First Principles Investigation of C, Cl[sub.2] and CO Co-Adsorption on ZrSiO[sub.4] Surfaces for Carbochlorination Reaction

The study of the adsorption behavior of C, CO and Cl[sub.2] on the surface of ZrSiO[sub.4] is of great significance for the formulation of the technological parameters in the carbochlorination reaction process. Based on first principles, the adsorption structure, adsorption energy, Barder charge, differential charge density, partial density of states and energy barrier were calculated to research the adsorption and reaction mechanism of C and Cl[sub.2] on ZrSiO[sub.4] surfaces. The results indicated that when C, CO and Cl[sub.2] co-adsorbed on the surface of ZrSiO[sub.4], they interacted with surface atoms and the charge transfer occurred. The Cl[sub.2] molecules dissociated and formed Zr-Cl bonds, while C atoms formed C1=O1 bonds with O atoms. Compared with CO, the co-adsorption energy and reaction energy barrier of C and Cl[sub.2] are lower, and the higher the C content, the lower the adsorption energy and energy barrier, which is beneficial for promoting charge transfer and the dissociation of Cl[sub.2]. The 110-2C-2Cl[sub.2] has the lowest adsorption energy and the highest reaction activity, with adsorption energy and energy barriers of −13.45 eV and 0.02 eV. The electrons released by C are 2.30 e, while the electrons accepted by Cl[sub.2] are 2.37 e.