Trends and descriptors of heterogeneous hydroformylation activity and selectivity of RhM3 (M = Fe, Co, Ni, Cu and Zn) catalysts

Monometallic Rh/MCM-41 and bimetallic RhM3/MCM-41 (M = Fe, Co, Ni, Cu, or Zn) catalysts are synthesized and tested for vapor-phase ethylene hydroformylation reaction. Co is found to exhibit a significant promotion effect on the selectivity of hydroformylation to C-3 oxygenates, followed by Fe and Cu, with Ni and Zn showing a negative effect. DFT calculations reveal that the addition of a secondary metal can provide a new type of site, being able to selectively tune the binding energies of reaction intermediates, and thus lead to different catalytic performances.

Automated summary

Monometallic and bimetallic catalysts consisting of Rh/MCM-41 and RhM3/MCM-41 (M = Fe, Co, Ni, Cu, or Zn) were synthesized and tested for vapor-phase ethylene hydroformylation reaction. Co showed a significant promotion effect on the selectivity of hydroformylation to C-3 oxygenates, followed by Fe and Cu, while Ni and Zn had a negative effect. Density functional theory (DFT) calculations revealed that the addition of a secondary metal can create a new type of site, allowing for selective tuning of the binding energies of reaction intermediates, thereby leading to different catalytic performances.