Surface Heterogeneity Effect on Azodyes Adsorption on to Multiwalled Carbon Nanotubes
DOI:
https://doi.org/10.66000/3110-9772.2025.01.04Keywords:
Isothermal titration calorimetry, Surface modification, Wastewater treatmentAbstract
The adsorption thermodynamics of the azo dyes acid yellow 42 (AY), acid black 210 (AB) and acid green 68:1 (AG) onto pristine multi-walled carbon nanotubes (MWCNTs) was evaluated by determining the following thermodynamic adsorption parameters: adsorption standard free energy (ΔadsGº), adsorption standard enthalpy (ΔadsH°) and adsorption standard entropy (ΔadsS°). The adsorption of all azo dyes onto MWCNTs was a thermodynamically spontaneous process and the decrease in ΔadsGº values follows the order AG < AB < AY. The increase of oxidized sites on MWCNT surface enabled a decrease of adsorption capacity of AY, compared with raw MWCNT. The adsorption of all azodyes is directly proportional with the ionic strength of solution. Isothermal Titration Calorimetry (ITC) data show that the adsorption process is enthalpically driven for all azodyes with contribution of entropy change in the spontaneity of AY adsorption onto MWCNT. The surface of the MWCNT has sites with different energetic potentials that allow electrostatic interactions with azo dye compounds, not only π−π dispersion interactions. The ITC technique provides a more reliable interpretation of the surface chemistry of MWCNT and of the interactions in an adsorption process in comparison with the van’t Hoff approximation.
References
Machado FM, Bergmann CP, Fernandes THM, Lima EC, Royer B, Calvete T, Fagan SB. Adsorption of Reactive Red M-2BE dye from water solutions by multi-walled carbon nanotubes and activated carbon. J Hazard Mater 2011; 192(3): 1122-31. https://doi.org/10.1016/j.jhazmat.2011.06.020
Nethaji S, Sivasamy A. Adsorptive removal of an acid dye by lignocellulosic waste biomass activated carbon: Equilibrium and kinetic studies. Chemosphere 2011; 82(10): 1367-72. https://doi.org/10.1016/j.chemosphere.2010.11.080
Wang L. Application of activated carbon derived from ‘waste’ bamboo culms for the adsorption of azo disperse dye: Kinetic, equilibrium and thermodynamic studies. J Environ Manage 2012; 102: 79-87. https://doi.org/10.1016/j.jenvman.2012.02.019
Jiang R, Fu YQ, Zhu HY, Yao J, Xiao L. Removal of methyl orange from aqueous solutions by magnetic maghemite/chitosan nanocomposite films: Adsorption kinetics and equilibrium. J Appl Polym Sci 2012; 125: E540-49. https://doi.org/10.1002/app.37003
Mahmoodi NM, Najafi F. Preparation of surface modified zinc oxide nanoparticle with high capacity dye removal ability. Mater Res Bull 2012; 47: 1800-09. https://doi.org/10.1016/j.materresbull.2012.03.026
Zahra A, Imran M, Kanwal F. Comparative Adsorption Studies of Methyl Orange Using Different Varieties of Melon Seeds as Adsorbents. Asian J Chem 2012; 24(6): 2668-70.
Wang F, Li C, Yu JC. Hexagonal tungsten trioxide nanorods as a rapid adsorbent for methylene blue. Sep Purif Technol 2012; 91: 103-07. https://doi.org/10.1016/j.seppur.2011.12.001
Zhao S, Zhou F, Li L, Cao M, Zuo D, Liu H. Removal of anionic dyes from aqueous solutions by adsorption of chitosan-based semi-IPN hydrogel composites. Composites: Part B-Eng 2012; 43(3): 1570-78. https://doi.org/10.1016/j.compositesb.2012.01.015
Hameed BH, Ahmad AL, Latiff KNA. Adsorption of basic dye (methylene blue) onto activated carbon prepared from rattan sawdust. Dyes Pigments, 2007; 75: 143-49. https://doi.org/10.1016/j.dyepig.2006.05.039
Mane VS, Mall ID, Srivastava VC. Use of bagasse fly ash as an adsorbent for the removal of brilliant green dye from aqueous solution. Dyes Pigments, 2007; 73: 269-78. https://doi.org/10.1016/j.dyepig.2005.12.006
Yao Y, Xu F, Chen M, Xu Z, Zhu Z. Adsorption behavior of methylene blue on carbon nanotubes. Bioresource Technol, 2010; 101: 3040-46. https://doi.org/10.1016/j.biortech.2009.12.042
Gong JL, Wang B, Zeng GM, Yang CP, Niu CG, Niu QY, ZhouWJ, Liang Y. Removal of cationic dyes from aqueous solution using magnetic multi-wall carbon nanotube nanocomposite as adsorbent. J Hazard Mater, 2009; 164: 1517-22. https://doi.org/10.1016/j.jhazmat.2008.09.072
Kuo CY, Wu CH, Wu JY. Adsorption of direct dyes from aqueous solutions by carbon nanotubes: Determination of equilibrium, kinetics and thermodynamics parameters. J Colloid and Interf Sci, 2008; 327: 308-15. https://doi.org/10.1016/j.jcis.2008.08.038
Mishra AK, Arockiadoss T, Ramaprabhu S. Study of removal of azo dye by functionalized multi walled carbon nanotubes. Chem Eng J, 2010; 162: 1026-34. https://doi.org/10.1016/j.cej.2010.07.014
Wu CH. Adsorption of reactive dye onto carbon nanotubes: Equilibrium, kinetics and thermodynamics. J Hazard Mater, 2007; 144: 93-100. https://doi.org/10.1016/j.jhazmat.2006.09.083
Shapour R, Mehrorang G, Kianoosh M. Multiwalled carbon nanotubes as efficient adsorbent for the removal of congo red. Fresen Environ Bull, 2011; 20(10): 2514-20.
El-Sheikh AH. Effect of oxidation of activated carbon on its enrichment efficiency of metal ions: Comparison with oxidized and non-oxidized multi-walled carbon nanotubes. Talanta, 2008; 75: 127-34. https://doi.org/10.1016/j.talanta.2007.10.039
Salam MA, Burk RC. Thermodynamics of pentachlorophenol adsorption from aqueous solutions by oxidized multi-walled carbon nanotubes. Appl Surf Sci, 2008; 255: 1975-81. https://doi.org/10.1016/j.apsusc.2008.06.168
Christensen JJ; Hansen LD, Izatt RM. Handbook of proton ionization heats and related thermodynamic quantities; New York: John Wiley and Sons; 1976.
Dąbrowski A, Podkościelny P, Hubicki Z, Barczak M. Adsorption of phenolic compounds by activated carbon—a critical review. Chemosphere, 2005; 58: 1049-70. https://doi.org/10.1016/j.chemosphere.2004.09.067
Liao P, Malik I Z, Zhang W, Yuan S, Tong M, Wang K, Bao, J. Adsorption of dyes from aqueous solutions by microwave modified bamboo charcoal. Chemical Engineering Journal, 195-196, 339-346, 2012. https://doi.org/10.1016/j.cej.2012.04.092
Lin D, Xing B. Adsorption of phenolic compounds by carbon nanotubes: role of aromaticity and substitution of hydroxyl groups, Environ. Sci. Technol., 2008; 42: 7254-59. https://doi.org/10.1021/es801297u
Yan Y, Zhang M, Gong K, Su L, Guo Z, Mao L. Adsorption of Methylene Blue Dye onto Carbon Nanotubes : A Route to an electrochemically functional nanostructure and its layer-by-layer assembled nanocomposite, Chem. Mater., 2005; 17: 3457-3463. https://doi.org/10.1021/cm0504182
Liu CH, Li JJ, Zhang HL, Li BR, Guo Y. Structure dependent interaction between organic dyes and carbon nanotubes, Colloid. Surf. A, 2008; 313: 9-12. https://doi.org/10.1016/j.colsurfa.2007.04.062
Wang S, Ng CW, Wang W, Li Q, Hao Z. Synergistic and competitive adsorption of organic dyes on multiwalled carbon nanotubes. Chem. Eng. J., 2012; 197: 34-40. https://doi.org/10.1016/j.cej.2012.05.008
R.L. Lavall, C.R. Oliveira, A.B. Mageste, M.C.H. da Silva, L.H.M. da Silva. Adsorção de compostos fenólicos em nanotubos de carbono de paredes múltiplas: uma abordagem termodinâmica. Proceedings of the 34ª Reunião Anual da Sociedade Brasileira de Química; 2012 May 23-26; Florianóplis, Brazil.