Hydroformylation Catalysis in Multiphase Systems

Hydroformylation, the addition of a formyl group and hydrogen to an alkene, is a cornerstone reaction in both academic research and industrial practice. When conducted in multiphase systems—typically involving an aqueous phase and an organic phase or a thermomorphic solvent blend—this transformation offers distinct advantages in catalyst recovery, product purification and process intensification. In aqueous biphasic arrangements, water-soluble ligands and transition-metal complexes remain in the aqueous compartment, while hydrophobic aldehyde products partition into the organic phase. Thermomorphic solvent systems exploit temperature-dependent miscibility to achieve homogeneous reaction conditions at elevated temperature and facile phase separation upon cooling. Key challenges include mass transfer limitations at the liquid–liquid interface, control of regioselectivity towards linear versus branched aldehydes and minimising catalyst leaching. Recent engineering of supramolecular mass transfer agents such as cyclodextrins, alongside the design of amphiphilic ligand frameworks and micellar environments, has significantly enhanced substrate solubility and interfacial transport. Continuous-flow implementations in miniplant and pilot scales demonstrate the feasibility of long-duration operation with high chemoselectivity and minimal metal loss. Such multiphase strategies contribute to greener production of fine chemicals, fragrances and polymer precursors by reducing solvent usage, simplifying downstream processing and enabling catalyst reuse on an industrially relevant scale.

Research from Nature Portfolio

No recent Nature Portfolio content available.

Hydroformylation Catalysis in Multiphase Systems publication trend

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

Technical terms

Hydroformylation: Catalytic reaction that converts alkenes into aldehydes by addition of syngas (CO and H₂).

Biphasic catalysis: Process in which reactants and products reside in one liquid phase while catalyst remains soluble in a second, immiscible phase, allowing for facile separation.

Thermomorphic solvent system: Solvent mixture that is homogeneous at reaction temperature but separates into two phases upon cooling, enabling catalyst recovery.

Mass transfer agent: Additive (e.g. cyclodextrin or amphiphilic ligand) that enhances substrate transport across phase boundaries.

Catalyst leaching: Loss of catalytic metal species from the intended phase, typically measured as a percentage of initial loading.

References

1. Continuous hydroformylation of 1-decene in an aqueous biphasic system enabled by methylated cyclodextrins. Green Chemistry (2020).
2. Thermomorphic solvent selection for homogeneous catalyst recovery based on COSMO-RS. Chemical Engineering and Processing - Process Intensification (2016).
3. Miniplant-Scale Evaluation of a Semibatch-Continuous Tandem Reactor System for the Hydroformylation of Long-Chain Olefins. Industrial & Engineering Chemistry Research (2019).
4. Effect of Liquid–Liquid Interfacial Area on Biphasic Catalysis Exemplified by Hydroformylation. ACS Catalysis (2022).
5. Micellar Catalysis for Sustainable Hydroformylation. ChemCatChem (2021).
6. Unconventional Approaches Involving Cyclodextrin-Based, Self-Assembly-Driven Processes for the Conversion of Organic Substrates in Aqueous Biphasic Catalysis. Catalysts (2017).
7. Rhodium-Catalyzed Aqueous Biphasic Olefin Hydroformylation Promoted by Amphiphilic Cyclodextrins. Catalysts (2020).
8. Synthesis of Nixantphos Core-Functionalized Amphiphilic Nanoreactors and Application to Rhodium-Catalyzed Aqueous Biphasic 1-Octene Hydroformylation. Polymers (2020).