Catalytic Aerobic Oxidation Processes in Hydrocarbon Systems

Catalytic aerobic oxidation of hydrocarbons harnesses molecular oxygen to convert simple aliphatic and aromatic substrates into value-added oxygenates under mild conditions. Central to these processes is the generation and propagation of radical species, often mediated by catalysts that facilitate the homolytic activation of O₂. Both homogeneous organocatalysts—such as N-hydroxyphthalimide (NHPI) and its analogues—and heterogeneous solids, including mixed-metal oxides and supported ionic-liquid phases, have been developed to enhance activity, selectivity and catalyst longevity. Recent advances have focused on metal-free systems to avoid contamination, precise control of radical chain propagation to suppress over-oxidation, and the design of solid supports that ensure high oxygen mobility and easy catalyst recovery. Industrial relevance spans from large-scale production of hydroperoxides as chemical intermediates to the synthesis of fine chemicals such as benzaldehyde, acetophenone and nicotinic acid. Interdisciplinary efforts now integrate mechanistic insights, advanced materials characterisation and process intensification, underscoring the global importance of sustainable aerobic oxidation in reducing reliance on hazardous oxidants and minimising energy consumption.

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Catalytic Aerobic Oxidation Processes in Hydrocarbon Systems publication trend

The graph below shows the total number of articles in catalytic aerobic oxidation processes in hydrocarbon systems across all publications each year (not limited to Nature Index journals).

Technical terms

Aerobic oxidation: Oxidation process that employs molecular oxygen as the electron acceptor, often via radical intermediates.

N-hydroxyphthalimide (NHPI): An organocatalyst that generates phthalimide N-oxyl (PINO) radicals to abstract hydrogen atoms from hydrocarbons.

Phase-transfer catalyst: A compound that facilitates the transport of reactive species between immiscible liquid phases, enhancing reaction rates and selectivity.

Hydroperoxide: An intermediate or product bearing the –OOH functional group, commonly generated in radical chain oxidation of alkanes or aromatics.

Lattice oxygen: Oxygen ions within a solid oxide’s crystal structure that can participate in redox reactions and influence catalytic activity and oxygen mobility.

References

1. An Investigation of N-Hydroxyphthalimide Catalyzed Aerobic Oxidation of Toluene without Metal Ions in Liquid Phase: Effect of Solvents and Phase Transfer Catalysts. Molecules (2024).
2. Oxidation of Picoline with Oxygen to Nicotinic Acid against Co2+, NHPI, and Phosphonium or Ammonium Bromides. Catalysts (2023).
3. A new highly active La 2 O 3 –CuO–MgO catalyst for the synthesis of cumyl peroxide by catalytic oxidation. RSC Advances (2021).