Yunpeng Long, Yue Peng, Yarong Bai, Xinbo Li, Chuan Gao, Junhua Li
Abstract N 2 O decomposition over spinel catalysts suffers from a spin‐forbidden oxygen recombination step, resulting in substantial kinetic barriers of O 2 formation. Herein, we present a redox‐induced interfacial engineering strategy to activate lattice oxygen in spinel oxides, thereby effectively overcoming the kinetic constraints associated with oxygen recombination. In a Co 3 O 4 ‐based model system, controlled permanganate etching partially substitutes Mn into octahedral Co 3+ sites, while simultaneously generating heterointerfaces. The enhanced hybridization between Co 3 d and O 2 p orbitals and high Co–O–Mn covalency induced by the interface between δ‐MnO 2 and Co 3‐x Mn x O 4 , lead to the formation of highly active lattice oxygen species adjacent to the interface. 18 O isotope labeling experiment further confirms a dominant lattice‐oxygen‐mediated Mars–van Krevelen mechanism for N 2 O decomposition, whereas pristine Co 3 O 4 predominantly follows the Langmuir–Hinshelwood mechanism. Therefore, the optimized catalyst exhibits enhanced N 2 O decomposition activities, maintaining stability under impurity‐rich conditions. This work offers a promising approach for the rational design of efficient catalysts for N 2 O abatement and provides mechanistic insights into redox‐induced lattice oxygen activation.