Zn-MOF as a Single Catalyst with Dual Lewis Acidic and Basic Reaction Sites for CO2 Fixation

Continuous increase in carbon dioxide (CO2) emissions are causing imbalances in the environment, which impact biodiversity and human health. The conversion of CO2 to cyclic carbonates by means of metal–organic frameworks (MOFs) as a heterogeneous catalyst is a prominent strategy for rectifying this imbalance. Herein, we have developed nitrogen-rich Zn (II) based metal–organic framework, [Zn(CPMT)(bipy)]n (CPMT = 1-(4-carboxyphenyl)-5-mercapto-1H-tetrazole; bipy = 4,4′-bipyridine), synthesized via a mixed ligand strategy. This Zn-MOF showed high chemical stability in both acidic and basic conditions, and in organic solvents for a long time. On account of the concurrent presence of acid–base active sites and strong chemical stability under abrasive conditions, this Zn-MOF was employed as an effective catalyst for the coupling of CO2 and epoxides, under atmospheric pressure, mild temperature, and neat conditions. This Zn-MOF shows remarkable activity by producing high yields of epichlorohydrin carbonate (98%) and styrene carbonate (82%) at atmospheric CO2 pressure, 70 °C temperature, and 24 h reaction time, with turnover numbers (TON) of 217 and 181, respectively. The Zn-MOF could be reused for up to seven cycles with structural and framework integrity. Overall, this work demonstrates the synthesis of a novel and highly efficient MOF for CO2 conversion.