Department of Chemistry and Biochemistry, The City College of New York, New York, NY 10031, USA.
Department of Chemistry and Biochemistry, The City College of New York, New York, NY 10031, USA; Ph.D. Program in Chemistry, The Graduate Center of the City University of New York, New York, NY 10016, USA.
J Colloid Interface Sci. 2018 Dec 1;531:233-244. doi: 10.1016/j.jcis.2018.07.053. Epub 2018 Jul 19.
Barium titanate nanoparticles (BTO-NPs) in the size range 8-12 nm, prepared by gel collection, are found to be a photoreactive detoxifier for Chemical Warfare Agent vapors, specifically, the sulfur mustard surrogate (2-chloroethyl ethyl sulfide). The relatively monodisperse, uniformly spherical BTO-NPs, initially dispersed in alcohol solvents, form a stable and porous aggregated structure reminiscent of a nanostructured material with voids/pores of an average diameter of 4.6 nm and a relatively narrow distribution of their sizes (2.5-8.7 nm). Due to the interparticle porosity and a polar, chemically active surface, signifcant amounts of CWA surrogate and its decomposition products were adsorbed on the BTO-NPs. The recorded weight uptake on the perovskite was the highest among a series of materials and nanocomposites known for their detoxification activity and tested at the same conditions (169 mg/g, compared to 117 mg/g for zinc oxide and <100 mg/g for other transition metal oxides). Besides adsorption, BTO nanomaterial acts simultaneously as an efficient heterogeneous catalyst by degrading the toxic vapors to alcohols, sulfides and thiols - molecules of significantly lower toxicity than the CWA surrogate. Hydrolysis and dehydrohalogenation were the predominant detoxification pathways, via the formation of the intermediate cyclic sulfonium, whether under light or in the dark. Ambient light irradiation promoted the photo-oxidation and photo-degradation by radical intermediates formed. With an unhindered oxygen rich surface, underlying highly polarizable lattice structure, and large accessible surface area, barium titanate nanoparticles are investigated as a potentially useful medium for photoreactive detoxification of chemical warfare agent vapors.
粒径在 8-12nm 范围内的钛酸钡纳米粒子（BTO-NPs）通过凝胶收集法制备，被发现是一种对化学战剂蒸气具有光反应解毒作用的物质，特别是硫芥类似物（2-氯乙基乙基硫醚）。这些相对单分散、均匀球形的 BTO-NPs 最初分散在醇溶剂中，形成一种稳定且多孔的聚集结构，类似于具有平均直径为 4.6nm 的纳米结构材料的空隙/孔和相对较窄的尺寸分布（2.5-8.7nm）。由于颗粒间的孔隙和极性、化学活性表面，大量 CWA 类似物及其分解产物被吸附在 BTO-NPs 上。与已知具有解毒活性且在相同条件下测试的一系列材料和纳米复合材料相比，BTO-NPs 的记录载药量最高（169mg/g，相比之下，氧化锌为 117mg/g，其他过渡金属氧化物<100mg/g）。除了吸附作用外，BTO 纳米材料还同时作为一种高效的多相催化剂，通过将有毒蒸气降解为醇、硫化物和硫醇，从而发挥作用，这些分子的毒性明显低于 CWA 类似物。水解和脱卤化氢是主要的解毒途径，通过形成中间环状硫翁，无论是在光照下还是在黑暗中。环境光照射通过形成自由基中间体促进光氧化和光降解。由于具有不受阻碍的富含氧的表面、高度极化的晶格结构和较大的可及表面积，钛酸钡纳米粒子被研究作为一种潜在有用的光反应解毒化学战剂蒸气的介质。
