Applied Catalysis A: General 467 (2013) 3337

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Applied Catalysis A: General

journal homepage: www.elsevier.com/locate/apcata

One-pot synthesis of potassium-loaded MgAl oxide as solid superbase

catalyst for Knoevenagel condensation
Jin Zhao a , Jun Xie a , Chak-Tong Au a,b , Shuang-Feng Yin a,
a
State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082,
Hunan, China
b
Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong

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.

1. Introduction [1820]). However, there is no report on superbases of MgAl mixed

According to the denition of Tanabe et al. [1], solid superbases
are materials that possess basic sites with strength (H ) higher
than 26 (H corresponding to the pKa value of the indicator). With
increasing demand on environment-benign processes, the use of
solid superbases has become attractive because they catalyze a
number of organic reactions under mild conditions with signi-
cant reduction in pollutant generation [13]. In the past decades,
there has been rapid development in research of solid superbase
catalysts such as KNO3 /-Al2 O3 [4,5], KNO3 /ZrO2 [6,7], KF/-Al2 O3
[8], KOH/ZrO2 [9], K2 CO3 /-Al2 O3 [10], and Ca(NO3 )2 /SBA-15 [11].
It is noted that only a few types of support materials were employed
for the preparation of superbases: -Al2 O3 [4,5,8], ZrO2 [6,7,9] and
mesoporous molecular sieves like SBA-15 [11]. For synthesis of
novel superbases in the future, the selection and/or synthesis of
suitable support materials should be considered as essential. It is
known that the generation of superbases is a complicated business
[411].
In recent years, MgAl mixed oxides are widely used as solid base
catalysts or basic supports in chemical reactions (e.g. aldol conden-
sation [12,13], Knoevenagel condensation [14,15], ClaisenSchmidt
condensation [16], Michael addition [17] and transesterication
Corresponding author. Tel.: +86 731 88821171; fax: +86 731 88821171.
E-mail address: sf yin@hnu.edu.cn (S.-F. Yin).
oxides or MgAl mixed oxides that have been modied with alkali or
alkine earth elements. Nonetheless, a study of Clacens et al. demon-
strated that the use of a basic support favored the generation of
stronger basic sites [21]. Herein, we report a new strategy for one-
pot synthesis of potassium-loaded MgAl oxides, using KOH for pH
adjustment. Compared to the known grinding and wet impregna-
tion methods, the adopted one-pot approach for the generation of
solid superbases is both time and energy saving because post treat-
ment is not required. We characterized the structure and surface
properties of the potassium-loaded MgAl oxides, and examined
their catalytic activity toward Knoevenagel condensation reactions
at room temperature (RT).
2. Experiment
2.1. Chemicals and reagents
Most of the reagents and chemicals (analytic grade unless
stated otherwise) were obtained from Kemiou Chemical Reagent
Company and Tianjin Damao Chemical Reagent Co. Ltd. (Tianjin,
China). Ethyl cyanoacetate and malononitrile were purchased from
Aladdin Chemistry Co. Ltd. (Shanghai, China), and were dehydrated
using 3 A molecular sieves at RT before use. Cyclohexane was dried
by sodium under reux. Aldehydes were puried by reduced pres-
sure distillation (to remove benzoic acid) prior to use.

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
Scheme 1. Knoevenagel condensation of various aldehydes with active methylene
compounds.
2.2. Catalysts preparation
In a typical procedure, 3.846 g of Mg(NO3 )2 6H2 O and 1.876 g of
Al(NO3 )3 9H2 O were dissolved separately in deionized water, and
then mixed homogeneously (Mg/Al molar ratio = 3). An aqueous
solution of 1 M KOH containing 0.047 mmol of potassium was then
added dropwise with vigorous stirring. The mixture was digested
under reux at 366 K for 24 h. The obtained solid was washed with
25, 50, 100, or 200 mL of water for the adjustment of potassium con-
tent. Finally, the material was dried at 110 C overnight and calcined
at 550 C under a ow of N2 (Purity: 99.999%) for 3 h. Hereinafter,
the catalysts are denoted as MgAl(O) when there was no potassium
loading, and nK-MgAl(O) where n stands for the weight percentage
of loaded potassium.
2.3. Catalyst characterization
XRD patterns were recorded on a Brucker D8 advance diffrac-
tometer with monochromatized Cu K radiation ( = 0.15406 nm)
at a setting of 40 kV and 40 mA. The content of potassium was
determined using an energy-dispersive X-ray spectroscopic (EDXS)
analyzer. The specic surface areas of catalysts were deter-
mined by BET method based on nitrogen adsorptiondesorption
isotherms (at 77 K) collected over a Beckman (SA 3100) sur-
face area analyzer. The FTIR spectra were determined using a
Bruker vector 22 FTIR spectrophotometer (using KBr tablets).
CO2 -TPD measurements were conducted on a Micromeritics 2920
apparatus using thermal conductivity detector. The base strength
(H ) of the sample was also determined by Hammett indica-
tors [22]. To measure the total basicity, the activated samples
was immersed in 0.05 mol/L HCl (20 mL) with stirring, and the
remaining acid was then titrated against standard NaOH solution
(0.02 mol/L).
2.4. Catalyst evaluation
Catalytic activity of the prepared materials was evaluated in
the base-catalyzed Knoevenagel condensation of aldehydes and
methylene compounds (Scheme 1). In a typical run, aldehyde
(2 mmol), active methylene reagent (2 mmol), catalyst (20 mg),
and DMF (1 mL) were mixed in a 25 mL round-bottomed ask.
The reaction was monitored by thin layer chromatography
(TLC). After the reaction, the mixture was subject to centrifuga-
tion for catalyst recovery. The reaction mixtures were analyzed
using an Agilent Technologies 7820 gas chromatograph equipped
with a ame ionization detector and AB-FFAP capillary column
(30 m 0.25 mm 0.25 m). The conversion of aldehydes was
determined using biphenyl as internal standard. All the products
were analyzed over an Agilent 6890-5973 MSD GCMS equipment,
and conrmed by 1 H NMR. The 1 H NMR spectra were recorded at
25 C over an INOVA-400 M (Varian) instrument calibrated using
tetramethylsilane (TMS) as internal standard.
*
* * * (d)
Intensity(a.u.)
(c)
(b)
(a)
5 15 25 35 45 55 65 75
2(degree)
Fig. 1. XRD patterns of (a) MgAl(O), (b) 5.9% K-MgAl(O), (c) 10.3% K-MgAl(O) and
(d) 16.6% K-MgAl(O). , K2 O; *, KNO3 .
3. Results and discussion
3.1. Catalyst characterization
3.1.1. EDXS
The potassium contents in MgAl(O) as determined by EDXS are
listed in Table 1. For each of the samples, potassium content was
similar at randomly selected spots, suggesting homogeneous dis-
tribution of potassium species.
3.1.2. XRD
Displayed in Fig. 1 are the XRD patterns of MgAl(O) and nK-
MgAl(O) samples. In Fig. 1a, the MgAl(O) sample shows peaks at
2 = 35.7, 43.3 and 62.8, attributable to the MgAlO phase or a phase
that is MgO-like [19,23]. The XRD pattern of 5.9% K-MgAl(O) is sim-
ilar to that of MgAl(O) (Fig. 1b). Over 10.3% K-MgAl(O), there is
the detection of weak signals ascribable to K2 O (JCPDS le 23-493)
(Fig. 1c). In other words, below a K-loading of 10.3%, there is high
dispersion of potassium species. However, over 16.6% K-MgAl(O),
there is the detection of signals attributable to KNO3 (JCPDS le
5-377) (Fig. 1d). The results indicate that there exists a dispersion
threshold on MgAl(O), a kind similar to the dispersion of KNO3 on
zirconia [7] or K2 CO3 on alumina [10]. The highest spontaneous
dispersion capacity of potassium on MgAl(O) is around 10.3%.
3.1.3. N2 adsorption/desorption isotherm
N2 adsorption/desorption isotherms and pore-size distributions
of nK-MgAl(O) samples are given in Fig. 2. The corresponding BET
surface area, pore volume, and average pore diameter are listed in
Table 1. The isotherms are type-IV, showing no or little uptake at
high partial pressure. Every isotherm has a clear hysteresis loop
that indicates mesoporosity of materials [5]. Additionally, the sam-
ples exhibit uniformity in terms of pore-size distribution. The BET
surface area of MgAl(O) is 154.1 m2 /g. The introduction of potas-
sium species leads to gradual decrease of BET surface area: 121.9,
46.2, and 19.6 m2 /g at potassium loadings of 5.9, 10.3 and 16.6%,
respectively. The pore volumes of samples follow a similar trend,
being 0.604, 0.474, 0.286 and 0.136 cm3 /g for MgAl(O), 5.9% K-
MgAl(O), 10.3% K-MgAl(O) and 16.6% K-MgAl(O), respectively. Di
Cosimo et al. reported that the modication of MgO with alkali
metals would result in a decline of specic surface area and pore
volume [24,25]. Based on the results, we deduce that with increase
of potassium content, there is rise of MgAl(O) pore blockage, and
hence drop in specic surface area and pore volume.
 J. Zhao et al. / Applied Catalysis A: General 467 (2013) 3337 35

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)

MgAl(O) 154.1 0.604 9.7 18.4 H < 22.5 0 0.416

5.9% K MgAl(O) 121.9 0.474 12.5 26.5 H < 33.0 0.325c , 0.312d 0.975
10.3% K MgAl(O) 46.2 0.286 12.7 26.5 H < 33.0 0.411c , 0.390d 1.783
16.6% K MgAl(O) 19.6 0.136 17.8 26.5 H < 33.0 0.369c , 0.328d 2.361
a
K loading contents detected by EDXS.
b
SBET , BET specic surface area; V , pore volume; Dp , average pore diameter.
c
Measured by Hammett indicators method.
d
Measured by CO2 -TPD.

(A) (B)

(a)

(a)
(b)
(b)
(c)
(c)
(d) (d)

0 0.2 0.4 0.6 0.8 1 0 50 100

P/P0 Dp/nm

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
Fig. 3 gives the IR spectra of as-synthesized MgAl(O) and 10.3% K-
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,
10.3% K-MgAl(O) shows IR bands at 1440 and 1385 cm1 ascrib-
able to C O symmetric stretching vibration of surface bicarbonate
species and O C O stretching vibration of monodentate carbon-
ate species, respectively, with the latter being stronger than the
former [27]. The results demonstrate that with the introduction of
(b)
Transmittance(a.u.)
potassium species, there is the creation of basic sites and promoted
CO2 adsorption.
3.1.5. Basicity measurement
3.1.5.1. Hammett indicator method. The base strength (H ) and
amount of basic sites of samples were measured using Ham-
mett indicators (Table 1). One can see that the base strength of
MgAl(O) is in the 18.4 H < 22.5 range. 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)
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

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

The emergence of desorption peaks at ca. 726 C is a clear indica-

tion of superbasicity [27,28]. The amounts of superbasic sites of
K-MgAl(O) samples were also calculated by the integral method
3600 2800 2000 1200 400 based on the area of the corresponding desorption peaks; they are
-1 0.312, 0.390 and 0.328 mmol/g, respectively (Table 1). It is apparent
Wavenumber(cm )
that the CO2 -TPD results are in good agreement with those obtained
Fig. 3. FT-IR spectra of (a) MgAl(O) and (b) 10.3% K-MgAl(O). by the Hammett-indicator method (Table 1).
36 J. Zhao et al. / Applied Catalysis A: General 467 (2013) 3337

Table 2
Knoevenagel condensation of various aldehydes with active methylene compounds over 10.3% K-MgAl(O).

Entry Aldehydes Methylene compounds (R1 ) Time (min) Yield (%)

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.

Cycle Yield (%)

CO2 desorbed(a.u.)

(b) 0 93.9
1 92.7
2 91.4
3 90.7

(a) Reaction conditions: benzaldehyde, 2 mmol; ethyl cyanoacetate, 2 mmol; catalyst,

0.02 g; DMF, 1 mL; time, 60 min.

potassium loading, reaching a maximum at 10.3% and then declines,

showing a trend similar to that of the amount of superbasic sites. In
addition, 16.6% K-MgAl(O) is higher than 10.3% K-MgAl(O) in total
basic sites, but in terms of catalytic activity, the former is lower
100 200 300 400 500 600 700 800 than the latter. In other words, catalytic activity can be related to
superbasic sites rather than to the total amount of basic sites. It is
Temperature(oC)
hence rational to infer that the superbasic sites thus generated are
Fig. 4. CO2 -TPD proles of (a) MgAl(O) and (b) 10.3% K-MgAl(O). responsible for the high catalytic activity: the higher the superba-
sicity and/or the more the amount of superbasic sites, the better is
the catalytic activity. Based on the results, the optimum potassium
3.2. Catalytic activity
loading is 10.3%, in agreement with the results of XRD and basicity
investigation.
3.2.1. Effect of potassium loading
Fig. 5 depicts the effects of potassium loading on activity along
3.2.2. Knoevenagel condensation of various aldehydes with active
with the amount of superbasic sites of the obtained samples.
methylene compounds
It is noted that catalytic activity rst increases with increase of
Depicted in Table 2 are the results of Knoevenagel condensation
of various aldehydes with active methylene compounds over 10.3%
100 0.5 K-MgAl(O). One can see that in all cases products were generated
in good to excellent yield, comparable or superior to those reported
Benzaldehyde conv. (%)

Supersic sites (mmol/g)

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
26.533.0 with the amount of superbasic sites up to 0.411 mmol/g.
They are efcient catalysts for Knoevenagel condensation reactions,
and the higher the superbasicity and/or the more the amount of
superbasic sites, the better is the catalytic activity. The ndings
open up a new strategy for the synthesis of new functional super-
bases using composite oxides as supports.
Acknowledgments
The project was nancially supported by the National Natural
Science Foundation of China (Grant nos. U1162109, 20873038),
Hunan Provincial Natural Science Foundation of China (10JJ1003),
the program for New Century Excellent Talents in Universities
(NCET-10-0371), Program for Changjiang Scholars and Innova-
tive Research Team in University (IRT1238), and the Fundamental
Research Funds for the Central Universities. C.T. Au thanks the
Hunan University for an adjunct professorship.
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