Hydroformylation of olefins catalyzed by single-atom Co(II) sites in zirconium phosphate

Hydroformylation of olefins over ligand-free heterogeneous catalysts is highly attractive chemical process owning to both fundamental research interests and potential commercial applications for manufacturing aldehydes. Herein, we report that the Co(II) sites were bound to the surface phosphate group on zirconium phosphate (ZrP), and the resulting CoZrP-2.0 (P/Zr = 2) catalyst showed a full conversion of 1-octene and 91.3% selectivity to C9 aldehydes in 1-octene hydroformylation. The catalyst also demonstrated high stability in consecutive catalytic recycles under batch-wise operation conditions. The activity tests and characterizations that Co single atoms existed in CoZrP-2.0 catalyst and acted as active sites for olefins hydroformylation. A strong coordination interaction between single-atom Co(II) sites and the phosphate group on ZrP has been identified, being favorable for improving catalytic performance and stability by suppressing Co(II) leaching. Notably, the present Co(II)-based single-atom catalyst exhibited excellent performance for both hydroformylation and the reductive hydroformylation of the various olefins.