Escolar Documentos
Profissional Documentos
Cultura Documentos
a r t i c l e i n f o a b s t r a c t
Article history: We report a new strategy for one-pot synthesis of potassium-loaded MgAl oxides using KOH to adjust
Received 2 March 2013 the pH value of the reaction system. The as-prepared solid superbases were studied by N2 physisorp-
Received in revised form 26 June 2013 tion method, energy-dispersive X-ray spectroscopy, powder X-ray diffraction, and Fourier transform
Accepted 29 June 2013
infrared. The superbasic sites were characterized by the use of Hammett indicators and CO2 temperature-
Available online 9 July 2013
programmed desorption. We found that with a base strength (H ) above 26.5, the potassium-loaded MgAl
oxides showed high catalytic activity for Knoevenagel condensation at room temperature. Furthermore,
Keywords:
the higher the superbasicity and/or the more the amount of superbasic sites, the better is the catalytic
Solid superbase
MgAl oxides
activity. The ndings open up a new route for the synthesis of new functional superbases using composite
Catalyst oxides as supports.
Knoevenagel condensation 2013 Elsevier B.V. All rights reserved.
0926-860X/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.apcata.2013.06.054
34 J. Zhao et al. / Applied Catalysis A: General 467 (2013) 3337
*
* * * (d)
Intensity(a.u.)
(c)
(a)
Table 1
Physicochemical characteristics of MgAl(O) and nK-MgAl(O) samples.
Samplea SBET b (m2 /g) V b (cm3 /g) Dp b (nm) Base strength (H ) Superbasic sites (mmol/g) Total basicity (mmol/g)
(A) (B)
(a)
(a)
(b)
(b)
(c)
(c)
(d) (d)
Fig. 2. (A) N2 adsorption/desorption isotherms and (B) pore-size distributions of (a) MgAl(O), (b) 5.9% K-MgAl(O), (c) 10.3% K-MgAl(O) and (d) 16.6% K-MgAl(O).
3.1.4. FT-IR potassium species, there is the creation of basic sites and promoted
Fig. 3 gives the IR spectra of as-synthesized MgAl(O) and 10.3% K- CO2 adsorption.
MgAl(O). For the two samples, the broad band at around 3450 cm1
is assigned to OH stretching vibration of the hydroxyl groups
attached to Al and Mg. The bands in the 450-655 cm1 region are
attributable to the vibration of metal oxides [19,26]. In addition, 3.1.5. Basicity measurement
10.3% K-MgAl(O) shows IR bands at 1440 and 1385 cm1 ascrib- 3.1.5.1. Hammett indicator method. The base strength (H ) and
able to C O symmetric stretching vibration of surface bicarbonate amount of basic sites of samples were measured using Ham-
species and O C O stretching vibration of monodentate carbon- mett indicators (Table 1). One can see that the base strength of
ate species, respectively, with the latter being stronger than the MgAl(O) is in the 18.4 H < 22.5 range. With the introduction of
former [27]. The results demonstrate that with the introduction of potassium species, basic strength of K-MgAl(O) samples are in the
26.5 H < 33.0 range. It is clear that the K-MgAl(O) materials can
be regarded as solid superbases [1]. The superbases are different in
the amount of superbasic sites, with a maximum (0.411 mmol/g)
(b) observed at potassium loading of 10.3%. In other words, to opti-
mize the generation of superbasic sites, a potassium loading around
10.3% is the most appropriate, in consistent with the results of XRD
Transmittance(a.u.)
investigation.
(a) 3.1.5.2. CO2 -TPD. The basicity of samples was further investigated
by CO2 -TPD. As depicted in Fig. 4, the MgAl(O) sample shows main
desorption peaks at ca. 139 and 643 C. After introducing potas-
sium, desorption peaks are observed at ca. 286, 610, and 726 C.
1440
1385
Table 2
Knoevenagel condensation of various aldehydes with active methylene compounds over 10.3% K-MgAl(O).
1 Benzaldehyde CN 10 97.8
2 Benzaldehyde COOEt 60 93.9
3 4-Nitro benzaldehyde CN 10 99.1
4 4-Nitro benzaldehyde COOEt 60 98.9
5 3-Nitro benzaldehyde CN 10 99.4
6 3-Nitro Benzaldehyde COOEt 60 99.9
7 2-Nitro benzaldehyde CN 10 99.8
8 2-Nitro benzaldehyde COOEt 60 98.9
9 4-Chloro benzaldehyde CN 10 94.9
10 4-Chloro benzaldehyde COOEt 60 98.5
11 2-Chloro benzaldehyde CN 10 99.6
12 2-Chloro benzaldehyde COOEt 60 99.5
13 4-Methyl benzaldehyde CN 10 96.2
14 4-Methyl benzaldehyde COOEt 60 93.3
15 4-Methoxy benzaldehyde CN 10 98.6
16 4-Methoxy benzaldehyde COOEt 60 88.9
17 Furfural CN 10 99.4
18 Furfural COOEt 60 99.9
Reaction conditions: aldehyde, 2 mmol; active methylene compound, 2 mmol; catalyst, 0.02 g; DMF, 1 mL.
Table 3
Recycling test results over 10.3% K-MgAl(O) samples.
(b) 0 93.9
1 92.7
2 91.4
3 90.7
80 0.4 by Choudary et al. [29] and Postole et al. [30]. That is to say, 10.3%
K-MgAl(O) can be regarded as an excellent catalyst for Knoevenagel
(a) condensation reactions.
60 0.3
3.2.3. Catalyst recyclability
40 0.2 The recyclability of catalyst was tested by carrying out repeated
(b)
runs of the same reaction system (Table 3). For each recycle, the
catalyst was recovered by centrifugation, and was immediately
20 0.1
reused (with the addition of reactants) without any treatment. It
was observed that the activity of catalyst slightly decreased after
0 0 the third cycle.
0 5 10 15 20
4. Conclusions
K loading amount (wt%)
Fig. 5. Effects of potassium loading on (a) catalytic activity and (b) the amount of Potassium-loaded MgAl oxides were synthesized by a one-pot
superbasic sites of the obtained samples. method. The strength of the solid superbases is in the H range of
J. Zhao et al. / Applied Catalysis A: General 467 (2013) 3337 37
26.533.0 with the amount of superbasic sites up to 0.411 mmol/g. [7] Y. Wang, W.Y. Huang, Y. Chun, J.R. Xia, J.H. Zhu, Chem. Mater. 13 (2001)
They are efcient catalysts for Knoevenagel condensation reactions, 670677.
[8] H. Tsuji, H. Kabashima, H. Kita, H. Hattori, React. Kinet. Catal. Lett. 56 (1995)
and the higher the superbasicity and/or the more the amount of 363369.
superbasic sites, the better is the catalytic activity. The ndings [9] S.F. Yin, B.Q. Xu, S.J. Wang, C.T. Au, Appl. Catal. A: Gen. 301 (2006) 202210.
open up a new strategy for the synthesis of new functional super- [10] Y. Wang, J.H. Zhu, W.Y. Huang, Phys. Chem. Chem. Phys. 3 (2001) 25372543.
[11] L.B. Sun, J.H. Kou, Y. Chun, J. Yang, F.N. Gu, Y. Wang, J.H. Zhu, Z.G. Zou, Inorg.
bases using composite oxides as supports. Chem. 47 (2008) 41994208.
[12] K.K. Rao, M. Gravelle, J.S. Valente, F. Figueras, J. Catal. 173 (1998) 115121.
Acknowledgments [13] D. Tichit, B. Coq, S. Cerneaux, R. Durand, Catal. Today 75 (2002) 197202.
[14] A. Corma, V. Fornes, R. Martin-Aranda, F. Rey, J. Catal. 134 (1992) 5865.
[15] M. Lakshmi Kantam, B.M. Choudary, B. Choudary, Ch. Venkat Reddy, K.
The project was nancially supported by the National Natural Koteswara Rao, F. Figueras, Chem. Commun. (1998) 10331034.
Science Foundation of China (Grant nos. U1162109, 20873038), [16] A. Guida, M.H. Lhouty, D. Tichit, F. Figueras, P. Geneste, Appl. Catal. A: Gen. 164
(1997) 251264.
Hunan Provincial Natural Science Foundation of China (10JJ1003), [17] B.M. Choudary, M. Lakshmi Kantam, Ch. Venkat Reddy, K. Koteswara Rao, F.
the program for New Century Excellent Talents in Universities Figueras, J. Mol. Catal. A: Chem. 146 (1999) 279284.
(NCET-10-0371), Program for Changjiang Scholars and Innova- [18] L.J. Gao, B. Xu, G.M. Xiao, J.H. Lv, Energy Fuels 22 (2008) 35313535.
[19] T. Tittabut, W. Trakarnpruk, Ind. Eng. Chem. Fundam. 47 (2008) 21762181.
tive Research Team in University (IRT1238), and the Fundamental
[20] W. Trakarnpruk, S. Porntangjitlikit, Renew. Energy 33 (2008) 15581563.
Research Funds for the Central Universities. C.T. Au thanks the [21] J.M. Clacens, D. Genuit, L. Delmotte, A. Garcia-Ruiz, G. Bergeret, R. Montiel, J.
Hunan University for an adjunct professorship. Lopez, F. Figueras, J. Catal. 221 (2004) 483490.
[22] S.G. Zhang, Y.D. Wei, S.F. Yin, C.T. Au, Catal. Commun. 12 (2011) 712716.
[23] X. Deng, Z. Fang, Y.H. Liu, C.L. Yu, Energy 36 (2011) 777784.
References [24] V.K. Dez, C.R. Apestegua, J.I. Di Cosimo, J. Catal. 240 (2006) 235244.
[25] V.K. Dez, C.R. Apestegua, J.I. Di Cosimo, Catal. Today 63 (2000) 5362.
[1] K. Tanabe, M. Misono, Y. Ono, H. Hattori, New Solid Acids and Bases, Their [26] X.F. Liu, B.B. Fan, S.C. Gao, R.F. Li, Fuel Process. Technol. 106 (2013) 761768.
Catalytic Properties, Tokoy, Kodansha, 1989, pp. 3. [27] T.T. Li, L.B. Sun, L. Gong, X.Y. Liu, X.Q. Liu, J. Mol. Catal. A: Chem. 352 (2012)
[2] H. Hattori, Chem. Rev. 95 (1995) 537558. 3844.
[3] Y.D. Wei, S.G. Zhang, G.X. Li, S.Y. Yin, C.T. Au, Chin. J. Catal. 32 (2011) 891898. [28] S.G. Zhang, Y.D. Wei, S.F. Yin, S.L. Luo, C.T. Au, Appl. Catal. A: Gen. 406 (2011)
[4] J.H. Zhu, Y. Wang, Y. Chun, X.S. Wang, J. Chem. Soc., Faraday Trans. 94 (1998) 113118.
11631169. [29] B.M. Choudary, M. Lakshmi Kantam, V. Neeraja, K. Koteswara Rao, F. Figueras,
[5] L.B. Sun, J. Yang, J.H. Kou, F.N. Gu, Y. Chun, Y. Wang, J.H. Zhu, Z.G. Zou, Angew. L. Delmotte, Chem. Commun. (2001) 257260.
Chem. Int. Ed. 47 (2008) 34183421. [30] G. Postole, B. Chowdhury, B. Karmakar, K. Pinki, J. Banerji, A. Auroux, J. Catal.
[6] Y. Wang, W.Y. Huang, Z. Wu, Y. Chun, J.H. Zhu, Mater. Lett. 46 (2000) 198204. 269 (2010) 110121.