Anion‐Doped Manganese Oxides Enabling Relay Catalysis for Aerobic Alcohol Ammoxidation

ABSTRACT

The development of noble‐metal‐free heterogeneous catalysts for room‐temperature aerobic ammoxidation of alcohols to nitriles represents an enduring challenge, primarily hampered by unselective lattice‐oxygen over‐oxidation via the classical Mars–van Krevelen (MvK) pathway and strong site‐blocking effects. Herein, we report a dual‐anion (C/N) doped MnO _x (C/N–MnO _x ) synthesized via a green, solvent‐free crystallization strategy, which exhibits excellent catalytic performance (95.3% benzyl alcohol conversion, >99% benzonitrile selectivity) and broad substrate versatility (35 diverse alcohol substrates) under ambient conditions (25°C, 1 atm O ₂ ) without external energy inputs. Structural analyses and theoretical calculations demonstrate that N‐doping introduces medium‐strong Lewis acidic Mn–N sites to capture NH ₃ , while C‐doping generates localized oxygen vacancies for O ₂ activation. Crucially, kinetic isotope effect experiments and density functional theory (DFT) calculations prove that this anion dopant‐programmed relay catalysis successfully bypasses the MvK pathway, fundamentally shifting the rate‐determining step from initial alcohol dehydrogenation to the homolytic α –C–H bond scission of the aldimine intermediate. This work presents a paradigm shift in designing multifunctional non‐precious catalysts for ambient‐condition green organic transformations.