In Situ S-Doping Engineering for Highly Efficient NH3–SCR over Metal-Free Carbon Catalysts: A Novel Synergetic Promotional Mechanism

Cyclic desulfurization-regeneration-denitrification based on metal-free carbon materials is one of the most promising ways to remove NO_x and SO₂ simultaneously. However, the impact of S-doping induced by the cyclic desulfurization and regeneration (C-S-R) process on the selective catalytic reduction (SCR) is not well understood. Herein, it is demonstrated that the C-S-R process at 500 °C induces in situ S-doping with a significant accumulation of C-S-C structures. NO_x conversion was dramatically enhanced from 18.95% of the original sample to 84.55% of the S-doped sample. Density functional theory calculations revealed that the C-S-C structure significantly regulates the electronic structure of the C atom adjacent to the ketonic carbonyl group, thereby significantly altering the NH₃ adsorption configuration with superior adsorption capacity. Moreover, S-doping induces an extra electron transfer between the N atom of the NH₃ molecule and the C atom of the carbon plane, thereby promoting the activation of NH₃ over the ketonic carbonyl group with a reduced energy barrier. This study elucidates a synergetic promotional mechanism between the ketonic carbonyl group and the C-S-C structure for SCR, offering a novel design strategy for high-performance heteroatom-doped carbon catalysts in industrial applications.