Selective dechlorination degradation of chlorobenzenes by dual single-atomic Fe/Ni catalyst with M-N/M-O active sites synergistic

Abstract

Removal and detoxification of chlorobenzenes have attracted public concern, multiple active sites single-atom Fe and single-atom Ni composite nitrogen-doped graphene (FeSA/CN/NiSA) cathode catalyst supplied generation and adsorption capacity of hydrogen and hydroxyl active species. M-O active sites coupled with M-N improved activity and stability of the catalyst, and decreased bond breaking energy barrier of C-Cl, FeSA/CN/NiSA-NiF cathode showed superior removal performance of chlorinated aromatic hydrocarbons (monochlorobenzene: 98.9%, dichlorobenzene: over 90.4%, trichlorobenzene: over 85.7%) and selectivity. Chlorobenzenes were dechlorinated under low stepwise voltage on the FeSA/CN/NiSA-NiF cathode. The efficiencies of stepwise dechlorination reactions of chlorobenzenes were all above 76%, Faradaic efficiencies were above 71.8%. The FeSA/CN/NiSA-NiF cathode was not sensitive to the molecular structure and has overcome the high energy barrier of chlorobenzenes molecular structure. The electrophilic attack of H*ads formed hyperconjugation bond weakened the possibility of the Cl atom forming a bond with the benzene ring, and was favorable for the Cl position to achieve single-electron transfer dechlorination. The selective stepwise dechlorination degradation of chlorobenzenes by FeSA/CN/NiSA-NiF cathode with multiple active sites demonstrated the advantaged performance of M-O and M-N active sites coupled synergistic in electrochemical reduction and degradation, providing a strategy for product-selective degradation of chlorinated aromatic hydrocarbons.