Promoting C–F bond activation via proton donor for CF4 decomposition

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.