Amine Functionalization of Channels of Metal-Organic Frameworks for Effective Chemical Fixation of Carbon Dioxide: A Comparative Study with Three Newly Designed Porous Networks.

Abstract

Catalytic transformation of CO2 into value-added chemical products can provide an appropriate solution for the raising environmental issues. To date, various metal-organic frameworks (MOFs) with transition metal ions have been explored for CO2 capture and conversion, but alkaline earth metal-based MOFs are comparatively less studied. Metal ions like Sr(II) having relatively large radius give rise to a high coordination number resulting in higher stability of the MOFs. Moreover, the introduction of N-rich functional group in organic linker like -NH2, -CONH- and triazole into MOF backbone enhance their CO2 capture and conversion efficiency. Herein, the effect of amine group on the catalytic efficiency of MOFs for CO2 cycloaddition with epoxides under solvent free and ambient conditions are presented. The di-carboxylates, such as 5-aminoisophthalate (AmIP) and 5-bromoisophthalate (BrIP) were utilized to synthesize Sr(II) based MOFs. The Zn(II) MOF was synthesized using tetra-carboxylate containing amide spacer (OAT) and 4-amino-4H-1,2,4-triazole (AMT). All three MOFs exhibited porous networks with guest available volume ranging from 15 to 58 %. The catalytic efficiency of the MOFs towards carbon dioxide fixation reaction was explored. The catalytic performances revealed that the presence of amine group in the channels enhances the catalytic efficiency of the MOFs.