Diamine-modified porous indium frameworks with crystalline porous materials (CPM)-5 structure for carbon dioxide fixation under co-catalyst and solvent free conditions

Abstract

In the present work, functional diamine groups into indium frameworks to synthesize cyclic carbonates from CO₂ and epoxides with efficient catalytic activity in the absence of co-catalyst and solvent are reported for the first time. Crystalline porous materials (CPM)-5 modified with 1,2-phenylene diamine and ethylene diamine (CPM-5-PhDA and CPM-5-EDA), were prepared using a post-synthetic modification (PSM) method. The properties of the modified CPM-5 were characterized by powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), N₂-adsorption, scanning electron microscopy (SEM), CO₂ adsorption, and temperature programmed desorption TPD methods. The presence of diamine groups as basic sites and indium Lewis acid sites in the framework structure were desirable for high catalytic activity. For a given catalyst weight, CPM-5-PhDA was the best candidate to appear with great catalytic activity and selectivity for the cycloaddition reaction at 100°C and 1 MPa CO₂ under co-catalyst and solvent free conditions. CPM-5-PhDA also was found to afford large and bulky epoxides. The catalyst can be easily separated and reused five times without any decline in activity.

Keywords: CO(2) fixation; Co-catalyst free; Cyclic carbonate; Metal-organic frameworks; Post-synthesis.