Toluene is an important compound in the chemical industry as well as an often chosen simple surrogate compound for aromatic components in transport fuels. As a result, an improved understanding of the liquid phase oxidation of toluene is of interest to both the chemical industry and the transportation sector. In this work, a detailed autoxidation mechanism for the liquid phase oxidation of toluene is developed using an automated mechanism generation tool. The resultant mechanism is significantly improved using quantum chemistry calculations to update the thermodynamic parameters of key species in solution. Comparisons are made between the predicted and experimentally measured induction period and the obtained mechanism. The agreement between both is found to be within 1 order of magnitude. Rate of production analysis and sensitivity analysis are carried out to explain and understand the reactions paths present in the mechanism. The behavior of the mechanism is commented upon qualitatively; however, no quantitative data could be obtained with the selected test method.
Density functional theory (DFT) calculations can be used to help elucidate the structures of active sites on the surface of fuel cell cathode catalysts, which are exceptionally difficult to identify by experimental techniques. The cathode catalysts were modeled in nitrogen‐, boron‐, sulfur‐, and phosphorus‐doped graphene basal planes. Dually‐doped graphene structures combining nitrogen with phosphorus or sulfur are also studied. Potential energy profiles were obtained, and the energies and activation barriers of molecular oxygen binding to the doped graphene model structures were estimated in order to identify potentially active sites for the oxygen reduction reaction in fuel cells. Among the investigated doped graphene structures, the active sites for molecular oxygen chemisorption are identified in graphene doped with either two nitrogen, or two phosphorus, or one sulfur and one phosphorus atoms. Further, the analysis of atomic spin densities and charges in the model structures enables the correlation of the catalytic activity with electron density distribution.
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