Zhu Bao-Wei, Lim Teik-Thye, Feng Jing
School of Civil and Environmental Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798, Republic of Singapore.
Environ Sci Technol. 2008 Jun 15;42(12):4513-9. doi: 10.1021/es800227r.
The influences of amphiphiles on the catalytic dechlorination of 1,2,4-trichlorobenzene (124TCB) bythe nanoscale Pd/Fe particles were comprehensively examined. The fresh and reacted Pd/ Fe particles were characterized with XRD, TEM, SEM, FTIR spectrometry, and goniometry. Adsorption of amphiphiles on the Pd/Fe particles, iron dissolution, and H2 evolution in the Pd/Fe-water system were quantified to expound the influences of the various amphiphiles on the dechlorination process. The Langmuir-Hinshelwood model is used to elucidate the dechlorination kinetics, and it provides insight into the influence of amphiphiles on 124TCB partitioning to the interfacial layer and the resulting dechlorination rates. The rate constants increased by a factor of 1.5--2.5 with the presence of cationic cetyltrimethylammonium bromide (CTAB). In the anionic sodium deodecyl sulfate(SDS) or nonionic nonylphenol ethoxylate (NPE) and octylphenolpoly (ethylene glycol ether)x (TX-100) surfactant solutions, the 124TCB dechlorination rates were slightly increased over those observed in ultrapure water. However, when concentrations of the surfactants were above their CMCs, the dechlorination rates decreased. The findings also showed that DPC (dodecylpyridinium chloride) and NOM (natural organic matter) might be the competitive H2 acceptors to 124TCB, and they significantly retarded its catalytic dechlorination by the Pd/Fe particles. CTAB at a concentration below the CMC appeared to be the most benign to the 124TCB dechlorination.
全面研究了两亲物对纳米级钯/铁颗粒催化脱氯1,2,4 - 三氯苯(124TCB)的影响。采用X射线衍射(XRD)、透射电子显微镜(TEM)、扫描电子显微镜(SEM)、傅里叶变换红外光谱(FTIR)和测角术对新鲜的和反应后的钯/铁颗粒进行了表征。对两亲物在钯/铁颗粒上的吸附、铁的溶解以及钯/铁 - 水体系中的氢气析出进行了定量分析,以阐述各种两亲物对脱氯过程的影响。使用朗缪尔 - 欣谢尔伍德模型来阐明脱氯动力学,并深入了解两亲物对124TCB分配到界面层以及由此产生的脱氯速率的影响。在阳离子十六烷基三甲基溴化铵(CTAB)存在的情况下,速率常数增加了1.5 - 2.5倍。在阴离子十二烷基硫酸钠(SDS)或非离子壬基酚聚氧乙烯醚(NPE)和辛基酚聚(乙二醇醚)x(TX - 100)表面活性剂溶液中,124TCB的脱氯速率比在超纯水中观察到的速率略有增加。然而,当表面活性剂的浓度高于其临界胶束浓度(CMC)时,脱氯速率降低。研究结果还表明,十二烷基氯化吡啶(DPC)和天然有机物(NOM)可能是124TCB的竞争性氢气受体,它们显著阻碍了钯/铁颗粒对其的催化脱氯。浓度低于CMC的CTAB似乎对124TCB脱氯最为有利。