Reductive dechlorination of chlorinated ethenes by ball milled and mechanochemically sulfidated microscale zero...

Ball milling is an effective technique to not only activate and reduce the size of commercial microscale zero valent iron (mZVI) but also to mechanochemically sulfidate mZVI. Yet, little is known about the difference between how chlorinated ethenes (CEs) interact with ball milled mZVI (mZVI^bm) and mechanochemically sulfidated mZVI (S-mZVI^bm). We show that simple ball milling exposed the active Fe⁰ sites, while mechanochemical sulfidation diminished Fe⁰ sites and meanwhile increased S^2- sites. Mechanochemical sulfidation with [S/Fe]_dosed increased from 0 to 0.20 promoted the particle reactivity most for TCE dechlorination (∼14-fold), followed by PCE and 1,1-DCE while it diminished the reactivity for trans-DCE (∼0.4-fold), cis-DCE (∼0.02-fold) and VC (∼0.002-fold) compared to simple ball milling. Sulfidation also improved the electron efficiency of CE dechlorination, except for cis-DCE and VC. The k_SA of cis-DCE, VC and trans-DCE dechlorination positively correlated with surface Fe⁰ content, suggesting their dechlorination was mainly mediated by Fe⁰ site or reactive atomic hydrogen. The k_SA of TCE dechlorination positively correlated with surface S^2- content and the dechlorination mainly occurred on S^2- sites via direct electron transfer. Increased sulfidation favored direct electron transfer mechanism. The k_SA of PCE and 1,1-DCE was not dependent on either parameter and their dechlorination was equally achieved through either mechanism.