d-π Orbital Interaction Promoting NOx Selective Reduction on the Mn-Doped α-Fe2O3(001) Catalyst

Understanding the structure–activity relationship on a solid surface is crucial for developing an efficient low-temperature NH3–SCR catalyst. Herein, an in-depth investigation was conducted on a single-atom Mn-doped α-Fe2O3 catalyst by combining experimental studies and density functional theory calculations. Mn doping not only facilitates N–H cleavage in the Eley–Rideal (E–R) pathway but also promotes the adsorption of NO and the cleavage of the N–O bond, lowering the energy barrier of the rate-determining step in the Langmuir–Hinshelwood (L–H) pathway. Thus, Mn doping facilitates the catalytic reaction along both potential pathways, which promotes the NH3–SCR reaction. Further analysis reveals that the doping of Mn introduces an unoccupied dxy orbital, which facilitates the interaction with the π orbital of NO, thereby augmenting NO adsorption. Moreover, Mn doping redistributes the electron density, enhancing the flexibility of electrons on the Fe atom and facilitating electron transfer from Fe to the π* orbital of Mn–N–O, thus promoting N–O cleavage. The present study demonstrates that the incorporation of unoccupied d orbitals with appropriate energy and symmetry facilitates a d-π interaction between the dopant and reactant, thereby significantly enhancing catalytic efficiency. These findings provide valuable new insights into the design of high-performance NH3–SCR catalysts.