The Room Temperature Decomposition Mechanism of Dimethyl Methylphosphonate (DMMP) on Alumina-Supported Cerium Oxide − Participation of Nano-Sized Cerium Oxide Domains

Abstract

The adsorption and decomposition reactions of dimethyl methylphosphonate (DMMP) on cerium oxide supported on aluminum oxide have been examined at 25 °C. Experiments were carried out that involved dosing the reactive adsorbent with small doses of DMMP, followed by quantitative determination of the decomposition products. The results suggest that the formation reactions of methanol and dimethyl ether are competitive processes involving the same surface intermediate, which is most likely a surface methoxy species. Based on the observed results, it is proposed that the formation of dimethyl ether is due to the combination of two surface methoxy groups, while an important, if not the dominant, reaction producing methanol involves a surface methoxy group interacting with a vapor phase or physisorbed DMMP molecule. The presence of significant amounts of methoxy fragments formed upon DMMP adsorption is supported by results from diffuse reflectance spectroscopy, which also show that those groups are primarily associated with the cerium oxide domains. FT-Raman spectroscopy shows that the most active cerium oxide domains are highly dispersed two-dimensional domains or very small (<1 nm) crystallites. Somewhat larger (<6 nm) three-dimensional crystallites add to the decomposition yield, but less strongly. The FT-Raman evidence also supports the formation of a relatively narrow particle size distribution of cerium oxide crystallites on the alumina support surface from the sample preparation method. The alumina-supported cerium oxide reactive adsorbents developed as part of this study are the most active that have been reported in the literature for ambient temperature applications, decomposing approximately 775 μmol of DMMP per gram of adsorbent at 25 °C, and strongly or irreversibly adsorbing an additional 400 μmol, for a total capacity at room temperature of 1.1−1.2 mmol of DMMP per gram.