School of Environmental Science and Engineering, Pohang University of Science and Technology (POSTECH), Pohang 790-784, Republic of Korea.
Department of Environmental Engineering, Kwangwoon University, Seoul 139-701, Republic of Korea.
J Hazard Mater. 2016 Jun 5;310:135-42. doi: 10.1016/j.jhazmat.2016.02.027. Epub 2016 Feb 12.
In this study, the environmentally benign citric acid (CA) was utilized to improve the aerobic degradation of 4-chlorophenol (4-CP) over bismuth modified nanoscale zero-valent iron (Bi/Fe(0)). The characterization results revealed the existence of bismuth covering on the Fe(0) surface under zero-valent state. And, the Bi/Fe(0)-CA+O2 system performed excellent reactivity in degradation of 4-CP due to the generation of reactive oxygen species (ROS), which was confirmed by electron spin resonance (ESR) spectroscopy. After 30min of reaction, 80% of 4-CP was removed using Bi/Fe(0)-CA+O2 accompanying with high dechlorination rate. The oxidative degradation intermediates were analyzed by HPLC and LC-MS. We found that CA could promote the bismuth-iron system to produce much reactive oxygen species ROS under both aerobic and anaerobic conditions due to its ligand function, which could react with Fe(3+) to form a ligand complex (Fe(III)Cit), accompanying with a considerable production of Fe(2+) and H2O2. This study provides a new strategy for generating ROS on nZVI and suggests its application for the mineralization of many recalcitrant pollutants.
在这项研究中,采用环保型柠檬酸(CA)来提高过铋修饰纳米零价铁(Bi/Fe(0))的好氧降解 4-氯苯酚(4-CP)的能力。表征结果表明,在零价态下,Fe(0)表面存在铋覆盖。并且,Bi/Fe(0)-CA+O2 体系在 4-CP 的降解中表现出优异的反应性,这是由于产生了活性氧物种(ROS),这一点通过电子顺磁共振(ESR)光谱得到了证实。反应 30 分钟后,Bi/Fe(0)-CA+O2 体系伴随高脱氯率去除了 80%的 4-CP。通过高效液相色谱(HPLC)和液质联用(LC-MS)分析了氧化降解中间产物。我们发现 CA 可以通过其配位功能,在有氧和无氧条件下促进铋-铁体系产生更多的活性氧物种 ROS,这可以与 Fe(3+)反应形成配位络合物(Fe(III)Cit),同时伴随着大量的 Fe(2+)和 H2O2 的产生。本研究为 nZVI 产生 ROS 提供了一种新策略,并为许多难降解污染物的矿化提供了应用前景。