RESUMO
Criegee intermediates exert a crucial influence on atmospheric chemistry, functioning as powerful oxidants that facilitate the degradation of pollutants, and understanding their reaction kinetics is essential for accurate atmospheric modeling. In this study, the kinetics of CH2OO and syn-CH3CHOO reactions with acetaldehyde (CH3CHO) were investigated using a flash photolysis reaction tube coupled with the OH laser-induced fluorescence (LIF) method. The experimental results indicate that the reaction of syn-CH3CHOO with CH3CHO is independent of pressure in the range of 5-50 Torr when using Ar as the bath gas. However, the rate coefficient for the reaction between CH2OO and CH3CHO at 5.5 Torr was found to be lower compared to the near-constant values observed between 10 and 100 Torr. Furthermore, the reaction of syn-CH3CHOO with CH3CHO demonstrated positive temperature dependence from 283 to 330 K, with a rate coefficient of (2.11 ± 0.45) × 10-13 cm3 molecule-1 s-1 at 298 K. The activation energy and pre-exponential factor derived from the Arrhenius plot for this reaction were determined to be 2.32 ± 0.49 kcal mol-1 and (1.66 ± 0.61) × 10-11 cm3 molecule-1 s-1, respectively. In comparison, the reaction of CH2OO with CH3CHO exhibited negative temperature dependence, with a rate coefficient of (2.16 ± 0.39) × 10-12 cm3 molecule-1 s-1 at 100 Torr and 298 K and an activation energy and a pre-exponential factor of -1.73 ± 0.31 kcal mol-1 and (1.15 ± 0.21) × 10-13 cm3 molecule-1 s-1, respectively, over the temperature range of 280-333 K.
RESUMO
The direct conversion of low alkane such as ethane into high-value-added chemicals has remained a great challenge since the development of natural gas utilization. Herein, we achieve an efficient one-step conversion of ethane to C2 oxygenates on a Rh1/AC-SNI catalyst under a mild condition, which delivers a turnover frequency as high as 158.5 h-1. 18O isotope-GC-MS shows that the formation of ethanol and acetaldehyde follows two distinct pathways, where oxygen and water directly participate in the formation of ethanol and acetaldehyde, respectively. In situ formed intermediate species of oxygen radicals, hydroxyl radicals, vinyl groups, and ethyl groups are captured by laser desorption ionization/time of flight mass spectrometer. Density functional theory calculation shows that the activation barrier of the rate-determining step for acetaldehyde formation is much lower than that of ethanol, leading to the higher selectivity of acetaldehyde in all the products.