Synthesis, characterization, and application of chemically interconnected carbon nanotube monolithic sorbents by photopolymerization in polypropylene caps

  • Yolanda Oliva-Lamarca
  • Beatriz Fresco-Cala
  • Soledad CárdenasEmail author
Research Paper


A facile and convenient approach for the preparation of interconnected multiwalled carbon nanotube (MWCNT) monolithic sorbents in recycled plastic caps has been developed. The method, which was based on the photopolymerization of the individual MWCNTs via the formation of a W/O medium internal phase emulsion (40/60 w/w%), provides control over the size of pores, rigidity, and the mechanical stability of the final solid. Pluronic L121 was used as a surfactant containing the water phase inside it and, consequently, the organic and non-polar phase, in which the MWCNTs and the cross-linker were trapped, remained on the outside of the droplets. Optical microscopy and scanning electron microscopy (SEM) were employed to characterize the morphology of both the emulsions and the final solids, respectively. In addition, nitrogen intrusion porosimetry was performed in order to study how the specific surface area of the final monolithic solid changed (from 19.6 to 372.2 m2 g−1) with the variables involved in the polymerization step. To exemplify the great sorbent potential of the synthesized material, a colorimetric assay based on the retention of methylene blue within the interconnected MWCNT monolithic structure was carried out. Finally, following the positive results, the carbon nanotube-monolithic stirred caps were applied for the determination of chlorophenols in a biological matrix such as human urine, obtaining excellent recovery values (91–98%) and good precision (5.4–9.1%) under optimized extraction conditions.

Graphical abstract


Multiwalled carbon nanotubes Monolithic stirred unit UV light photografting Microextraction Macroscopic 3D structures 



The authors would like to thank the Central Service for Research Support (SCAI) of the University of Córdoba for the service provided to obtain the micrographs.

Funding information

Financial support from the Spanish Ministry of Science and Innovation (CTQ2017-83175R) is gratefully recognized.

Compliance with ethical standards

Informed consent was obtained from all individual participants involved in the study. The study has been approved by the appropriate ethics committee (Comité de Ética de la Investigación de Córdoba) and has been performed in accordance with the ethical standards.

Conflict of interest

The authors declare that they have no conflicts of interest.

Supplementary material

216_2019_1795_MOESM1_ESM.pdf (333 kb)
ESM 1 (PDF 333 kb)


  1. 1.
    Intrchom W, Mitra S. Analytical sample preparation, preconcentration and chromatographic separation on carbon nanotubes. Curr Opin Chem Eng. 2017;16:102–14.CrossRefGoogle Scholar
  2. 2.
    Harris PJ. Carbon nanotubes and related structures: new materials for the twenty-first century. AAPT. 2004.Google Scholar
  3. 3.
    Herrera-Herrera AV, González-Curbelo MÁ, Hernández-Borges J, Rodríguez-Delgado MÁ. Carbon nanotubes applications in separation science: a review. Anal Chim Acta. 2012;734:1–30.CrossRefGoogle Scholar
  4. 4.
    Speltini A, Merli D, Profumo A. Analytical application of carbon nanotubes, fullerenes and nanodiamonds in nanomaterials-based chromatographic stationary phases: a review. Anal Chim Acta. 2013;783:1–16.CrossRefGoogle Scholar
  5. 5.
    Liu L, Ma W, Zhang Z. Macroscopic carbon nanotube assemblies: preparation, properties, and potential applications. Small. 2011;7:1504–20.CrossRefGoogle Scholar
  6. 6.
    Du R, Zhao Q, Zhang N, Zhang J. Macroscopic carbon nanotube-based 3D monoliths. Small. 2015;11:3263–89.CrossRefGoogle Scholar
  7. 7.
    De Marco M, Markoulidis F, Menzel R, Bawaked SM, Mokhtar M, Al-Thabaiti SA, et al. Cross-linked single-walled carbon nanotube aerogel electrodes via reductive coupling chemistry. J Mater Chem A. 2016;4:5385–9.CrossRefGoogle Scholar
  8. 8.
    Schütt F, Signetti S, Krüger H, Röder S, Smazna D, Kaps S, et al. Hierarchical self-entangled carbon nanotube tube networks. Nat Commun. 2017;8:1215.CrossRefGoogle Scholar
  9. 9.
    Zou J, Liu J, Karakoti AS, Kumar A, Joung D, Li Q, et al. Ultralight multiwalled carbon nanotube aerogel. ACS Nano. 2010;4:7293–302.CrossRefGoogle Scholar
  10. 10.
    Lalwani G, Kwaczala AT, Kanakia S, Patel SC, Judex S, Sitharaman B. Fabrication and characterization of three-dimensional macroscopic all-carbon scaffolds. Carbon. 2013;53:90–100.CrossRefGoogle Scholar
  11. 11.
    Fresco-Cala B, Cárdenas S. Potential of nanoparticle-based hybrid monoliths as sorbents in microextraction techniques. Anal Chim Acta. 2018.Google Scholar
  12. 12.
    Iacono M, Connolly D, Heise A. Fabrication of a GMA-co-EDMA monolith in a 2.0 mm id polypropylene housing. Materials. 2016;9:263.CrossRefGoogle Scholar
  13. 13.
    Huang X, Chen L, Lin F, Yuan D. Novel extraction approach for liquid samples: stir cake sorptive extraction using monolith. J Sep Sci. 2011;34:2145–51.Google Scholar
  14. 14.
    Huang X, Wang Y, Yuan D, Li X, Nong S. New monolithic stir-cake-sorptive extraction for the determination of polar phenols by HPLC. Anal Bioanal Chem. 2013;405:2185–93.CrossRefGoogle Scholar
  15. 15.
    Lin F, Nong S, Huang X, Yuan D. Sensitive determination of organic acid preservatives in juices and soft drinks treated by monolith-based stir cake sorptive extraction and liquid chromatography analysis. Anal Bioanal Chem. 2013;405:2077–81.CrossRefGoogle Scholar
  16. 16.
    Lucena R, Simonet B, Cárdenas S, Valcárcel M. Potential of nanoparticles in sample preparation. J Chromatogr A. 2011;1218:620–37.CrossRefGoogle Scholar
  17. 17.
    Jiménez-Soto JM, Lucena R, Cárdenas S, Valcárcel M. Solid phase (micro) extraction tools based on carbon nanotubes and related nanostructures. 2010.Google Scholar
  18. 18.
    Cárdenas S, Lucena R. Recent advances in extraction and stirring integrated techniques. Separations. 2017;4:6.CrossRefGoogle Scholar
  19. 19.
    Lucena R. Extraction and stirring integrated techniques: examples and recent advances. Anal Bioanal Chem. 2012;403:2213–23.CrossRefGoogle Scholar
  20. 20.
    Ahlborg UG, Thunberg TM, Spencer HC. Chlorinated phenols: occurrence, toxicity, metabolism, and environmental impact. CRC Crit Rev Toxicol. 1980;7:1–35.CrossRefGoogle Scholar
  21. 21.
    Honda M, Kannan K. Biomonitoring of chlorophenols in human urine from several Asian countries, Greece and the United States. Environ Pollut. 2018;232:487–93.CrossRefGoogle Scholar
  22. 22.
    Fresco-Cala B, Cárdenas S, Herrero-Martínez JM. Preparation of porous methacrylate monoliths with oxidized single-walled carbon nanohorns for the extraction of nonsteroidal anti-inflammatory drugs from urine samples. Microchim Acta. 2017;6:1863–71.CrossRefGoogle Scholar
  23. 23.
    Fresco-Cala B, Mompó-Roselló O, Simó-Alfonso EF, Cárdenas S, Herrero-Martínez JM. Carbon nanotube-modified monolithic polymethacrylate pipette tips for (micro)solid-phase extraction of antidepressants from urine samples. Microchim Acta. 2018;185:127.CrossRefGoogle Scholar
  24. 24.
    Garcia-Valverde MT, Lucena R, Cardenas S, Valcarcel M. 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. 2016;1464:42–9.CrossRefGoogle Scholar
  25. 25.
    Fresco-Cala B, Cárdenas S. Preparation of macroscopic carbon nanohorn-based monoliths in polypropylene tips by medium internal phase emulsion for the determination of parabens in urine samples. Talanta. 2019;198:295–301.CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Yolanda Oliva-Lamarca
    • 1
  • Beatriz Fresco-Cala
    • 1
  • Soledad Cárdenas
    • 1
    Email author
  1. 1.Departamento de Química Analítica, Instituto Universitario de Investigación en Química Fina y Nanoquímica IUNANUniversidad de CórdobaCórdobaSpain

Personalised recommendations