serious issues for the healthy and sustainable environment in modern civilization. Strategically, we have designed and introduced a Schiff base triggered dual chromo-fluorogenic probe BASO via condensation reaction between rhodamine B hydrazide and 3-formyl chromone, which can selectively recognize different toxic target analytes helping a reference to a healthy and sustainable environment. The BASO probe displays enhanced pink photoluminescence extraordinarily due to the introduction of sarin, tabun, and mustard gas mimics diethylchlorophosphate (DCP), diethylcyanophosphonate (DCNP), and 2-chloroethyl ethyl sulfide (2CEES), in a 1:1 water–dimethyl sulfoxide (DMSO) mixture while native one was non-fluorescent. The opening of the spirolactam ring owing to the addition of DCP, DCNP, and 2CEES shows a noticeable pink colorimetric and pink color fluorometric change, which is readily detectable by the naked eye in the µM range in neutral medium and found to be better than numerous available chemosensor (Table S1). We have also fabricated simple paper strip-based test kits as portable and displayable handy photonic tools for on-site detection without any expensive instrumental techniques. The probe BASO has also been employed for detecting the vapor phase and soil sample analysis as a practical applicability. The simple, rapid detection techniques make our probe unique and have significant utility for the recognition of DCP, DCNP, and vesicant or blistering agents mimicking 2CEES.

Research Progress in the Degradation of Chemical Warfare Agent Simulants Using Metal-Organic Frameworks.

Chemical warfare agents primarily comprise organophosphorus nerve agents, saliva alkaloids, cyanides, and mustard gas. Exposure to these agents can result in severe respiratory effects, including spasms, edema, and increased secretions leading to breathing difficulties and suffocation. Protecting public safety and national security from such threats has become an urgent priority. Porous metal-organic framework (MOF) materials have emerged as promising candidates for the degradation of chemical warfare agents due to their large surface area, tunable pore size distribution, and excellent catalytic performance. Furthermore, combining MOFs with polymers can enhance their elasticity and processability and improve their degradation performance. In this review, we summarize the literature of the past five years on MOF-based composite materials and their effectiveness in degrading chemical warfare agents. Moreover, we discuss key factors influencing their degradation efficiency, such as MOF structure, pore size, and functionalization strategies. Furthermore, we highlight recent developments in the design of MOF-polymer composites, which offer enhanced degradation performance and stability for practical applications in CWA degradation. These composite materials exhibit good performance in degrading chemical warfare agents, playing a crucial role in protecting public safety and maintaining national security. We can expect to see more breakthroughs in the application of metal-organic framework porous materials for degrading chemical warfare agents. It is hoped that these innovative materials will play a positive role in achieving social stability and security.

Interface-regulated S-type core–shell PCN-224@TiO2 heterojunction for visible-light-driven generation of singlet oxygen for selective photooxidation of 2-chloroethyl ethyl sulfide

Selective oxidation of sulfur mustard gas (HD) to non-toxic sulfoxide by the visible-light-catalyzed generation of singlet oxygen (1O2) is a promising degradation strategy. Although PCN-224 can absorb visible light, it suffers from rapid electron-hole recombination and low redox capacity, which limits the performance of HD degradation. Titanium dioxide (TiO2) is an excellent photocatalyst but it lacks visible-light-activity in degrading HD. In this study, PCN-224@TiO2 heterojunction with S-type core–shell structure was synthesized by in-situ growth method to prolong the visible light absorption capacity of TiO2 and inhibit the rapid recombination of PCN-224. The interface formation and internal electric field were optimized by adjusting the Zr/Ti ratio to enhance the charge transfer, redox capacity, electron-hole separation, and visible light absorption. In this study, the formation of heterojunction composites based on Zr-O-Ti linkages is demonstrated by a series of characterization methods. It is demonstrated by experiments and theoretical calculations that PCN-224@TiO2 can generate nearly 100 % 1O2 under visible light conditions without a sacrificial agent, resulting in efficient and selective oxidation of 2-chloroethyl ethyl sulfide (CEES), a simulant of HD, to non-toxic sulfoxide form.

Ultrathin WO3 Nanosheets/Pd with Strong Metal-Support Interactions for Highly Sensitive and Selective Detection of Mustard-Gas Simulants.

Exposure to mustard gas can cause damage or death to human beings, depending on the concentration and duration. Thus, developing high-performance mustard-gas sensors is highly needed for early warning. Herein, ultrathin WO3 nanosheet-supported Pd nanoparticles hybrids (WO3 NSs/Pd) are prepared as chemiresistive sulfur mustard simulant (e.g., 2-chloroethyl ethyl sulfide, 2-CEES) gas sensors. As a result, the optimal WO3 NSs/Pd-2 (2 wt % of Pd)-based sensor exhibits a high response of 8.5 and a rapid response/recovery time of 9/92 s toward 700 ppb 2-CEES at 260 °C. The detection limit could be as low as 15 ppb with a response of 1.4. Moreover, WO3 NSs/Pd-2 shows good repeatability, 30-day operating stability, and good selectivity. In WO3 NSs/Pd-2, ultrathin WO3 NSs are rich in oxygen vacancies, offer more sites to adsorb oxygen species, and make their size close to or even within the thickness of the so-called electron depletion layer, thus inducing a large resistance change (response). Moreover, strong metal-support interactions (SMSIs) between WO3 NSs and Pd nanoparticles enhance the catalytic redox reaction performance, thereby achieving a superior sensing performance toward 2-CEES. These findings in this work provide a new approach to optimize the sensing performance of a chemiresistive sensor by constructing SMSIs in ultrathin metal oxides.

Metabolomics Analysis of Rabbit Plasma after Ocular Exposure to Vapors of Sulfur Mustard.

Sulfur mustard (SM) is a highly potent alkylating vesicant agent and remains a relevant threat to both civilians and military personnel. The eyes are the most sensitive organ after airborne SM exposure, causing ocular injuries with no antidote or specific therapeutics available. In order to identify relevant biomarkers and to obtain a deeper understanding of the underlying biochemical events, we performed an untargeted metabolomics analysis using liquid chromatography coupled to high-resolution mass spectrometry of plasma samples from New Zealand white rabbits ocularly exposed to vapors of SM. Metabolic profiles (332 unique metabolites) from SM-exposed (n = 16) and unexposed rabbits (n = 8) were compared at different time intervals from 1 to 28 days. The observed time-dependent changes in metabolic profiles highlighted the profound dysregulation of the sulfur amino acids, the phenylalanine, the tyrosine and tryptophan pathway, and the polyamine and purine biosynthesis, which could reflect antioxidant and anti-inflammatory activities. Taurine and 3,4-dihydroxy-phenylalanine (Dopa) seem to be specifically related to SM exposure and correspond well with the different phases of ocular damage, while the dysregulation of adenosine, polyamines, and acylcarnitines might be related to ocular neovascularization. Additionally, neither cysteine, N-acetylcysteine, or guanine SM adducts were detected in the plasma of exposed rabbits at any time point. Overall, our study provides an unprecedented view of the plasma metabolic changes post-SM ocular exposure, which may open up the development of potential new treatment strategies.

Measuring Mass Transfer of n-Hexane and 2-Chloroethyl Ethyl Sulfide in Sorbent/Polymer Fiber Composites Using a Volumetric Adsorption Apparatus.

The integration of metal-organic frameworks (MOFs) into composite systems serves as an effective strategy to increase the processability of these materials. Notably, MOF/fiber composites have shown much promise as protective equipment for the capture and remediation of chemical warfare agents. However, the practical application of these composites requires an understanding of their mass transport properties, as both mass transfer resistance at the surface and diffusion within the materials can impact the efficacy of these materials. In this work, we synthesized composite fibers of MOF-808 and amidoxime-functionalized polymers of intrinsic microporosity (PIM-1-AX) and measured the adsorption and mass transport behavior of n-hexane and 2-chloroethyl ethyl sulfide (CEES), a sulfur mustard simulant. We developed a new Fickian diffusion model for cylindrical shapes to fit the dynamic adsorption data obtained from a commercial volumetric adsorption apparatus and found that mass transport behavior in composite fibers closely resembled that in the pure PIM fibers, regardless of MOF loading. Moreover, we found that n-hexane adsorption mirrors that of CEES, indicating that it could be used as a structural mimic for future adsorption studies of the sulfur mustard simulant. These preliminary insights and the new model introduced in this work lay the groundwork for the design of next-generation composite materials for practical applications.

Selective and Efficient Detoxification of Sulfur Mustard Gas Analogues with H2O2 Using Bioinspired Mo and W Dithiolene Catalysts

Selective and Efficient Detoxification of Sulfur Mustard Gas Analogues with H₂O₂ Using Bioinspired Mo and W Dithiolene Catalysts

Manganese Oxides with Different Morphologies In Situ Anchored onto Ti3C2Tx Nanosheets: Highly Effective Decontamination toward Sulfur Mustard Simulants.

Manganese oxides with porous structure and abundant active sites show potential in degrading sulfur mustard (HD). However, there is an interface effect between the oily liquid HD and nano oxides, and the powder is prone to agglomeration, which leads to incomplete contact and limited degradation ability. Here, we demonstrate a simple hydrothermal method for preparing MnO2/Ti3C2 composites to address this problem. The influence of morphology and crystal structure on performance are examined. Herein, flower-like MnO2 is loaded onto the surface or interlayer of Ti3C2-MXene nanosheets during in situ formation, significantly expanding the specific surface area. It also provides abundant acid-base sites and oxygen vacancies for the degradation of simulants 2-chloro-ethyl-ethyl thioether (2-CEES) without external energy, resulting in a reaction half-life as fast as 12.5 min. The relationship between structure and performance is clearly elaborated through temperature-programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS), and X-ray absorption fine structure (XAFS) analyses. Based on in situ attenuated total reflection-Fourier transform infrared (ATR-FTIR) analysis, gas chromatography-mass spectrometry (GC-MS) analysis, and density functional theory (DFT) calculation, the proposed degradation pathway of the 2-CEES molecule is a synergistic effect of hydrolysis, elimination, and oxidation. Furthermore, the products are nontoxic or low toxic. Metal oxide/MXene composites are first illustrated for their potential use in degrading sulfur mustard, suggesting new insights into these materials as novel decontamination for decomposing chemical warfare agents.

Monitoring of Sulfur Mustard (HD) Vapor in the Presence of Absorptive Building Materials.

In the event of an accidental or intentional release of a chemical warfare agent (CWA), environmental samples must be collected and analyzed to assess the level of the contamination. Equally important is an understanding of the fate and transport of a CWA in the presence of porous materials, which may impact the ability to collect environmental samples. Air monitoring techniques may be used to rule in/out the presence of a CWA. Here, relationships between the CWA sulfur mustard (HD) surface contamination levels and the associated HD vapor concentration were investigated. Results indicate that absorption of HD into vinyl, concrete, and sealed concrete followed by slow diffusion out of these materials significantly prolonged the presence of HD vapor concentrations. The extracted material recovery data suggest that positive correlations can be established between residual material contamination and vapor concentration but also that surface wiping alone would fail to detect absorbed HD.

{SeO2(OH)} Bridging Lanthanide-Containing Antimono-Seleno-Tungstates.

A series of new trigonal pyramidal {SeO2(OH)} bridging lanthanide-containing antimono-seleno-tungstates [H2N(CH3)2]8Na8Cs4H9[Ln2SeW4O11(OH)(H2O)4(SbW9O33)(SeW9O33)(Se1/2Sb1/2W9O33)]2·32H2O [Ln = Tb (1), Dy (2), Ho (3), Er (4)] have been prepared by the synthetic strategy of simultaneously using the antimonotungstate precursor and simple material in an acidic aqueous solution and structurally characterized by single-crystal X-ray diffraction, powder X-ray diffraction, IR spectrometry, and thermogravimetric analysis. Their molecular structures contain an unprecedented hexameric polyoxoanion [Ln2SeW4O11(OH)(H2O)4(SbW9O33)(SeW9O33)(Se1/2Sb1/2W9O33)]229- constituted by two equivalent trimeric subunits Ln2W4O9(H2O)4(SbW9O33)(SeW9O33)(Se1/2Sb1/2W9O33) bridged via two μ2-{SeO2(OH)} linkers. Furthermore, the catalytic oxidation of various aromatic sulfides and sulfur mustard simulant 2-chloroethyl ethyl sulfide (CEES) by compound 3 as the heterogeneous catalyst has been investigated, exhibiting high conversion and selectivity as well as good stability and recyclability.