Factors Determining the Selectivity of NO Reduction Catalyzed by Copper‐Vanadium Oxide Cluster Anions Cu2VO3−5

Catalytic NO reduction by CO is imperative to satisfy the increasingly rigorous emission regulations. Identifying the structural characteristic of crucial intermediate that governs the selectivity of NO reduction is pivotal to having a fundamental understanding on real‐life catalysis. Herein, benefiting from the state‐of‐the‐art mass spectrometry, we demonstrated experimentally that the Cu2VO3–5− clusters can mediate the catalysis of NO reduction by CO, and two competitive channels to generate N2O and N2 can co‐exist. Quantum‐chemical calculations were performed to rationalize this selectivity. The formation of the ONNO unit on the Cu2 dimer was demonstrated to be a precursor from which two pathways of NO reduction start to emerge. In the pathway of N2O generation, only the Cu2 dimer was oxidized and the VO3 moiety functions as a “support”, while both moieties have to contribute to anchor oxygen atoms from the ONNO unit and then N2 can be generated. This finding displays a clear picture to elucidate how and why the involvement of VO3 “support” can regulate the selectivity of NO reduction. The catalysis of NO reduction by CO mediated by the Cu2VO3–5− clusters were identified by mass spectrometry experiments and quantum‐chemical calculations. Two competitive pathways to reduce NO into N2O and N2 co‐exist and the crucial intermediate that governs the selectivity of NO reduction was demonstrated. The mechanisms were rationalized by quantum‐chemical calculations.