The catalytic reduction is known as an effective approach to remove the harmful nitrogen monoxide (NO) molecule. In this research, the potential application of the porphyrin‐like porous C24N24 fullerene decorated with a single Si atom (Si@C24N24) as a highly active catalyst for the reduction of NO in the presence of CO molecule is investigated through the dispersion-corrected DFT calculations. The results reveal that NO can be simply reduced into N2O molecule through the dimer mechanism. This reaction also produces Oads species which is attached to the Si atom of Si@C24N24. Thereafter, the Oads is eliminated by an incoming CO molecule by overcoming a small activation energy of 6.68 kcal/mol. These results demonstrate that the novel Si@C24N24 can be regarded as a pioneering and active metal-free catalyst for NO reduction in the presence of CO molecule. This study might provide new insights for designing novel active catalysts for the NO reduction.
