A DFT investigation of the catalytic oxidation of benzyl alcohol using graphene oxide

Metal-free heterogeneous materials have attracted great interest due to their potential to facilitate various organic transformations in line with circular economy and green chemistry principles. Among various 2D materials, graphene oxide (GO) is considered an attractive material for numerous applications in physics, chemistry, biology, material sciences, and catalysis. Furthermore, graphene-based catalysts exhibit good catalytic activity toward the selective oxidation of benzyl alcohol to benzaldehyde or benzoic acid under eco-friendly conditions. In this regard, a theoretical investigation was carried out to study both catalytic oxidation reaction pathways (i.e., benzyl alcohols to aldehyde and to benzoic acid) using GO as an eco-friendly and metal-free catalyst.

In this study, we report a theoretical investigation at the B3LYP/6-31G level to better understand the oxidation of benzyl alcohol using GO as a metal-free catalyst. The possible bond formation was investigated using the global and local reactivity indexes derived from Fukui functions. Furthermore, we performed a non-covalent interaction (NCI) analysis to unveil the stability and the interaction nature between both reagents and GO surface. The effect of the solvent on the oxidation efficiency was also performed and the results indicate that the solvent significantly affects the decrease of reactivity by increasing the activation barriers through oxidation reactions of benzyl alcohol. Additionally, the electron localization function (ELF) analysis was performed for all intermediates showing the ionic nature of the studied epoxide structure of GO and rules out any type of covalent interaction during the oxidation reaction of benzyl alcohol. All these obtained results are in good agreement with experimental observations and reveal that the epoxide functions on the graphene surface promote an excellent catalyst turnover.