Catalytic Hydroformylation of Olefins

Catalytic hydroformylation of olefins, also known as the oxo process, is an industrially pivotal reaction that converts alkenes into aldehydes by addition of syngas (a mixture of carbon monoxide and hydrogen). Initiated in the 1930s, the process underpins large‐scale manufacture of detergents, plasticisers and fine chemicals. Transition‐metal complexes, most commonly rhodium with phosphine ligands, mediate alkene coordination, migratory insertion of CO and subsequent hydrogenation to yield linear and branched aldehydes. Key performance metrics include activity (turnover frequency), selectivity for a particular isomer (regioselectivity) and catalyst stability under pressure and temperature. Homogeneous catalysts offer high activity and selectivity but pose separation and recycling challenges. Heterogeneous systems facilitate recovery yet often lack the precision of molecular catalysts. Recent advances seek to combine the advantages of both, employing novel supports, single‐atom active sites and tailored ligand environments to enhance performance, reduce energy consumption and broaden substrate scope. These developments aim at more sustainable, energy‐efficient routes to high‐value chemicals, with a growing emphasis on earth‐abundant metals and milder operating conditions.

Research from Nature Portfolio

Rhodium nanoparticles anchored on silanol‐rich MFI zeolite demonstrate a heterogeneous system whose turnover frequency exceeds that of the classical homogeneous Wilkinson catalyst by an order of magnitude. The siliceous framework enriches olefin molecules adjacent to Rh clusters, accelerating reaction rates without sacrificing selectivity. In a complementary approach, zeolites synthesised in one pot with phosphonium templates yield phosphorous‐stabilised Rh single sites capable of ethylene hydroformylation at just 50 °C. Confinement in the zeolite pores controls the electronic state of Rh, enabling high activity and linear aldehyde selectivity at low temperature. Beyond zeolite systems, a phosphorus‐coordinated Rh single‐atom catalyst supported on nanodiamond achieves >99 % conversion and >90 % regioselectivity for arylethylenes. Surface‐bound phosphide species anchor Rh atoms, delivering robust performance in styrene hydroformylation and facilitating efficient syntheses of pharmaceutical intermediates with excellent recyclability.

Catalytic Hydroformylation of Olefins publication trend

The graph below shows the total number of articles in catalytic hydroformylation of olefins across all publications each year (not limited to Nature Index journals).

Technical terms

Hydroformylation: Catalytic reaction that converts an alkene and syngas into aldehydes by adding a formyl group and hydrogen across the double bond.

Turnover frequency (TOF): Number of substrate molecules converted per active site per unit time, a measure of catalyst activity.

Regioselectivity: Preference for formation of one structural isomer (linear or branched aldehyde) over another in a chemical reaction.

Homogeneous catalysis: Catalysis by soluble molecular species, offering precise control over activity and selectivity but requiring separation from products.

Heterogeneous catalysis: Catalysis by solids or supported species, facilitating catalyst recovery and reuse but often with lower selectivity.

Single‐atom catalyst: Catalyst in which individual metal atoms are isolated on a support, combining high metal utilisation with tunable activity and selectivity.

References

1. Rhodium nanoparticles supported on silanol-rich zeolites beyond the homogeneous Wilkinson’s catalyst for hydroformylation of olefins. Nature Communications (2023).
2. Low-temperature hydroformylation of ethylene by phosphorous stabilized Rh sites in a one-pot synthesized Rh-(O)-P-MFI zeolite. Nature Communications (2023).
3. Phosphorus coordinated Rh single-atom sites on nanodiamond as highly regioselective catalyst for hydroformylation of olefins. Nature Communications (2021).
4. Active and Regioselective Ru Single-Site Heterogeneous Catalysts for Alpha-Olefin Hydroformylation. ACS Catalysis (2022).
5. Achieving rhodium-like activity for olefin hydroformylation by electronic metal-support interaction of single atomic cobalt catalyst. Cell Reports Physical Science (2022).
6. Highly dispersed Rh single atoms over graphitic carbon nitride as a robust catalyst for the hydroformylation reaction. Catalysis Science & Technology (2023).