Amine-functionalized bimetallic Co/Zn-zeolitic imidazolate frameworks as an efficient catalyst for the CO2 cycloaddition to epoxides under mild conditions.

Amine-functionalized bimetallic zeolitic imidazolate framework-8 (Co/Zn-ZIF-A) with 3-amino-1,2,4-triazole (Atz) was synthesized by a post-synthetic modification and utilized as a heterogeneous catalyst for the synthesis of cyclic carbonates from CO 2 and epoxides. Different amine contents in Co/Zn-ZIF-A materials were controlled by adjusting the ligand exchange reaction time of the of 2-mIM with Atz. Co/Zn-ZIF-A-24 h with the highest amine contents (32% of Atz) achieved an excellent result of 99% conversion of epichlorohydrin with high selectivity of > 99% after 24 h without co-catalyst and solvent under mild conditions (80 ^oC, 1 bar CO 2). The enhanced catalytic activity is attributed to the acid-base synergistic effect by the combination of bimetallic systems consisting of Zn and Co as Lewis acid sites and the abundant Lewis bases sites of -NH 2 , -NH groups from Atz ligand. A kinetic study of the cycloaddition reaction over Co/Zn-ZIF-A-24 h confirmed an approximately first-order dependence on the epichlorohydrin concentration and CO 2 pressure with an activation energy of approximately 39.5 kJ mol^-1. Co/Zn-ZIF-A-24 h catalyst showed good reusability with no obvious loss in catalytic activity during five recycling runs and its structural stability was also confirmed. A plausible reaction mechanism of Co/Zn-ZIF-A catalyst for CO 2 -epoxide cycloaddition was proposed. [Display omitted] • Amine-functionalized bimetallic Co/Zn-ZIFs (Co/Zn-ZIF-A) were synthesized by post-synthetic modification. • Co/Zn-ZIF-A was found to be catalytically efficient for CO 2 /epoxide coupling reaction under mild conditions. • Synergistic effect of amine groups and bimetallic systems on accelerating the epoxide ring-opening. • Co/Zn-ZIF-A demonstrates excellent catalytic activity without solvent and any co-catalyst. [ABSTRACT FROM AUTHOR]