Hydrodehalogenation of Trichlorofluoromethane over Biogenic Palladium Nanoparticles in Ambient Conditions

Among a number of persistent chlorofluorocarbons (CFCs, or freons), the emissions of trichlorofluoromethane (CFCl₃, CFC-11) have been increasing since 2002. Zero-valent-Pd (Pd⁰) catalysts are known to hydrodehalogenate CFCs; however, most studies rely on cost-inefficient and eco-unfriendly chemical synthesis of Pd⁰NPs and harsh reaction conditions. In this study, we synthesized Pd⁰ nanoparticles (Pd⁰NPs) using D. vulgaris biomass as the support and evaluated hydrodehalogenation of CFC-11 catalyzed by the biogenic Pd⁰NPs. The presence of D. vulgaris biomass stabilized and dispersed 3-6 nm Pd⁰NPs that were highly active. We documented, for the first time, Pd⁰-catalyzed simultaneous hydrodechlorination and hydrodefluorination of CFC-11 at ambient conditions (room temperature and 1 atm). More than 70% CFC-11 removal was achieved within 15 h with a catalytic activity of 1.5 L/g-Pd/h, dechlorination was 50%, defluorination was 41%, and selectivity to fully dehalogenated methane was >30%. The reaction pathway had a mixture of parallel and sequential hydrodehalogenation. In particular, hydrodefluorination was favored by higher H₂ availability and Pd⁰:CFC-11 ratio. This study offers a promising strategy for efficient and sustainable treatment of freon-contaminated water.