First Principles Investigation of C, Cl₂ and CO Co-Adsorption on ZrSiO₄ Surfaces for Carbochlorination Reaction

Abstract

The study of the adsorption behavior of C, CO and Cl2 on the surface of ZrSiO4 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 Cl2 on ZrSiO4 surfaces. The results indicated that when C, CO and Cl2 co-adsorbed on the surface of ZrSiO4, they interacted with surface atoms and the charge transfer occurred. The Cl2 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 Cl2 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 Cl2. The 110-2C-2Cl2 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 Cl2 are 2.37 e.

Keywords

• first principles
• co-adsorption
• carbochlorination reaction
• ZrSiO₄