Double metal cyanide (DMC) structures of Zn₃[Co(CN)₆]₂ were modified by different organicligands and tested for their catalytic activity in the cycloaddition of CO₂ and epoxides. ZnCoPBAs show anface-centred cubic structure with a high density of Lewis acidic Co(II)/Zn(II) metal sites and basic –CN–groups. The high crystallinity and excellent textural properties of the prepared ZnCoPBAs materials were confirmed by XRD and the N₂ adsorption-desorption. We found the morphology and structure of ZnCoPBAs are related to the polarity of organic ligands. Through the analysis of morphology, crystallinity, specific surface area and pore size, explored the influence of different organic ligands on the catalytic performance of ZnCoPBAs. ZnCoPBA-TBA exhibited higher catalytic activity than other catalysts (ZnCoPBA-DMF,ZnCoPBA-MT, ZnCoPBA-ET). For a given catalyst weight, ZnCoPBA-TBA showed the best catalytic performance among the tested ZnCoPBAs, and the conversion rate of propylene oxide higher than 95% under relatively qualitative reaction conditions (2.0 MPa, 353 K).

ZnCoPBAs show a face-centred cubic structure with a high density of Lewis acidic Co (II) /Zn (II) metal sites and basic -CN- groups. We successfully modified ZnCoPBAs with different organic ligands and their application in the cycloaddition of CO₂ and epoxides.