DFT study of mercury adsorption on AlO with presence of HCl.

mercury emission control from flue gas is a crucial issue for environment protection. Alumina is an important alkali metal oxide for mercury adsorption in particulate, meanwhile is the potential adsorbent for mercury removal. The cognition on mercury heterogeneous reaction mechanism with alumina in presence of hydrogen chloride is inadequate. In this work, the DFT calculation was applied to detect mercury's chlorides adsorption on α-AlO (001) surface, the Bader charge analysis was used to estimate electron transfer and the transition state theory was used to clarify reaction pathway and energy barrier, besides, the kinetic analysis based on Gibbs free energy was conducted to study the impact of temperature on chemical reaction. The results show that Hg can be captured by weak chemisorption on α-AlO (001) surface with the adsorption energy of -56.37 kJ/mol, HgCl, HgCl are intensively bonded on surface with adsorption energies of -276.90 kJ/mol and -231.87 kJ/mol, the surface unsaturated Al and O atoms are the active sites. Charge transfer and PDOS analysis prove that the forming of covalent bonding is responsible for Hg species adsorption. Two possible reaction pathways of Hg oxidization to HgCl are discussed, in which a smaller energy barrier of 0.1 eV implies the dominant pathway 1 via Eley-Rideal mechanism: two adsorbed HCl molecules dissociate on surface and then react with one Hg atom. High temperature can promote the reaction rate constants of pathway 1 and 2, but is only favorable for reducing energy barrier of pathway 2.