碳基纳米零价铁-铜复合材料去除水中三氯硝基甲烷
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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-Fe~0,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 m~2·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(R~2> 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Fe_3O_4和Fe_2O_3,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(R~2 > 0.9). The recycling experimental results showed that nano Fe~0 could be corroded to Fe(Ⅱ) and released into the solution, the iron oxides such as Fe_3O_4 and Fe_2O_3 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.
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(R~2 > 0.9). The recycling experimental results showed that nano Fe~0 could be corroded to Fe(Ⅱ) and released into the solution, the iron oxides such as Fe_3O_4 and Fe_2O_3 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.
引文
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[16] 刘爱荣,周文.石墨烯基金属氧化物纳米复合结构材料的制备及应用于水体中污染物的吸附研究进展[J].科学通报,2014,59:2039-2054.LIU A R,ZHOU W.Graphene-based metal oxide nanocomposites and their application as adsorbents in water treatment schemes [J].Chinese Science Bulletin,2014,59:2039-2054 (in Chinese).
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[18] ZHANG Z,CISSOKO N,WO J,et al.Factors influencing the dechlorination of 2,4-dichlorophenol by Ni-Fe nanoparticles in the presence of humic acid [J].J Hazard Mater,2009,165:78-86.
[19] ZHOU W,GUO L.Iron triad (Fe,Co,Ni) nanomaterials:structural design,functionalization and their applications [J].Chem Soc Rev,2015,44:6697-6707.
[20] DENISO C,BRENT S,MAGDALENA K,et al.Nanoscale zero valent iron and bimetallic particles for contaminated site remediation [J].Advances in Water Resources,2013,51:104-122.
[21] 楚文海,高乃云,赵世嘏,等.Fe /Cu 催化还原去除饮用水消毒副产物三氯乙酸[J].同济大学学报(自然科学版),2009,37(10):1355-1359.CHU WH,GAO NY,ZHAO S J,et al.Removal of halogenated disinfection by-products trichloroacetic acid by Fe/Cu catalytic reductionin drinking water [J].Journal of Tongji University (NATURAL SCience),2009,37(10):1355-1359 (in Chinese).
[22] 丁春生,马海龙,傅洋平,等.Fe /Cu 催化还原降解饮用水中溴氯乙腈的性能研究[J].环境科学,2015,36(6):2116-2121.DING C S,MA H L,FU Y P,et al.Performance study of bromochloracetonitrile degradation in drinking water by Fe /Cu catalytic reduction [J].Environmental Science,2015,36(6):2116-2121(in Chinese).
[23] HOSSEINI S M,ASHTIANI B A,KHOLGHI M.Nitrate reduction by nano-Fe/Cu particles in packed column [J].Desalination,2011,276:214-221.
[24] RSOARES O S G,ORFAO J J M,PEREIRA M F R.Nitrate reduction with Hydrogen in the presence of physical mixtures with mono and bimetallic catalysts and ions in solution [J].Appl Catal B:Environ,2011,102:424-432.
[25] ZHANG Z,CISSOKO N,WO J,et al.Factors influencing the dechlorination of 2,4-dichlorophenol by Ni-Fe nanoparticles in the presence of humic acid [J].J Hazard Mater,2009,165:78-86.
[26] FU F L,DIONYSIOU D D,LIU H.The use of zero-valent iron for groundwater remediation and wastewater treatment:A review [J].Journal of Hazardous Materials,2014,267:194-205.
[27] HOCH L B,MARK E J,HYDUTSKY B W,et al.Carbothermal synthesis of carbon-supported nanoscale zero-valent iron particles for the remediation of hexavalent chromium [J].Environ Sci Technol,2008,42(7):2600-2605.
[28] LIU Z G,ZHANG F S.Nano-zero valent iron contained porous carbons developed from waste biomass for the adsorption and dechlorination of PCBs [J].Bioresource Technology,2010,101 (7):2562-2564.
[29] ZHANG B B,SONG J L,YANG G Y,et al.Large-scale production of high-quality graphene using glucose and ferric chloride [J],Chem Sci,2014,5:4656-4660.
[30] CHEN H F,CAO Y,WEI E Z,et al.Facile synthesis of graphene nano zero-valent iron composites and their efficient removal of trichloronitromethane from drinking water [J].Chemosphere,2016,146:32-39.
[31] CAO J,XU R F,TANG H,et al.Synthesis of monodispersed CMC-stabilized Fe-Cu bimetal nanoparticles for in situ reductive dechlorination of 1,2,4-trichlorobenzene [J].Sci Total Environ,2011,409:2336-2341.
[2] LIVIAC D,WAGNER E D,MITCH W A,et al.Genotoxicity of water concentrates from recreational pools after various disinfection methods [J].Environ Sci Technol,2010,44:3527-3532.
[3] KRASNER S W,SCLIMENTI M J,MITCH W A,et al.Wastewater and Algal Derived N-DBPs [M].AWWA,Denver,CO,USA AWWA Annual Conference,2007.
[4] KRASNER S W,WESTERHOFF P,CHEN B,et al.Impact of wastewater treatment processes on organic carbon,organic nitrogen,and DBP precursors in effluent organic matter [J].Environ Sci Technol,2009,43:2911-2918.
[5] MONTESINOS I,GALLEGO M.Headspace gas chromatography–mass spectrometry for rapid determination of halonitromethanes in tap and swimming pool water [J].Anal Bioanal Chem,2012,402:2315-2323.
[6] 高乃云,方诚,楚文海.常规净水工艺中三氯硝基甲烷质量浓度分布调查[J].同济大学学报(自然科学版),2012,40(6):890-893.GAO N Y,FANG C,CHU W H.Concentration of trichloronitromethane in conventional water treatment process [J].Journal of Tongji University (Natural Science),2012,40(6):890-893 (in Chinese).
[7] WEI J,YE B,WANG W,Spatial and temporal evaluations of disinfection by-products in drinking water distribution systems in Beijing,China [J].Sci Total Environ,2010,408:4600-4606.
[8] GAN W,GUO W,MO J,et al.The occurrence of disinfection by-products in municipal drinking water in China′s Pearl River Delta and a multipathway cancer risk assessment [J].Sci Total Environ,2013,447:108-115.
[9] HONG H C,QIAN L Y,RUAN MY,et al.Use of multiple regression models to evaluate the formation of halonitromethane via chlorination/chloramination of water from Tai Lake and the Qiantang River,China [J].Chemosphere,2015,119:540-546.
[10] CHUN C L,HOZALSKI R M,ARNOLD W A.Degradation of drinking water disinfection by products by synthetic goethite and magnetite [J].Environ Sci Technol,2005,39(21):8525-8532.
[11] PEARSON C R,HOZALSKI R M,ARNOLD W A,Degradation of chloropicrin in the presence of Fe(0) [J].Environ Toxicol Chem,2005,24:3037-3042.
[12] LEE J Y,HOZALSKI R M,ARNOLD W A.Effects of dissolved oxygen and iron aging on the reduction of trichloronitromethane,trichloracetonitrile,and trichloropropanone [J].Chemosphere,2007,66:2127-2135.
[13] FU F L,DIONYSIOU D D,LIU H.The use of zero-valent iron for groundwater remediation and wastewater treatment:A review [J].J Hazard Mater,2014,267:194-205.
[14] TESH S J,SCOTT T B.Nano-composites for water remediation:A review [J].Adv Mater,2014,26:6056-6068.
[15] CRANE R A,SCOTT T B.Nanoscale zero-valent iron:Future prospects for an emerging water treatment technology [J].J Hazard Mater,2012,32:211-212.
[16] 刘爱荣,周文.石墨烯基金属氧化物纳米复合结构材料的制备及应用于水体中污染物的吸附研究进展[J].科学通报,2014,59:2039-2054.LIU A R,ZHOU W.Graphene-based metal oxide nanocomposites and their application as adsorbents in water treatment schemes [J].Chinese Science Bulletin,2014,59:2039-2054 (in Chinese).
[17] SREEPRASAD T,MALIYEKKAL S M,LISHA K.Reduced graphene oxide–metal/metal oxide composites:Facile synthesis and application in water purification [J].J Hazard Mater,2011,186:921-931.
[18] ZHANG Z,CISSOKO N,WO J,et al.Factors influencing the dechlorination of 2,4-dichlorophenol by Ni-Fe nanoparticles in the presence of humic acid [J].J Hazard Mater,2009,165:78-86.
[19] ZHOU W,GUO L.Iron triad (Fe,Co,Ni) nanomaterials:structural design,functionalization and their applications [J].Chem Soc Rev,2015,44:6697-6707.
[20] DENISO C,BRENT S,MAGDALENA K,et al.Nanoscale zero valent iron and bimetallic particles for contaminated site remediation [J].Advances in Water Resources,2013,51:104-122.
[21] 楚文海,高乃云,赵世嘏,等.Fe /Cu 催化还原去除饮用水消毒副产物三氯乙酸[J].同济大学学报(自然科学版),2009,37(10):1355-1359.CHU WH,GAO NY,ZHAO S J,et al.Removal of halogenated disinfection by-products trichloroacetic acid by Fe/Cu catalytic reductionin drinking water [J].Journal of Tongji University (NATURAL SCience),2009,37(10):1355-1359 (in Chinese).
[22] 丁春生,马海龙,傅洋平,等.Fe /Cu 催化还原降解饮用水中溴氯乙腈的性能研究[J].环境科学,2015,36(6):2116-2121.DING C S,MA H L,FU Y P,et al.Performance study of bromochloracetonitrile degradation in drinking water by Fe /Cu catalytic reduction [J].Environmental Science,2015,36(6):2116-2121(in Chinese).
[23] HOSSEINI S M,ASHTIANI B A,KHOLGHI M.Nitrate reduction by nano-Fe/Cu particles in packed column [J].Desalination,2011,276:214-221.
[24] RSOARES O S G,ORFAO J J M,PEREIRA M F R.Nitrate reduction with Hydrogen in the presence of physical mixtures with mono and bimetallic catalysts and ions in solution [J].Appl Catal B:Environ,2011,102:424-432.
[25] ZHANG Z,CISSOKO N,WO J,et al.Factors influencing the dechlorination of 2,4-dichlorophenol by Ni-Fe nanoparticles in the presence of humic acid [J].J Hazard Mater,2009,165:78-86.
[26] FU F L,DIONYSIOU D D,LIU H.The use of zero-valent iron for groundwater remediation and wastewater treatment:A review [J].Journal of Hazardous Materials,2014,267:194-205.
[27] HOCH L B,MARK E J,HYDUTSKY B W,et al.Carbothermal synthesis of carbon-supported nanoscale zero-valent iron particles for the remediation of hexavalent chromium [J].Environ Sci Technol,2008,42(7):2600-2605.
[28] LIU Z G,ZHANG F S.Nano-zero valent iron contained porous carbons developed from waste biomass for the adsorption and dechlorination of PCBs [J].Bioresource Technology,2010,101 (7):2562-2564.
[29] ZHANG B B,SONG J L,YANG G Y,et al.Large-scale production of high-quality graphene using glucose and ferric chloride [J],Chem Sci,2014,5:4656-4660.
[30] CHEN H F,CAO Y,WEI E Z,et al.Facile synthesis of graphene nano zero-valent iron composites and their efficient removal of trichloronitromethane from drinking water [J].Chemosphere,2016,146:32-39.
[31] CAO J,XU R F,TANG H,et al.Synthesis of monodispersed CMC-stabilized Fe-Cu bimetal nanoparticles for in situ reductive dechlorination of 1,2,4-trichlorobenzene [J].Sci Total Environ,2011,409:2336-2341.