Institute of Groundwater and Earth Science, Jinan University, 510632, Guangzhou, China.
School of Environmental Science and Engineering, Southern University of Science and Technology, Shenzhen, 518055, Guangdong Province, China.
Environ Pollut. 2021 Jul 15;281:116915. doi: 10.1016/j.envpol.2021.116915. Epub 2021 Mar 19.
This study demonstrated that nitrogen-doped carbon materials (NCMs) could effectively catalyze the chlorine elimination process in hexachloroethane (HCA) declorination in sulfide-containing environments for the first time. The k values of HCA dechlorination by sulfide in the presence of 10 mg/L NCMs were higher than that of no mediator at pH 7.3 by one or two orders of magnitude. The catalytic capabilities of NCMs on HCA dechlorination were evident in common ranges of natural pH (5.3-8.9) and it could be accelerated by the increase of pH but be suppressed by the presence of dissolved humic acid. Moreover, NCMs exhibited much better catalytic capability on HCA dechlorination compared to the carbon materials, mainly owing to the combined contributions of pyridine N, including enhanced nucleophilic attack to HCA molecule by generating newborn C-S-S and activation of HCA molecule by elongating C-Cl bonds. The functions of pyridine N in micron-sized NCMs with mesopores were better than in nano-sized NCMs on HCA dechlorination. These findings displayed the potential of NCMs, when released into sulfide-containing environments, may significantly increase the dechlorination of chlorinated aliphatic hydrocarbons.
本研究首次证明,氮掺杂碳材料(NCMs)可以有效地催化含硫环境中六氯乙烷(HCA)脱氯过程中的氯消除过程。在 pH 值为 7.3 时,10mg/L NCMs 存在下,HCA 脱氯过程中硫的 k 值比没有介质时高一个或两个数量级。NCMs 在 HCA 脱氯中的催化能力在常见的自然 pH 值范围(5.3-8.9)内明显,并且可以通过增加 pH 值来加速,但会被溶解的腐殖酸抑制。此外,与碳材料相比,NCMs 对 HCA 脱氯表现出更好的催化能力,主要归因于吡啶 N 的协同贡献,包括通过生成新的 C-S-S 基团增强对 HCA 分子的亲核攻击以及通过延长 C-Cl 键活化 HCA 分子。介孔微米级 NCMs 中吡啶 N 的功能比纳米级 NCMs 在 HCA 脱氯方面更好。这些发现表明,当 NCMs 释放到含硫环境中时,可能会显著增加氯化脂肪烃的脱氯。