Porous Hexacyanometallate(III) Complexes as Catalysts in the Ring-Opening Copolymerization of CO2 and Propylene Oxide

In this work, six porous hexacyanometallate complexes (Ni-3[Co(CN)(6)](2), Co-3[Co(CN)(6)](2), Fe-3[Co(CN)(6)](2), Ni-3[Fe(CN)(6)](2), Co-3[Fe(CN)(6)](2), Fe-4[Fe(CN)(6)](2)) were synthesized by a complexing agent assisted coprecipitation method and thoroughly characterized via X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), in situ high-temperature X-ray diffraction (HT-XRD), elemental analysis (EA), X-ray fluorescence (XRF), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N-2 physisorption, and gas-solid phase titration with NH3. The thermal stability, chemical composition, pore size and volume, crystallite size and density of surface acid sites were strongly sensitive to both the transition metal and the cyanometallate anion employed. On that basis, transition metal hexacyanometallates must be perceived as an adaptable class of zeolite-like microporous materials. The catalytic properties of these compounds were tested by copolymerization of propylene oxide and CO2, a green route to obtain biodegradable aliphatic polycarbonates. All compounds under study showed moderate activity in the target reaction. The obtained copolymers were characterized by modest CO2 content (carbonate units ranging from 16 to 33%), random structure (R-PEC approximate to 70%), and moderate molecular weight (M-w = 6000-85,400 g/mol) with broad dispersity values (D-M = 4.1-15.8).