One-Pot Room-Temperature Synthesis of Mg Containing MCM-41 Mesoporous Silica for Aldol Reactions

doi:10.1016/j.jmst.2016.08.025

Abstract

Abstract:

One-pot synthesis of Mg containing MCM-41 (Mg-MCM-41) materials was respectively carried out by a room temperature (RT) method and a hydrothermal (HT) method for aldol condensation of 4-nitrobenzaldehyde and acetone and self-condensation of acetone. The RT method can prepare MCM-41 materials containing large amounts of Mg while maintaining the structural characteristics of MCM-41 even at very low Si/Mg ratios (large Mg loadings), but the HT method cannot. The RT method can also give more active catalysts than the HT method, because the catalysts prepared by the RT method are more basic than those prepared by the HT one. The characterization indicates that Mg atoms in the Mg-MCM-41 prepared by the RT method exist as MgO disperses well on the wall surface of pores, while those in Mg-MCM-41 prepared by the HT method are included in the bulk with a smectite-like structure.

Key words: Aldol condensation, Solid base catalyst, Mg incorporated mesoporous silica, Magic angle spinning nuclear magnetic resonance

Shin-Ichiro Fujita, Shinji Segawa, Kazuki Kawashima, Xuejing Nie, Tomoki Erata, Masahiko Arai. One-Pot Room-Temperature Synthesis of Mg Containing MCM-41 Mesoporous Silica for Aldol Reactions[J]. J. Mater. Sci. Technol., 2018, 34(12): 2521-2528.

Figures/Tables 12

Scheme 1. (a) Aldol condensation of nitrobenzaldehyde and acetone and (b) self-condensation of acetone.

Fig. 1. Pore size distribution curves of some selected MCM-41 samples prepared by the RT method and by the HT method. The Si/Mg ratio was 2.7 for all Mg containing samples and the Si/Al ratio was 30 for all Al containing samples.

Table 1 Textural properties of MCM-41 materials prepared

Sample	S_BET (m² g^-1)	V_pore (mL g^-1)
MCM-RT	1045	1.52
Mg-MCM-RT^a	883	1.22
Mg-Al-MCM-RTa, b	852	1.53
MCM-HT	872	0.87
Mg-MCM-HT^a	556	0.92
Mg-Al-MCM-HTa, b	483	1.02

Fig. 2. Small-angle XRD patterns of some selected MCM-41 samples prepared (a) by the RT method and (b) by the HT method. The Si/Mg ratio was 2.7 for all Mg containing samples and the Si/Al ratio was 30 for all Al containing samples. The patterns were moved vertically for clarity.

Fig. 3. TEM images of Mg-Al-MCM-RT and Mg-Al-MCM-HT. For both the samples, the Si/Mg and Si/Al ratios were 2.7 and 30, respectively.

Fig. 4. Effects of the Mg loading and the preparation method on the catalytic activity of Mg incorporated MCM-41 for the aldol condensation of 4-nitrobenzaldehyde and acetone. (○) Mg-MCM-RT, (●) Mg-Al-MCM-RT, (□) Mg-MCM-HT, (■) Mg-Al-MCM-HT. Reaction conditions: 4-nitrobenzaldehyde 0.5 mmol, acetone 10 mL, catalyst 50 mg, 353 K, 7 h.

Fig. 5. Comparison between (○) Mg-MCM-RT and (□) Mg-MCM-HT in the catalytic activity for the self-condensation of acetone. Reaction conditions: acetone 10 mL, catalyst 50 mg, 353 K, 2 h.

Fig. 6. Large-angle XRD patterns of Mg-MCM-RT and Mg-MCM-HT. Numbers in the figure represent the Si/Mg ratios in the samples examined. The patterns were moved vertically for clarity.

Fig. 7. Diffuse reflectance UV-Vis spectra of (a) Mg-MCM-RT and (b) Mg-MCM-HT. Si/Mg ratio was 2.7 for both samples.

Fig. 8. 29Si MAS NMR spectra of (a) Mg-MCM-RT and (b) Mg-MCM-HT. Si/Mg ratio was 2.7 for both samples.

Fig. 9. 29Si CP MAS NMR spectra (a) of Mg-MCM-RT and (b) Mg-MCM-HT. Si/Mg ratio was 2.7 for both samples.

Scheme 2. States of Mg atoms in (a) Mg-MCM-RT and (b) Mg-MCM-HT.

References

[1]	C.T. Kresge, M.E. Leonowicz, W.J. Roth, J.C. Vartuli, J.S. Beck, Nature 359 (1992)710-713.
[2]	C.T. Kresge, J.S. Beck, J.C. Vartuli, W.J. Roth, M.E. Leonowicz, K.D. Schmitt,C.T.W. Chu, D.H. Olson, E.W. Sheppard, S.B. McCullen, J.B. Higgins, J.L.Schlenker, J. Am. Chem. Soc 114 (1992) 10834-10843.
[3]	G.J.A.A. Soler-Illia, C. Sanchez, B. Lebeau, J. Patarin, Chem. Rev 102 (2002)4093-4138.
[4]	Q.S. Huo, J.L. Feng, F. Schüth, G.D. Stucky, Chem. Mater 9 (1997) 14-17.
[5]	Q. Cai, Z.S. Luo, W.Q. Pang, Y.W. Fan, X.H. Chen, F.Z. Cui, Chem. Mater 13(2001) 258-263.
[6]	M. Grün, I. Lauer, K.K. Unger, Adv. Mater 9 (1997) 254-257.
[7]	R. Mokoya, W. Jones, Chem. Commun(1997) 2185-2186.
[8]	C.Y. Chen, H.X. Li, M.E. Davis, Microporous Mater 2 (1993) 17-26.
[9]	R. Schmidt, D. Akporiaye, M. St?cker, O.H. Ellestad, J. Chem. Soc.Chem.Commun(1994) 1493-1494.
[10]	A. Corma, V. Fornés, M.T. Navarro, J. Pérez-Pariente, J. Catal 148 (1994)569-574.
[11]	Z.H. Luan, C.F. Cheng, W.Z. Zhou, J. Klinowski, J. Phys. Chem 99 (1995)1018-1024.
[12]	R.B. Boade, A. Clearfield, Catal. Lett 32 (1995) 267-272.
[13]	Z. Luan, C.F. Cheng, W. Zhou, J. Klinowski, J. Phys. Chem 99 (1995) 1018-1024.
[14]	R. Mokaya, W. Jones, Z. Luan, M.D. Alba, J. Klinowski, Catal. Lett 37 (1996)113-120.
[15]	X.S. Zhao, G.Q. Lu, G.J. Millar, Ind. Eng. Chem. Res 35 (1996) 2075-2090.
[16]	F. Shang, H. Liu, J. Sun, B. Liu, C. Wang, J. Guan, Q. Kan, Catal. Commun 12(2011) 739-743.
[17]	K.M. Reddy, I. Moudrakouski, A. Sayari, J. Chem. Soc.Chem. Commun(1994)1059-1060.
[18]	P.T. Tanev, M. Chibwe, T.J. Pinnavaia, Nature 368 (1994) 321-323.
[19]	A. Corma, M.T. Navarro, J.P. Pariente, J. Chem. Soc.Chem. Commun(1994)148-149.
[20]	K. Lin, P.P. Pescarmona, H. Vandepitte, D. Liang, G.V. Tendeloo, P.A. Jacobs, J.Catal 254 (2008) 64-70.
[21]	K. Lin, P.P. Pescarmona, K. Houthoofd, D. Liang, G.V. Tendeloo, P.A. Jacobs, J.Catal 263 (2009) 75-82.
[22]	D. Zhao, D. Goldfarb, J. Chem. Soc.Chem. Commun(1995) 875-876.
[23]	L.Z. Wang, J.L. Shi, J. Yu, D.S. Yan, Nanostruct. Mater 10 (1998) 1289-1299.
[24]	Z.Y. Yuan, S.Q. Liu, T.H. Chen, Z.J.Z.Wang, H.X. Li, J. Chem. Soc. Chem. Commun9(1995) 973-974.
[25]	A. Sayari, C. Danumah, I.L. Moudrakovski, Chem. Mater 7 (1995) 813-815.
[26]	A. Matsumoto, H. Chen, K. Tsutsumi, M. Grün, K. Unger, Micropor. Mesopor.Mater 32 (1999) 55-62.
[27]	J. Aguado, D.P. Serrano, J.M. Escola, Micropor. Mesopor. Mater 34 (2000)45-54.
[28]	D.P. Serrano, R.V. Grieken, J. Antonio, A. Galcía, Appl. Catal. A Gen 319 (2007)171-180.
[29]	Z. Wang, Y. Jiang, R. Rachwalik, Z. Liu, J. Shi, M. Hunger, J. Huang, Chem. Chat.Chem 5 (2013) 3889-3896.
[30]	H. Hattori, Chem. Rev 95 (1995) 537-558.
[31]	K. Tanabe, W. H?lderich, Appl. Catal. A Gen 181 (1999) 399-434.
[32]	H. Hattori, Appl. Catal. A Gen 222 (2001) 247-259.
[33]	R.J. Davis, J. Catal 216 (2003) 396-405.
[34]	Y. Ono, J. Catal 216 (2003) 406-415.
[35]	J. Weitkamp, M. Hunger, U. Rysma, Micropor. Mesopor. Mater 48 (2001)255-270.
[36]	A.P. Wight, M.E. Davis, Chem. Rev 102 (2002) 3589-3614.
[37]	F. Hoffmann, M. Cornelius, J. Morell, M. Fr?ba, Angew. Chem. Int. Ed. Engl 45(2006) 3216-3251.
[38]	J.I. Yu, S. Yi, A.N. Ko, Catal. Lett 77 (2001) 165-169.
[39]	T. Wang, G. Wu, N. Guan, L. Li, Micropor. Mesopor. Mater 148 (2012) 184-190.
[40]	J. Tantirungrotechai, P. Thananupappaisal, B. Yoosuk, N. Viriya-empikul, K.Faungnawakij, Catal. Commun 16 (2011) 25-29.
[41]	R.K. Zeidan, S.J. Hwang, M.E. Davis, Angew. Chem. Int. Ed. Engl 45 (2006)6332-6335.