Promoting C–F bond activation via proton donor for CF ₄ decomposition

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.

Potential of Molecular Catalysts with Electron-Rich Transition Metal Centers for Addressing Long-Standing Chemistry Enigmas

“…PFCs are highly unreactive, making their recycling difficult. Different approaches have been probed for the activation and hydrolysis of the C–F bonds. − Presently, we present some preliminary results for the reaction of CH 3 Pd – with CF 4 to demonstrate that electron rich metals can efficiently activate C–F bonds. CH 3 Pd – was chosen as a simple representative of the molecular complex of Figure and CF 4 to represent the PFC molecules.…”

Reconstruction of Bi2S3 in CO2 Electroreduction via Topotactic Transformation

“…The extensive use of fossil fuels, such as coal, oil, and natural gas, has led to increased carbon dioxide emissions, resulting in significant environmental issues such as land desertification, sea level rise, and climate change. − To address this challenge, converting CO 2 into fuels or high-value chemicals has been suggested as an ideal way to mitigate CO 2 emissions. − Among various techniques, electrocatalytic CO 2 reduction reaction (CO 2 RR) has been identified as one of the most efficient and controllable methods, − as it reduces not only CO 2 emissions but also human dependence on fossil fuels by utilizing low-grade renewable electricity . However, the CO 2 RR requires high energy to activate the nonpolar and chemically inert linear CO 2 molecule with CO bonds under ambient conditions. − Additionally, the competition of hydrogen evolution reaction (HER) in aqueous CO 2 RR solution poses challenges to controlling product selectivity. , …”