Modulating Carbon Dioxide Storage by Facile Synthesis of Nanoporous Pillared-Layered Metal-Organic Framework with Different Synthetic Routes.

Abstract

A Zn(II)-based paddle wheel pillared-layered metal-organic framework, [Zn2 (DBrTPA)2(DABCO)].(DMF)2 (MUT-4), containing 1,4-diazabicyclo[2.2.2]octane (DABCO) and 2,5-dibromoterephthalic acid (DBrTPA) has been successfully synthesized with different synthetic methods, including solvothermal, sonochemical, and their mixing methods, some of which are energy-efficient, rapid, and room-temperature synthetic procedures. Structural characterization of MUT-4 with single-crystal X-ray crystallography showed that it crystallizes in the tetragonal I41/acd space group. MUT-4 has shown higher performance than known MOFs in the CO2 adsorption such as UiO-66, UiO-66-NH2, UiO-66-NO2, PCN-66, ZIF-68, UiO-67, bio-MOF-11, MIL-101, MOF-177, ZIF-8, and ZIF-82. It has shown even better CO2 adsorption performance in comparison to the previously reported DMOFs such as DMOF-1 and other DMOF analogues such as NO2-DMOF-1, NH2-DMOF-1, Br-DMOF-1, and Azo-DMOF-1. Furthermore, it has performed even better than modified known MOFs. Also, the carbon dioxide storage capacity of MUT-4 obtained using several different synthetic routes shows a significant difference. Thus, this study exhibited that CO2 gas adsorption of MUT-4 could be modulated by optimizing its synthetic methods.