A Sulfur-Tolerant MOF-Based Single-Atom Fe Catalyst for Efficient Oxidation of NO and Hg⁰

Catalytic oxidation of NO and Hg⁰ is a crucial step to eliminate multiple pollutants from emissions from coal-fired power plants. However, traditional catalysts exhibit low catalytic activity and poor sulfur resistance due to low activation ability and poor adsorption selectivity. Herein, a single-atom Fe decorated N-doped carbon catalyst (Fe₁ -N₄ -C), with abundant Fe₁ -N₄ sites, based on a Fe-doped metal-organic framework is developed to oxidize NO and Hg⁰ . The results demonstrate that the Fe₁ -N₄ -C has ultrahigh catalytic activity for oxidizing NO and Hg⁰ at low and room temperature. More importantly, Fe₁ -N₄ -C exhibits robust sulfur resistance as it preferably adsorbs reactants over sulfur oxides, which has never been achieved before with traditional catalysts. Furthermore, SO₂ boosts the catalytic oxidation of NO over Fe₁ -N₄ -C through accelerating the circulation of active sites. Density functional theory calculations reveal that the Fe₁ -N₄ active sites result in a low energy barrier and high adsorption selectivity, providing detailed molecular-level understanding for its excellent catalytic performance. This is the first report on NO and Hg⁰ oxidation over single-atom catalysts with strong sulfur tolerance. The outcomes demonstrate that single-atom catalysts are promising candidates for catalytic oxidation of NO and Hg⁰ enabling cleaner coal-fired power plant operations.