Series of M-MOF-184 (M = Mg, Co, Ni, Zn, Cu, Fe) Metal–Organic Frameworks for Catalysis Cycloaddition of CO2

In light of the chemical exploitation of CO2, new reusable materials for efficiently catalyzing the cycloaddition of CO2 and epoxides under moderate conditions are needed. Herein, a new series of isostructural metal–organic frameworks (MOFs) M2(EDOB) EDOB4– = 4,4′-(ethyne-1,2-diyl)bis(2-oxidobenzoate), M = Mg, Ni, Co, Zn, Cu, Fe, known as M-MOF-184, analogous to a well-studied MOF-74 structure, were synthesized and fully characterized. The M-MOF-184 (M = Mg, Co, Ni, Zn) frameworks exhibit accessible mesopore channels (24 Å) and high porosity. Among them, Mg-MOF-184 demonstrated the most upper surface area (>4000 m2 g–1) in any reported MOF-74-type frameworks. Furthermore, Co-MOF-184 revealed the highest CO2 uptake (73 cm3 g–1, at 298 K), and Zn-MOF-184 showed the highest catalytic activity upon the cycloaddition of CO2 (96% conversion, 86% selectivity, and 82% yield) under mild conditions (1 atm CO2, 80 °C, 6 h, and solvent-free). Notably, the catalytic performance of Zn-MOF-184 outperformed that of the original M-MOF-74 (M = Mg, Co, Zn) materials and various Zn-based MOFs. To evaluate the acidity and basicity of a series of M-MOF-184 (M = Mg, Co, Ni, Zn) frameworks, the interaction of these MOFs with acetonitrile vapor was investigated by vapor adsorption and ATR-FTIR spectroscopy measurements. As such, Zn-MOF-184 showed the strongest Lewis acidity derived by Zn cations, which was correlated to the highest catalytic activity upon the cycloaddition of CO2. Interestingly, the 2-oxidobenzoate anions from Co-MOF-184 showed the strongest basicity among the series, which was associated with the highest saturated acetonitrile uptake (544 cm3 g–1 at 298 K). Our findings suggest that the integration of Lewis acidic and basic sites, high surface area, and large accessible pores into the framework can facilitate the CO2 fixation reaction.