Designing Reactive Bridging O^2- at the Atomic Cu-O-Fe Site for Selective NH₃ Oxidation

Surface oxidation chemistry involves the formation and breaking of metal-oxygen (M-O) bonds. Ideally, the M-O bonding strength determines the rate of oxygen absorption and dissociation. Here, we design reactive bridging O^2- species within the atomic Cu-O-Fe site to accelerate such oxidation chemistry. Using in situ X-ray absorption spectroscopy at the O K-edge and density functional theory calculations, it is found that such bridging O^2- has a lower antibonding orbital energy and thus weaker Cu-O/Fe-O strength. In selective NH₃ oxidation, the weak Cu-O/Fe-O bond enables fast Cu redox for NH₃ conversion and direct NO adsorption via Cu-O-NO to promote N-N coupling toward N₂. As a result, 99% N₂ selectivity at 100% conversion is achieved at 573 K, exceeding most of the reported results. This result suggests the importance to design, determine, and utilize the unique features of bridging O^2- in catalysis.