Insights into the Adsorption, Alloy Formation, and Poisoning Effects of Hg on Monometallic and Bimetallic Adsorbents.

The removal of elemental mercury (Hg) from coal-derived syngas at high temperatures is desired to improve the thermal efficiency of the coal-to-chemical processes. First-principles density functional theory (DFT) calculations for Hg adsorption are performed using different exchange correlation functionals (PBE, optPBE-vdW, and optB88-vdW). Gibbs free energy (Δ) calculations are further performed to evaluate the feasibility of Hg adsorption on various exposed planes of metal nanoparticles and to obtain bimetallic compositions for Hg removal at various temperatures. Pd and Pt are shown to be suitable for Hg adsorption at high temperatures (473 K), whereas Rh and Ru are effective only until 373 K. The bimetallic adsorbents comprising Ag or Au along with Rh, Ru, Pd, or Pt are identified for Hg removal at high temperatures (473 K). The increase in Hg adsorption strength on various bimetallic surfaces is correlated to the upward shift in the d-band center. Further, calculations predict the tendency of Hg to segregate toward the surface of amalgams and disturb the perfect planar geometry of the Pd, Pt, Rh, Ru, Ir, Cu, Ag, and Au surfaces to form a noncrystalline Hg-rich amalgam surface. An analysis of the binding of various adsorbates (H, O, N, and S) shows that the adsorption becomes significantly weaker on various sites in close proximity to pre-adsorbed Hg. Moreover, for specific combinations of the adsorbate, surface composition, and the site location, the adsorption does not take place on the proximal sites. These results are complemented by the partial density of states calculations, which show changes in the electronic properties of the amalgam surface, thus explaining the poisoning effect of Hg on metallic catalysts.