Oxidative decomposition of dimethyl methylphosphonate on rutile TiO2(110): the role of oxygen vacancies

Abstract

The decomposition of dimethyl methylphosphonate (DMMP, (CH₃O)₂P(O)(CH₃)), a simulant to the toxic nerve agent Sarin, on the rutile TiO₂(110) surface has been studied with temperature programmed desorption (TPD) and density functional theory (DFT) calculations. The reactivity of the TiO₂(110) surface for DMMP decomposition is shown to be low, with mainly molecular desorption and only a small fraction of methanol and formaldehyde decomposition products seen from TPD at around 650 K. In addition, this amount of products is similar to the number of O vacancies on the surface. DFT calculations show that O vacancies are key for P–OCH₃ bond cleavage of DMMP, lowering the barrier by 0.7 eV and enabling the reactive process to occur at around 600 K. This is explained by the closer position of DMMP with respect to the surface in the presence of O vacancies. Calculations show that the produced methoxy groups can transform into gas phase formaldehyde and methanol at the considered temperature (600 K), in agreement with experiments. O–C bond cleavage of DMMP is also a viable pathway at such a high temperature (600 K) for DMMP decomposition on r-TiO₂, even in the absence of O vacancies, but the formation of a gas phase product is energetically unfavorable. O vacancies hence are the active sites for decomposition of DMMP into gas phase products on r-TiO₂(110).