Per- and polyfluoroalkyl substances (PFAS) are a class of synthetic chemicals widely used in various industrial and consumer products due to their chemical stability and resistance to heat, oil, and water. However, PFAS are extremely persistent in the environment and resistant to natural degradation processes because of the exceptional strength of the carbon–fluorine (C–F) bond, which contributes to their overall stability. Growing awareness of their toxicity has led to increasingly strict global regulations, prompting an urgent need for effective degradation strategies. Among various approaches, catalytic degradation offers a promising route, yet there remains a lack of comprehensive theoretical guidance for designing and screening suitable catalyst materials. In this study, we present a density functional theory (DFT) method to screen pure transition metal (TM) catalysts capable of breaking the strong C–F bonds in PFAS molecules. Specifically, we designed a total of 72 TM surfaces, investigating their adsorption behavior and evaluating their activity toward C–F bond dissociation. Beyond evaluating activity alone, we systematically incorporated additional factors that may inhibit catalytic performance, including hydrogen evolution as a competing reaction, surface oxidation under electrochemical conditions, and fluorine poisoning due to fluorine accumulation on the surface. Our results reveal that while some TM surfaces exhibit low reaction potentials for C–F bond cleavage, many of these materials are ultimately inactivated due to surface fluorine poisoning and surface oxidation. This insight is critical, as prior studies have often overlooked long-term catalyst stability and focused solely on reaction energetics even though their surfaces have fluorine poisoning and oxidation on the surfaces. Therefore, we provide a theoretical screening guideline that not only identifies promising candidates but also systematically excludes materials likely to deactivate over time. Furthermore, we present the reaction potential values required for stepwise C–F bond cleavage, which can serve as important reference data for designing more advanced TM-based materials, including transition metal oxides (TMOs), single-atom catalysts (SACs), and metal cluster systems. Overall, this study provides a focused theoretical framework that supports early-stage screening of PFAS-degrading catalysts and helps identify key factors influencing their activity and deactivation.
