Vacancy‐Anchored Sub‐Nanometer Ru Catalyst with High Activity and Strong Durability at 800 °C Dry Reforming of Methane

Abstract Dry reforming of methane (DRM) represents an important way to convert both CO 2 and CH 4 to reduce greenhouse effects and produce valuable chemical products. Owing to the strong bonding energies of both CO 2 and CH 4 molecules, DRM usually proceeds at a high temperature, which inevitably causes catalyst sintering, leading to catalyst deactivation. This work develops a highly stable sub‐nanometer Ru catalyst on a Ni‐doped MgO support using Mg 2+ vacancies as anchors. The optimized Ru 1.5 /Ni 1 ‐MgO‐R catalyst displays 90% CH 4 conversion and 92% CO 2 conversion to syngas in DRM at 800 °C. More importantly, it exhibits strong durability and can run continuously for more than 1200 h. Both the characterizations and the density functional theory (DFT) calculations demonstrate that the Ni 2+ substituted Mg 2+ in the MgO matrix produces Mg 2+ vacancies (Mg V ), which can stabilize sub‐nanometer Ru clusters of ≈0.9 nm. Moreover, the presence of Mg v ‐Ru 8 clusters strongly stabilizes sub‐nanometer Ru. This study contributes valuable insights into the design of sub‐nanometer metal catalysts with strong sintering resistance at high temperatures.