Synthesis and Characterization of Mesoporous Ce-Mn-MCM-41 Molecular Sieves

Se Ho Park; Byong Hoo Kim; Manickam Selvaraj; Tai Gyu Lee

Journal of Industrial and Engineering Chemistry, Vol.13, No.4, 637-643, July, 2007

Export Citation

Synthesis and Characterization of Mesoporous Ce-Mn-MCM-41 Molecular Sieves

Se Ho Park, Byong Hoo Kim, Manickam Selvaraj, and Tai Gyu Lee^†

Yonsei Center for Clean Technology, Yonsei University, Seoul 120-749, Korea

E-mail:

Mesoporous Ce-Mn-MCM-41 molecular sieves with Si/(Ce+Mn) molar ratios of 43, 61, 79, and 97 were synthesized under hydrothermal conditions using CTMABr (cetyltrimethylammonium bromide) as surfactant and manganese acetate and cerium sulfate as sources of Mn and Ce, respectively . The Ce4+ and Mn3+ ions were coordinated to the silica surface. They were then characterized using several techniques, e.g., XRD (X-ray Diffraction), FTIR (Fourier Transform Infra-Red Spectroscopy), N2 physisorption, TG/DTA (Thermogravimetric/Differential Thermal Analysis), UV-vis/DRS (Diffuse Reflectance UV-vis Spectroscopy), and SEM (Scanning Electron Microscopy). XRD studies indicated that the materials had the standard MCM-41 structure. FTIR studies showed that cerium and manganese ions were incorporated into the hexagonal mesoporous materials. The thermal stabilities of the as-synthesized materials were studied using TG/DTA. A nitrogen adsorption isotherm was used to determine the specific surface area, pore diameter, and wall thickness of the calcined Ce-Mn-MCM-41. The morphology of Ce-Mn-MCM-41 was examined using SEM. The oxidation states of the incorporated cerium and manganese ions were determined using UV-vis/DRS; from these results we conclude that the Lewis acidity of the Ce-Mn-MCM-41 with Si(Ce+Mn) = 43 was higher than that of other Ce-Mn-MCM-41 samples.

Keywords:Ce-Mn-MCM-41;molecular sieves;thermal stability;acidity;CTMABr

[References]

Kresge CT, Leonowicz ME, Roth WJ, Vartuli JC, Beck JS, Nature, 359, 710 (1992)
Beck JS, Vartuli JC, Roth WJ, Leonowicz ME, Kresge CT, Schmitt KD, Chu CTW, Olson DH, Sheppard EW, McCullen SB, Higgins JB, Schlenker JL, J. Am. Chem. Soc., 114, 10834 (1992)
Sayari A, Chem. Mater., 8, 1840 (1996)
Corma A, Chem. Rev., 97(6), 2373 (1997)
Biz S, Occelli ML, Catal. Rev.-Sci. Eng., 40(3), 329 (1998)
Ying JY, Mehnert CP, Wong MS, Angew. Chem.-Int. Edit., 38, 56 (1999)
Ku HJ, Ahn BJ, Jeon BE, Chang W, J. Ind. Eng. Chem., 11(6), 841 (2005)
Jeon JK, Park YK, Kim S, Kim SS, Yim JH, Sohn JM, J. Ind. Eng. Chem., 13(2), 176 (2007)
Borade RB, Clearfield A, Catal. Lett., 31(2-3), 267 (1995)
Luan ZH, Cheng CF, Zhou WZ, Klinowski J, J. Phys. Chem., 99(3), 1018 (1995)
Corma A, Navarro MT, Prez-Pariente J, J. Chem. Soc. Chem. Commun., 147 (1994)
Reddy KM, Moudrakovski I, Sayari A, J. Chem. Soc. Chem. Commun., 1059 (1994)
Luan Z, Xu J, He HY, Klinowski J, Kevan L, J. Phys. Chem., 100, 19995 (1996)
On DT, Joshi PN, Kaliaguine S, J. Phys. Chem., 100(16), 6743 (1996)
Sayari A, Moudrakovski I, Danumah C, Ratcliffe CI, Ripmeester JA, Preston KF, J. Phys. Chem., 99(44), 16373 (1995)
Zhao DY, Goldfarb D, J. Chem. Soc. Chem. Commun., 875 (1995)
Zhao DY, Goldfarb D, in: Zeolites: A Refined Tool for Designing Catalytic Sites, L. Bonneviot, S. Kaliaguine, Eds., pp. 181-188, Elsevier, Amsterdam (1995)
Antonelli DM, Ying JY, Chem. Mater., 8, 874 (1996)
Yuan ZY, Liu SQ, Chen TH, Wang JZ, Li HX, J. Chem. Soc. Chem. Commun.,, 973 (1995)
Cheng CF, He HY, Zhou WZ, Klinowski J, Goncalves JA, Gladden LF, J. Phys. Chem., 100(1), 390 (1996)
Caps V, Tsang SC, Catal. Today, 61(1-4), 19 (2000)
Burch R, Cruise N, Gleeson D, Tsang SC, J. Chem. Soc. Chem. Commun., 951 (1996)
Yonemitsu M, Tanaka Y, Iwamoto M, Chem. Mater., 9, 2679 (1997)
Selvaraj M, Pandurangan A, Seshadri KS, Sinha PK, Lal KB, Appl. Catal. A: Gen., 242(2), 347 (2003)
Selvaraj M, Min BR, Shul YG, Lee TG, Microporous Mesoporous Mater., 74, 143 (2004)
Selvaraj M, Min BR, Shul YG, Lee TG, Microporous Mesoporous Mater., 74, 157 (2004)
Selvaraj M, Sinha PK, Lee K, Ahn I, Pandurangan A, Lee TG, Microporous Mesoporous Mater., 78, 139 (2005)
Katsuki T, J. Mol. Catal. A-Chem., 113, 87 (1996)
Kim SS, Zhang WZ, Pinnavaia TJ, Catal. Lett., 43(1-2), 149 (1997)
Kiseler AV, Lygin VI, Infrared Spectra of Surface Compounds and Adsorbed Substances, Nauka, Moskow, Russian (1992)
Shannon RD, Prewitt CT, Acta Crystallogr. Sect. B-Struct. Sci., B26, 1046 (1970)
Camblor MA, Corma A, Pereg-Pariente J, J. Chem. Soc. Chem. Commun., 557 (1993)
Greggand SJ, Sing KSW, Adsorption Surface Area and Porosity, 2nd Edn., Academic Press, New York (1982)
Pauly TR, Liu Y, Pinnavaia TJ, Billinge SJL, Rieler P, J. Am. Chem. Soc., 121, 8835 (1992)
Morey M, Davidson A, Eckert H, Stucky G, Chem. Mater., 8, 486 (1996)
Grubert G, Rathousky J, Schulz-Ekloff G, Wark M, Zukal A, Microporous Mesoporous Mater., 22, 225 (1998)
Occelli ML, Biz S, Auroux A, Ray GJ, Microporous Mesoporous Mater., 26, 193 (1998)
Chen CY, Li HX, Davis ME, Microporous Mesoporous Mater., 2, 17 (1993)
Laha SC, Mukherjee P, Sainkar SR, Kumar R, J. Catal., 207(2), 213 (2002)
Velu S, Shah N, Jyothi TM, Sivasanker S, Microporous Mesoporous Mater., 33, 61 (1999)
Steel A, Carr SW, Anderso MW, J. Chem. Soc. Chem. Commun., 1571 (1994)

[Referenced By]

[Related Articles]

[1] Kresge CT, Leonowicz ME, Roth WJ, Vartuli JC, Beck JS, Nature, 359, 710 (1992)

[2] Beck JS, Vartuli JC, Roth WJ, Leonowicz ME, Kresge CT, Schmitt KD, Chu CTW, Olson DH, Sheppard EW, McCullen SB, Higgins JB, Schlenker JL, J. Am. Chem. Soc., 114, 10834 (1992)

[3] Sayari A, Chem. Mater., 8, 1840 (1996)

[4] Corma A, Chem. Rev., 97(6), 2373 (1997)

[5] Biz S, Occelli ML, Catal. Rev.-Sci. Eng., 40(3), 329 (1998)

[6] Ying JY, Mehnert CP, Wong MS, Angew. Chem.-Int. Edit., 38, 56 (1999)

[7] Ku HJ, Ahn BJ, Jeon BE, Chang W, J. Ind. Eng. Chem., 11(6), 841 (2005)

[8] Jeon JK, Park YK, Kim S, Kim SS, Yim JH, Sohn JM, J. Ind. Eng. Chem., 13(2), 176 (2007)

[9] Borade RB, Clearfield A, Catal. Lett., 31(2-3), 267 (1995)

[10] Luan ZH, Cheng CF, Zhou WZ, Klinowski J, J. Phys. Chem., 99(3), 1018 (1995)

[11] Corma A, Navarro MT, Prez-Pariente J, J. Chem. Soc. Chem. Commun., 147 (1994)

[12] Reddy KM, Moudrakovski I, Sayari A, J. Chem. Soc. Chem. Commun., 1059 (1994)

[13] Luan Z, Xu J, He HY, Klinowski J, Kevan L, J. Phys. Chem., 100, 19995 (1996)

[14] On DT, Joshi PN, Kaliaguine S, J. Phys. Chem., 100(16), 6743 (1996)

[15] Sayari A, Moudrakovski I, Danumah C, Ratcliffe CI, Ripmeester JA, Preston KF, J. Phys. Chem., 99(44), 16373 (1995)

[16] Zhao DY, Goldfarb D, J. Chem. Soc. Chem. Commun., 875 (1995)

[17] Zhao DY, Goldfarb D, in: Zeolites: A Refined Tool for Designing Catalytic Sites, L. Bonneviot, S. Kaliaguine, Eds., pp. 181-188, Elsevier, Amsterdam (1995)

[18] Antonelli DM, Ying JY, Chem. Mater., 8, 874 (1996)

[19] Yuan ZY, Liu SQ, Chen TH, Wang JZ, Li HX, J. Chem. Soc. Chem. Commun.,, 973 (1995)

[20] Cheng CF, He HY, Zhou WZ, Klinowski J, Goncalves JA, Gladden LF, J. Phys. Chem., 100(1), 390 (1996)

[21] Caps V, Tsang SC, Catal. Today, 61(1-4), 19 (2000)

[22] Burch R, Cruise N, Gleeson D, Tsang SC, J. Chem. Soc. Chem. Commun., 951 (1996)

[23] Yonemitsu M, Tanaka Y, Iwamoto M, Chem. Mater., 9, 2679 (1997)

[24] Selvaraj M, Pandurangan A, Seshadri KS, Sinha PK, Lal KB, Appl. Catal. A: Gen., 242(2), 347 (2003)

[25] Selvaraj M, Min BR, Shul YG, Lee TG, Microporous Mesoporous Mater., 74, 143 (2004)

[26] Selvaraj M, Min BR, Shul YG, Lee TG, Microporous Mesoporous Mater., 74, 157 (2004)

[27] Selvaraj M, Sinha PK, Lee K, Ahn I, Pandurangan A, Lee TG, Microporous Mesoporous Mater., 78, 139 (2005)

[28] Katsuki T, J. Mol. Catal. A-Chem., 113, 87 (1996)

[29] Kim SS, Zhang WZ, Pinnavaia TJ, Catal. Lett., 43(1-2), 149 (1997)

[30] Kiseler AV, Lygin VI, Infrared Spectra of Surface Compounds and Adsorbed Substances, Nauka, Moskow, Russian (1992)

[31] Shannon RD, Prewitt CT, Acta Crystallogr. Sect. B-Struct. Sci., B26, 1046 (1970)

[32] Camblor MA, Corma A, Pereg-Pariente J, J. Chem. Soc. Chem. Commun., 557 (1993)

[33] Greggand SJ, Sing KSW, Adsorption Surface Area and Porosity, 2nd Edn., Academic Press, New York (1982)

[34] Pauly TR, Liu Y, Pinnavaia TJ, Billinge SJL, Rieler P, J. Am. Chem. Soc., 121, 8835 (1992)

[35] Morey M, Davidson A, Eckert H, Stucky G, Chem. Mater., 8, 486 (1996)

[36] Grubert G, Rathousky J, Schulz-Ekloff G, Wark M, Zukal A, Microporous Mesoporous Mater., 22, 225 (1998)

[37] Occelli ML, Biz S, Auroux A, Ray GJ, Microporous Mesoporous Mater., 26, 193 (1998)

[38] Chen CY, Li HX, Davis ME, Microporous Mesoporous Mater., 2, 17 (1993)

[39] Laha SC, Mukherjee P, Sainkar SR, Kumar R, J. Catal., 207(2), 213 (2002)

[40] Velu S, Shah N, Jyothi TM, Sivasanker S, Microporous Mesoporous Mater., 33, 61 (1999)

[41] Steel A, Carr SW, Anderso MW, J. Chem. Soc. Chem. Commun., 1571 (1994)