Quantum chemical study on the atmospheric photooxidation of ethyl acetate

Abstract

The mechanism for OH radical initiated atmospheric photoxidation reaction of ethyl acetate was carried out by using the density functional theory method. Geometries have been optimized at the B3LYP level with a standard 6-31G(d,p) basis set. The single-point energy calculations have been performed at the MP2/6-31G(d), MP2/6-311++G(d,p), and CCSD(T)/6-31G(d) levels, respectively. All of the possible degradation channels involved in the oxidation of ethyl acetate by OH radicals have been presented and discussed. Among the five possible hydrogen abstraction pathways of the reaction of ethyl acetate with OH radicals, the hydrogen abstractions from the C1-H3 and C2-H5 bonds are the dominant reaction pathways due to the low potential barriers and strong exothermicity. The ␤-ester rearrangement of IM6 is energetically favorable but is not expected to be important. The ␣-ester rearrangement reaction and O 2 direct abstraction from IM17 are the more favorable pathways and are strongly competitive. In addition, the ␣-ester rearrangement reaction is confirmed to be a one-step process. Acetic acid, formic acetic anhydride, acetoxyacetaldehyde, and acetic anhydride are the main products for the reaction of ethyl acetate with OH radicals.

Mechanism of Photocatalytic CO2 Reduction by Bismuth-Based Perovskite Nanocrystals at the Gas–Solid Interface

“…For instance, the most commonly used solvent, ethyl ethanoate, can be decomposed into CO and CH 4 via its own photoreaction with UV light. 41 The ultraviolet photoelectron spectral data in Figure S5, SI, indicate that the energy levels of all three PeNCs are suitable for CO 2 reduction. 36,42 In our experiments, we loaded the PeNCs, as prepared, at the bottom of a quartz reactor.…”

“…We applied Bi-based PeNCs as photocatalysts to investigate the reduction of CO 2 at a gas–solid interface, whereas a gas–liquid interface faces problems of limited solubility of CO 2 and detrimental products produced via photoreaction of the solvent molecules. For instance, the most commonly used solvent, ethyl ethanoate, can be decomposed into CO and CH 4 via its own photoreaction with UV light . The ultraviolet photoelectron spectral data in Figure S5, SI, indicate that the energy levels of all three PeNCs are suitable for CO 2 reduction. , In our experiments, we loaded the PeNCs, as prepared, at the bottom of a quartz reactor.…”