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.

A Cerium-Containing Metal-Organic Framework: Synthesis and Heterogeneous Catalytic Activity toward Fenton-Like Reactions.

A cerium-based metal-organic framework, namely MOF-589, was synthesized using benzoimidephenanthroline tetracarboxylic acid (H4 BIPA-TC) as an organic linker. Full characterization including single-crystal and powder X-ray diffraction analysis, thermogravimetrical analysis, scanning electron microscopy, and N2 adsorption measurements at low pressure and 77 K were carried out. The material was employed as an efficient heterogeneous catalyst for decomposition of methylene blue (MB) dye (40 ppm) in the presence of H2 O2 in 15 minutes. Interestingly, comparison studies showed that the activity of MOF 589 was higher than that of other iron-based heterogeneous and cerium-based catalysts. Further experiments to clarify the MOF 589 activity indicated that the BIPA-TC linker might have an important impact through a cooperative effect on the metal cluster. Control studies confirmed that the presence of catalyst was necessary for the reaction to occur and the catalyst recyclability. In particular, catalysis from leached cerium in the reaction filtrate is unlikely and the solid material could be reused at least eight times without a remarkable loss in activity.

A Series of Metal-Organic Frameworks for Selective CO2 Capture and Catalytic Oxidative Carboxylation of Olefins.

Three new lanthanide-based metal-organic frameworks (Ln-MOFs), namely MOF-590, -591, and -592 constructed from a tetratopic linker, benzoimidephenanthroline tetracarboxylic acid (H4BIPA-TC), were synthesized under solvothermal conditions and fully characterized. All of the new MOFs exhibit three-dimensional frameworks, which adopt unprecedented topologies in MOF field. Gas adsorption measurements of MOF-591 and -592 revealed good adsorption of CO2 (low pressure, at room temperature) and moderate CO2 selectivity over N2 and CH4. Consequently, breakthrough experiments illustrated the separation of CO2 from binary mixture of CO2 and N2 with the use of MOF-592. Accordingly, MOF-592 revealed the selective CO2 capture effectively without any loss in performance after three cycles. Moreover, MOF-590, -591, and -592 showed to be catalytically active in the oxidative carboxylation of styrene and CO2 for a one-pot synthesis of styrene carbonate under mild conditions (1 atm CO2, 80 °C, and without solvent). Among the new materials, MOF-590 revealed a remarkable efficiency with exceptional conversion (96%), selectivity (95%), and yield (91%).