MIL-101(Cr)/aminoclay nanocomposites for conversion of CO₂ into cyclic carbonates

We present the use of an amine functionalized two-dimensional clay i.e., aminoclay (AC), in the chemistry of a three-dimensional metal-organic framework (MOF) i.e., MIL-101(Cr), to prepare MIL-101(Cr)/AC composites, which are exploited as catalysts for efficient conversion of CO₂ gas into cyclic carbonates under ambient reaction conditions. Three different MOF nanocomposites, denoted as MIL-101(Cr)/AC-1, MIL-101(Cr)/AC-2, and MIL-101(Cr)/AC-3, were synthesized by an in situ process by adding different amounts of AC to the precursor solutions of the MIL-101(Cr). The composites were characterized by various techniques such as FT-IR, PXRD, FESEM, EDX, TGA, N₂ adsorption, as well as CO₂ and NH₃-TPD measurements. The composites were exploited as heterogeneous catalysts for CO₂ cycloaddition reactions with different epoxides and the catalytic activity was investigated at atmospheric pressure under solvent-free conditions. Among all the materials, MIL-101(Cr)/AC-2 shows the best catalytic efficiency under the optimized conditions and exhibits enhanced efficacy compared to various MIL-101(Cr)-based MOF catalysts, which typically need either high temperature and pressure or a longer reaction time or a combination of all the parameters. The present protocol using MIL-101(Cr)/AC-2 as the heterogeneous catalyst gives 99.9% conversion for all the substrates into the products at atmospheric pressure.