Dechlorination of Excess Trichloroethene by Bimetallic and Sulfidated Nanoscale Zero-Valent Iron

Nanoscale zerovalent iron (nZVI) likely finds its application in source zone remediation. Two approaches to modify nZVI have been reported: bimetal (Fe–Me) and sulfidated nZVI (S-nZVI). However, previous research has primarily focused on enhancing particle reactivity with these two modifications under more plume-like conditions. In this study, we systematically compared the trichloroethene (TCE) dechlorination pathway, rate, and electron selectivity of Fe-Me (Me: Pd, Ni, Cu, and Ag), S-nZVI, and nZVI with excess TCE simulating source zone conditions. TCE dechlorination on Fe-Me was primarily via hydrogenolysis while that on S-nZVI and nZVI was mainly via β-elimination. The surface-area normalized TCE reduction rate (k^′_SA) of Fe–Pd, S-nZVI, Fe–Ni, Fe–Cu, and Fe–Ag were ∼6800-, 190-, 130-, 20-, and 8-fold greater than nZVI. All bimetallic modification enhanced the competing hydrogen evolution reaction (HER) while sulfidation inhibited HER. Fe–Cu and Fe–Ag negligibly enhanced electron utilization efficiency (ε_e) while Fe–Pd, Fe–Ni, and S-nZVI dramatically increased ε_e from 2% to ∼100%, 69%, and 72%, respectively. Adsorbed atomic hydrogen was identified to be responsible for the TCE dechlorination on Fe–Me but not on S-nZVI. The enhanced dechlorination rate along with the reduced HER of S-nZVI can be explained by that FeS conducting major electrons mediated TCE dechlorination while Fe oxides conducting minor electrons mediated HER.