Enhanced Catalytic Oxidation of CO on Sulfur‐Doped Boron Nitride

Abstract Bridging the gap between homogeneous and heterogeneous catalysis, the single‐atom catalyst supported on a substrate shows extremely high atom efficiency, low cost, excellent stability, and high activity for CO oxidation. Here, we report the catalytic mechanism of CO oxidation on sulfur‐doped h‐BN. The chemisorption activates O₂ via electron transfer from sulfur‐doped h‐BN, inducing a reduction in the bond order of O₂ and lengthening the O−O distance. This variation is helpful for the subsequent oxidation of CO. The oxidation process includes O₂ adsorption, electron reorganization, and two instances each of CO adsorption, oxygen transfer, and CO₂ desorption. The first oxygen transfer from O₂ to CO occurs exothermically by ∼−63.8 kcal/mol with a barrier of ∼12.1 kcal/mol, which is thus the rate‐determining step. The significantly enhanced catalytic performance implies that sulfur doping on h‐BN should have potential applications in the areas of metal‐free catalysts with low cost and high activity.