FLUORINATED BIMETALLIC MOFs AS HETEROGENOUS CATALYSTS FOR CO2 TO DMC CONVERSION

The pressing demand to reduce the carbon footprint of all significant polluting industrial sectors has drawn interest in the conversion of CO2 into valuable compounds. Among the proposed routes, an effective strategy for CO2 recycling is represented by the catalyst-driven synthesis of dimethyl carbonate (DMC) from CO2 and methanol.[1] However, the large-scale application of this process has been limited by the high thermodynamic requirements and risk of catalyst deactivation due to the significant amount of water produced by the reaction.[2] Metal-organic frameworks offer a viable catalytic platform for CO2 to DMC conversion, by virtue of their highly tunable structural features and synthetic control over the final materials’ functional properties. To this aim, we are developing a series of bimetallic (Zr,Ce)UiO-66 MOFs containing dicarboxylate linkers with different degrees of fluorination. As has already been demonstrated,[3] the presence of both Zr(IV) and Ce(IV) centers ensures the frameworks' chemical and thermal stability as well as their catalytic activity, making them suitable for application as heterogeneous catalysts. Additionally, the fluorine content, imparted by the functionalized ligands, is responsible for an increase in the hydrophobicity of the MOFs surface, which is crucial to prevent water from obstructing the pores and impeding the desired reaction. These materials were obtained through an environmentally-friendly synthetic approach and their structural characteristics were determined via a combination of X-Ray-based techniques, infrared spectroscopy, and elemental analysis. [1] A. Otto, T. Grube, S. Schiebahna, D. Stolten, Energy Environ. Sci. (2015) 8, 3283. [2] J. Gandara-Loe, L. Pastor-Perez, L.F. Bobadilla, J.A. Odriozola, T.R. Reina, React. Chem. Eng. (2021) 6, 787. [3] a) S. Rojas-Buzo, D. Salusso, F. Bonino, M.C. Paganini, S. Bordgia, Mater. Today Chem. (2023) 27, 101337; b) M. Lammert, C. Glißmann, N. Stock, Dalton Trans. (2017) 46, 2425.