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

CONTEXT: 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. METHODS: 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.

Unveiling the effect of 2D silagraphene structural diversity on electronic properties: DFT, DOS, and ELF studies.

Recently, fully π-functional two-dimensional (2D) materials have been reported for electronic device applications. Graphene is one of these 2D materials that is attributed to 2D electron confinement effects and exhibits an aromatic character; however, it is characterized by vanishing the bandgap energy. Hence, research was focused on the discovery of graphene-based 2D materials to reduce the bandgap energy. Herein, we investigate the silagraphene structures (SixCy) using DFT calculations to undertake and improve structural, physico-chemical, and electronic properties. Various types of 2D networks have been investigated by considering C-C and C-Si bonds in relative positions. Both conjugation and hyperconjugation phenomenon have been deeply examined and it seemed that they take advantage of each other depending on the C-C and C-Si bond positions. Localized orbital locator (LOL) and electron localization function (ELF) were also performed to examine the electronic densities in the investigated 2D networks and unveil the electronic properties of the studied materials.