Copper MOFs performance in the cycloaddition reaction of CO2 and epoxides
The research in advanced materials for effective CO2 capture and conversion is an imperative duty for the next years. In this sense MOF materials are being intensively tested for this purpose. Herein, seven different copperbased MOF materials with different functional organic groups in their linkers have been assessed to comprehend some structural features that influence the CO2 transformation via cycloaddition reaction with epoxides: CuURJC-1 (tetrazole group), Cu-URJC-8 (primary amine group), Cu-MOF-74 (hydroxyl group), JUC-62 (azo group), PCN-16 (triple bond group), HNUST-1 (amide group) and HKUST-1. When epichlorohydrin was used as a substrate, Cu-URJC-8 produced the best epoxide conversion (90%) and selectivity to cyclic carbonate (>99%), despite showing a modest surface area. This result can be explained by the higher basicity of primary amines than other basic functional organic groups of the MOFs. However, when styrene oxide was used as substrate, CuURJC-1 led to the best reaction results with a conversion and selectivity toward cyclic carbonate of 60 and 86%, respectively. This result was achieved because this material presents the synergic effect of having in its flexible structure 12 Å channels, that favors the styrene oxide diffusion, and a great number of basic nitrogen atoms, which can increase the reactivity of carbon dioxide. In summary, the presence of nitrogen atoms in the organic linker increases the CO2 conversion by promoting the reactivity of this molecule.
This work has been financed by the Regional Government of Madrid (Project ACES2030-CM, S2018/EMT-4319) and the Universidad Rey Juan Carlos IMPULSO and PUENTE Projects (grants MATER M−3000 and M−3032).
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