Atomic-level engineering of metal–metal interaction in intermetallic catalysts for efficient propene hydroformylation

Hydroformylation, a pivotal industrial reaction heavily reliant on Rh-based catalysts, remains limited by Rh scarcity and cost. While Co-based catalysts are potential alternatives, they still face dual challenges of insufficient activity and stability. In this work, Co-based intermetallic catalysts (CoMoIMC and CoWIMC) were synthesized through a layered double hydroxide precursor strategy. During propylene hydroformylation, CoMoIMC exhibited a butyraldehyde production rate of 105 mmol·g −1 ·h −1 (97 % selectivity) with >90 % activity retention over 10 cycles under mild conditions (140 °C, 4.5 MPa), outperforming conventional CoAl 2 O 3 by 2.4-fold. Reactant-TPD experiments and DFT calculations revealed that the ordered Co 3 Mo/Co 3 W structures altered CO adsorption from hollow to top sites, reducing the desorption energy from 29.7 to 19.7 kJ·mol −1 and lowering the CO insertion barrier from 1.28 to 1.09 eV. This work proposes a new strategy for preparing highly active and stable non-noble metal hydroformylation catalysts, which has a promising potential for industrial applications.