Kim Y H, Carraway E R
Clemson University, Department of Environmental Toxicology, Clemson Institute of Environmental Toxicology, 509 Westinghouse Rd., Pendleton, SC 29670-0709, USA.
Environ Technol. 2003 Jul;24(7):809-19. doi: 10.1080/09593330309385618.
The degradation of chlorinated ethenes and acetylenes by palladium coated iron was studied in batch experiments. The reactivity of palladium coated iron with tetrachloroethene and its less chlorinated ethene and acetylene derivatives showed that dechlorination rates increased as the number of chlorines decreased. Thus, vinyl chloride, the most toxic compound in the chlorinated ethenes, was most rapidly degraded by the palladium coated iron. This reactivity order is opposite to the results previously observed with plain zero valent metals. The major dechlorination products of trichloroethene were ethane, ethene, and acetylene and the carbon mass balance was found to be about 81-91%. No chlorinated products were detected indicating that multiple or concerted dechlorinations rather than sequential reactions were occurring on palladium coated iron. The proposed reaction pathway is that once the chlorinated ethenes have adsorbed on the metal surface, all the chlorines are removed before desorption without release of less chlorinated products such as dichloroethenes and vinyl chloride. As the palladium content increased from 0.025% to 0.77%, the reaction rate was increased. The reaction rate increased linearly up to 0.098% of palladium, however, the increasing rate diminished with higher amounts of Pd. Results of Energy Dispersive X-ray Spectroscopy showed that uneven palladium coatings were formed on the iron at high contents of palladium.
通过批次实验研究了钯包覆铁对氯乙烯和乙炔的降解情况。钯包覆铁与四氯乙烯及其氯取代程度较低的乙烯和乙炔衍生物的反应活性表明,脱氯速率随着氯原子数的减少而增加。因此,氯乙烯作为氯乙烯类中毒性最强的化合物,被钯包覆铁降解的速度最快。这种反应活性顺序与之前用普通零价金属观察到的结果相反。三氯乙烯的主要脱氯产物是乙烷、乙烯和乙炔,碳质量平衡约为81%-91%。未检测到氯代产物,这表明在钯包覆铁上发生的是多步或协同脱氯反应,而非顺序反应。提出的反应途径是,一旦氯乙烯吸附在金属表面,所有氯原子在解吸前都会被去除,不会释放出二氯乙烯和氯乙烯等氯取代程度较低的产物。随着钯含量从0.025%增加到0.77%,反应速率增加。钯含量达到0.098%之前,反应速率呈线性增加,然而,钯含量更高时,增加速率减小。能量色散X射线光谱分析结果表明,钯含量较高时,铁表面形成的钯涂层不均匀。