Degradation of Chloroform by Zerovalent Iron: Effects of Mechanochemical Sulfidation and Nitridation on the Kinetics and Mechanism

Abstract

Chloroform (CF) is a widely used chemical reagent and disinfectant and a probable human carcinogen. The extensive literature on halocarbon reduction with zerovalent iron (ZVI) shows that transformation of CF is slow, even with nano, bimetallic, sulfidated, and other modified forms of ZVI. In this study, an alternative method of ZVI modificationinvolving simultaneous sulfidation and nitridation through mechanochemical ball millingwas developed and shown to give improved degradation of CF (i.e., higher degradation rate and inhibited H2 evolution reaction). The composite material (denoted as S–N­(C)–ZVI) gave synergistic effects of nitridation and sulfidation on CF degradation. A complete chemical reaction network (CRN) analysis of CF degradation suggests that O-nucleophile-mediated transformation pathways may be the main route for the formation of the terminal nonchlorinated products (formate, CO, and glycolic polymers) that have been used to explain the undetected products needed for mass balance. Material characterizations of the ZVI recovered after batch experiments showed that sulfidation and nitridation promoted the formation of Fe3O4 on the S–N­(C)–ZVI particles, and the effect of aging on CF degradation rates was minor for S–N­(C)–ZVI. The synergistic benefits of sulfidation and nitridation on CF degradation were also observed in experiments performed with groundwater.

Unveiling the Mechanistic Role of Surface Nitrogen and Sulfur in Boosting the Dechlorination Performance of Zero-Valent Iron

“…For N-ZVI urea , A values, indicating the hydrogen evolution at the Fe 0 phase, remained relatively stable across various [N/Fe] groups (Figure D). This suggests that nitridation did not directly influence the HER at the Fe 0 site, which is consistent with our previous works. , In contrast, the B values, related to the Fe(II) phase, exhibited a positive correlation with the surface pyridinic N content, especially at lower [N/Fe] ( R 2 = 0.80) (Figure E), highlighting the role of pyridinic N in the HER.…”