Skip to main content
SpringerLink
Log in

Micro-solid phase extraction of chlorophenols using reduced graphene oxide functionalized with magnetic nanoparticles and graphitic carbon nitride as the adsorbent

  • Original Paper
  • Published:
Microchimica Acta Aims and scope Submit manuscript

Abstract

A magnetic micro-solid phase extraction method was applied for the extraction of trace levels of various chlorophenols prior to their determination by high performance liquid chromatography. The reduced graphene oxide functionalized with magnetic iron oxide nanoparticles and graphitic carbon nitride was prepared and used as adsorbent. It was characterized by scanning electron microscope, X-ray diffraction and vibrating sample magnetometer. Placed in a polypropylene hollow tube, the material was applied to the extraction of 3-chlorophenol, 2,3-dichlorophenol, 2,4-dichlorophenol, and 2,4,6-trichlorophenol in cosmetic samples. Several experimental parameters that affect extraction efficiency were optimized. Following desorption with alkaline methanol, the chlorophenols were quantified by high performance liquid chromatography. A linear response was observed in the 1.0–200 μg·kg−1 CP concentration ranges. The detection limits (at a signal-to-noise ratio of 3) are between 0.20 and 0.30 μg·kg−1. The relative recoveries of the CPs from spiked cosmetics samples were in the range from 80.5 to 104%, with relative standard deviations lower than 12%. The filled extraction tube is high durable and stable. It can be used for 120 extraction cycles without a significant loss of extraction efficiency. The good adsorption ability of the sorbent was attributed to the strong π stacking interaction between the graphitic carbon nitride functionalized reduced graphene oxide and the aromatic rings in the CPs.

A magnetic micro-solid phase extraction (M-μSPE) method was applied to the extraction of various trace chlorophenols prior to their determination by high performance liquid chromatography. The M-μSPE method combines the advantages of both MSPE and μSPE.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4

Similar content being viewed by others

References

  1. Kostrhounová R, Hrdlička A, Sommer L (2003) Solid phase extraction of phenol and chlorophenols on octadecylsilica and amberlite XAD 2 sorbents in the presence of cationic surfactant. Mikrochim Acta 142(1–2):95–99. https://doi.org/10.1007/s00604-003-0014-4

    Article  Google Scholar 

  2. Ghazaghi M, Mousavi HZ, Shirkhanloo H, Rashidi A (2016) Ultrasound assisted dispersive micro solid-phase extraction of four tyrosine kinase inhibitors from serum and cerebrospinal fluid by using magnetic nanoparticles coated with nickel-doped silica as an adsorbent. Mikrochim Acta 183(10):2779–2789. https://doi.org/10.1007/s00604-016-1927-z

    Article  CAS  Google Scholar 

  3. Bagheri H, Manouchehri M, Allahdadlalouni M (2017) A magnetic multifunctional dendrimeric coating on a steel fiber for solid phase microextraction of chlorophenols. Mikrochim Acta 184(7):2201–2209. https://doi.org/10.1007/s00604-017-2220-5

    Article  CAS  Google Scholar 

  4. Abolghasemi MM, Parastari S, Yousefi V (2016) A nanoporous anodized alumina wire with a nanosized hydroxyapatite coating for headspace solid-phase microextraction of phenol and chlorophenols. Microchim Acta 183(1):241–247. https://doi.org/10.1007/s00604-015-1631-4

    Article  CAS  Google Scholar 

  5. Farhadi K, Firuzi M, Hatami M (2014) Stir bar sorptive extraction of propranolol from plasma samples using a steel pin coated with a polyaniline and multiwall carbon nanotube composite. Mikrochim Acta 182(1–2):323–330. https://doi.org/10.1007/s00604-014-1336-0

    Google Scholar 

  6. Diao CP, Li C, Yang X, Sun AL, Liu R (2016) Magnetic matrix solid phase dispersion assisted dispersive liquid liquid microextraction of ultra trace polychlorinated biphenyls in water prior to GC-ECD determination. Microchim Acta 183:1261–1268. https://doi.org/10.1007/s00604-016-1761-3

    Article  CAS  Google Scholar 

  7. Marube LC, Caldas SS, Soares KL, Primel EG (2015) Dispersive liquid–liquid microextraction and HPLC to analyse fluoxetine and metoprolol enantiomers in wastewaters. Microchim Acta 182:1765–1774. https://doi.org/10.1007/s00604-015-1507-7

    Article  CAS  Google Scholar 

  8. Saraji M, Ghani M (2015) Hollow fiber liquid-liquid-liquid microextraction followed by solid-phase microextraction and in situ derivatization for the determination of chlorophenols by gas chromatography-electron capture detection. J Chromatogr A 1418:45–53. https://doi.org/10.1016/j.chroma.2015.09.062

    Article  CAS  Google Scholar 

  9. Ghambarian M, Yamini Y, Esrafili A (2012) Developments in hollow fiber based liquid-phase microextraction: principles and applications. Mikrochim Acta 177(3–4):271–294. https://doi.org/10.1007/s00604-012-0773-x

    Article  CAS  Google Scholar 

  10. Andrade-Eiroa A, Canle M, Leroy-Cancellieri V, Cerdà V (2016) Solid-phase extraction of organic compounds: a critical review. Part ii. TrAC Trends Anal Chem 80:655–667. https://doi.org/10.1016/j.trac.2015.08.014

    Article  CAS  Google Scholar 

  11. Basheer C, Alnedhary AA, Rao BSM, Valliyaveettil S, Lee HK (2006) Development and application of porous membrane-protected carbon nanotube micro-solid-phase extraction combined with gas chromatography/mass spectrometry. Anal Chem 78:2853–2858. https://doi.org/10.1021/ac060240i

    Article  CAS  Google Scholar 

  12. Abbasghorbani M, Attaran A, Payehghadr M (2013) Solvent-assisted dispersive micro-SPE by using aminopropyl-functionalized magnetite nanoparticle followed by GC-PID for quantification of parabens in aqueous matrices. J Sep Sci 36(2):311–319. https://doi.org/10.1002/jssc.201200556

    Article  CAS  Google Scholar 

  13. Spietelun A, Marcinkowski L, de la Guardia M, Namiesnik J (2013) Recent developments and future trends in solid phase microextraction techniques towards green analytical chemistry. J Chromatogr A 1321:1–13. https://doi.org/10.1016/j.chroma.2013.10.030

    Article  CAS  Google Scholar 

  14. Wang L, Zang X, Wang C, Wang Z (2014) Graphene oxide as a micro-solid-phase extraction sorbent for the enrichment of parabens from water and vinegar samples. J Sep Sci 37(13):1656–1662. https://doi.org/10.1002/jssc.201400028

    Article  CAS  Google Scholar 

  15. Feng Q, Zhao L, Lin JM (2009) Molecularly imprinted polymer as micro-solid phase extraction combined with high performance liquid chromatography to determine phenolic compounds in environmental water samples. Anal Chim Acta 650(1):70–76. https://doi.org/10.1016/j.aca.2009.04.016

    Article  CAS  Google Scholar 

  16. Liu Q, Shi JB, Jiang GB (2012) Analysis and assessment of the occurrence, the fate and the behavior of nanomaterials in the environment. TrAC. Trends Anal Chem 37(7–8):1–11. https://doi.org/10.1016/j.trac.2012.03.011

    Article  Google Scholar 

  17. Qiu HJ, Guan Y, Luo P, Wang Y (2017) Recent advance in fabricating monolithic 3D porous graphene and their applications in biosensing and biofuel cells. Biosens Bioelectron 89(Pt 1):85–95. https://doi.org/10.1016/j.bios.2015.12.029

    Article  CAS  Google Scholar 

  18. Dreyer DR, Park S, Bielawski CW, Ruoff RS (2010) The chemistry of graphene oxide. Chem Soc Rev 39(1):228–240. https://doi.org/10.1039/b917103g

    Article  CAS  Google Scholar 

  19. Li M, Wang J, Jiao C, Wang C, Wu Q, Wang Z (2016) Graphene oxide framework: an adsorbent for solid phase extraction of phenylurea herbicides from water and celery samples. J Chromatogr A 1469:17–24. https://doi.org/10.1016/j.chroma.2016.09.056

    Article  CAS  Google Scholar 

  20. Zhao Z, Sun Y, Dong F (2015) Graphitic carbon nitride based nanocomposites: a review. Nano 7(1):15–37. https://doi.org/10.1039/c4nr03008g

    Google Scholar 

  21. Chen Q, Zhao Y, Huang X, Chen N, Qu L (2015) Three-dimensional graphitic carbon nitride functionalized graphene-based high-performance supercapacitors. J Mater Chem A 3(13):6761–6766. https://doi.org/10.1039/c5ta00734h

    Article  CAS  Google Scholar 

  22. Yang J, Si L, Cui SH, Bi WT (2015) Synthesis of a graphitic carbon nitride nanocomposite with magnetite as a sorbent for solid phase extraction of phenolic acids. Microchim Acta 182(3–4):737–744. https://doi.org/10.1007/s00604-014-1381-8

    Article  CAS  Google Scholar 

  23. Wang M, Yang XD, Bi WT (2015) Application of magnetic graphitic carbon nitride nanocomposites for the solid-phase extraction of phthalate esters in water samples. J Sep Sci 38(3):445–452. https://doi.org/10.1002/jssc.201400991

    Article  CAS  Google Scholar 

  24. Sun YP, Wei H, Chen J, Qi HY, Shi YP (2016) Advances and applications of graphitic carbon nitride as sorbent in analytical chemistry for sample pretreatment: a review. TrAC. Trends Anal Chem 84:12–21. https://doi.org/10.1016/j.trac.2016.03.002

    Article  CAS  Google Scholar 

  25. Naing NN, Yau Li SF, Lee HK (2016) Magnetic micro-solid-phase-extraction of polycyclic aromatic hydrocarbons in water. J Chromatogr A 1440:23–30. https://doi.org/10.1016/j.chroma.2016.02.046

    Article  CAS  Google Scholar 

  26. Vlastos D, Antonopoulou M, Konstantinou I (2016) Evaluation of toxicity and genotoxicity of 2-chlorophenol on bacteria, fish and human cells. Sci Total Environ 551-552:649–655. https://doi.org/10.1016/j.scitotenv.2016.02.043

    Article  CAS  Google Scholar 

  27. Gonzalez Paredes RM, Garcia Pinto C, Perez Pavon JL, Moreno Cordero B (2014) In situ derivatization combined to automated microextraction by packed sorbents for the determination of chlorophenols in soil samples by gas chromatography mass spectrometry. J Chromatogr A 1359:52–59. https://doi.org/10.1016/j.chroma.2014.07.048

    Article  CAS  Google Scholar 

  28. Zhang C, Suzuki D, Li Z, Ye L, Katayama A (2012) Polyphasic characterization of two microbial consortia with wide dechlorination spectra for chlorophenols. J Biosci Bioeng 114(5):512–517. https://doi.org/10.1016/j.jbiosc.2012.05.025

    Article  CAS  Google Scholar 

  29. Sarafraz-Yazdi A, Dizavandi ZR, Amiri A (2012) Determination of phenolic compounds in water and urine samples using solid-phase microextraction based on sol–gel technique prior to GC-FID. Anal Methods 4(12):4316. https://doi.org/10.1039/c2ay25970b

    Article  CAS  Google Scholar 

  30. Garcia-Valverde MT, Lucena R, Cardenas S, Valcarcel M (2016) In-syringe dispersive micro-solid phase extraction using carbon fibres for the determination of chlorophenols in human urine by gas chromatography/mass spectrometry. J Chromatogr A 1464:42–49. https://doi.org/10.1016/j.chroma.2016.08.036

    Article  CAS  Google Scholar 

  31. Guo F, Liu Q, J-b S, F-s W, G-b J (2014) Direct analysis of eight chlorophenols in urine by large volume injection online turbulent flow solid-phase extraction liquid chromatography with multiple wavelength ultraviolet detection. Talanta 119:396–400. https://doi.org/10.1016/j.talanta.2013.11.006

    Article  CAS  Google Scholar 

  32. Villar-Navarro M, Ramos-Payan M, Perez-Bernal JL, Fernandez-Torres R, Callejon-Mochon M, Angel Bello-Lopez M (2012) Application of three phase hollow fiber based liquid phase microextraction (HF-LPME) for the simultaneous HPLC determination of phenol substituting compounds (alkyl-, chloro- and nitrophenols). Talanta 99:55–61. https://doi.org/10.1016/j.talanta.2012.05.020

    Article  CAS  Google Scholar 

  33. Cai MQ, Su J, JQ H, Wang Q, Dong CY, Pan SD, Jin MC (2016) Planar graphene oxide-based magnetic ionic liquid nanomaterial for extraction of chlorophenols from environmental water samples coupled with liquid chromatography-tandem mass spectrometry. J Chromatogr A 1459:38–46. https://doi.org/10.1016/j.chroma.2016.06.086

    Article  CAS  Google Scholar 

  34. Cheng NY, Tian JQ, Liu Q, Ge CJ, Qusti AH, Asiri AM, Al-Youbi AO, Sun XP (2013) Au-nanoparticle-loaded graphitic carbon nitride Nanosheets: green Photocatalytic synthesis and application toward the degradation of organic pollutants. ACS Appl Mater Interfaces 5:6815–6819. https://doi.org/10.1021/am401802r

    Article  CAS  Google Scholar 

  35. Gao D, Xu Q, Zhang J, Yang Z, Si M, Yan Z, Xue D (2014) Defect-related ferromagnetism in ultrathin metal-free g-C3N4 nanosheets. Nano 6(5):2577–2581. https://doi.org/10.1039/c3nr04743a

    CAS  Google Scholar 

  36. Xu C, Wu Y, Zhao X, Wang X, Du G, Zhang J, Tu J (2015) Sulfur/three-dimensional graphene composite for high performance lithium–sulfur batteries. J Power Sources 275:22–25. https://doi.org/10.1016/j.jpowsour.2014.11.007

    Article  CAS  Google Scholar 

  37. Luo WB, Chou SL, Wang JZ, Zhai YC, Liu HK (2015) A metal-free, free-standing, macroporous Graphene@g-C3N4 composite air electrode for high-energy lithium oxygen batteries. Small 11(23):2817–2824. https://doi.org/10.1002/smll.201403535

    Article  CAS  Google Scholar 

  38. Zhao PP, Hua X, Xu W, Luo W, Chen SL, Cheng GZ (2016) Metal–organic framework-derived hybrid of Fe3C nanorod-encapsulated, N-doped CNTs on porous carbon sheets for highly efficient oxygen reduction and water oxidation. Catal Sci Technol 6:6365–6371. https://doi.org/10.1039/c6cy01031h

    Article  CAS  Google Scholar 

  39. Jiang HL, Yao YF, Zhu YH, Liu YY, YH S, Yang XL, Li CZ (2016) Iron carbide nanoparticles encapsulated in Mesoporous Fe-N-doped graphene-like carbon hybrids as efficient bifunctional oxygen electrocatalysts. ACS Appl Mater Interfaces 7(38):21511–21520. https://doi.org/10.1021/acsami.5b06708

    Article  Google Scholar 

  40. Wang C, Ma R, Wu Q, Sun M, Wang Z (2014) Magnetic porous carbon as an adsorbent for the enrichment of chlorophenols from water and peach juice samples. J Chromatogr A 1361:60–66. https://doi.org/10.1016/j.chroma.2014.08.002

    Article  CAS  Google Scholar 

  41. Yang F, Shen R, Long Y, Sun X, Tang F, Cai Q, Yao S (2011) Magnetic microsphere confined ionic liquid as a novel sorbent for the determination of chlorophenols in environmental water samples by liquid chromatography. J Environ Monit 13(2):440–445. https://doi.org/10.1039/c0em00389a

    Article  CAS  Google Scholar 

Download references

Acknowledgements

Financial support from the National Natural Science Foundation of China (No. 31471643, 31571925 and 31671930), the Hebei “Double First Class Discipline” Construction Foundation for the Discipline of Food Science and Engineering of Hebei Agricultural University (2016SPGCA18), the Youth Scientific and Technological Research Foundation of the Department of Education of Hebei for Hebei Provincial Universities (QN2017085), and the Natural Science Foundation of Hebei Agricultural University (ZD201507) is gratefully acknowledged.

Author information

Author notes

  1. Xiaohuan Zang and Qingyun Chang contributed equally to this work.

Authors and Affiliations

  1. Department of Chemistry, College of Science, Hebei Agricultural University, Baoding, 071001, China

    Xiaohuan Zang, Qingyun Chang, Weiqian Liang, Tong Wu, Chun Wang & Zhi Wang

Authors
  1. Xiaohuan Zang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Qingyun Chang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Weiqian Liang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Tong Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Chun Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Zhi Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Qingyun Chang or Zhi Wang.

Ethics declarations

The author(s) declare that they have no competing interests.

Electronic supplementary material

ESM 1

(DOCX 801 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zang, X., Chang, Q., Liang, W. et al. Micro-solid phase extraction of chlorophenols using reduced graphene oxide functionalized with magnetic nanoparticles and graphitic carbon nitride as the adsorbent. Microchim Acta 185, 18 (2018). https://doi.org/10.1007/s00604-017-2546-z

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s00604-017-2546-z

Keywords

Search

Navigation