Designing Reactive Bridging O 2- at the Atomic Cu-O-Fe Site for Selective NH 3 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 NH ₃ oxidation, the weak Cu-O/Fe-O bond enables fast Cu redox for NH ₃ conversion and direct NO adsorption via Cu-O-NO to promote N-N coupling toward N ₂ . As a result, 99% N ₂ 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.
Competing Interests: The authors declare no competing financial interest.
(© 2022 The Authors. Published by American Chemical Society.)