Formation of Low-Volatile Products and Unexpected High Formaldehyde Yield from the Atmospheric Oxidation of Methylsiloxanes.

With stricter regulation of atmospheric volatile organic compounds (VOCs) originating from fossil fuel-based vehicles and industries, the use of volatile chemical products (VCPs) and the transformation mechanism of VCPs have become increasingly important to quantify air quality. Volatile methylsiloxanes (VMS) are an important class of VCPs and high-production chemicals. Using quantum chemical calculations and kinetics modeling, we investigated the reaction mechanism of peroxy radicals of VMS, which are key intermediates in determining the atmospheric chemistry of VMS. L2-RSiCH2O2• and D3-RSiCH2O2• derived from hexamethyldisiloxane and hexamethylcyclotrisiloxane, respectively, were selected as representative model systems. The results indicated that L2-RSiCH2O2• and D3-RSiCH2O2• follow a novel Si-C-O rearrangement-driven autoxidation mechanism, leading to the formation of low volatile silanols and high yield of formaldehyde at low NO/HO2• conditions. At high NO/HO2• conditions, L2-RSiCH2O2• and D3-RSiCH2O2• react with NO/HO2• to form organic nitrate, hydroperoxide, and active alkoxy radicals. The alkoxy radicals further follow a Si-C-O rearrangement step to finally form formate esters. The novel Si-C-O rearrangement mechanism of both peroxy and alkoxy radicals are supported by available experimental studies on the oxidation of VMS. Notably, the high yield of formaldehyde is estimated to significantly contribute to formaldehyde pollution in the indoor environment, especially during indoor cleaning.