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)] (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.