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Adsorption and decomposition of dimethyl methylphosphonate (DMMP) on expanded graphite/metal oxides

机译:膨胀的石墨/金属氧化物上对甲基膦酸二甲酯(DMMP)的吸附和分解

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摘要

Composites based on expanded graphite (EG) and metal oxides (MOs) were prepared by an explosive combustion and blending method. A metal oxide (Ag2O, CuO or ZnO)-containing phase was employed as a component with reactive functionality, which was supported on EG as a component with adsorptive functionality. The physical properties of the EG/MO composites were examined using SEM and FTIR spectroscopy, the results of which indicated that the MOs were incorporated in the EG matrix after impregnation. Solid state magic angle spinning (MAS) H-1, P-31 and cross polarization (CP) MAS C-13 NMR studies of the EG/MO composites were performed after adsorption of dimethyl methylphosphonate (DMMP). The FTIR and NMR data showed that the initial uptake occurred through both molecular and reactive adsorption. Molecular adsorption occurred by van der Waals interaction of M(Zn, Cu, Ag) center dot center dot center dot O=P and hydrogen-bond formation to isolated hydroxyl groups. Reactive chemisorption appeared to occur through interaction with both Lewis acid sites and active oxygen species present on the MO surface. The FTIR and NMR results exhibited a trend of reactivity towards DMMP in the order Ag2O ZnO Cu O, which indicated stronger interaction between the Lewis acid sites and the phosphoryl O atom of DMMP for Ag2O as compared with ZnO and CuO, with concomitant formation of surface-coordinated DMMP and bridge-bonded OAPAO phosphorus oxide species. (C) 2018 Elsevier B.V. All rights reserved.
机译:通过爆炸燃烧和共混方法制备了基于膨胀石墨(EG)和金属氧化物(MOs)的复合材料。含金属氧化物(Ag2O,CuO或ZnO)的相被用作具有反应性官能团的组分,该相被负载在EG上作为具有吸附性官能团的组分。使用SEM和FTIR光谱检查了EG / MO复合材料的物理性能,结果表明,在浸渍后,MOs被掺入了EG基质中。吸附了甲基膦酸二甲酯(DMMP)之后,对EG / MO复合材料进行了固态幻角纺丝(MAS)H-1,P-31和交叉极化(CP)MAS C-13 NMR研究。 FTIR和NMR数据表明,初始吸收是通过分子吸附和反应吸附而发生的。 M(Zn,Cu,Ag)中心点中心点中心点中心点O = P的范德华相互作用和氢键形成对孤立的羟基进行分子吸附。反应性化学吸附似乎是通过与路易斯酸位点和MO表面上存在的活性氧相互作用而发生的。 FTIR和NMR结果显示出对DMMP的反应性趋势,依次为Ag2O> ZnO> Cu O,这表明与ZnO和CuO相比,Ag2的路易斯酸位与DMMP的磷酸O原子之间的相互作用比ZnO和CuO强,同时形成配位的DMMP和桥键结合的OAPAO氧化磷的种类(C)2018 Elsevier B.V.保留所有权利。

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