Strong metal–support interactions between atomically dispersed Ru and CrOx for improved durability of chlorobenzene oxidation

Abstract

In this work, two single-atom catalysts (SACs) with atomically dispersed RuO₂ supported on CrO_x were successfully synthesized with a simple reduction strategy for the efficient catalytic oxidation of chlorobenzene (CB). With characterizations like Cs-corrected STEM, XPS, H₂-TPR, and O₂-TPD, the structure–activity relationship is addressed. The noble metal precursor Ru³⁺ was anchored with different oxygen species and exposed facets based on the physicochemical properties of catalyst supports. Based on the analysis results, the Ru³⁺ precursor could be mainly anchored into the surface lattice oxygen of Cr₂O₃-M over high-index facets (223) and adsorbed oxygen of Cr₂O₃-P over low-index facets (104), where the precursor Ru³⁺ was all oxidized to RuO₂ when being anchored with the oxygen species of Cr₂O₃-M and Cr₂O₃-P, respectively according to XPS analysis. There is a stronger metal–support interaction (SMSI) between Ru ions and the surface lattice oxygen of Cr₂O₃-M, according to H₂-TPR and O₂-TPD characterizations. Further, the catalytic performance for CB combustion at a high space velocity of 120 000 mL (g⁻¹ h⁻¹) was tested, and 1RuCr₂O₃-M performed better than 1RuCr₂O₃-P in both durability and activity. This could be attributed to the SMSI between single-atom Ru and the lattice oxygen of the 1RuCr₂O₃-M catalyst and the abundant active sites from the exposed high-index facets. The study provided a novel synthesis strategy for Ru-based SACs with SMSI effect, and the good durability of the catalyst (1RuCr₂O₃-M) extended the great potential for practical application.