Synthesis of cyclic carbonate by CO2 fixation to epoxides using interpenetrated MOF-5/n-Bu4NBr

• Published in: Journal of materials science 2019-09, Vol.54 (18), p.11796-11803
• Main Authors: Kim, Hyunuk, Moon, Hyun-Sik, Sohail, Muhammad, Yoon, Yang-No, Shah, Syed Fawad Ali, Yim, Kanghoon, Moon, Jong-Ho, Park, Young Cheol
• Format: Article
• Language: English
• Subjects: Carbon dioxide; Carbonates; Catalysis; Catalytic activity; Characterization and Evaluation of Materials; Chemical industry; Chemical Routes to Materials; Chemistry and Materials Science; Classical Mechanics; Control stability; Crystallography and Scattering Methods; Density functional theory; Fixation; Materials Science; pH control; Polymer Sciences; Propylene oxide; Reaction kinetics; Solid Mechanics; Steric effects; Tetrabutylammonium bromide; X ray powder diffraction; X-ray diffraction
• ISSN: 0022-2461; 1573-4803
• DOI: 10.1007/s10853-019-03702-6

Phase-pure interpenetrated MOF-5 ([Zn 4 (O)(BDC) 3 ]) was synthesized by pH* control in a reaction medium, and its stability in the presence of epoxides was confirmed by powder X-ray diffraction analysis. Interpenetrated MOF-5/tetra-n-butylammonium bromide ( int -MOF-5/ n -Bu 4 NBr) showed a high catalytic activity toward CO 2 fixation to epoxide to synthesize cyclic carbonates. The conversions of propylene oxide (PO) and styrene oxide (SO) by int -MOF-5/ n -Bu 4 NBr were almost two times higher than those by MOF-5/ n -Bu 4 NBr under the same conditions. From a kinetics point of view, the coupling reaction rate of PO and CO 2 was much higher than that of SO and CO 2 , which may be due to steric effects. The optimized geometries by the density functional theory calculation revealed that Lewis acidic Zn(II) sites of tetranuclear {Zn 4 O} clusters can work as the catalytic center to bind epoxides to open the rings by a nucleophilic attack. This co-catalyst system may be useful for the synthesis of cyclic carbonate by CO 2 fixation.