Glycerol adsorption and mechanism of dehydration to acrolein over TiO2 surface: A density functional theory study

[Display omitted] •DFT calculations were used for the investigation of dehydration mechanism of glycerol to acrolein by anatase TiO2 (1 0 0).•Supercell of anatase TiO2 (1 0 0) with two types of oxygen and one type titanium atoms was optimized.•The adsorption energies and distances of the glycerol from the surface after adsorption were calculated.•Three paths were proposed for the glycerol dehydration.•The third path with 89.1 kcal/mol activation energy was suggested as a proper path for this research. Glycerol as major by-product of biodiesel production cab be converted to high-value added materials such as acrolein. The details of this transformation mechanism is obscure using metal oxide catalysts. In this study, DFT calculations using the generalized gradient approximation with periodic boundary conditions was used to study the mechanism of dehydration of glycerol to acrolein on the (1 0 0) surface of anatase TiO2. For this purpose, the (1 0 0) TiO2 crystal face was built with a slab of Ti24O48. The various interaction of glycerol with the surface was surveyed, and energy barriers and reaction energies were employed to analyze the possible dehydration mechanisms. Three paths were proposed for dehydration of glycerol to acrolein that starts with adsorption through central hydroxyl group. According to the third path, TiO2 surface shows the most activity in proton transfer reaction with 89.1 kcal/mol activation energy in comparison with path 1 and 2 is the appropriate path for the formation of acrolein. The rate-limiting step of this pathway is the adsorption of H2′ and Oγ on the surface and simultaneous creation of a double bond between Cα and Cβ (G1h → G1o).