Tunable synthesis of alcohols and aldehydes by reductive hydroformylation of alkenes over heterogeneous Co catalysts†

Hydroformylation of alkenes constitutes a substantial industrial catalytic process. Tunable synthesis of alcohols and aldehydes by hydroformylation is challenging in heterogeneous catalysis. Here, we describe the encapsulation of single-atom Co catalysts in a porous phosphine polymer for the tunable synthesis of alcohols and aldehydes in olefin hydroformylation. With the polymer encapsulated single atom Co₂(CO)₈@PPh₃-1/10 as the catalyst, almost complete conversion of 1-octene and a selectivity to alcohols of 94% at 170 °C while aldehydes with 87% yield was obtained at 140 °C, and was eco-friendly with a 100% atomic efficiency reaction and in line with principles of ‘green chemistry’. Various catalyst characterization methods including XRD, TEM, HADDF-STEM and in situ FT-IR spectroscopy showed that Co species were homogeneously distributed in the pores of PPh₃ and the formation of HCo(CO)_x as the catalytically active species was successful. This work provides meaningful insights into the development of non-noble metal heterogeneous catalysts for the selective hydroformylation reaction.