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Promoting C–F bond activation via proton donor for CF <sub>4</sub> decomposition

Yingkang Chen, Wenqiang Qu, Tao Luo, Hang Zhang, Junwei Fu, Hongmei Li, Changxu Liu, Dengsong Zhang, Min Liu

2023Proceedings of the National Academy of Sciences37 citationsDOIOpen Access PDF

Abstract

Tetrafluoromethane (CF 4 ), the simplest perfluorocarbons, is a permanently potent greenhouse gas due to its powerful infrared radiation adsorption capacity. The highly symmetric and robust C–F bond structure makes its activation a great challenge. Herein, we presented an innovated approach that efficiently activates C–F bond utilizing protonated sulfate (–HSO 4 ) modified Al 2 O 3 @ZrO 2 (S-Al 2 O 3 @ZrO 2 ) catalyst, resulting in highly efficient CF 4 decomposition. By combining in situ infrared spectroscopy tests and density function theory simulations, we demonstrate that the introduced –HSO 4 proton donor has a stronger interaction on the C–F bond than the hydroxyl (–OH) proton donor, which can effectively stretch the C–F bond for its activation. Consequently, the obtained S-Al 2 O 3 @ZrO 2 catalyst achieved a stable 100% CF 4 decomposition at a record low temperature of 580 °C with a turnover frequency value of ~8.3 times higher than the Al 2 O 3 @ZrO 2 catalyst without –HSO 4 modification, outperforming the previously reported results. This work paves a new way for achieving efficient C–F bond activation to decompose CF 4 at a low temperature.

Topics & Concepts

CatalysisDecompositionChemistryProtonationProtonHydrogen bondInfrared spectroscopyInfraredAdsorptionPhysical chemistryPhotochemistryComputational chemistryMoleculeOrganic chemistryIonPhysicsOpticsQuantum mechanicsInorganic Fluorides and Related CompoundsAtmospheric Ozone and ClimateFluorine in Organic Chemistry