Impregnation of Fe3+ into MCM-41 Pores: Effect of Fe3+ Concentration on the Weight Percent of Fe-Frameworks and Fe-Non-Frameworks

Suyanta Suyanta(1*), Agus Kuncaka(2), Mudasir Mudasir(3)

(1) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada, Sekip Utara, Yogyakarta 55281, Indonesia
(2) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada, Sekip Utara, Yogyakarta 55281, Indonesia
(3) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada, Sekip Utara, Yogyakarta 55281, Indonesia
(*) Corresponding Author


Silica from rice husks (RH) has been used as a starting ingredient in the sonication synthesis of MCM-41 (RH-MCM-41). The impregnation of Fe3+ into RH-MCM-41 pores to produce RH-MCM-41 containing Fe2O3 and Fe (denoted as Fe2O3-Fe-RH-MCM-41) was carried out by examining the effect of various Fe3+ concentrations on the weight percent of Fe-frameworks (Fe3+ that replaces Si4+ in silicate frameworks) and Fe-non-frameworks, i.e., the iron oxide formed outside the silicate frameworks. Fe2O3-Fe-RH-MCM-41 was washed with a 0.01 M HCl solution to remove Fe-non-frameworks from the materials and give Fe-RH-MCM-41 containing Fe-frameworks. The Fe content in Fe2O3-Fe-RH-MCM-41 (Fe-total) and Fe-RH-MCM-41 (Fe-frameworks) for each sample was determined by an AAS (atomic absorption spectrometer), whereas the content of Fe-non-frameworks was calculated from the difference between Fe-total and Fe-frameworks. The XRD (X-ray diffraction) pattern, N2 adsorption-desorption isotherm profile, as well as the TEM (transmission electron microscope) image clearly demonstrate that the RH-MCM-41 exhibits an ordered p6mm hexagonal mesostructure with a large specific surface area and uniform pore size. Based on the weight percents of Fe-frameworks found in each sample, it is clear that the content of Fe-non-frameworks is significantly enhanced compared to that of Fe-frameworks when the more concentrated Fe3+ is used.


RH-MCM-41; impregnation; Fe-frameworks; Fe-non-frameworks

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[1] Li, S.C., Lin, Y.C., and Li, Y.P., 2021, Understanding the catalytic activity of microporous and mesoporous zeolites in cracking by experiments and simulations, Catalysts, 11 (9), 1114.

[2] Ho, P.H., Yao, D., Creaser, D., and Olsson, L., 2022, Advantages of high-siliceous zeolites in the reactivity and stability of diesel oxidation catalysts, ACS Eng. Au, 2 (3), 219–235.

[3] Bingre, R., Louis, B., and Nguyen, P., 2018, An overview on zeolite shaping technology and solutions to overcome diffusion limitations, Catalysts, 8 (4), 163.

[4] Costa, J.A.S, de Jesus, R.A., Santos, D.O., Mano, J.F., Romão, L.P.C., and Paranhos, C.M., 2020, Recent progresses in the adsorption of organic, inorganic, and gas compounds by MCM-41-based mesoporous materials, Microporous Mesoporous Mater., 291, 109698.

[5] Dinh Du, P., Hieu, N.T., To, T.C., Bach, L.G., Tinh, M.X., Mau, T.X., and Quang Khieu, D., 2019, Aminopropyl functionalised MCM-41: Synthesis and application for adsorption of Pb(II) and Cd(II), Adv. Mater. Sci. Eng., 2019, 8573451.

[6] Valiey, E., Dekamin, M.G., and Alirezvani, Z., 2021, Sulfamic acid pyromellitic diamide-functionalized MCM-41 as a multifunctional hybrid catalyst for melting-assisted solvent-free synthesis of bioactive 3,4-dihydropyrimidin-2-(1H)-ones, Sci. Rep., 11 (1), 11199.

[7] Oliveira, D.M., and Andrada, A.S., 2019, Synthesis of ordered mesoporous silica MCM-41 with controlled morphology for potential application in controlled drug delivery systems, Cerâmica, 65 (374), 170–179.

[8] Ng, E.P., Goh, J.Y., Ling, T.C., and Mukti, R.R., 2013, Eco-friendly synthesis for MCM-41 nanoporous materials using the non-reacted reagents in mother liquor, Nanoscale Res. Lett., 8 (1), 120.

[9] Parangi, T.F., Patel, R.M., and Chudasama, U.V., 2014, Synthesis and characterization of mesoporous Si-MCM-41 materials and their application as solid acid catalysts in some esterification reactions, Bull. Mater. Sci., 37 (3), 609–615.

[10] Juárez-Serrano, N., Berenguer, D., Martínez-Castellanos, I., Blasco, I., Beltrán, M., and Marcilla, A., 2021, Effect of reaction time and hydrothermal treatment time on the textural properties of SBA-15 synthesized using sodium silicate as silica source and its efficiency for reducing tobacco smoke toxicity, Catalysts, 11 (7), 808.

[11] Fu, P., Yang, T., Feng, J., and Yang, H., 2015, Synthesis of mesoporous silica MCM-41 using sodium silicate derived from copper ore tailings with an alkaline molted-salt method, J. Ind. Eng. Chem., 29, 338–343.

[12] Yang, G., Deng, Y., Ding, H., Lin, Z., Shao, Y., and Wang, Y., 2015, A facile approach to synthesize MCM-41 mesoporous materials from iron ore tailing: Influence of the synthesis conditions on the structural properties, Appl. Clay Sci., 111, 61–66.

[13] Yang, G., Deng, Y., and Wang, J., 2014, Non-hydrothermal synthesis and characterization of MCM-41 mesoporous materials from iron ore tailing, Ceram. Int., 40 (5), 7401–7406.

[14] Shah, B.A., Patel, A.V., Bagia, M.I., and Shah, A.V., 2017, Green approach towards the synthesis of MCM-41 from siliceous sugar industry waste, Int. J. Appl. Chem., 13 (3), 497–514.

[15] Lin, Y.W., Lee, W.H., Lin, K.L., and Kuo, B.Y., 2021, Synthesis and grafted NH2-Al/MCM-41 with amine functional groups as humidity control material from silicon carbide sludge and granite sludge, Processes, 9 (12), 2107.

[16] Ali-Dahmane, T., Brahmi, L., Hamacha, R., Villieras, F., and Bengueddach, A., 2016, Synthesis of MCM-41 nanomaterial from Algerian bentonite: Influence of synthesis pH, J. Fundam. Appl. Sci., 9 (2), 636–649.

[17] Zhang, X., and Du, T., 2022, Study of rice husk ash derived MCM-41-type materials on pore expansion, Al incorporation, PEI impregnation, and CO2 adsorption, Korean J. Chem. Eng., 39 (3), 736–759.

[18] Abbas, S.H., Adam, F., and Muniandy, L., 2020, Green synthesis of MCM-41 from rice husk and its functionalization with nickel(II) salen complex for the rapid catalytic oxidation of benzyl alcohol, Microporous Mesoporous Mater., 305, 110192.

[19] Suyanta, S., and Kuncaka, A., 2011, Utilization of rice husk as raw material in synthesis of mesoporous silicates MCM-41, Indones. J. Chem., 11 (3), 279–284.

[20] Nguyen, T.T., Ma, H.T., Avti, P., Bashir, M.J.K., Ng, C.A., Wong, L.Y., Jun, H.K., Ngo, Q.M., and Tran, N.Q., 2019, Adsorptive removal of iron using SiO2 nanoparticles extracted from rice husk ash, J. Anal. Methods Chem., 2019, 6210240.

[21] Jongpradist, P., Homtragoon, W., Sukkarak, R., Kongkitkul, W., and Jamsawang, P., 2018, Efficiency of rice husk ash as cementitious material in high-strength cement-admixed clay, Adv. Civ. Eng., 2018, 8346319.

[22] Xu, K., Sun, Q., Guo, Y., and Dong, S., 2013, Effects on modifiers on the hydrophobicity of SiO2 films from nano-husk ash, Appl. Surf. Sci., 276, 796–801.

[23] Nguyen, M.N., 2020, Worldwide bans of rice straw burning could increase human arsenic exposure, Environ. Sci. Technol., 54 (7), 3728–3729.

[24] Cazula, B.B., Oliveira, L.G., Machado, B., and Alves, H.J., 2021, Optimization of experimental conditions for the synthesis of Si-MCM-41 molecular sieves using different methods and silica sources, Mater. Chem. Phys., 266, 124553.

[25] Meléndez-Ortiz, H.I., Mercado-Silva, A., García-Cerda, L.A., Castruita, G., and Perera-Mercado, Y.A., 2013, Hydrothermal synthesis of mesoporous silica MCM-41 using commercial sodium silicate, J. Mex. Chem. Soc., 57 (2), 73–79.

[26] Golezani, A.S., Fateh, A.S., and Mehrabi, H.A., 2016, Synthesis and characterization of silica mesoporous material produced by hydrothermal continues pH adjusting path way, Prog. Nat. Sci.: Mater. Int., 26 (4), 411–414.

[27] Santos, E.C., Costa, L.S., Oliveira, E.S., Bessa, R.A., Freitas, A.D.L., Oliveira, C.P., Nascimento, R.F., and Loiola, A.R., 2018, Al-MCM-41 synthesized from kaolin via hydrothermal route: Structural characterization and use as an efficient adsorbent of methylene blue, J. Braz. Chem. Soc., 29 (11), 2378–2386.

[28] Deka, J.R., Vetrivel, S., Wu, H.Y., Pan, Y.C., Ting, C.C., Tsai, Y.L., and Kao, H.M., 2014, Rapid sonochemical synthesis of MCM-41 type benzene-bridged periodic mesoporous organosilicas, Ultrason. Sonochem., 21 (1), 387–394.

[29] Sönmez, D.M., Gudovan, D., Truşca, R. Ficai, D., Andronescu, E., and Vasile, B.S., 2015, Synthesis, characterization and testing of MCM-41/TiO2 catalyst for organic dye degradation, Dig. J. Nanomater. Biostruct., 10 (4), 1329–1341.

[30] Soltani, R., Dinari, M., and Mohammadnezhad, G., 2018, Ultrasonic-assisted synthesis of novel nanocomposite of poly (vinyl alcohol) and amino-modified MCM-41: A green adsorbent for Cd(II) removal, Ultrason. Sonochem., 40, 533–542.

[31] Wang, X., Chen, W., Zhou, M., Zhang, Z., and Zhang, L., 2022, Dynamics of double bubbles under the driving of burst ultrasound, Ultrason. Sonochem., 84, 105952.

[32] Yu, X., and Williams, C.T., 2022, Recent advances in the applications of mesoporous silica in heterogeneous catalysis, Catal. Sci. Technol., 12 (19), 5765–5794.

[33] Srividhya, N., 2014, Synthesis characterization and catalytic evaluation of mesoporous Fe-MCM-41 and Si-MCM-41 materials, IOSR J. Appl. Chem., 7 (6), 41–49.

[34] Zhang, Q., Wang, Y., Itsuki, S., Shishido, T., and Takehira, K., 2001, Fe-MCM-41 for selective epoxidation of styrene with hydrogen peroxide, Chem. Lett., 30 (9), 946–947.

[35] Dhal, J.P., Dash, T., and Hota, G., 2020, Iron oxide impregnated mesoporous MCM-41: Synthesis, characterization and adsorption studies, J. Porous Mater., 27 (1), 205–216.

[36] Mokhonoana, M.P., and Coville, N.J., 2009, Highly loaded Fe-MCM-41 materials: Synthesis and reducibility studies, Materials, 2 (4), 2337–2359.

[37] Sasieekhumar, A.R., Somanathan, T., Abilarasu, A., and Shanmugam, M., 2017, Mesoporous Fe/MCM-41 as heterogeneous photocatalyst for the photodegradation of methylene blue, Res. J. Pharm. Technol., 10 (10), 3398–3400.

[38] Guo, Y., Chen, B., Zhao, Y., and Yang, T., 2021, Fabrication of the magnetic mesoporous silica Fe-MCM-41-A as efficient adsorbent: Performance, kinetics and mechanism, Sci. Rep., 11 (1), 2612.

[39] Huo, C., Ouyang, J., and Yang, H., 2014, CuO nanoparticles encapsulated inside Al-MCM-41 mesoporous materials via direct synthetic route, Sci. Rep., 4 (1), 3682.

[40] Yang, G., Xu, Y., Su, X., Xie, Y., Yang, C., Dong, Z., and Wang, J., 2014, MCM-41 supported CuO/Bi2O3 nanoparticles as potential catalyst for 1,4-butynediol synthesis, Ceram. Int., 40 (3), 3969–3973.

[41] Li, X., Liu, W., Ma, J., Wen, Y., and Wu, Z., 2015, High catalytic activity of magnetic FeOx/NiOy/SBA-15: The role of Ni in the bimetallic oxides at the nanometer level, Appl. Catal., B, 179, 239–248.

[42] Hassanzadeh-Afruzi, F., Asgharnasl, S., Mehraeen, S. Amiri-Khamakani, Z., and Maleki, A., 2021, Guanidinylated SBA-15/Fe3O4 mesoporous nanocomposite as an efficient catalyst for the synthesis of pyranopyrazole derivatives, Sci. Rep., 11 (1), 19852.

[43] Pieterse, J.A.Z., Booneveld, S., and van den Brink, R.W., 2005, Evaluation of Fe-zeolite catalysts prepared by different methods for the decomposition of N2O, Appl. Catal., B, 45, 156–172.

[44] Atchudan, R., Perumal, S., Jebakumar Immanuel Edison, T.N., and Lee, Y.R., 2015, Highly graphitic carbon nanosheets synthesized over tailored mesoporous molecular sieves using acetylene by chemical vapor deposition method, RSC Adv., 5 (113), 93364–93373.

[45] Erdem, S., Erdem, B., Öksüzoglu, R.M., and Çitak, A., 2013, Bifunctional Fe-SBA-15-SO3H mesoporous catalysts with different Si/Fe molar ratios: Synthesis, characterization and catalytic activity, Bull. Korean Chem. Soc., 34 (5), 1481–1486.

[46] Costa, M.B.G., Juárez, J.M., and Anunziata, O.A., 2016, “Synthesis and Characterization of CMK Porous Carbons Modified with Metals Applied to Hydrogen Uptake and Storage” in Microporous and Mesoporous Materials, Eds. Dariani, R.S., IntechOpen, Rijeka, Croatia, 51–85

[47] Cotton, F.A., and Wilkinson, G., 1976, Basic Inorganic Chemistry, Wiley, New York, US.

[48] Qian, W., Wang, H., Chen, J., and Kong, Y., 2015, Spherical V-Fe-MCM-48: The synthesis, characterization and hydrothermal stability, Materials, 8 (4), 1752–1765.

[49] AlDhawi, Z.A., Alomair, N.A., Kochkar, H., and Grevathy, C.G., 2022, One pot synthesis of chromium incorporated SBA-16 under acid medium-application in the selective oxidation of benzyl alcohol derivatives, Arabian J. Chem., 15 (7), 103861.

[50] Yusuf, M.O., 2023, Bond characterization in cementitious material binders using Fourier-transform infrared spectroscopy, Appl. Sci., 13 (5), 3353.

[51] Casillas, P.E.G., Pérez, C.A.M., Gonzalez, C.A.R., 2012, “Infrared Spectroscopy of Functionalized Magnetic Nanoparticles” in Infrared Spectroscopy - Materials Science, Engineering and Technology, Eds. Theophanides, T., IntechOpen, Rijeka, Croatia, 405–420.

[52] Ulu, A., Noma, S., Koytepe, S., and Ates, B., 2018, Magnetic Fe3O4@MCM-41 core–shell nanoparticles functionalized with thiol silane for efficient L-asparaginase immobilization, Artif. Cells, Nanomed., Biotechnol., 46, 1035–1045.

[53] Quy, D.V., Hieu, N.M., Tra, P.T., Nam, N.H., Hai, N.H., Thai Son, N., Nghia, P.T., Anh, N.T.V., Hong, T.T., and Luong, N.H., 2013, Synthesis of silica-coated magnetic nanoparticles and application in the detection of pathogenic viruses, J. Nanomater., 2013, 603940.

[54] Sing, K.S.W., Everett, D.H., Haul., R.A.W., Moscou, L., Pierotti, R.A., Rouquérol, J., and Siemieniewska, T., 1985, Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity, Pure Appl. Chem., 57 (4), 603–619.

[55] Huang, S., Fan, Y., Cheng, Z., Kong, D., Yang, P., Quan, Z., Zhang, C., and Lin, J., 2009, Magnetic mesoporous silica spheres for drug targeting and controlled release, J. Phys. Chem. C, 113 (5), 1775–1784.

[56] He, N.Y., Cao, J.M., Bao, S.L., and Xu, Q.H., 1997, Room-temperature synthesis of an Fe-containing mesoporous molecular sieve, Mater. Lett., 31 (1-2), 133–136.

[57] Pasqua, L., Testa, F., Aiello, R., Di Renzo, F., and Fajula, F., 2001, Influence of pH and nature of the anion on the synthesis of pure and iron-containing mesoporous silica, Microporous Mesoporous Mater., 44-45, 111–117.

[58] Chastukhin, A.E., Izotov, A.D., Gorichev, I.G., and Kutepov, A.M., 2004, Analysis of the kinetics of iron(II, III) oxide dissolution in hydrochloric acid using a generalized Delmon Model, Theor. Found. Chem. Eng., 38 (1), 81–85.


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