Theoretical and experimental investigations of mercury adsorption on hematite surfaces

One of the biggest environmental concerns caused by coal-fired power plants is the emission of mercury (Hg), which is toxic metal. To control the emission of Hg from coal-derived flue gas, it is important to understand the behavior and speciation of Hg as well as the interaction between Hg and solid materials in the flue gas stream. In this study, atomic-scale theoretical investigations using density functional theory (DFT) were carried out in conjunction with laboratory-scale experimental studies to investigate the adsorption behavior of Hg on hematite (α-Fe₂O₃). According to the DFT simulation, the adsorption energy calculation proposes that Hg physisorbs to the α-Fe₂O₃(0001) surface with an adsorption energy of -0.278 eV, and the subsequent Bader charge analysis confirms that Hg is slightly oxidized. In addition, Cl introduced to the Hg-adsorbed surface strengthens the Hg stability on the α-Fe₂O₃(0001) surface, as evidenced by a shortened Hg-surface equilibrium distance. The projected density of states (PDOS) analysis also suggests that Cl enhances the chemical bonding between the surface and the adsorbate, thereby increasing the adsorption strength. In summary, α-Fe₂O₃ has the ability to adsorb and oxidize Hg, and this reactivity is enhanced in the presence of Cl. For the laboratory-scale experiments, three types of α-Fe₂O₃ nanoparticles were prepared using the precursors Fe(NO₃)₃, Fe(ClO₄)₃, and FeCl₃, respectively. The particle shapes varied from diamond to irregular stepped and subrounded, and particle size ranged from 20 to 500 nm depending on the precursor used. The nanoparticles had the highest surface area (84.5 m²/g) due to their highly stepped surface morphology. Packed-bed reactor Hg exposure experiments resulted in this nanoparticles adsorbing more than 300 μg Hg/g. The Hg L_III-edge extended X-ray absorption fine structure spectroscopy also indicated that HgCl₂ physisorbed onto the α-Fe₂O₃ nanoparticles.

Atomic-scale theoretical simulations proposes that Hg physisorbs to the α-Fe₂O₃(0001) surface with an adsorption energy of -0.278 eV, and the subsequent Bader charge analysis confirms that Hg is slightly oxidized. In addition, Cl introduced to the Hg-adsorbed surface strengthens the Hg stability on the α-Fe₂O₃(0001) surface, as evidenced by a shortened Hg-surface equilibrium distance. The PDOS analysis also suggests that Cl enhances the chemical bonding between the surface and the adsorbate, thereby increasing the adsorption strength. Following laboratory-scale experiment of Hg sorption also shows that HgCl₂ physisorbs onto α-Fe₂O₃ nanoparticles which have highly stepped structure.