碳基纳米零价铁-铜复合材料去除水中三氯硝基甲烷  

Fabrication of carbon-based Fe-Cu nanoparticles for the removal of trichloronitromethane in water

作　　者：陈海峰 龚婷婷[1] 鲜啟鸣 CHEN Haifeng;GONG Tingling;XIAN Qiming(State Key Laboratory of Pollution Control and Resource Reuse,School of the Environment,Nanjing University,Nanjing,210023,China;Jiangsu Engineering Center of the Pesticide Waste water Treatment and Resource Reuse,School of Chemical and Biological Engineering,Nantong Vocational University,Nantong,226007,China)

机构地区：[1]污染控制与资源化研究国家重点实验室,南京大学环境学院,南京210023 [2]江苏省农药废水处理及资源化利用工程研究中心,南通职业大学化学与生物工程学院,南通226007

出　　处：《环境化学》2019年第6期1385-1395,共11页Environmental Chemistry

基　　金：国家自然科学基金(21876078);江苏省社会发展项目(BE2017711);南通市科技计划(MS12017019-1)资助~~

摘　　要：卤代硝基甲烷(HNMs)是一类典型的含氮消毒副产物(N-DBPs),具有较强的毒性,在饮用水、污水和泳池水中频繁检出.以葡萄糖、氯化铁和氯化铜为原料,通过碳化和煅烧,制备得到纳米零价铁、铜均匀负载的碳基复合材料,材料中的铁为体心立方的α-Fe0,铜为面心立方体铜,颗粒呈球形且未发生明显的团聚,其平均粒径为18 nm,复合材料比表面积为417 m2·g^-1.铜的添加能显著加快复合材料去除三氯硝基甲烷(TCNM)的效率,当Fe与Cu的质量比为10∶1时,复合材料对水中的TCNM具有最高的去除效率和最快的去除速率.在材料投加量为10 mg·L^-1(以铁计),TCNM初始浓度为10μg·L^-1,初始pH值为6.0,温度为25℃,且体系无氧、无余氯的条件下,60 min内可以去除99.7%的TCNM,去除TCNM的反应符合准一级反应动力学方程(R2> 0.9).复合材料在降解TCNM过程中会发生铁的流失,多次使用后的复合材料表面出现了铁的氧化产物,主要为Fe3O4和Fe2O3,经过二次煅烧,可以恢复复合材料的活性.Halonitromethanes,as an emerging class of nitrogenous disinfection by-products(N-DBPs),have been frequently detected in drinking water,swimming pool and sewage water,and showed a strong mutagenicity and genotoxicity.Based on XRD,TEM,XPS and BET data,nano zero-valent Fe^0/Cu^0 has been successfully combined into carbon-based nano-composites via facile carbonization and calcinations of glucose,ferric chloride and copper chloride mixtures.Fe^0 and Cu^0 nanoparticles were a body centered cubic structure and a face centered cubic structure,respectively in the nano-composites without obvious aggregation.The results showed that the average particles size and specific surface area were 18 nm and 417 m^2·g^-1,respectively.The as-prepared composites with the addition of Cu could accelerate the removal of trichloronitromethane(TCNM) in water,and the highest removal was obtained under the ratio of 10:1 for Fe/Cu.With the initial concentration of TCNM 10 μg·L^-1,pH 6.0,reaction temperature 25 ℃,and the removal of the dissolved oxygen and the residual chlorine,more than 99% TCNM could be removed within 60 mins using 10 mg·L^-1 of the composite(calculated with Fe).Kinetic studies indicated that the removal of TCNM by the composites followed a pseudo first order rate equation(R2 > 0.9).The recycling experimental results showed that nano Fe0 could be corroded to Fe(Ⅱ) and released into the solution,the iron oxides such as Fe3O4 and Fe2O3 were the main corrosion products which covered on the surface of the nano-composites eventually resulting in the decrease of the reduction capacity.The reactivity of nano-composites can be regenerated by calcinations again in an Ar atmosphere.

关 键 词：纳米零价铁 碳基复合材料 卤代硝基甲烷(HNMs) 去除技术 饮用水 

分 类 号：X703[环境科学与工程—环境工程]