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首页> 外文期刊>The journal of physical chemistry, C. Nanomaterials and interfaces >Oxidation, Destruction, and Persistence of Multilayer Dimethyl Methylphosphonate Films during Exposure to O(P-3) Atomic Oxygen
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Oxidation, Destruction, and Persistence of Multilayer Dimethyl Methylphosphonate Films during Exposure to O(P-3) Atomic Oxygen

机译：暴露于O（P-3）原子氧过程中多层甲基二膦酸二甲酯薄膜的氧化，破坏和持久性

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摘要

We present work detailing the oxidative reactivity of the nerve agent simulant dimethyl methylphosphonate (DMMP) with atomic oxygen using time-resolved in situ reflection-absorption infrared spectroscopy (RAIRS) and X-ray photoelectron spectroscopy (XPS). When exposed to a supersonic beam containing O(P-3) with average translational energy of 0.12 eV, thermally annealed DMMP films (less than 50 layers) on single-crystal Au(111) are observed to react, likely via hydrogen abstraction, and followed by various secondary reactions with resultant hydroxyl and DMMP-derived radicals. This reaction is accompanied by the appearance of hydrogen bonding interactions with the DMMP phosphoryl (P=O) groups on the film surface, and it is also observed to result in both a loss of carbon and an uptake of oxygen by the film. These trends, when considered with the additional thermal stability of reaction products left on the surface, suggest that the mechanism entails reaction with DMMP methyl groups and the formation of various polymeric species; the presence of these polymers hinders continuous, effective destruction for films thicker than roughly ten layers. This work has specific implications for the implementation of plasma-bated and oxidative decontamination methods based upon an improved fundamental understanding of the chemistry of the important class of phosphoryl containing molecules.
机译：我们目前的工作详细描述了使用时间分辨原位反射吸收红外光谱（RAIRS）和X射线光电子能谱（XPS）来模拟神经毒剂模拟物甲基膦酸二甲酯（DMMP）与原子氧的氧化反应性。当暴露于包含平均平移能为0.12 eV的O（P-3）的超声束中时，观察到单晶Au（111）上的热退火DMMP膜（少于50层）会发生反应，可能是通过夺氢而发生的，并且然后与产生的羟基和DMMP衍生的自由基发生各种次级反应。该反应伴随着与膜表面上的DMMP磷酰基（P ＝ O）基团的氢键相互作用的出现，并且还观察到其导致碳的损失和氧的吸收。考虑到留在表面上的反应产物的额外热稳定性时，这些趋势表明该机理需要与DMMP甲基进行反应并形成各种聚合物。这些聚合物的存在会阻碍连续，有效地破坏厚度超过约十层的薄膜。这项工作基于对含磷酰基的重要分子的化学性质的基本了解，对实施等离子体腐蚀和氧化去污方法具有特定意义。

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