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

Monometallic Rh/MCM-41 and bimetallic RhM 3 /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. The origin of superior C 3 oxygenate selectivity of RhCo 3 catalysts during hydroformylation was studied, which provided the design principles for catalyst improvements.