Promoting C-F bond activation via proton donor for CF₄ decomposition.

Abstract

Tetrafluoromethane (CF₄), 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 (-HSO₄) modified Al₂O₃@ZrO₂ (S-Al₂O₃@ZrO₂) catalyst, resulting in highly efficient CF₄ decomposition. By combining in situ infrared spectroscopy tests and density function theory simulations, we demonstrate that the introduced -HSO₄ 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-Al₂O₃@ZrO₂ catalyst achieved a stable 100% CF₄ decomposition at a record low temperature of 580 °C with a turnover frequency value of ~8.3 times higher than the Al₂O₃@ZrO₂ catalyst without -HSO₄ modification, outperforming the previously reported results. This work paves a new way for achieving efficient C-F bond activation to decompose CF₄ at a low temperature.