Electrocatalytic dechlorination of chloroethylenes using nitrogen-doped graphene electrodes

Abstract

Electro-dehalogenation for the clean-up of carcinogenic chloroethylenes (CEs) in groundwater is hindered by the high operating costs of metal electrodes and low efficiency due to competing water reduction and hydrogen formation. This study prepared metal-free electrodes with high Faradaic efficiency (FE) up to 50 % in aqueous solution by coating nitrogen-doped graphene nanoplatelets (N-GPs) on carbon paper. Dechlorination rates at these N-GPs electrodes were enhanced by ∼15 times compared with the plain graphene-based electrode, with first-order rate constants of 0.28, 0.33, 0.41, and 0.048 h⁻¹ for tetrachloroethylene (PCE, 22 μM), trichloroethylene (TCE, 22 μM), cis-dichloroethylene (cis-DCE, 22 μM), and vinyl chloride (VC, 11 μM) dechlorination to acetylene and ethene (VC), respectively, at −1.0 V vs standard hydrogen electrode (SHE), and initial neutral pH. Surprisingly, extremely low N or no-N containing GP was detected from highly reactive N-GPs. Despite the N-doping process has been wildly used for improving electrocatalytic reactivity of catalysts by inducing N-functional groups, this study suggests that, the polygonal intrinsic defects formed after N burn-off may act as dechlorination active sites. The N-GP electrodes showed appreciable stable performance over 24 h (five cycles). Simultaneous electrolysis of a mixture of CEs in groundwater without the addition of supporting electrolytes achieved >90 % reduction of PCE, TCE, and cis-DCE and ∼60 % reduction of VC within 24 h at −1.23 V vs SHE, demonstrating its superior performance and great potential of these electrodes in practical applications.