Nox impact on mercury removal based on TAC: A comprehensive DFT and XAFS analysis

The simplification of surface chemical reactions is crucial for comprehending the role of nitrogen oxides (NOx) in the adsorption behavior of elemental mercury (Hg0) onto carbon-based sorbents, thereby contributing to technological advancements in reducing mercury emissions. In this study, we developed two fundamental models for activated carbon and investigated the interactions among the carbon surface, NO/NO2, and Hg0 using density functional theory (DFT) calculations. Additionally, thermally-treated activated carbon (TAC) was utilized for Hg0 adsorption, and X-ray absorption fine structure (XAFS) analysis was conducted to examine the morphology and bonding environment of captured Hg. The results suggest that the carbon surface exhibits weak physisorption towards Hg0, but effectively adsorbs NO/NO2. Adsorption of NO/NO2 on the carbon surface with a zigzag edge leads to a decrease in the ADCH charge and surrounding electrostatic potential (ESP) of neighboring carbon vertices, thereby enhancing Hg0 adsorption in those regions through the Eley-Rideal reaction mechanism. The interaction between Hg0 and the surface with ZNO1, ZNO2, or ZNOO2 configurations involves electron transfer and subsequent formation of Hg-C ionic bonds, resulting in adsorption energies ranging from −91.33 to −87.56 kJ/mol. Notably, the adsorption of Hg0 onto the surface with ZNOO1 configuration results in a more extensive electron transfer, facilitating the formation of a robust Hg-O ionic bond and leading to a further reduction in Hg0 adsorption energy to −430.02 kJ/mol. XAFS analysis confirms that predominant formation of Hg-O species occurs following Hg0 adsorption on TAC under syngas containing NO2.