Heteroatom-Engineered Atomic Electric Fields Activate C–F Bond for Efficient Perfluorocarbon Decomposition

Tetrafluoromethane (CF₄), among the most chemically inert per- and polyfluoroalkyl substances (PFAS), poses a formidable challenge for catalytic decomposition due to its exceptionally strong C-F bonds. Here, we report a strong atomic-scale local electric-field (LEF) engineering strategy that enables efficient CF₄ activation and decomposition. By incorporating Ga-Zn dual-atom into Al₂O₃ (Ga₁Zn₁/Al₂O₃), it generates a highly intensified and spatially confined electric field (∼3 × 10¹⁰ N/C). Spectroscopic characterizations reveal that this LEF amplifies the Lewis acidity of neighboring tricoordination Al (AlIII) sites, significantly strengthens CF₄ adsorption through interfacial polarization, and promotes C-F bond stretching and cleavage. As a result, the Ga₁Zn₁/Al₂O₃ catalyst delivers complete CF₄ conversion at an ultralow temperature of 540 °C, exhibiting an apparent turnover frequency 4.5 times higher and an apparent activation energy nearly half that of pristine Al₂O₃. The catalyst also demonstrates exceptional durability, maintaining 100% conversion for over 600 h under continuous operation, indicating robust structural and catalytic stability. This work establishes dual-atom-induced LEF engineering as a powerful strategy for activating ultrastable fluorocarbons and offers a promising pathway toward sustainable degradation of persistent perfluorinated pollutants.