Diversity-Oriented Metal Decoration on UiO-Type Metal-Organic Frameworks: an Efficient Approach to Increase CO2 Uptake and Catalytic Conversion to Cyclic Carbonates

A library of metallo-bipyridine UiO-type metal-organic frameworks (MOFs) has been successfully synthesized by postmetallation of a wide range of metal complexes into bidentate bipyridine moieties. Then, a systematic investigation is devoted to a catalytic evaluation of the resultant MOFs containing a binary Lewis acid function for the synthesis of cyclic carbonates from epoxides and carbon dioxide (CO2). The result indicated that the metal-grafted MOFs exhibit improvement in terms of CO2 uptake capacity and catalytic activity in comparison with their nonmetallated counterparts. The comprehensive investigation provides a valuable insight into the synergetic effects of MOF functionalities including metal node, grafted metal, and its counterion in the cycloaddition reaction. Furthermore, the metal coordination modulation due to its benefits such as being a solvent-free process, nearly full conversion to cyclic carbonates, high selectivity and high CO2 uptake, applying atmospheric CO2 pressure, and excellent stability and easy recyclability of the catalyst demonstrates them as promising candidates for practical utilization of CO2 conversion into value-added chemicals.