Environmental Science and Pollution Research

, Volume 25, Issue 35, pp 35602–35613 | Cite as

Facile preparation of magnetic carbon nanotubes@ZIF-67 for rapid removal of tetrabromobisphenol A from water sample

  • Tingting Zhou
  • Yun Tao
  • Yinghu Xu
  • Dan Luo
  • Liqin Hu
  • Jingwen Feng
  • Tao Jing
  • Yikai Zhou
  • Surong MeiEmail author
Research Article


In this work, a novel magnetic carbon nanotube@zeolitic imidazolate framework-67 (MCNT@ZIF-67) composite was prepared facilely by a one-pot method using Fe3O4@SiO2 as the magnetic element, CNTs as the carbon matrix, and 2-methylimidazole (2-MIM) and cobaltous nitrate (Co(NO3)2·6H2O) as the organic and inorganic elements, respectively. The obtained MCNT@ZIF-67 composite was characterized by transmission electron microscopy (TEM), Fourier transform-infrared spectroscopy (FT-IR), X-ray diffraction (XRD), and vibrating sample magnetometry (VSM). Static adsorption experiments demonstrated that the maximum adsorption capacity of MCNTs@ZIF-67 for tetrabromobisphenol A (TBBPA) is 83.23 mg g−1, and the sorption isotherm was fitted well by the Freundlich adsorption model. Dynamic adsorption experiments illustrated that the adsorption of TBBPA on MCNTs@ZIF-67 can reach equilibrium in 20 min, and the adsorption kinetics of TBBPA were fitted well by a pseudo-second-order kinetic model. The adsorption of TBBPA on MCNTs@ZIF-67 showed favorable selectivity. The pH and the NaCl and NH4Cl common salts did not affect the TBBPA adsorption. Then, the proposed magnetic composite was applied as the adsorbent for the rapid removal of TBBPA in water samples, and the removal ratio of MCNTs@ZIF-67 for TBBPA in different spiked water samples with different volumes was above 95% with RSD < 5%. Furthermore, as a new removal sorbent, the removal reproducibility of MCNTs@ZIF-67 for TBBPA was favorable and stable, with only a 6.0% decrease after 6 cycles.


Tetrabromobisphenol A Metal organic frameworks Carbon nanotubes Magnetic separation Pollutant removal 



We appreciated the Analytical and Testing Center of Huazhong University of Science and Technology for analyzing the TEM, FT-IR, VSM, and XRD spectra.

Funding information

This work was supported by the National Natural Science Foundation of China (No. 21577043) and the National Basic Research Grant (973) of China (Grant No. 2015CB352100).

Supplementary material

11356_2018_3239_MOESM1_ESM.doc (2.8 mb)
ESM 1 (DOC 2914 kb)


  1. Catherine HN, Ou MH, Manu B, Shih YH (2018) Adsorption mechanism of emerging and conventional phenolic compounds on graphene oxide nanoflakes in water. Sci Total Environ 635:629–638CrossRefGoogle Scholar
  2. Dai Y, Zhang K, Li J, Jiang Y, Chen Y, Tanaka S (2017) Adsorption of copper and zinc onto carbon material in an aqueous solution oxidized by ammonium peroxydisulphate. Sep Purif Technol 186:255–263CrossRefGoogle Scholar
  3. Dam ten G, Pardo O, Traag W, Van der Lee M, Peters R (2012) Simultaneous extraction and determination of HBCD isomers and TBBPA by ASE and LC-MSMS in fish. J Chromatogr B 898:101–110CrossRefGoogle Scholar
  4. De RM, Majewski PJ, Scales N, Luca V (2013) Hydrolytic stability of mesoporous zirconium titanate frameworks containing coordinating organic functionalities. ACS Appl Mater Interfaces 5:4120–4128CrossRefGoogle Scholar
  5. Du XD, Wang CC, Liu JG, Zhao XD, Zhong J, Li YX, Li J, Wang P (2017) Extensive and selective adsorption of ZIF-67 towards organic dyes: performance and mechanism. J Colloid Interface Sci 506:437–441CrossRefGoogle Scholar
  6. Fasfous II, Radwan ES, Dawoud JN (2010) Kinetics, equilibrium and thermodynamics of the sorption of tetrabromobisphenol A on multiwalled carbon nanotubes. Appl Surf Sci 256:7246–7252CrossRefGoogle Scholar
  7. Han T, Xiao Y, Tong M, Huang H, Liu D, Wang L, Zhong C (2015) Synthesis of CNT@MIL-68(Al) composites with improved adsorption capacity for phenol in aqueous solution. Chem Eng J 275:134–141CrossRefGoogle Scholar
  8. Hasan Z, Jhung SH (2015) Removal of hazardous organics from water using metal-organic frameworks (MOFs): plausible mechanisms for selective adsorptions. J Hazard Mater 283:329–339CrossRefGoogle Scholar
  9. Ji L, Zhou L, Bai X, Shao Y, Zhao G, Qu Y, Wang C, Li Y (2012) Facile synthesis of multiwall carbon nanotubes/iron oxides for removal of tetrabromobisphenol A and Pb(II). J Mater Chem 22:15853–15862CrossRefGoogle Scholar
  10. Jugan ML, Levi Y, Blondeau JP (2010) Endocrine disruptors and thyroid hormone physiology. Biochem Pharmacol 79:939–947CrossRefGoogle Scholar
  11. Katsumata H, Kawabe S, Kaneco S, Suzuki T, Ohta K (2004) Degradation of bisphenol A in water by the photo-Fenton reaction. J Photochem Photobiol A Chem 162:297–305CrossRefGoogle Scholar
  12. Kim UJ, Oh JE (2014) Tetrabromobisphenol A and hexabromocyclododecane flame retardants in infant–mother paired serum samples, and their relationships with thyroid hormones and environmental factors. Environ Pollut 184:193–200 [10]CrossRefGoogle Scholar
  13. Lankova D, Lacina O, Pulkrabova J, Hajslova J (2013) The determination of perfluoroalkyl substances, brominated flame retardants and their metabolites in human breast milk and infant formula. Talanta 117:318–325CrossRefGoogle Scholar
  14. Li Y, Huo X, Xu X (2007) Toxic effects of brominated flame retardants on human and mammals. J Environ Health 24:119–121Google Scholar
  15. Li L, Huang Y, Wang Y, Wang W (2009) Hemimicelle capped functionalized carbon nanotubes-based nanosized solid-phase extraction of arsenic from environmental water samples. Anal Chim Acta 631:182–188CrossRefGoogle Scholar
  16. Li G, Xiong J, Wong PK, An T (2016a) Enhancing tetrabromobisphenol A biodegradation in river sediment microcosms and understanding the corresponding microbial community. Environ Pollut 208:796–802CrossRefGoogle Scholar
  17. Li X, Zhang Y, Jing L, He X (2016b) Novel N-doped CNTs stabilized Cu2O nanoparticles as adsorbent for enhancing removal of malachite green and tetrabromobisphenol A. Chem Eng J 292:326–339CrossRefGoogle Scholar
  18. Liang L, Ju L, Hu J, Zhang W, Wang X (2016) Transport of sodium dodecylbenzene sulfonate (SDBS)-dispersed carbon nanotubes and enhanced mobility of tetrabromobisphenol A (TBBPA) in saturated porous media. Colloids Surf A Physicochem Eng Asp 497:205–213CrossRefGoogle Scholar
  19. Lin KYA, Chang HA (2015a) Ultra-high adsorption capacity of zeolitic imidazole framework-67 (ZIF-67) for removal of malachite green from water. Chemosphere 139:624–631CrossRefGoogle Scholar
  20. Lin KYA, Chang HA (2015b) Zeolitic imidazole framework-67 (ZIF-67) as a heterogeneous catalyst to activate peroxymonosulfate for degradation of rhodamine B in water. J Taiwan Inst Chem Eng 53:40–45CrossRefGoogle Scholar
  21. Lin K, Ding J, Huang X (2012) Debromination of tetrabromobisphenol A by nanoscale zerovalent iron: kinetics, influencing factors, and pathways. Ind Eng Chem Res 51:8378–8385CrossRefGoogle Scholar
  22. Liu GB, Dai L, Gao X, Li MK, Thiemann T (2006) Reductive degradation of tetrabromobisphenol A (TBBPA) in aqueous medium. Green Chem 8:781–783CrossRefGoogle Scholar
  23. Liu K, Li J, Yan S, Zhang W, Li Y, Han D (2016) A review of status of tetrabromobisphenol A (TBBPA) in China. Chemosphere 148:8–20CrossRefGoogle Scholar
  24. Liu L, Liu A, Zhang Q, Shi J, He B, Yun Z, Jiang G (2017) Determination of tetrabromobisphenol-A/S and their main derivatives in water samples by high performance liquid chromatography coupled with inductively coupled plasma tandem mass spectrometry. J Chromatogr A 1497:81–86CrossRefGoogle Scholar
  25. Luebke R, Belmabkhout Y, Weseliński ŁJ, Cairns AJ, Alkordi M, Norton G, Wojtas Ł, Adil K, Eddaoudi M (2015) Versatile rare earth hexanuclear clusters for the design and synthesis of highly-connected ftw-MOFs. Chem Sci 6:4095–4102CrossRefGoogle Scholar
  26. Malarvannan G, Isobe T, Covaci A, Prudente M, Tanabe S (2013) Accumulation of brominated flame retardants and polychlorinated biphenyls in human breast milk and scalp hair from the Philippines: levels, distribution and profiles. Sci Total Environ 442:366–379CrossRefGoogle Scholar
  27. McAvoy DC, Pittinger CA, Willis AM (2016) Biotransformation of tetrabromobisphenol A (TBBPA) in anaerobic digester sludge, soils, and freshwater sediments. Ecotoxicol Environ Saf 131:143–150CrossRefGoogle Scholar
  28. Nijem N, Canepa P, Kaipa U, Tan K, Roodenko K, Tekarli S, Halbert J, Oswald IW, Arvapally RK, Yang C (2013) Water cluster confinement and methane adsorption in the hydrophobic cavities of a fluorinated metal-organic framework. J Am Chem Soc 135:12615–12626CrossRefGoogle Scholar
  29. Qu R, Feng M, Wang X, Huang Q, Lu J, Wang L, Wang Z (2015) Rapid removal of tetrabromobisphenol A by ozonation in water: oxidation products, reaction pathways and toxicity assessment. PLoS One 10:e0139580CrossRefGoogle Scholar
  30. Qu G, Liu A, Hu L, Liu S, Shi J, Jiang G (2016) Recent advances in the analysis of TBBPA/TBBPS, TBBPA/TBBPS derivatives and their transformation products. TrAC Trend Anal Chem 83:14–24CrossRefGoogle Scholar
  31. Sun Z, Yu Y, Mao L, Feng Z, Yu H (2008) Sorption behavior of tetrabromobisphenol A in two soils with different characteristics. J Hazard Mater 160:456–461CrossRefGoogle Scholar
  32. Vander der ven LT, Van de Kuil T, Verhoef A, Verwer CM, Lilienthal H, Leonards PE, Schauer UM, Canton RF, Litens S, De Jong FH et al (2008) Endocrine effects of tetrabromobisphenol-A (TBBPA) in Wistar rats as tested in a one-generation reproduction study and a subacute toxicity study. Toxicology 245:76–89CrossRefGoogle Scholar
  33. Wang X, Liu J, Liu Q, Du X, Jiang G (2013) Rapid determination of tetrabromobisphenol A and its main derivatives in aqueous samples by ultrasound-dispersive liquid-liquid microextraction combined with high-performance liquid chromatography. Talanta 116:906–911CrossRefGoogle Scholar
  34. Yang B, Ying GG, Chen ZF, Zhao JL, Peng FQ, Chen XW (2014a) Ferrate (VI) oxidation of tetrabromobisphenol A in comparison with bisphenol A. Water Res 62:211–219CrossRefGoogle Scholar
  35. Yang J, Li JY, Qiao JQ, Cui SH, Lian HZ, Chen HY (2014b) Magnetic solid phase extraction of brominated flame retardants and pentachlorophenol from environmental waters with carbon doped Fe3O4 nanoparticles. Appl Surf Sci 321:126–135CrossRefGoogle Scholar
  36. Yang Q, Ren SS, Zhao Q, Lu R, Cheng H, Chen Z, Zheng H (2018) Selective separation of methyl orange from water using magnetic ZIF-67 composites. Chem Eng J 333:49–57CrossRefGoogle Scholar
  37. Yin Y, Chen Y, Wang X, Liu Y, Liu H, Xie M (2012) Dummy molecularly imprinted polymers on silica particles for selective solid-phase extraction of tetrabromobisphenol A from water samples. J Chromatogr A 1220:7–13CrossRefGoogle Scholar
  38. Zhang Y, Tang Y, Li S, Yu S (2013) Sorption and removal of tetrabromobisphenol A from solution by graphene oxide. Chem Eng J 222:94–100CrossRefGoogle Scholar
  39. Zhang Y, Jing LY, He XH, Li YF, Ma X (2015) Sorption enhancement of TBBPA from water by fly ash-supported nanostructured g-MnO2. J Ind Eng Chem 21:610–619CrossRefGoogle Scholar
  40. Zhang WW, Chen JF, Hu YY, Fang Z, Chen JH, Chen YC (2018) Adsorption characteristics of tetrabromobisphenol A onto sodium bisulfate reduced graphene oxide aerogels. Colloids Surf A Physicochem Eng Asp 538:781–788CrossRefGoogle Scholar
  41. Zhou L, Ji L, Ma PC, Shao Y, He Z, Gao W, Li Y (2014a) Development of carbon nanotubes/CoFe2O4 magnetic hybrid material for removal of tetrabromobisphenol A and Pb(II). J Hazard Mater 265:104–114CrossRefGoogle Scholar
  42. Zhou L, He Z, Ji L, Shao Y, Li Y (2014b) Fe3O4/MWCNT as a heterogeneous Fenton catalyst: degradation pathways of tetrabromobisphenol A. RSC Adv 4:24900–24908CrossRefGoogle Scholar
  43. Zhou X, Huang W, Shi J, Zhao Z, Xia Q, Li Y, Wang H, Li Z (2014c) A novel MOF/graphene oxide composite GrO@MIL-101 with high adsorption capacity for acetone. J Mater Chem A 2:4722–4730CrossRefGoogle Scholar
  44. Zhou YS, He Z, Tao Y, Xiao Y, Zhou TT, Jing T, Zhou YK, Mei SR (2016) Preparation of a functional silica membrane coated on Fe3O4 nanoparticle for rapid and selective removal of perfluorinated compounds from surface water sample. Chem Eng J 303:156–166CrossRefGoogle Scholar
  45. Zou G, Xiong K, Jiang C, Li H, Li T, Du J, Qian Y (2005) Fe3O4 nanocrystals with novel fractal. J Phys Chem B 109:18356–18360CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Tingting Zhou
    • 1
    • 2
  • Yun Tao
    • 1
  • Yinghu Xu
    • 2
  • Dan Luo
    • 1
  • Liqin Hu
    • 1
  • Jingwen Feng
    • 1
  • Tao Jing
    • 1
  • Yikai Zhou
    • 1
  • Surong Mei
    • 1
    Email author
  1. 1.State Key Laboratory of Environment Health (Incubation), Key Laboratory of Environment and Health, Ministry of Education, Key Laboratory of Environment and Health (Wuhan), Ministry of Environmental Protection, School of Public Health, Tongji Medical CollegeHuazhong University of Science and TechnologyWuhanChina
  2. 2.Department of Clinical LaboratoryThe Affiliated Hospital of Qingdao UniversityQingdaoChina

Personalised recommendations