Asymmetrically Steering Excited-State Reaction Channels for Ambient N 2 Catalytic Oxidation.

Precise control of catalytic reactions in the excited state is challenging, as the highly reactive chemical environment strengthens both forward and reverse reactions simultaneously. Here, we propose a strategy to asymmetrically regulate the reaction channels via the physical mixing of the model catalyst Co₃O₄/Al₂O₃ with 13X zeolite, enabling efficient plasma-driven N₂ oxidation with minimized reverse reaction kinetics. In situ characterization combined with molecular dynamics simulations reveals that the diffusion of the product NO is selectively accelerated through Na⁺-mediated transport channels. This promotes NO turnover on octahedral Co³⁺ active sites, thereby unidirectionally shifting the reaction equilibrium. Thus, we demonstrate N₂ oxidation performance under ambient conditions that surpasses the efficiency of thermochemical conversion at 1,800 K, achieving more than a 3-fold improvement in the N₂ conversion rate compared to the conventional plasma-catalysis system. This work provides an approach to orderly modulate heterogeneous catalytic reactions in the excited state.