TiO2 Nanoparticles for Removal of Malachite Green Dye from Waste Water
ABSTRACT
In this research, we present a simple and successful route for synthesis titania nanoparticles by controlled solgel progress. Chitosan as bio-template is involved in the progress of preparation to increase the surface area and manipulate defined particle and pore structure. The crystalline behavior and the nanostructure of the prepared nanoparticles were investigated using X-ray diffraction [XRD] and transmission electron microscope [TEM]. The crystalline results have pointed out the predominant existence of anatase phase that reveals the successful role of chitosan in stabilizing titania nanoparticles and preventing the growth of these particles into rutile phase. It is obvious to notice that a change in sample crystallography from anatase to completely amorphous nanoparticles upon adsorption of malachite green dye indicates a strong adsorption of this dye that destroys the crystalline feature of titania sample. TEM analysis reveals the existence of spherical nanoparticles with size about 25 nm. The adsorption isotherm indicates the adsorption capacity 6.3 mg.g-1 TiO2. The value of enthalpy change (ΔH°) for malachite green dye adsorption is 19 kJ/mol, which indicates that the removal process is endothermic. The adsorption process follows pseudo-second order rate equation and the negative values of standard free energy (ΔG°) suggest that the adsorption process is spontaneous.
In this research, we present a simple and successful route for synthesis titania nanoparticles by controlled solgel progress. Chitosan as bio-template is involved in the progress of preparation to increase the surface area and manipulate defined particle and pore structure. The crystalline behavior and the nanostructure of the prepared nanoparticles were investigated using X-ray diffraction [XRD] and transmission electron microscope [TEM]. The crystalline results have pointed out the predominant existence of anatase phase that reveals the successful role of chitosan in stabilizing titania nanoparticles and preventing the growth of these particles into rutile phase. It is obvious to notice that a change in sample crystallography from anatase to completely amorphous nanoparticles upon adsorption of malachite green dye indicates a strong adsorption of this dye that destroys the crystalline feature of titania sample. TEM analysis reveals the existence of spherical nanoparticles with size about 25 nm. The adsorption isotherm indicates the adsorption capacity 6.3 mg.g-1 TiO2. The value of enthalpy change (ΔH°) for malachite green dye adsorption is 19 kJ/mol, which indicates that the removal process is endothermic. The adsorption process follows pseudo-second order rate equation and the negative values of standard free energy (ΔG°) suggest that the adsorption process is spontaneous.
Cite this paper
Abou-Gamra, Z. and Ahmed, M. (2015) TiO2 Nanoparticles for Removal of Malachite Green Dye from Waste Water. Advances in Chemical Engineering and Science, 5, 373-388. doi: 10.4236/aces.2015.53039.
Abou-Gamra, Z. and Ahmed, M. (2015) TiO2 Nanoparticles for Removal of Malachite Green Dye from Waste Water. Advances in Chemical Engineering and Science, 5, 373-388. doi: 10.4236/aces.2015.53039.
References
[1] Rafatullah, M., Sulaiman, O., Hashim, R. and Ahmad, A. (2010) Adsorption of Methylene Blue on Low-Cost Adsorbents: A Review. Journal of Hazardous Materials, 177, 70-80.
http://dx.doi.org/10.1016/j.jhazmat.2009.12.047 [2] Li, J., Feng, J. and Yan, W. (2013) Excellent Adsorption and Desorption Characteristics of Polypyrrole/TiO2 Composite for Methylene Blue. Applied Surface Science, 279, 400-408.
http://dx.doi.org/10.1016/j.apsusc.2013.04.127 [3] Gong, R., Ding, Y., Li, M., Yang, C., Liu, C. and Sun, Y. (2005) Utilization of Powdered Peanut Hull as Biosorbent for Removal of Anionic Dyes from Aqueous Solution. Dyes and Pigments, 64, 187-192.
http://dx.doi.org/10.1016/j.dyepig.2004.05.005 [4] Sarmah, S. and Kumar, A. (2011) Photocatalytic Activity of Polyaniline-TiO2 Nanocomposites. Indian Journal of Physics, 85, 713-726.
http://dx.doi.org/10.1007/s12648-011-0071-1 [5] Culp, S.J. and Beland, F.A. (1996) Malachite Green: A Toxicological Review. International Journal of Toxicology, 15, 219-238.
http://dx.doi.org/10.3109/10915819609008715 [6] Srivastava, S., Rangana, S. and Roy, D. (2004) Toxicological Effects of Malachite Green. Aquatic Toxicology, 66, 319- 329.
http://dx.doi.org/10.1016/j.aquatox.2003.09.008 [7] Papinutti, L., Mouso, N. and Forchiassin, F. (2006) Removal and Degradation of the Fungicide Dye Malachite Green from Aqueous Solution Using the System Wheat Bran-Fomes Sclerodermeus. Enzyme and Microbial Technology, 39, 848-853.
http://dx.doi.org/10.1016/j.enzmictec.2006.01.013 [8] Dogan Uluozlu, O., Sari, A., Tuzen, M. and Soylak, M. (2008) Biosorption of Pb(II) and Cr(III) from Aqueous Solution Bylichen (Parmelina tiliaceae) Biomass. Bioresource Technology, 99, 2972-2880.
http://dx.doi.org/10.1016/j.biortech.2007.06.052 [9] Gupta, V.K., Jain, R., Mittal, A., Saleh, T.A., Nayak, A., Agarwal, S. and Sikarwar, S. (2012) Photo-Catalytic Degradation of Toxic Dye Amaranth on TiO2/UV in Aqueous Suspensions. Materials Science and Engineering: C, 32, 12-17.
http://dx.doi.org/10.1016/j.msec.2011.08.018 [10] Hu, A., Liang, R. Zhang, X., Kurdi, S., Luong, D., Huang, H., Peng, P., Marzbanrad, E., Oakes, K.D., Zhou, Y. and Servos, M.R. (2013) Enhanced Photocatalytic Degradation of Dyes by TiO2 Nanobelts with Hierarchical Structures. Journal of Photochemistry and Photobiology A: Chemistry, 256, 7-15.
http://dx.doi.org/10.1016/j.jphotochem.2013.01.015 [11] Chen, X. and Mao, S.S. (2007) Titanium Dioxide Nanomaterials: Synthesis, Properties, Modifications and Applications. Chemical Reviews, 107, 2891-2959.
http://dx.doi.org/10.1021/cr0500535 [12] Ahmed, M.A. (2012) Synthesis and Structural Feature of Mesoporous NiO/TiO2 Nanocomposites Prepared by Sol-Gel Method for Photodegradation of Methylene Blue Dye. Journal of Photochemistry and Photobiology A: Chemistry, 238, 63-70.
http://dx.doi.org/10.1016/j.jphotochem.2012.04.010 [13] Ahmed, M.A., El-Katori, E.E. and Gharni, Z.H. (2013) Photocatalytic Degradation of Methylene Blue Dye Using Fe2O3/TiO2 Nanoparticles Prepared by Sol-Gel Method. Journal of Alloys and Compounds, 553, 19-29.
http://dx.doi.org/10.1016/j.jallcom.2012.10.038 [14] Ahmed, M.A., Abdel-Messih, M.F. and El-Sayed, A.S. (2013) Photocatalytic Decolorization of Rhodamine B Dye Using Novel Mesoporous SnO2-TiO2 Nano Mixed Oxides Prepared by Sol-Gel Method. Journal of Photochemistry and Photobiology A: Chemistry, 260, 1-8.
http://dx.doi.org/10.1016/j.jphotochem.2013.03.011 [15] Ismail, A.A. (2012) Facile Synthesis of Mesoporous Ag-Loaded TiO2 Thin Film and Its Photocatalytic Properties. Microporous and Mesoporous Materials, 149, 69-75.
http://dx.doi.org/10.1016/j.micromeso.2011.08.030 [16] Habibi, M.H., Hassanzadeh, A. and Mahdavi, S. (2005) The Effect of Operational Parameters on the Photocatalytic Degradation of Three Textile Azo Dyes in Aqueous TiO2 Suspensions. Journal of Photochemistry and Photobiology A: Chemistry, 172, 89-96.
http://dx.doi.org/10.1016/j.jphotochem.2004.11.009 [17] Gautam, S., Kamble, S.P., Sawant, S.B. and Pangarkar, V.G. (2005) Photocatalytic Degradation of 4-Nitroaniline Using Solar and Artificial UV Radiation. Chemical Engineering Journal, 110, 129-137.
http://dx.doi.org/10.1016/j.cej.2005.03.021 [18] Fan, L., Zhang, Y., Li, X., Luo, C., Lu, F. and Qiu, H. (2012) Removal of Alizarin Red from Water Environment Using Magnetic Chitosan with Alizarin Red as Imprinted Molecules. Colloids and Surfaces B: Biointerfaces, 91, 250-257.
http://dx.doi.org/10.1016/j.colsurfb.2011.11.014 [19] Deniz, A., Arzu, Y. and Ufuk, G. (2015) Synthesis of Magnetic Fe3O4-Chitosan Nanoparticles by Ionic Gelation and Their Dye Removal Ability. Water Environment Research, 87, 425-436.
http://dx.doi.org/10.2175/106143014X14062131178673 [20] Langmuir, I. (1918) The Adsorption of Gases on Plane Surfaces of Glass, Mica and Platinum. Journal of the American Chemical Society, 40, 1361-1403.
http://dx.doi.org/10.1021/ja02242a004 [21] Freundlich, H.M.F. (1906) Over the Adsorption in Solution. The Journal of Physical Chemistry, 57, 385-471. [22] Temkin, M.J. and Pyzhev, V. (1940) Recent Modifications to Langmuir Isotherms. Acta Physiochim URSS, 12, 217- 225. [23] Dubinin, M.M. (1965) Modern State of the Theory of Volume Filling of Micropore Adsorbents during Adsorption of Gases and Steams on Carbon Adsorbents. Zhurnal Fizicheskoi Khimii, 39, 1305-1317. [24] Lagergren, S. (1898) Zur theorie der sogenannten adsorption geloster stoffe, Kungliga Svenska Vetenskapsakademiens. Handlingar, 24, 1-39. [25] Ho, Y.S. and McKay, G. (1999) Pseudo-Second-Order Model for Sorption Processes. Process Biochemistry, 34, 451- 465.
http://dx.doi.org/10.1016/S0032-9592(98)00112-5 [26] Weber, W.J. and Morris, J.C. (1963) Kinetics of Adsorption of Carbon from Solution. Journal of the Sanitary Engineering Division, American Society of Civil Engineering, 89, 31-60. [27] Chien, S.H. and Clayton, W.R. (1980) Application of Elovich Equation to the Kinetics of Phosphate Release and Sorption in Soils. Soil Science Society of America Journal, 44, 265-268.
http://dx.doi.org/10.2136/sssaj1980.03615995004400020013x [28] Reichenberg, D. (1953) Properties of Ion-Exchange Resins in Relation to Their Structure. III. Kinetics of Exchange. Journal of the American Chemical Society, 75, 589-597.
http://dx.doi.org/10.1021/ja01099a022 [29] Ghaedi, M. (2012) Comparison of Cadmium Hydroxide Nanowires and Silver Nanoparticles Loaded on Activated Carbon As New Adsorbents for Efficient Removal of Sunset Yellow: Kinetics and Equilibrium Study. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 94, 346-351.
http://dx.doi.org/10.1016/j.saa.2012.02.097 [30] Venkatesha, T.G., Nayaka, Y.A. and Chethana, B.K. (2013) Adsorption of Ponceau S from Aqueous Solution by MgO Nanoparticles. Applied Surface Science, 276, 620-627.
http://dx.doi.org/10.1016/j.apsusc.2013.03.143 [31] Ahmed, I.M. and Gasser, M.S. (2012) Adsorption Study of Anionic Reactive Dye from Aqueous Solution to Mg-Fe- CO3 Layered Double Hydroxide (LDH). Applied Surface Science, 259, 650-656.
http://dx.doi.org/10.1016/j.apsusc.2012.07.092
[1] Rafatullah, M., Sulaiman, O., Hashim, R. and Ahmad, A. (2010) Adsorption of Methylene Blue on Low-Cost Adsorbents: A Review. Journal of Hazardous Materials, 177, 70-80.
http://dx.doi.org/10.1016/j.jhazmat.2009.12.047 [2] Li, J., Feng, J. and Yan, W. (2013) Excellent Adsorption and Desorption Characteristics of Polypyrrole/TiO2 Composite for Methylene Blue. Applied Surface Science, 279, 400-408.
http://dx.doi.org/10.1016/j.apsusc.2013.04.127 [3] Gong, R., Ding, Y., Li, M., Yang, C., Liu, C. and Sun, Y. (2005) Utilization of Powdered Peanut Hull as Biosorbent for Removal of Anionic Dyes from Aqueous Solution. Dyes and Pigments, 64, 187-192.
http://dx.doi.org/10.1016/j.dyepig.2004.05.005 [4] Sarmah, S. and Kumar, A. (2011) Photocatalytic Activity of Polyaniline-TiO2 Nanocomposites. Indian Journal of Physics, 85, 713-726.
http://dx.doi.org/10.1007/s12648-011-0071-1 [5] Culp, S.J. and Beland, F.A. (1996) Malachite Green: A Toxicological Review. International Journal of Toxicology, 15, 219-238.
http://dx.doi.org/10.3109/10915819609008715 [6] Srivastava, S., Rangana, S. and Roy, D. (2004) Toxicological Effects of Malachite Green. Aquatic Toxicology, 66, 319- 329.
http://dx.doi.org/10.1016/j.aquatox.2003.09.008 [7] Papinutti, L., Mouso, N. and Forchiassin, F. (2006) Removal and Degradation of the Fungicide Dye Malachite Green from Aqueous Solution Using the System Wheat Bran-Fomes Sclerodermeus. Enzyme and Microbial Technology, 39, 848-853.
http://dx.doi.org/10.1016/j.enzmictec.2006.01.013 [8] Dogan Uluozlu, O., Sari, A., Tuzen, M. and Soylak, M. (2008) Biosorption of Pb(II) and Cr(III) from Aqueous Solution Bylichen (Parmelina tiliaceae) Biomass. Bioresource Technology, 99, 2972-2880.
http://dx.doi.org/10.1016/j.biortech.2007.06.052 [9] Gupta, V.K., Jain, R., Mittal, A., Saleh, T.A., Nayak, A., Agarwal, S. and Sikarwar, S. (2012) Photo-Catalytic Degradation of Toxic Dye Amaranth on TiO2/UV in Aqueous Suspensions. Materials Science and Engineering: C, 32, 12-17.
http://dx.doi.org/10.1016/j.msec.2011.08.018 [10] Hu, A., Liang, R. Zhang, X., Kurdi, S., Luong, D., Huang, H., Peng, P., Marzbanrad, E., Oakes, K.D., Zhou, Y. and Servos, M.R. (2013) Enhanced Photocatalytic Degradation of Dyes by TiO2 Nanobelts with Hierarchical Structures. Journal of Photochemistry and Photobiology A: Chemistry, 256, 7-15.
http://dx.doi.org/10.1016/j.jphotochem.2013.01.015 [11] Chen, X. and Mao, S.S. (2007) Titanium Dioxide Nanomaterials: Synthesis, Properties, Modifications and Applications. Chemical Reviews, 107, 2891-2959.
http://dx.doi.org/10.1021/cr0500535 [12] Ahmed, M.A. (2012) Synthesis and Structural Feature of Mesoporous NiO/TiO2 Nanocomposites Prepared by Sol-Gel Method for Photodegradation of Methylene Blue Dye. Journal of Photochemistry and Photobiology A: Chemistry, 238, 63-70.
http://dx.doi.org/10.1016/j.jphotochem.2012.04.010 [13] Ahmed, M.A., El-Katori, E.E. and Gharni, Z.H. (2013) Photocatalytic Degradation of Methylene Blue Dye Using Fe2O3/TiO2 Nanoparticles Prepared by Sol-Gel Method. Journal of Alloys and Compounds, 553, 19-29.
http://dx.doi.org/10.1016/j.jallcom.2012.10.038 [14] Ahmed, M.A., Abdel-Messih, M.F. and El-Sayed, A.S. (2013) Photocatalytic Decolorization of Rhodamine B Dye Using Novel Mesoporous SnO2-TiO2 Nano Mixed Oxides Prepared by Sol-Gel Method. Journal of Photochemistry and Photobiology A: Chemistry, 260, 1-8.
http://dx.doi.org/10.1016/j.jphotochem.2013.03.011 [15] Ismail, A.A. (2012) Facile Synthesis of Mesoporous Ag-Loaded TiO2 Thin Film and Its Photocatalytic Properties. Microporous and Mesoporous Materials, 149, 69-75.
http://dx.doi.org/10.1016/j.micromeso.2011.08.030 [16] Habibi, M.H., Hassanzadeh, A. and Mahdavi, S. (2005) The Effect of Operational Parameters on the Photocatalytic Degradation of Three Textile Azo Dyes in Aqueous TiO2 Suspensions. Journal of Photochemistry and Photobiology A: Chemistry, 172, 89-96.
http://dx.doi.org/10.1016/j.jphotochem.2004.11.009 [17] Gautam, S., Kamble, S.P., Sawant, S.B. and Pangarkar, V.G. (2005) Photocatalytic Degradation of 4-Nitroaniline Using Solar and Artificial UV Radiation. Chemical Engineering Journal, 110, 129-137.
http://dx.doi.org/10.1016/j.cej.2005.03.021 [18] Fan, L., Zhang, Y., Li, X., Luo, C., Lu, F. and Qiu, H. (2012) Removal of Alizarin Red from Water Environment Using Magnetic Chitosan with Alizarin Red as Imprinted Molecules. Colloids and Surfaces B: Biointerfaces, 91, 250-257.
http://dx.doi.org/10.1016/j.colsurfb.2011.11.014 [19] Deniz, A., Arzu, Y. and Ufuk, G. (2015) Synthesis of Magnetic Fe3O4-Chitosan Nanoparticles by Ionic Gelation and Their Dye Removal Ability. Water Environment Research, 87, 425-436.
http://dx.doi.org/10.2175/106143014X14062131178673 [20] Langmuir, I. (1918) The Adsorption of Gases on Plane Surfaces of Glass, Mica and Platinum. Journal of the American Chemical Society, 40, 1361-1403.
http://dx.doi.org/10.1021/ja02242a004 [21] Freundlich, H.M.F. (1906) Over the Adsorption in Solution. The Journal of Physical Chemistry, 57, 385-471. [22] Temkin, M.J. and Pyzhev, V. (1940) Recent Modifications to Langmuir Isotherms. Acta Physiochim URSS, 12, 217- 225. [23] Dubinin, M.M. (1965) Modern State of the Theory of Volume Filling of Micropore Adsorbents during Adsorption of Gases and Steams on Carbon Adsorbents. Zhurnal Fizicheskoi Khimii, 39, 1305-1317. [24] Lagergren, S. (1898) Zur theorie der sogenannten adsorption geloster stoffe, Kungliga Svenska Vetenskapsakademiens. Handlingar, 24, 1-39. [25] Ho, Y.S. and McKay, G. (1999) Pseudo-Second-Order Model for Sorption Processes. Process Biochemistry, 34, 451- 465.
http://dx.doi.org/10.1016/S0032-9592(98)00112-5 [26] Weber, W.J. and Morris, J.C. (1963) Kinetics of Adsorption of Carbon from Solution. Journal of the Sanitary Engineering Division, American Society of Civil Engineering, 89, 31-60. [27] Chien, S.H. and Clayton, W.R. (1980) Application of Elovich Equation to the Kinetics of Phosphate Release and Sorption in Soils. Soil Science Society of America Journal, 44, 265-268.
http://dx.doi.org/10.2136/sssaj1980.03615995004400020013x [28] Reichenberg, D. (1953) Properties of Ion-Exchange Resins in Relation to Their Structure. III. Kinetics of Exchange. Journal of the American Chemical Society, 75, 589-597.
http://dx.doi.org/10.1021/ja01099a022 [29] Ghaedi, M. (2012) Comparison of Cadmium Hydroxide Nanowires and Silver Nanoparticles Loaded on Activated Carbon As New Adsorbents for Efficient Removal of Sunset Yellow: Kinetics and Equilibrium Study. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 94, 346-351.
http://dx.doi.org/10.1016/j.saa.2012.02.097 [30] Venkatesha, T.G., Nayaka, Y.A. and Chethana, B.K. (2013) Adsorption of Ponceau S from Aqueous Solution by MgO Nanoparticles. Applied Surface Science, 276, 620-627.
http://dx.doi.org/10.1016/j.apsusc.2013.03.143 [31] Ahmed, I.M. and Gasser, M.S. (2012) Adsorption Study of Anionic Reactive Dye from Aqueous Solution to Mg-Fe- CO3 Layered Double Hydroxide (LDH). Applied Surface Science, 259, 650-656.
http://dx.doi.org/10.1016/j.apsusc.2012.07.092