Reductive Dehalogenation of Herbicides Catalyzed by Pd⁰NPs in a H₂-Based Membrane Catalyst-Film Reactor

More food production required to feed humans will require intensive use of herbicides to protect against weeds. The widespread application and persistence of herbicides pose environmental risks for nontarget species. Elemental-palladium nanoparticles (Pd⁰NPs) are known to catalyze reductive dehalogenation of halogenated organic pollutants. In this study, the reductive conversion of 2,4-dichlorophenoxyacetic acid (2,4-D) was evaluated in a H₂-based membrane catalyst-film reactor (H₂-MCfR), in which Pd⁰NPs were in situ-synthesized as the catalyst film and used to activate H₂ on the surface of H₂-delivery membranes. Batch kinetic experiments showed that 99% of 2,4-D was removed and converted to phenoxyacetic acid (POA) within 90 min with a Pd⁰ surface loading of 20 mg Pd/m², achieving a catalyst specific activity of 6.6 ± 0.5 L/g-Pd-min. Continuous operation of the H₂-MCfR loaded with 20 mg Pd/m² sustained >99% removal of 50 μM 2,4-D for 20 days. A higher Pd⁰ surface loading, 1030 mg Pd/m², also enabled hydrosaturation and hydrolysis of POA to cyclohexanone and glycolic acid. Density functional theory identified the reaction mechanisms and pathways, which involved reductive hydrodechlorination, hydrosaturation, and hydrolysis. Molecular electrostatic potential calculations and Fukui indices suggested that reductive dehalogenation could increase the bioavailability of herbicides. Furthermore, three other halogenated herbicides─atrazine, dicamba, and bromoxynil─were reductively dehalogenated in the H₂-MCfR. This study documents a promising method for the removal and detoxification of halogenated herbicides in aqueous environments.