MSA  Vol.8 No.11 , October 2017
Structural Analysis of Magnesium-Aluminium Hydrotalcites Modified with Iron III Obtained by Hydroxide Precipitation Method
Abstract: Hydrotalcite-type anionic clays are a group of important materials used in adsorption processes, mainly for organic pollutants removal due the layered double hydroxide structure. The layer-interlayer interactions provide a structural memory even after dehydration and dehydroxylation process, since a very stable interlayer anions are part of material composition, like the carbonate one. A limited numbers of trivalent modifier cations can replace the aluminium cation due the ionic radii mismatch or oxidation state restrictions. Transition metal cations can replace the aluminium one in octahedral site of hydroxide lamellas in order to improve the adsorptive behaviors. In this work, we have investigate three compositions of carbonated magnesium-aluminium hydrotalcite with dif-ferent iron (III) contents through the co-precipitation method at pH 11 and aging step at 60°C for 6 hours. Thermal analysis was performed aiming the determination of the hydration water and hydroxyl amounts in dried precipitate samples, taking in account the results obtained for X-ray diffractometry, infrared spectroscopy, and nitrogen adsorption-desorption characterization for several thermally treated samples. All of synthesized samples showed high surface areas, even for high temperature of thermal treatment. The co-substitution with iron (III) reduced the temperature of dehydration and dehydroxylation process, but the co-substitution at 5 mol% provides other desirables characteristics, like a more amount of rhombohedral HDL phase and higher porosity, even after the thermal treatment at 500°C for 4 hours. This result makes that composition very applicable as a reusable adsorbent material in order to removal several types of micro-pollutant compounds in aqueous media.
Cite this paper: Barbosa, G. , Zaghete, M. , Amoresi, R. , da Silva, M. , Cavalheiro, A. and de Lara da Silva, R. (2017) Structural Analysis of Magnesium-Aluminium Hydrotalcites Modified with Iron III Obtained by Hydroxide Precipitation Method. Materials Sciences and Applications, 8, 784-797. doi: 10.4236/msa.2017.811057.

[1]   Wiyantokoa, B., Kurniawatia, P., Purbaningtias, T.E. and Fatimah, I. (2015) Synthesis and Characterization of Hydrotalcite at Different Mg/Al Molar Ratios. Procedia Chemistry, 17, 21-26.

[2]   Nguyen, H.K.D., Nguyen, T.D., Hoang, D.N., Dao, D.S., Nguyen, T.T., Wanwisa, L. and Hoang, L.L (2007) X-Ray Absorption Spectroscopies of Mg-Al-Ni Hydrotalcite Like Compound for Explaining the Generation of Surface Acid Sites. Korean Journal of Chemical Engineering, 34, 314-319.

[3]   Lukashin, A.V., Vertegel, A.A., Eliseev, A.A., Nikiforov, M.P., Gornert, P. and Tretyako, Y.D. (2003) Chemical Design of Magnetic Nanocomposites Based on Layered Double Hydroxides. Journal of Nanoparticle Research, 5, 455-464.

[4]   Ardhayantia, L.I. and Santosa, S.J. (2016) Synthesis of Magnetite-Mg/Al Hydrotalcite and Its Application as Adsorbent for Navy Blue and Yellow F3G Dyes. Procedia Engineering, 148, 1380-1387.

[5]   Rodilla, J.M., Neves, P.P., Pombala, S., Rives, V., Trujillano, R. and Díezc, D. (2015) Hydrotalcite Catalysis for the Synthesis of New Chiral Building Blocks. Natural Product Research, 30, 834-840.

[6]   Hafshah, H., Prajitno, D.H. and Roesyadi, A. (2017) Hydrotalcite Catalyst for Hydrocracking Calophyllum inophyllum Oil to Biofuel: A Comparative Study with and without Nickel Impregnation. Bulletin of Chemical Reaction Engineering & Catalysis, 12, 273-280.

[7]   Sikander, U., Sufian, S. and Salam, M.A. (2017) A Review of Hydrotalcite Based Catalysts for Hydrogen Production Systems. International Journal of Hydrogen Energy, 42, 19851-19868.

[8]   Fahami, A., Al-Hazmib, F.S., Al-Ghamdib, A., Mahmoudb, W.E. and Beall, G.W (2016) Structural Characterization of Chlorine Intercalated Mg-Al Layered Double Hydroxides: A Comparative Study between Mechanochemistry and Hydrothermal Methods. Journal of Alloys and Compounds, 683, 100-107.

[9]   Crepaldi, E.L. and Valim, J.B. (1998) Hidróxidos Duplos Lamelares: Síntese, Estrutura, Propriedades e Aplicacoes. Química Nova, 21, 300-311.

[10]   Miyata, S. (1980) Physico-Chemical Properties of Synthetic Hydrotalcites in Relation to Composition. Clays and Clay Minerals, 28, 50-56.

[11]   Rowland, R.A. (1951) Differential Thermal Analysis of Clays and Carbonates. Clays and Clay Technology, 169, 151-163.

[12]   Niu, M., Qiu, M., Han, Q. and Wang, Y. (2016) The Influence on Synthetising Mg-Al Hydrotalcite by using Different Mg and Al Sources as the Precursors. American Chemical Science Journal, 15, 1-7.

[13]   Belloto, M., Rebours, B., Clause, O., Lynch, J., Bazin, D. and Elkain, E. (1996) Hydrotalcite Decomposition Mechanism: A Clue to the Structure and Reactivity of Spinel like Mixed Oxides. The Journal of Physical Chemistry, 100, 8535-8542.

[14]   Yang, C., Liao, L., Lv, G., Wu, L., Mei, L. and Li, Z. (2016) Synthesis and Characterization of Mn Intercalated Mg-Al Hydrotalcite. Journal of Colloid and Interface Science, 479, 115-120.

[15]   Velu, S. and Swamy, C.S. (1997) Effect of Substitution of Fe3+/Cr3+ on the Alkylation of Phenol with Methanol over Magnesium-Aluminium Calcined Hydrotalcite. Applied Catalysis A: General, 162, 81-91.

[16]   Prakash, A.S., Kamath, V. and Hegde, M.S. (2000) Synthesis and Characterization of the Layered Double Hydroxides of Mg with Cr. Materials Research Bulletin, 35, 2189-2197.

[17]   Labajos, F.M. and Rives, V. (1996) Thermal Evolution of Chromium (III) Ions Hidrotalcite like Compounds. Inorganic Chemistry, 34, 5313-5318.

[18]   Ma, W., Zhao, N., Yang, G., Tian, L. and Wang, R. (2011) Removal of Fluoride Ions from Aqueous Solution by the Calcination Product of Mg-Al-Fe Hydrotalcite-like Compound. Desalination, 268, 20-26.

[19]   Yang, Y., Gao, N., Chu, W., Zhang, Y. and Ma, Y. (2012) Adsorption of Perchlorate from Aqueous Solution by the Calcination Product of Mg/(Al-Fe) Hydrotalcite-like Compounds. Journal of Hazardous Materials, 209-210, 318-325.

[20]   Kato, M., Azimi, M.D., Fayaz, S.H., Shah, M.D., Hoque, M.Z., Hamajima, N., Ohnuma, S., Ohtsuka, T., Maeda, M. and Yoshinaga, M. (2016) Uranium in Well Drinking Water of Kabul, Afghanistan and Its Effective, Low-Cost Depuration using Mg-Fe Based Hydrotalcite-Like Compounds. Chemosphere, 165, 27-32.

[21]   Carpani, I., Berrettoni, M., Giorgetti, M. and Tonelli, D. (2006) Intercalation of Iron(III) Hexacyano Complex in a Ni, Al Hydrotalcite-Like Compound. The Journal of Physical Chemistry B, 110, 7265-7269.

[22]   Debek, R., Motak, M., Galvez, M. E., Grzybek, T, Da Costa, P. and Pieńkowski, L. (2017) Ceria Promotion over Ni-Containing Hydrotalcite-Derived Catalysts for CO2 Methane Reforming. E3S Web of Conferences, 14, 02039.

[23]   Carpentier, J., Siffert, S., Lamonier, J.F., Laversin, H. and Aboukais, A. (2007) Synthesis and Characterization of Cu-Co-Fe Hydrotalcites and Their Calcined Products. Journal of Porous Materials, 14, 103-110.

[24]   Puttaswamy, N.S. and Kamath, V. (1997) Reversible Thermal Behavior of Layered Double Hydroxides a Thermogravimetric Study. Journal of Materials Chemistry, 7, 1941-1945.

[25]   Beck, C.W. (1950) Differential Thermal Analysis Curves of Carbonate Minerals. American Mineralogist, 35, 985-1013.

[26]   Baskaran, T., Christopher, J. and Sakthivel, A. (2015) Progress on Layered Hydrotalcite (HT) Materials as Potential Support and Catalytic Materials. RSC Advances, 5, 98853-98875.

[27]   Shannon, R.D. (1976) A Revised Effective Ionic Radii and Systematic Studies of Interatomic Distances in Halides and Chalcogenides. Acta Crystallographica, A32, 751-767.

[28]   Tamura, H., Chiba, J., Ito, M., Takeda, T., Kikkawa, S., Mawatari, Y. and Tabata, M. (2006) Formation of Hydrotalcite in Aqueous Solutions and Intercalation of ATP by Anion Exchange. Journal of Colloid and Interface Science, 300, 648-654.

[29]   Ebitani, K., Motokura, K., Mori, K., Mizugaki, T. and Kaneda, K. (2006) Reconstructed Hydrotalcite as a Highly Active Heterogeneous Base Catalyst for Carbon-Carbon Bond Formations in the Presence of Water. The Journal of Organic Chemistry, 71, 5440-5447.

[30]   Bhat, B.M. (2012) Synthesis and Characterization of Hydrotalcite and Hydrotalcite Compounds and Their Application as a Base Catalyst for Aldol Condensation Reaction. Oriental Journal of Chemistry, 28, 1751-1760.

[31]   Timofeeva, M.N., Kapustin, A.E., Panchenko, V.N., Butenko, E.O., Krupskaya, V.V., Gil, A. and Vicente, M.A. (2016) Synthetic and Natural Materials with the Brucite-Like Layers as High Active Catalyst for Synthesis of 1-Methoxy-2-Propanol from Methanol and Propylene Oxide. Journal of Molecular Catalysis A: Chemical, 423, 22-30.

[32]   Lide, D.R. (2007) Handbook of Chemistry and Physics. 87th Edition, Taylor and Francis, Boca Raton.

[33]   JCPDS Joint Committee on Powder Diffraction Standards/International Center for Diffraction Data (2003) Pennsylvania, Powder Diffraction File 2003.

[34]   Landers, J., Gor, G.Y. and Neimark, A.V. (2003) Density Functional Theory Methods for Characterization of Porous Materials. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 437, 33.

[35]   Marsh, H. and Rand, B. (1970) Adverse Criticism of the Use of the t-Plot to Characterize Microporosity. Journal of Colloid and Interface Science, 33, 478-479.

[36]   Vágvolgyi, V., Palmer, S.J., Kristóf, J., Frost, R.L., and Horváth, E. (2008) Mechanism for Hydrotalcite Decomposition: A Controlled Rate Thermal Analysis Study. Journal of Colloid and Interface Science, 318, 302-308.

[37]   Wright, C.M.R., Ruengkajorn, K., Kilpatrick, A.F.R., Buffet, J.-C. and O’Hare, D. (2017) Controlling the Surface Hydroxyl Concentration by Thermal Treatment of Layered Double Hydroxides. Inorganic Chemistry, 56, 7842-7850.

[38]   Alvarez Acevedo, N.I., Rocha, M.C.G. and Bertolino, L.C. (2017) Mineralogical Characterization of Natural Clays from Brazilian Southeast Region for Industrial Applications. Ceramica, 63, 253-262.

[39]   Santos, R.M.M., Tronto, J., Briois, V. and Santilli, C.V. (2017) Thermal Decomposition and Recovery Properties of ZnAl-CO3 Layered Double Hydroxide for Anionic Dye Adsorption: Insight into the Aggregative Nucleation and Growth Mechanism of the LDH Memory Effect. Journal of Materials Chemistry A, 5, 9998-10009.

[40]   Olfs, H.-M., Torres-Dorante, L.O., Eckelt, R. and Kosslick, H. (2009) Comparison of Different Synthesis Routes for Mg-Al Layered Double Hydroxides (LDH): Characterization of the Structural Phases and Anion Exchange Properties. Applied Clay Science, 43, 459-464.