College of Water Sciences, Beijing Normal University, Beijing 100875, PR China.
College of Water Sciences, Beijing Normal University, Beijing 100875, PR China.
J Hazard Mater. 2022 Jul 5;433:128744. doi: 10.1016/j.jhazmat.2022.128744. Epub 2022 Mar 22.
Research on the stepwise hydrogenation dechlorination of chlorinated alkenes forms an important basis for eliminating toxic intermediate incomplete dechlorination products. The low-cost Fe-Ni/rGO/Ni foam cathode both supplied electrons and exhibited hydrogen conversion activity, and it was an excellent tool for the study of stepwise dechlorination. Electrochemical reduction experiments were carried out on homologous chlorinated alkenes. The conditions affecting the dechlorination efficiency and the repeatability of the catalytic electrode were analyzed. The trichloroethylene (TCE) removal rates were all above 78.0% over 8 cycles. The maximum EHDC efficiency was as high as 86.1%, and the faradaic efficiency was over 78.8%. Electrochemical methods combined with the calculation of the electron transfer number are proposed to verify the good hydrogenation ability of the electrode and the stepwise reduction ability at proper voltages. The stepwise dechlorination electroreduction characteristics of chlorinated alkenes were explained. The C-Cl bond dissociation enthalpies of chlorinated alkenes were calculated by density functional theory (DFT), and the 4-Cl and 5-Cl of TCE were expected to be removed first. The stepwise cleavage of chlorinated alkenes on Fe-Ni/rGO/Ni foam during dichlorination provided a reference for controlling the reduction products of chlorinated alkenes and preventing the pollution caused by toxic intermediate products formed during incomplete dechlorination.
关于氯代烯烃分步加氢脱氯的研究为消除有毒中间不完全脱氯产物奠定了重要基础。低成本的 Fe-Ni/rGO/Ni 泡沫阴极既提供了电子,又表现出了氢转化活性,是研究分步脱氯的理想工具。在同源氯代烯烃上进行了电化学还原实验,分析了影响脱氯效率和催化电极重复性的条件。在 8 个循环中,三氯乙烯 (TCE) 的去除率均高于 78.0%。EHDC 的最大效率高达 86.1%,法拉第效率超过 78.8%。提出了电化学方法与电子转移数计算相结合,以验证电极的良好加氢能力和在适当电压下的分步还原能力。解释了氯代烯烃的分步还原电还原特性。通过密度泛函理论 (DFT) 计算了氯代烯烃的 C-Cl 键离解焓,预计 TCE 的 4-Cl 和 5-Cl 将首先被去除。在二氯代过程中,氯代烯烃在 Fe-Ni/rGO/Ni 泡沫上的分步裂解为控制氯代烯烃的还原产物和防止不完全脱氯过程中形成的有毒中间产物造成的污染提供了参考。