New insights into stoichiometric efficiency and synergistic mechanism of persulfate activation by zero-valent bimetal (Iron/Copper) for organic pollutant degradation

Extensive studies have been devoting to investigating the catalytic efficiency of zero-valent iron (Fe0)-based bimetals with persulfate (PS), while little is known in the stoichiometric efficiency, underlying mechanisms and reaction center of zero-valent bimetallic catalysts in activating PS. Herein, nanoscale zero-valent Fe/Cu catalysts in decomposing 2,4-dichlorophenol (DCP) have been investigated. The results show that the increase of Cu ratio from 0 to 0.75 significantly enhances the DCP degradation with a rate constant of 0.025 min-1 for Fe0 to 0.097 min-1 for Fe/Cu(0.75) at pH ∼3.3, indicating Cu is likely the predominate reaction centers over Fe. The PS decomposition is reduced with the increase of Cu ratios, suggesting the stoichiometric efficiency of Fe/Cu in activating PS is notably enhanced from 0.024 for Fe0 to 0.11 for Fe/Cu(0.75). Analyses indicate Cu atoms are likely the predominant reaction site for DCP decomposition, and Fe atoms synergistically enhance the activity of Cu as indicated by DFT calculations. Both SO4⦁- and ⦁OH radicals are responsible for reactions, and the contribution of SO4⦁- is decreased at higher pH conditions. The findings of this work provide insight into the stoichiometric efficiency and the reaction center of Fe/Cu catalysts to activate PS for pollutant removals.