Selective Oxidation Catalysis of Hydrocarbons

Selective oxidation catalysis of hydrocarbons constitutes a central pillar in modern chemical synthesis, enabling the direct conversion of inert C–H bonds into valuable oxygenated products under mild conditions. This field encompasses heterogeneous and homogeneous catalyst systems that activate molecular oxygen or peroxide species to introduce oxygen functionalities with high chemo-, regio- and stereoselectivity. Advances in nanostructuring, support engineering and metal-ligand design have imparted precise control over active-site environments, facilitating synthesised pathways to alcohols, ketones, epoxides and acids from alkanes, alkenes and aromatic substrates. The global demand for sustainable processes has spurred research into earth-abundant metals, biomimetic catalytic motifs and solvent-free protocols, with an emphasis on atom economy, catalyst recyclability and minimal by-product formation. Mechanistic insights—gleaned from spectroscopic and computational studies—illuminate the roles of radical intermediates, metal–oxo species and surface redox cycles, guiding the rational optimisation of catalysts for petrochemical upgrading, fine-chemical synthesis and biomass valorisation.

Research from Nature Portfolio

A foundational investigation has demonstrated that two-dimensional gold nanosheets, synthesised via a layered-template method, exhibit exceptionally high activity and stability for solvent-free selective oxidation of C–H bonds using molecular oxygen. The ultra-thin morphology and low gold–gold coordination number facilitate facile activation of oxygen and efficient turnover, while the negatively charged sheet surface endows remarkable resistance to sintering. This work has set the stage for exploring atomically precise noble-metal architectures in selective oxidation chemistry.

Selective Oxidation Catalysis of Hydrocarbons publication trend

The graph below shows the total number of articles in selective oxidation catalysis of hydrocarbons across all publications each year (not limited to Nature Index journals).

Technical terms

Selectivity: The preference of a catalyst to convert a specific bond or substrate into a desired product over other possible pathways.

Heterogeneous catalysis: Catalytic processes in which the catalyst is in a different phase (usually solid) from the reactants.

Support: A porous material that disperses and stabilises active catalyst species, often influencing activity and selectivity.

C–H activation: The cleavage of a carbon–hydrogen bond by a catalyst to enable subsequent functionalisation steps.

Turnover frequency (TOF): The number of substrate molecules converted to product per active site per unit time, indicating catalyst efficiency.

References

1. Two-dimensional gold nanostructures with high activity for selective oxidation of carbon–hydrogen bonds. Nature Communications (2015).
2. Atmospheric and Efficient Selective Oxidation of Ethylbenzene Catalyzed by Cobalt Oxides Supported on Mesoporous Carbon Nitride. Catalysts (2023).
3. Transition Metal Salts of Carboxylated Multiwalled Carbon Nanotubes in Combination with N-hydroxyphthalimide as Catalytic Systems for Hydrocarbon Oxidation. Materials (2021).
4. Recent Development of Catalytic Materials for Ethylbenzene Oxidation. Journal of Nanomaterials (2020).