4d–2p–4f Gradient Orbital Coupling Enables Tandem Catalysis for Simultaneous Abatement of N2O and CO on Atomically Dispersed Rh/CeO2 Catalyst

N₂O and CO coexist in various industrial and mobile sources. The synergistic reaction of N₂O and CO to generate N₂ and CO₂ has garnered significant research interest, but it remains extremely challenging. Herein, we constructed an atomically dispersed Rh-supported CeO₂ catalyst with asymmetric Rh–O–Ce sites through gradient Rh 4d–O 2p–Ce 4f orbital coupling. This design effectively regulates the 4f electron states of Ce and promotes the electron filling of the O 3π* antibonding orbital to facilitate N–O bond cleavage. Near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) reveals that CO reacts with the surface-adsorbed O* generated by N₂O decomposition through self-tandem catalysis, accelerating the rate-limiting step in N₂O decomposition and activating the synergistic reaction of N₂O and CO at temperatures as low as 115 °C. This work can guide the development of high-performance catalysts using the strategy of high-order orbital hybridization combined with the tandem concept to achieve versatile catalytic applications.