Skip to main content
SpringerLink
Log in

Heterogeneity of multiwalled carbon nanotubes based on adsorption of simple aromatic compounds from aqueous solutions

  • Published:
Adsorption Aims and scope Submit manuscript

Abstract

The surface heterogeneity of multiwalled carbon nanotubes (MWCNTs) is studied on the basis of adsorption isotherms from dilute aqueous phenol and dopamine solutions at various pH values. The generalized Langmuir–Freundlich isotherm equation was applied to investigate the cooperative effect of the surface heterogeneity and the lateral interactions between the adsorbates. The theoretical isosteric heats of adsorption were obtained assuming that the heat of adsorption profile reveals both the energetic heterogeneity of the adsorption system and the strength of the interactions between the neighboring molecules. The adsorption energy distribution functions were calculated by using algorithm based on a regularization method. The great advantage of this method is that the regularization makes no assumption about the shape of the obtained energy distribution functions. Analysis of the isosteric heats of adsorption for MWCNTs showed that the influence of the surface heterogeneity is much stronger than the role of the lateral interactions. The most typical adsorption heat is 20–22 kJ/mol for both phenol and dopamine. After purification of nanotubes, heat value for phenol dropped to 16–17 kJ/mol. The range of the energy distribution is only slightly influenced by the surface chemistry of the nanotubes in the aqueous conditions.

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
Fig. 5
Fig. 6

Similar content being viewed by others

References

  • Abdel Salam, M., Mokhtar, M., Basahel, S.N., Al-Thabaiti, S.A., Obaid, A.Y.: Removal of chlorophenol from aqueous solutions by multi-walled carbon nanotubes: kinetic and thermodynamic studies. J. Alloys Compd. 500, 87–92 (2010)

    Article  Google Scholar 

  • Agnihotri, S., Rostam-Abadi, M., Rood, M.J.: Temporal changes in nitrogen adsorption properties of single-walled carbon nanotubes. Carbon 42, 2699–2710 (2004)

    Article  CAS  Google Scholar 

  • Arasteh, R., Masoumi, M., Rashidi, A.M., Moradi, L., Samimi, V., Mostafavi, S.T.: Adsorption of 2-nitrophenol by multi-wall carbon nanotubes from aqueous solutions. Appl. Surf. Sci. 256, 4447–4455 (2010)

    Article  CAS  Google Scholar 

  • Bendjemil, B., Borowiak-Palen, E., Graff, A., Pichler, T., Guerioune, M., Fink, J., Knupfer, M.: Elimination of metal catalyst and carbon-like impurities from single-wall carbon nanotube raw material. Appl. Phys. A 78, 311–314 (2004)

    Article  CAS  Google Scholar 

  • Cerofolini, G.F.: Localized adsorption on heterogeneous surfaces. Thin Solid Films 23, 129–152 (1974)

    Article  CAS  Google Scholar 

  • Chen, W., Duan, L., Wang, L.L., Zhu, D.Q.: Adsorption of hydroxyl- and amino-substituted aromatics to carbon nanotubes. Environ. Sci. Technol. 42, 6862–6868 (2008)

    Article  CAS  Google Scholar 

  • Dąbrowski, A., Podkościelny, P., Hubicki, Z., Barczak, M.: Adsorption of phenolic compounds by activated carbon—a critical review. Chemosphere 58, 1049–1070 (2005)

    Article  Google Scholar 

  • Deryło-Marczewska, A., Miroslaw, K., Marczewski, A.W., Sternik, D.: Studies of adsorption equilibria and kinetics of o-, m-, p-nitro- and chlorophenols on microporous carbons from aqueous solutions. Adsorption 16, 359–375 (2010)

    Article  Google Scholar 

  • Fernandez, E., Hugi-Cleary, D., Lopez-Ramon, M.V., Stoeckli, F.: Adsorption of phenol from dilute and concentrated aqueous solutions by activated carbons. Langmuir 19, 9719–9723 (2003)

    Article  CAS  Google Scholar 

  • Fowler, R.H., Guggenheim, E.A.: Statistical Thermodynamics. Cambridge University Press, London (1949)

    Google Scholar 

  • Giles, C.H., Smith, D., Huitson, A.: A general treatment and classification of the solute adsorption isotherm. I. Theoretical. J. Colloid Interface Sci. 47, 755–765 (1974)

    Article  CAS  Google Scholar 

  • Heuchel, M., Bräuer, P., von Szombathely, M., Messow, U., Einicke, W.D., Jaroniec, M.: Evaluation of the energy distribution function from liquid/solid adsorption measurements. Langmuir 9, 2547–2554 (1993)

    Article  CAS  Google Scholar 

  • Heuchel, M., Jaroniec, M.: Comparison of energy distributions calculated for active carbons from benzene gas/solid and liquid/solid adsorption data. Langmuir 11, 1297–1303 (1995)

    Article  CAS  Google Scholar 

  • Hua, C., Zhang, R.H., Li, L., Zheng, X.Y.: Adsorption of phenol from aqueous solutions using activated carbon prepared from crofton weed. Desalin. Water Treat. 37, 230–237 (2012)

    Article  CAS  Google Scholar 

  • Ishimitsu, T., Hirose, S., Sakurai, H.: Microscopic acid dissociation constants of 3,4-dihydroxyphenethylamine (dopamine). Chem. Pharm. Bull. 26, 74–78 (1978)

    Article  CAS  Google Scholar 

  • Jaroniec, M., Madey, E.: Physical Adsorption on Heterogeneous Solids. Elsevier, Amsterdam (1988)

    Google Scholar 

  • Ji, L., Shao, Y., Xu, Z., Zheng, S., Zhu, D.: Adsorption of monoaromatic compounds and pharmaceutical antibiotics on carbon nanotubes activated by KOH etching. Environ. Sci. Technol. 44, 6429–6436 (2010)

    Article  CAS  Google Scholar 

  • László, K., Szűcs, A.: Surface characterization of polyethyleneterephthalate PET based activated carbon and the effect of pH on its adsorption capacity from aqueous phenol and 2,3,4-trichlorophenol solutions. Carbon 39, 1945–1953 (2001)

    Article  Google Scholar 

  • László, K., Podkościelny, P., Dąbrowski, A.: Heterogeneity of polymer-based active carbons in adsorption of aqueous solutions of phenol and 2,3,4-trichlorophenol. Langmuir 19, 5287–5294 (2003a)

    Article  Google Scholar 

  • László, K., Tombácz, E., Kerepesi, P.: Surface chemistry of nanoporous carbon and the effect of pH on adsorption from aqueous phenol and 2,3,4-trichlorophenol solutions. Colloids Surf. A 230, 13–22 (2003b)

    Article  Google Scholar 

  • László, K., Podkościelny, P., Dąbrowski, A.: Heterogeneity of activated carbons with different surface chemistry in adsorption of phenol from aqueous solutions. Appl. Surf. Sci. 252, 5752–5762 (2006)

    Article  Google Scholar 

  • Lehman, J.H., Terrones, M., Mansfield, E., Hurst, K.E., Meunier, V.: Evaluating the characteristics of multiwall carbon nanotubes. Carbon 49, 2581–2602 (2011)

    Article  CAS  Google Scholar 

  • Li, M.H., Hsieh, T.C., Doong, R.A., Huang, C.P.: Tuning the adsorption capability of multi-walled carbon nanotubes to polar and non-polar organic compounds by surface oxidation. Sep. Purif. Technol. 117, 98–103 (2013)

    Article  CAS  Google Scholar 

  • Liao, Q., Sun, J., Gao, L.: Adsorption of chlorophenols by multi-walled carbon nanotubes treated with HNO3 and NH3. Carbon 46, 544–561 (2008)

    Article  Google Scholar 

  • Lin, D., Xing, B.: Adsorption of phenolic compounds by carbon nanotubes: role of aromaticity and substitution of hydroxyl groups. Environ. Sci. Technol. 42, 7254–7259 (2008)

    Article  CAS  Google Scholar 

  • Marczewski, A.W.: Extension of Langmuir kinetics in dilute solutions to include lateral interactions according to regular solution theory and Kiselev association model. J. Colloid Interface Sci. 361, 603–611 (2011)

    Article  CAS  Google Scholar 

  • Marczewski, A.W., Deryło-Marczewska, A., Slota, A.: Adsorption and desorption kinetics of benzene derivatives on mesoporous carbons. Adsorption 19, 391–406 (2013)

    Article  CAS  Google Scholar 

  • Nieszporek, K., Banach, T.: Adsorption of binary gas mixtures on strongly heterogeneous surfaces. Sep. Sci. Technol. 47, 482–493 (2012)

    Article  CAS  Google Scholar 

  • Nieszporek, K., Drach, M., Podkościelny, P.: Theoretical studies of hydrocarbon homologous series adsorption on activated carbons: adsorption equilibria and calorimetry. Sep. Purif. Technol. 69, 174–184 (2009)

    Article  CAS  Google Scholar 

  • Pan, B., Xing, B.S.: Adsorption mechanisms of organic chemicals on carbon nanotubes. Environ. Sci. Technol. 42, 9005–9013 (2008)

    Article  CAS  Google Scholar 

  • Płaziński, W., Rudziński, W.: Modeling the effect of pH on kinetics of heavy metal ion biosorption. A theoretical approach based on the statistical rate theory. Langmuir 25, 298–304 (2009a)

    Article  Google Scholar 

  • Płaziński, W., Rudziński, W.: Modeling the effect of surface heterogeneity in equilibrium of heavy metal ion biosorption by using the ion exchange model. Environ. Sci. Technol. 43, 7465–7471 (2009b)

    Article  Google Scholar 

  • Podkościelny, P., Dąbrowski, A., Bülow, M.: Heterogeneity of nanoporous solids in adsorption from solutions-evaluation of energy distribution functions for adsorption in micropores of activated carbons by a comparative method. Appl. Surf. Sci. 196, 312–321 (2002)

    Article  Google Scholar 

  • Podkościelny, P., László, K.: Heterogeneity of activated carbons in adsorption of aniline from aqueous solutions. Appl. Surf. Sci. 253, 8762–8771 (2007)

    Article  Google Scholar 

  • Podkościelny, P.: The cooperative effect of the surface heterogeneity and of the lateral interactions between adsorbed molecules on adsorption of simple aromatic compounds from dilute aqueous solutions on activated carbons. Colloids Surf. A 318, 227–237 (2008)

    Article  Google Scholar 

  • Podkościelny, P., Nieszporek, K.: Adsorption of phenols from aqueous solutions: equilibria, calorimetry and kinetics of adsorption. J. Colloid Interface Sci. 354, 282–291 (2011)

    Article  Google Scholar 

  • Postma, A., Yan, Y., Wang, Y., Zelikin, A.N., Tjipto, E., Caruso, F.: Self-polymerization of dopamine as a versatile and robust technique to prepare polymer capsules. Chem. Mater. 21, 3042 (2009)

    Article  CAS  Google Scholar 

  • Radovic, L.R., Moreno-Castilla, C., Rivera-Utrilla, J.: Carbon materials as adsorbents in aqueous solutions. In: Radovic, L.R. (ed.) Chemistry of Physics of Carbon, vol. 27, pp. 227–405. Marcel Dekker, New York (2001)

    Google Scholar 

  • Rudziński, W., Nieszporek, K., Moon, H., Rhee, H.-K.: Fundamentals of mixed-gas adsorption on heterogeneous solid surfaces. Heterog. Chem. Rev. 1, 275–308 (1994)

    Google Scholar 

  • Rudziński, W., Nieszporek, K., Cases, J.M., Michot, L.I., Villieras, F.: A new molecular probe method to study surface topography of carbonaceous solid surfaces. Langmuir 12, 170–182 (1996)

    Article  Google Scholar 

  • Rudziński, W., Płaziński, W.: Kinetics of metal ions adsorption at heterogeneous solid/solution interfaces: a theoretical treatment based on statistical rate theory. J. Colloid Interface Sci. 327, 36–43 (2008)

    Article  Google Scholar 

  • Shen, X.-E., Shan, X.-Q., Dong, D.-M., Hua, X.-Y., Owens, G.: Kinetics and thermodynamics of sorption of nitroaromatic compounds to as-grown and oxidized multiwalled carbon nanotubes. J. Colloid Interface Sci. 330, 1–8 (2009)

    Article  CAS  Google Scholar 

  • Sheng, G.D., Shao, D.D., Ren, X.M., Wang, X.Q., Li, J.X., Chen, Y.X., Wang, X.K.: Kinetics and thermodynamics of adsorption of ionizable aromatic compounds from aqueous solutions by as-prepared and oxidized multiwalled carbon nanotubes. J. Hazard. Mater. 178, 505–516 (2010)

    Article  CAS  Google Scholar 

  • Soliman, E.M., Albishri, H.M., Marwani, H.M., Batterjee, M.G.: Removal of 2-chlorophenol from aqueous solutions using activated carbon-impregnated Fe(III). Desalin. Water Treat. 51, 6655–6662 (2013)

    Article  CAS  Google Scholar 

  • Star, A., Han, T.R., Gabriel, J.-C.P., Bradley, K., Gruner, G.: Interaction of aromatic compounds with carbon nanotubes: correlation to the Hammett parameter of the substituent and measured carbon nanotube FET response. Nano Lett. 3, 1421–1423 (2003)

    Article  CAS  Google Scholar 

  • Stoeckli, F., López-Ramón, M.V., Moreno-Castilla, C.: Adsorption of phenolic compounds from aqueous solutions, by activated carbons, described by the Dubinin–Astakhov equation. Langmuir 17, 3301–3306 (2001)

    Article  CAS  Google Scholar 

  • Terzyk, A.P.: Molecular properties and intermolecular forces—factors balancing the effect of carbon surface chemistry in adsorption of organics from dilute aqueous solutions. J. Colloid Interface Sci. 275, 9–29 (2004)

    Article  CAS  Google Scholar 

  • Tóth, A., Törőcsik, A., Tombácz, E., Oláh, E., Heggen, M., Li, C., Klumpp, E., Geissler, E., László, K.: Interaction of phenol and dopamine with commercial MWCNTs. J. Colloid Interface Sci. 364, 469–475 (2011)

    Article  Google Scholar 

  • Tóth, A., Törőcsik, A., Tombácz, E., László, K.: Competitive adsorption of phenol and 3-chlorophenol on purified MWCNTs. J. Colloid Interface Sci. 387, 244–249 (2012)

    Article  Google Scholar 

  • Tóth, A., László, K.: Water adsorption by carbons. Hydrophobicity and hydrophilicity. In: Tascon, J.M.D. (ed.) Novel Carbon Adsorbents, p. 147. Elsevier Ltd, Oxford (2012)

    Chapter  Google Scholar 

  • von Szombathely, M., Bräuer, P., Jaroniec, M.: The solution of adsorption integral equations by means of the regularization method. J. Comput. Chem. 13, 17–32 (1992)

    Article  Google Scholar 

  • Wang, Z., Shirley, M.D., Meikle, S.T., Whitby, R.L.D., Mikhalovsky, S.V.: The surface acidity of acid oxidised multi-walled carbon nanotubes and the influence of in situ generated fulvic acids on their stability in aqueous dispersions. Carbon 47, 73–79 (2009)

    Article  CAS  Google Scholar 

  • Wiśniewski, M., Terzyk, A.P., Gauden, P.A., Kaneko, K., Hattori, Y.: Removal of internal caps during hydrothermal treatment of bamboo-like carbon nanotubes and application of tubes in phenol adsorption. J. Colloid Interface Sci. 381, 36–42 (2012)

    Article  Google Scholar 

  • Woods, L.M., Badescu, S.C., Reinecke, T.L.: Adsorption of simple benzene derivatives on carbon nanotubes. Phys. Rev. B 75, 155415 (2007)

    Article  Google Scholar 

  • Yang, K., Wu, W., Jing, Q., Zhu, L.: Aqueous adsorption of aniline, phenol, and their substitutes by multi-walled carbon nanotubes. Environ. Sci. Technol. 42, 7931–7936 (2008)

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Faculty of Chemistry, Department of Theoretical Chemistry, Maria Curie-Skłodowska University, pl. M. Curie-Skłodowskiej 3, 20-031, Lublin, Poland

    Przemysław Podkościelny & Krzysztof Nieszporek

  2. Department of Physical Chemistry and Materials Science, Budapest University of Technology and Economics, 1521, Budapest, Hungary

    Ajna Tóth, Barbara Berke & Krisztina László

Authors
  1. Przemysław Podkościelny
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Ajna Tóth
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Barbara Berke
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Krisztina László
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Krzysztof Nieszporek
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Przemysław Podkościelny.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 401 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Podkościelny, P., Tóth, A., Berke, B. et al. Heterogeneity of multiwalled carbon nanotubes based on adsorption of simple aromatic compounds from aqueous solutions. Adsorption 20, 789–800 (2014). https://doi.org/10.1007/s10450-014-9622-z

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10450-014-9622-z

Keywords

Search

Navigation