New Mechanism via Dichlorocarbene Intermediate for Activated Carbon-Mediated Reductive Dechlorination of Carbon...

Although activated carbon (AC) is widely used as an adsorbent and barrier for contaminated sediment remediation, little attention has been paid to its mediation effects on reductive dechlorination of chlorinated solvents by commonly presenting sulfide. Here, we reported that highly porous, graphitized AC (250 mg L^-1) suspended in deoxygenated aqueous solutions could increase the pseudo-first-order rate constant of sulfide-induced dechlorination of carbon tetrachloride (CCl₄) by more than 1 order of magnitude. Carbon disulfide (CS₂) was the only main product, with no production of chloroform or dichloromethane. The minimum promotion of CCl₄ reduction observed with electro-conductive but nonporous graphite and a microporous but electro-insulative resin (XAD-4) indicates that graphitic carbons and micropores both play key roles in AC-mediated dechlorination of CCl₄ by sulfide. The detection of dichlorocarbene (:CCl₂) by free radical trapping experiments combined with the high suitability of the Langmuir-Hinshelwood model led us to propose a new mediation mechanism: CCl₄ molecules adsorbed within the deep regions of AC micropores formed by graphitic carbons accept two electrons transferred from sulfide to form :CCl₂, which is impeded from hydrolysis and hydrogenolysis by the hydrophobic micropore and further reacts with sulfide to generate CS₂. Consistently, the production of :CCl₂ was very low when AC was replaced with graphite or XAD-4. The proposed mechanism was further validated by the enhanced mediation effects of another two carbonaceous materials (template-synthesized mesoporous carbon and covalent triazine-based framework) that are electro-conductive and have well-developed micropore structures. These findings highlight the importance of pore properties of carbonaceous materials as mediators or catalysts for reductive dechlorination reactions and shed light on the development of coupled adsorption-reaction systems for remediation.