Heterogeneous Aerobic Oxidation With Molecular Oxygen: A Versatile Platform for Sustainable Production of Oxygenates and Nitrogen‐Containing Chemicals

Heterogeneous aerobic oxidation using molecular oxygen (O₂) represents a versatile and sustainable platform for the synthesis of oxygenates and nitrogen-containing chemicals. This review systematically summarizes recent advances in fundamental principles of molecular oxygen activation, catalyst design, reaction mechanisms for key oxidative transformations, including the oxidative dehydrogenation of alkanes, the epoxidation of alkenes, ammoxidation, ammoximation, oxidative cleavage or nitridation, and the oxidative upcycling of waste plastics. The fundamental challenge of activating triplet O₂ is addressed through strategies such as altering electron transfer, chemisorption-dissociation, lattice oxygen participation (Mars-van Krevelen mechanism), and the formation of active oxygen complexes. By comparing catalytic systems, such as MoVNbTeO_x for ethane ODH, Ag/α-Al₂O₃ for ethylene epoxidation, Au/TS-1 for propylene epoxidation, and emerging oxidative upcycling of plastics, we extract general principles for enhancing catalytic activity, selectivity, and stability. Future perspectives highlight the role of advanced characterization, atomic-scale catalyst engineering, and process intensification in enabling the industrial implementation of aerobic oxidation technologies, ultimately contributing to a greener and circular chemical economy.