Skip to main content Accessibility help

Effective removal of anionic and cationic dyes by kaolinite and TiO2/kaolinite composites

  • W. Hajjaji (a1) (a2), S. Andrejkovičová (a1), R.C. Pullar (a3), D.M. Tobaldi (a3), A. Lopez-Galindo (a4), F. Jammousi (a5), F. Rocha (a1) and J.A. Labrincha (a3)...


The present study investigated the removal of methylene blue (MB) and orange II (OII) dyes from synthetic wastewater by means of adsorption and photocatalysis using natural kaolins. ForMB adsorption, the raw kaolinite-rich samples showed the greatest adsorption capacity, with rapid uptake (90% after 20 min). The experimental results were fitted better using the Langmuir isotherm model parameters compared to the Freundlich model, suggesting that the adsorption corresponds to monolayer coverage of MB molecules over the kaolinite surface. For OII, neither the Langmuir nor the Freundlich model gave reliable results, because the adsorption of anionic dye molecules by the clayey particles is not favoured.

Mixtures of kaolinite/Degussa TiO2 were also prepared, and their photocatalytic properties under UVlight exposure were investigated. Decolourization of MB solutions was observed, even in a mixture with low TiO2 content. This is related to the combined effect of adsorption and photocatalysis and, unlike the pure clay samples, the efficiency of such mixtures against OII was only slightly weaker (80–94%).

For TiO2-impregnated clays, with the kaolinite layers separated by sol-gel TiO2 particles, the MB removal was slow and effective only after >24 h due to the complexity of the bonding of MB molecules. On the other hand, the removal performance against OII solutions was very efficient (nearly 100%) within only 2 h. This excellent performance was attributed to morphological changes in clay particles.


Corresponding author



Hide All
Aksu, Z. (2005) Application of biosorption for the removal of organic pollutants: a review. Process Biochemistry, 40, 9971026.
Al-Futaisi, A., Jamrah, A. & Al-Hanai, R. (2007) Aspects of cationic dye molecule adsorption to palygorskite. Desalination, 214, 327342.
Ali, I. & Gupta, V.K. (2007) Advances in water treatment by adsorption technology. Nature Protocols, 1, 26612667.
Brunauer, S., Emmett, P.H. & Teller, E.J. (1938) Adsorption of gases on multimolecular layers. Journal of the American Chemical Society, 60, 309319.
Carp, O., Huisman, C.L. & Reller, A. (2004) Photoinduced reactivity of titanium dioxide. Progress in Solid State Chemistry, 32, 33177.
Chong, M.N., Vimonses, V., Lei, S., Jin, B., Chow, C. & Saint, C. (2009) Synthesis and characterisation of novel titania impregnated kaolinite nano-photocatalyst. Microporous and Mesoporous Materials, 117, 233242.
Christie, R.M. (2007) Environmental Aspects of Textile Dyeing. Woodhead, Boca Raton, Florida, and Cambridge, UK.
Eren, E. & Afsin, B. (2008) Investigation of a basic dye adsorption from aqueous solution onto raw and pre-treated bentonite surfaces. Dyes and Pigments, 76, 220225.
Fujishima, A., Rao, T.N. & Tryk, D.A. (2000) Titanium dioxide photocatalysis. Journal of Photochemistry and Photobiology C: Photochemistry Reviews, 1, 121.
Fujishima, A., Zhang, X. & Tryk, D.A. (2008) TiO2 photocatalysis and related surface phenomena. Surface Science Reports, 63, 515582.
Gao, X., Liu, J. & Chen, P. (2009) Nitrogen-doped titania photocatalysts induced by shock wave. Materials Research Bulletin, 44, 18421845.
Gupta, V.K. & Suhas (2009) Application of low-cost adsorbents for dye removal: a review. Journal of Environmental Management, 90, 23132342.
Herrmann, J.-M., Duchamp, C., Karkmaz, M., Hoai Bui, Thu, Lachheb, H., Puzenat, E. & Guillard, C. (2007) Environmental green chemistry as defined by photocatalysis. Journal of Hazardous Materials, 146, 624629.
Hunger, K. (2002) Industrial Dyes. Chemistry Properties, Applications., Wiley-VCH, Weinheim, Germany.
Kuznetsov, A.Y., Machado, R., Gomes, L.S., Achete, C.A., Swamy, V., Muddle, B.C. & Prakapenka, Y. (2009) Size dependence of rutile TiO2 lattice parameters determined via simultaneous size, strain, and shape modeling. Applied Physics Letters, 94, 193-117.
Li, G., Li, L., Boerio-Goates, I. & Woodfield, B.F. (2005) High purity anatase TiO2 nanocrystals: Near room-temperature synthesis, grain growth kinetics, and surface hydration chemistry. Journal of the American Chemical Society, 127, 86598666.
Liu, J.J., Dong, M.Q., Zuo, S.L. & Yu, Y.C. (2009) Solvothermal preparation of TiO2/montmorillonite and photocatalytic activity. Applied Clay Science, 43, 156159.
Lopez-Galindo, A., Torres-Ruis, I. & Gonazlez-Lopez, J.M. (1996) Mineral quantification in sepiolite-palygors-kite deposits using X-ray diffraction and chemical data. Clay Minerals, 31, 217224.
Lv, K., Zuo, H., Sun, J., Deng, K., Liu, S., Li, X. & Wang, D. (2009) (Bi, C and N) codoped TiO2 nanoparticles. Journal of Hazardous Materials, 161, 396401.
Moore, D.M. & Reynolds, R.C. (1989) X-ray diffraction and Identification and Analysis of Clay Minerals. Oxford University Press, New York.
Ohtani, B., Prieto-Mahaney, O.O., Li, D. & Abe, R. (2010) What is Degussa (Evonik) P25? Crystalline composition analysis, reconstruction from isolated pure particles and photocatalytic activity test. Journal of Photochemistry and Photobiology A: Chemistry, 216, 179182.
Ozcan, A., Oncu, E.M. & Ozcan, A.S. (2006) Kinetics, isotherm and thermodynamic studies of adsorption of Acid Blue 193 from aqueous solutions onto natural sepiolite. Colloids and Surfaces A, 277, 9097.
Quintelas, C., Figueiredo, H. & Tavares, T. (2011) The effect of clay treatment on remediation of diethylketone contaminated wastewater: Uptake, equilibrium and kinetic studies. Journal of Hazardous Materials, 186, 12411248.
Robinson, T., McMullan, G., Marchant, R. & Nigam, P. (2001) Remediation of dyes in textile effluent: a critical review on current treatment technologies with a proposed alternative. Bioresource Technology, 77, 247255.
Santos, S.C.R., Boaventura, R.A.R. & Oliveira, Á.F.M. (2006) Preliminary study on the adsorption of the cationic dye Astrazon red by a Portuguese bentonite. Pp. 111-116 in: Combined and Hybrid Adsorbents. NATO Security through Science Series.
Slokar, Y.M. & Majcen-Le Marechal, A. (1998) Methods of decoloration of textile wastewaters. Dyes and Pigments, 37, 33535.
Tobaldi, D.M., Pullar, R.C., Gualtieri, A.F., Seabra, M.P. & Labrincha, J.A. (2013a) Sol-gel synthesis and characterisation of pure, W-, Ag-, and W/Ag co-doped TiO2 nanopowders. Chemical Engineering Journal, 214, 364375.
Tobaldi, D.M., Pullar, R.C., Gualtieri, A.F., Seabra, M.P. & Labrincha, J.A. (2013b) Phase composition, crystal structure and micro structure of silver and tungsten doped TiO2 nanopowders, with tuneable photochromic behavior. Acta Materialia, 61, 55715585.
Wang, S., Li, H., Xie, S., Liu, S. & Xu, L. (2006) Physical and chemical regeneration of zeolitic adsorbents for dye removal in wastewater treatment. Chemosphere, 65, 8287.
Wang, S., Ang, H.M. & Tadé, M.O. (2008) Novel applications of red mud as coagulant, adsorbent and catalyst for environmentally benign processes. Chemosphere, 72, 16211635.
Zevin, L.S. & Kimmel, G. (1995) Quantitative X-ray Diffractometry. Springer, New York.


Effective removal of anionic and cationic dyes by kaolinite and TiO2/kaolinite composites

  • W. Hajjaji (a1) (a2), S. Andrejkovičová (a1), R.C. Pullar (a3), D.M. Tobaldi (a3), A. Lopez-Galindo (a4), F. Jammousi (a5), F. Rocha (a1) and J.A. Labrincha (a3)...


Full text views

Total number of HTML views: 0
Total number of PDF views: 0 *
Loading metrics...

Abstract views

Total abstract views: 0 *
Loading metrics...

* Views captured on Cambridge Core between <date>. This data will be updated every 24 hours.

Usage data cannot currently be displayed