Effects of chemical functional groups on elemental mercury adsorption on carbonaceous surfaces

A systematic theoretical study using density functional theory is performed to provide molecular-level understanding of the effects of chemical functional groups on mercury adsorption on carbonaceous surfaces. The zigzag and armchair edges were used in modeling the carbonaceous surfaces to simulate different adsorption sites. The edge atoms on the upper side of the models are unsaturated to simulate active sites. All calculations (optimizations, energies, and frequencies) were made at B3PW91 density functional theory level, using RCEP60VDZ basis set for mercury and 6-31G(d) pople basis set for other atoms. The results indicate that the embedding of halogen atom can increase the activity of its neighboring site which in turn increases the adsorption capacity of the carbonaceous surface for Hg0. The adsorption belongs to chemisorptions, which is in good agreement with the experimental results. For the effects of oxygen functional groups, lactone, carbonyl and semiquinone favor Hg0 adsorption because they increase the neighboring site's activity for mercury adsorption. On the contrary, phenol and carboxyl functional groups show a physisorption of Hg0, and reduce Hg capture. This result can explain the seemingly conflicting experimental results reported in the literature concerning the influence of oxygen functional groups on mercury adsorption on carbonaceous surface.