Journal of Molecular Catalysis A: Chemical 390 (2014) 198205

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Journal of Molecular Catalysis A: Chemical

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

Amino-functionalized Zr(IV) metalorganic framework as

bifunctional acidbase catalyst for Knoevenagel condensation
Yang Yang, Hong-Fei Yao, Fu-Gui Xi, En-Qing Gao
Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Department of Chemistry, East China Normal University, Shanghai 200062, China

a r t i c l e i n f o a b s t r a c t

Article history: The amino-functionalized metalorganic framework of Zr(IV) with 2-aminoterephthalate, UiO-66-NH2 ,
Received 6 December 2013 was studied as a solid catalyst for Knoevenagel condensation. The material can efciently catalyze the
Received in revised form 1 April 2014 condensation reaction of benzaldehyde with ethyl cyanoacetate or malononitrile in highly polar solvents
Accepted 3 April 2014
such as DMF, DMSO and ethanol. The catalytic system has also been tested for various aromatic alde-
Available online 13 April 2014
hydes, the conversion easily reaching more than 90% under mild conditions. It was demonstrated that the
catalytic process is heterogeneous and shows size effects, characteristic of a porous catalyst. The catalyst
Keywords:
can be recycled without losing its framework integrity and catalytic activity. The catalytic activity has
Metalorganic frameworks
Bifunctional acidbase catalysts
been compared with dimethyl 2-aminoterephthalate and the isostructural amino-free MOF (UiO-66).
Knoevenagel condensation The superior performance of UiO-66-NH2 has been attributed to the site-isolated acidbase bifunctional
Heterogeneous catalysis character. It has been proposed that the Zr site in close proximity to the amino group activates aldehydes
to promote the formation of aldimine intermediates from the aldehydes and the amino group.
2014 Elsevier B.V. All rights reserved.

1. Introduction may be inherent in the frameworks or generated by post-synthetic

In recent years, metalorganic frameworks (MOFs) have
attracted considerable attention due to their special characteristics
such as hybrid compositions, diverse networks, tunable porosity
and tailorable surfaces [1,2]. Owing to these characteristics, MOFs
are promising materials for various technological applications such
as gas storage/capture [35], separation [6,7], and heterogeneous
catalysis [811]. Heterogeneous catalysis is superior to homoge-
neous catalysis for easier separation, reusability, minimized waste
and cleaner products. Heterogeneous catalysts also offer the possi-
bility of combining isolated acidic and basic sites for cooperative or
tandem catalysis [1215]. Furthermore, porous solid catalysts may
provide conned space to inuence reactivity and selectivity. The
application of MOFs as porous heterogeneous catalysts alternative
or complementary to microporous zeolites is especially interesting,
since the pore size and chemical functionality of MOFs can be mod-
ulated within a wider range [2,11,16]. In principle, the active sites
of MOF catalysts can be metal centers with unsaturated (or labile)
coordination environments, catalytic functional groups attached
to any components of the frameworks, or other catalytic species
(molecules, metals, etc.) encapsulated in the pores, and the sites
Corresponding author. Tel.: +86 21 62233404; fax: +86 21 62233404.
E-mail address: eqgao@chem.ecnu.edu.cn (E.-Q. Gao).
methods [11,1722].
The three-dimensional (3D) Zr(IV) MOFs of formula
[Zr6 O4 (OH)4 (L)6 ], such as UiO-66 [l = 1,4-benzenedicarboxylate
(BDC)] and UiO-66-NH2 [l = 2-amine-1,4-benzenedicarboxylate
(BDC-NH2 )], are based on the octahedral [Zr6 (3 -O)4 (3 -OH)4 (2 -
COO)12 ] cluster and featured by alternating octahedral and
tetrahedral cages sharing triangular windows [23] (Fig. 1). The
MOFs contain potential Lewis-acid sites (Zr(IV) centers) upon
activation and/or base sites (NH2 groups), and remarkably, they
show exceptionally high thermal and chemical stability. However,
for only a few reactions have these MOFs been studied as hetero-
geneous catalysts, including the cross-aldol condensation between
benzaldehyde and heptanal [24], the cyclization of citronellal to
isopulegol [25,26], the cycloaddition of CO2 to styrene oxide [27],
the acetalization of benzaldehyde with methanol [28], and photo-
catalytic reactions [2934]. Electronic effects of linker substitution
on Lewis acid catalysis have been studied [28]. It was found that
the Lewis acidity and the catalytic activity increase in the order of
UiO-66-NH2 < UiO-66 < UiO-66-NO2 . It was also demonstrated that
the introduction of amino groups into linkers leads to an increase
in basicity [25,28].
In this paper, we report the catalytic study of UiO-66-NH2 for
Knoevenagel condensation. The Knoevenagel condensation of a
carbonyl group with the methylene group activated by two elec-
tron withdrawing groups (Scheme 1) is an important C C bond
coupling reaction and has been widely used in the synthesis of ne

http://dx.doi.org/10.1016/j.molcata.2014.04.002
1381-1169/ 2014 Elsevier B.V. All rights reserved.
 Y. Yang et al. / Journal of Molecular Catalysis A: Chemical 390 (2014) 198205
Fig. 1. Structure of UiO-66. (a) A [Zr6 (3 -O)4 (3 -OH)4 (2 -COO)12 ] cluster. (b) The
porous systems in which octahedral and tetrahedral cages share triangular windows.
chemicals and pharmaceuticals. The condensation can be catalyzed
by bases or Lewis acids, either homogeneous (such as amines
[35,36], ZnCl2 and Mg(ClO4 )2 [37,38]) or heterogeneous (such as
hydrotalcite [39], silica-supported basic catalysts [40,41]). Consid-
ering the demand for environmentally friendly heterogeneous
catalysts and the intriguing features of MOFs, the exploration of
MOF catalysts for the Knoevenagel condensation has become a
topic of increasing interest in recent years [4250]. The MOFs
used are diverse in composition and structure, and most of them
contain the amino group as Lewis base sites, such as the BDC-NH2 -
base metalcarboxylate frameworks IRMOF-3, MIL-101(Al)-NH2 ,
MIL-53-NH2 , and UMCM-1-NH2 [45,46]. MIL-101(Cr) with post-
synthetically introduced amino groups has also been studied for
Knoevenagel condensation [51]. In this work, we demonstrate that
UiO-66-NH2 is an efcient, size-selective, stable, and recyclable
heterogeneous catalyst and that the superior catalytic performance
to UiO-66 is attributable to the bifunctional acidbase character.
2. Experimental
2.1. Synthesis
All chemicals (A. R. grade, purity 98 wt% or higher) were
obtained from commercial sources and used without further
purication. UiO-66-NH2 and UiO-66 synthesized by follow-
ing a solvothermal procedure reported in the literature [52,53],
using acetic acid as modulator. ZrCl4 (0.7 mmol, 0.164 g) and
H2 BDC-NH2 (0.7 mmol, 0.127 g) were dissolved in the mixture
of N,N -dimethylformamide (DMF, 8 ml), acetic acid (1.2 ml) and
deionized water (0.05 ml) at room temperature. After stirring for
about 5 minutes, the mixture was sealed in a 23 ml Teon liner,
heated in an oven at 120 C for 48 h, and then cooled to room
temperature. A yellow solid powder was obtained by ltration,
washed three times with DMF. The product was soaked and stirred
in reuxing methanol for 24 h, ltered and dried at 70 C in an oven.
The formula of the material thus obtained was estimated to be
[Zr6 O4 (OH)4 (BDC-NH2 )6 ]14H2 O according to elemental analysis.
Found: C 29.2, H 3.8, N 4.4%; calculated: C 28.7, H 3.1, N 4.2%.
Scheme 1. Knoevenagel condensation.
199
2.2. Characterization
The X-ray powder diffraction patterns of the samples were
measured using a Rigaku Ultima IV X-ray Diffractometer with
Cu K radiation ( = 1.54 A) at a scanning rate of 10 C/min, with
accelerating voltage and current of 35 kV and 25 mA, respec-
tively. SEM study was carried out with a S-4800 HITACHI scanning
electron microscope. Elemental analyses were determined on an
Elementar Vario ELIII analyzer. FT-IR spectra were recorded in
the range 5004000 cm1 using KBr pellets on a Nicolet NEXUS
670 spectrophotometer. The leached metal amount was detected
by inductively coupled plasma atomic emission spectroscopy
(ICP-AES) using a IRIS Intrepid II XSP spectrometer. Gas chromatog-
raphy (GC) was conducted using a Linghua GC 9890E instrument
equipped with an FID detector and an SE-54 capillary column
(30 m 0.25 mm 0.25 m). The temperature program for GC
analysis was set as follows: the temperature was held at 40 C for
1 min, then raised to 260 C at 30 C/min and held for 5 min. Inlet
and detector temperatures were 280 C. The analysis was carried
out directly after sampling to avoid any additional conversion.
2.3. Catalytic test
In a typical catalytic experiment, 0.144 g of the catalyst (corre-
sponding to 0.45 mmol amino groups) was placed in a ask and
heated at 150 C for 4 h. After three cycles of vacuum pumping
and nitrogen injection, the solution of ethyl cyanoacetate or other
active methylene compounds (10 mmol) in an appropriate solvent
(5 mL) was added with stirring and heated to a given temperature.
After temperature equilibrium, benzaldehyde (5 mmol) was added
to initiate the reaction. The reaction mixture was stirred under a
static nitrogen atmosphere, and small aliquots of the supernatant
were withdrawn at different time intervals to monitor the reaction
conversion by GC.
3. Results and discussion
3.1. Characterization of the UiO-66-NH2 catalyst
UiO-66-NH2 was synthesized according to literature proce-
dures. The XRD pattern of the as-synthesized sample (Fig. 2a) is
in good agreement with the literature data and with the simu-
lated pattern of pristine UiO-66 [24], evidencing good synthetic
reproducibility and phase purity. The SEM morphology (Fig. 2b)
shows that the particles are of nanometer size with a distribu-
tion in the range 4090 nm. After thermal activation at 150 C, the
reections at large angles become less intensive, but the main char-
acteristic peaks remain, indicating that the overall phase integrity
is retained although the activation leads to some degree of disor-
der in the framework. Fig. 2a also shows the XRD patterns of the
UiO-66-NH2 sample after one and three cycles of catalytic reac-
tions. It is interesting to note that the reections at large angles
are recovered after the catalytic reaction, indicating that the dis-
order caused by thermal treatment is repaired. It can be deduced
that the original crystalline phase of the material is retained with-
out signicant degradation in structural integrity after the catalytic
reactions.
3.2. Catalytic properties
3.2.1. Inuence of catalytic dose, solvent, and temperature
The condensation reaction of benzaldehyde with ethyl cyanoac-
etate, which affords -cyanocinnamate, was performed as test
reaction to study the effects of different reaction conditions, includ-
ing the catalytic dose, the solvent, and the reaction temperature.
200 Y. Yang et al. / Journal of Molecular Catalysis A: Chemical 390 (2014) 198205
Fig. 2. PXRD patterns (a) and SEM picture (b) of UiO-66-NH2 .
The results obtained for the reactions performed in ethanol at
80 C in the presence of different amount of catalysis are given
in Table 1 (entries 13). While the blank reaction in the absence
of any catalyst gave a benzaldehyde conversion of only 27% after
2 h, introducing UiO-66-NH2 and increasing the amount led to
signicant increase in the conversion. With 0.144 g UiO-66-NH2
(corresponding to 9 mol% amino groups), the conversion reached
94% after 2 h. For comparison, the blank reaction needs 17 h to reach
a conversion of >90% (complete conversion needs more than 21 h).
These results clearly conrm that UiO-66-NH2 is active in catalyz-
ing the Knoevenagel reaction. No by-product was observed during
the reaction, so the selectivity for -cyanocinnamate is 100%.
Strong effects of solvent polarity have been observed for cat-
alytic Knoevenagel reactions. To establish the solvent effects for
UiO-66-NH2 , we performed the reaction in different solvents
(Table 1). It proved that the catalyst has the highest activity (>90%
conversion within 2 h) in DMSO and DMF (entries 5, 8), which have
the highest polarity (dielectric constants = 48.9 for DMSO and 36.7
for DMF). Ethanol (protic, = 24.3) is also a good medium for the
reaction (entry 4). By contrast, nonprotic and less polar solvents,
including DCM ( = 9.1), THF ( = 7.5), EtOAc ( = 6.02) and toluene
( = 2.4), are not good media (entries 912). The effects can be
generally explained by the assumption that polar solvents help to
stabilize the charged transition-state complex of the reaction [36].
Besides, the strong hydrogen-bonding acceptor ability of DMSO and
DMF can facilitate proton transfer [45]. On the one hand, the solvent
effects are similar to those observed for some basic organocatalysts
[35,36] and for the amine-functionalized MOF catalysts IRMOF-
3 [45,46] and NH2 -MIL-101(Al) [48], although sometimes ethanol
was found to be better than DMF and DMSO due to its amphiprotic
character. On the other hand, the effects are in clear contrast with
those observed for some amino-tagged silicas, for which toluene is
better than polar solvents [40,41]. For some other catalysts, the
solvent effects are not necessarily related to the polarity or the
amphiprotic nature. For example, the catalytic activity of ZIF-8, -
9 and -10 (ZIF = zeolite imidazolate framework) for Knoevenagel
condensation in toluene was found to be intermediate between
that in THF (higher) and that in DCM (lower) [49,50]. For solid-
supported base catalysts, it has been reported that the higher the
hydrophilicity (or the surface polarity) of the support, the lower the
effect of the solvent [41,46], but the opposite trend has also been
reported [40]. Therefore, there is no general trend for the effect of
solvents on the Knoevenagel reaction. Nevertheless, the results for
UiO-66-NH2 , IRMOF-3 and NH2 -MIL-101(Al) consistently indicate
that amino-tagged MOFs perform better in highly polar solvents.
The temperature dependence of the catalytic performance of
UiO-66-NH2 was checked by performing the Knoevenagel reaction
in DMF at 40, 60 and 80 C (Table 1, entries 57). As expected, the
reaction rate increases quickly with the temperature, the conver-
sion within 30 min changing from 27% at 40 C to 91% at 80 C. The
conversion at 40 C can reach a high level (>90%) within 2 h.
3.2.2. The inuence of different substrates
Having established that UiO-66-NH2 is a good catalyst for
the Knoevenagel condensation between benzaldehyde and ethyl
cyanoacetate, we extend the study to various substrates, includ-
ing different aromatic aldehydes and methylene compounds. The
results are listed in Table 2.
Diethyl malonate and malononitrile have been compared with
ethyl cyanoacetate (entries 13). Under the same catalytic condi-
tions, diethyl malonate led to a trace conversion of benzaldehyde
after 2 h, whereas malononitrile caused a conversion of 98% within
40 min. The different reactivity of the methylene compounds is
consistent with their different acidity, which increases in the
order of diethyl malonate (pKa = 16.4 [54]) < ethyl cyanoacetate
(pKa = 13.1 [55]) < malononitrile (pKa = 11.1 [56]). Actually, no Ar-
NH2 -functionalized materials (including MOFs) have been found
to be able to efciently catalyze the Knoevenagel reaction between
benzaldehyde and diethyl malonate, because the pKa is too high
for the amine group or the in situ formed imine group to induce
deprotonation.
Various aromatic aldehydes have been tested for catalytic Kno-
evenagel condensation with malononitrile. It was found that the
activity of UiO-66-NH2 for 2-nitrobenzaldehyde is much higher
than that for benzaldehyde, as the reaction for the former alde-
hyde can reach completion within only 5 min (entry 4 in Table 2).
This reects the great accelerating effect of the strong electron-
withdrawing nitro group, as would be expected for a reaction
involving nucleophilic attack at the carbonyl group. The catalyzed
reactions of the three methyl-substituted benzaldehydes proceed
readily to give 97% conversions after 40 min (entries 57). The
conversions are similar to that for benzaldehyde, but the initial
reaction rates of these substrates are different. As shown in Fig. 3,
compared with the non-substituted benzaldehyde, the initial reac-
tion rate of 2-methylbenzaldehyde is similar (or slightly faster),
the reaction of the 3-isomer is obviously slower, and notably, the
4-isomer was more reactive, though methyl is an electron-donating
group. The position effect of methyl substitution on the reactivity
of benzaldehyde is similar to that observed for the Knoeve-
nagel condensation catalyzed by ZIF-8 [49] and ZIF-9 [50], where
the reactivity varies in the order of 4-methylbenzaldehyde 2-
methylbenzaldehyde > benzaldehyde > 3-methylbenzaldehyde.
 Y. Yang et al. / Journal of Molecular Catalysis A: Chemical 390 (2014) 198205
Table 1
UiO-66-NH2 catalyzed Knoevenagel condensation between benzaldehyde and ethyl cyanoacetate: inuence of catalytic dose, solvent, and temperature.
Entry Solvent T ( C)
1 EtOH 80
2 80
3 80
4 40
5 DMF 40
6 60
7 80
8 DMSO 40
9 DCM 40
10 EtOAc 40
11 THF 40
12 Toluene 40
Conditions: reactants: benzaldehyde (5 mmol), ethyl cyanoacetate (10 mmol); solvent: 5 ml; Cat: UiO-66-NH2 , 0.144 g (corresponding to 0.45 mmol amino groups), except
for entry 1 (no catalyst) and entry 2 (0.072 g, corresponding to 0.23 mmol amino groups).
The catalyst system is also efcient for the Knoevenagel
reactions of larger aromatic aldehydes (1-naphthaldehyde and
9-anthraldehyde) with malononitrile, though the conversion is
somewhat decreased when the aldehyde substrate becomes more
bulky (comparing entries 3, 8 and 9 in Table 2). The decreased
conversion may be a (weak) indicator of size effects. The effects
are more appreciable for the reactions of different aldehydes with
ethyl cyanoacetate (molecular dimensions 3.4 7.3 A 2 ), which
are bulkier than malononitrile (2.8 4.3 A 2 ). As shown by entries
1 and 10, the conversion of 9-anthraldehyde (56%, 5.9 9.2 A 2 )
reacting with ethyl cyanoacetate is much lower than that of benz-
aldehyde (92%, 6.0 4.3 2 ). The results could reect that the
probability of two bulky substrates forming transition-state com-
plexes is signicantly reduced due to the limited space in the
catalyst.
To further conrm the size effects, 9-anthraldehyde was
reacted with a still bulkier methylene substrate, tert-butyl
cyanoacetate (4.3 8.2 A 2 ). The independent control reactions of
9-anthraldehyde with ethyl and tert-butyl cyanoacetates in the
absence of any catalyst give similar conversions (around 20% after
2 h, entries 10 and 11), indicating that the intrinsic reactivity of
the two methylene substrates is comparable. In the presence of
Fig. 3. Time dependence of reaction conversion for the condensation of differ-
ent monosubstituted bezaldehydes (5 mmol) with malononitrile (10 mmol) in DMF
(5 ml, 40 C) in the presence of 0.144 g catalyst (corresponding to 0.45 mmol amino
groups).
201
.
Time (h) Conv. (%)
2 27
2 67
2 94
0.5/2 25/79
0.5/2 27/92
0.5 58
0.5 91
0.5/2 31/95
2 5
2 3
2 2
2 <1
UiO-66-NH2 , the reaction with ethyl cyanoacetate shows a much
higher conversion (56%), indicating a catalytic process. By contrast,
the use of UiO-66-NH2 for the reaction with tert-butyl cyanoac-
etate leads to a conversion (15%) comparable to (or even slightly
lower than) that for the reaction without any catalyst, indicating
that UiO-66-NH2 is not active for the two bulky substrates. Thus, it
is very likely that the catalytic reaction over UiO-66-NH2 proceeds
inside the pores. The pore system of perfect UiO-66 crystals con-
sists of interconnected tetrahedral and octahedral cages with free
diameters of about 8 and 11 A, respectively. Notably, some recent
studies have demonstrated that real UiO-66 and analogs contains
an amount of defects due to missing linkers between Zr6 clusters
[26,57,58]. The linker vacancies lead to expanded pores so that
the real pore dimensions can be larger. The failure in catalyzing
the reaction between 9-anthraldehyde and tert-butyl cyanoacetate
could be because the pores are still too small for the two bulky sub-
strates diffuse into the pores of the catalyst to access the active sites
and to form the transition state required for the reaction.
3.2.3. Heterogeneity and reusability
With a solid catalyst for liquid-phase reactions, an issue of great
concern is whether the catalytic process is heterogeneous or homo-
geneous. In the latter case, the species leached into the liquid phase
is partially or fully responsible for the observed catalytic activity.
This is practically undesirable. The heterogeneous nature of our cat-
alyst system for Knoevenagel reactions is implied in some results
of the above catalytic experiments. For example, the dependence of
benzaldehyde conversion on the amount of solid catalyst (Table 1)
could be an implication. The solid shows no appreciable solvabil-
ity. It means that if there were any dissolved species, it would be
quite easy for the liquid phase to be saturated by the species. Once
saturated, the amount of the species in a given volume of liquid
would be independent of the dose of the solid. Then, if the dissolved
species were responsible for the catalytic activity, the reaction con-
version would be independent of the amount of the solid. Therefore,
the dependence of conversion on solid dose may be taken as a
(weak) indication of heterogeneous catalysis. A stronger evidence
is the size selectivity for substrates (Table 2), which is difcult to
achieve with homogeneous catalysts but characteristic of porous
heterogeneous catalysts. In order to give a more direct conrma-
tion, a control reaction was performed between benzaldehyde and
ethyl cyanoacetate in DMF. After the reaction proceeded at 40 C
for 2 h, the catalyst was removed by hot ltration. The ltrate was
further heated at the same temperature and the composition was
202 Y. Yang et al. / Journal of Molecular Catalysis A: Chemical 390 (2014) 198205

Table 2
UiO-66-NH2 catalyzed Knoevenagel condensation of different substrates.a

Entry Aldehyde Methylene Time (min) Conv. (%)

O
N
1 120 92
O

2 120 <2

3 40 98

4 5 100

5 40 98

6 40 97

7 40 98

8 40 92

9 40 87

10 120 56 (21)b

11 120 15 (19)b

a
Conditions: aldehyde (5 mmol), methylene compound (10 mmol), DMF (5 ml), Catalyst (0.144 g, corresponding to 0.45 mmol amino groups), 40 C.
b
The conversion for the control test in the absence of any catalyst is given in parentheses for comparison.

monitored at given time intervals. The results are compared in Fig. 4
with those obtained for the reaction under the same conditions but
without the ltering procedure. Obviously, no appreciable reaction
took place after removal of the catalyst, indicating that no active
species were leached into the liquid phase and providing a direct
evidence for the heterogeneity of the catalyst system. This is also
conrmed by ICP-AES analysis, which suggests no detectable Zr in
the liquid phase.
Another issue of great concern for solid catalysts is the recycla-
bility. To check this for UiO-66-NH2 , the catalyst was used for three
cycles for the reaction between benzaldehyde and malononitrile.
After each cycle, the solid was ltered out, soaked and stirred in
methanol for 24 h, ltered out again and washed with methanol.
The recovered solid was heated at 150 C for 4 h and then reused
in the next cycle. The results of the three cycles are very simi-
lar. As shown in Fig. 5a, the conversion of benzaldehyde after 1 h
remains at the high level of 97%, indicating that the catalyst could
be reused without signicant degradation in catalytic performance.
The recyclability is consistent with the good chemical resistance
of the structure against the reaction conditions, which has been
 Y. Yang et al. / Journal of Molecular Catalysis A: Chemical 390 (2014) 198205
Fig. 4. Filtration test of the catalyst. Conditions: benzaldehyde (8 mmol), ethyl
cyanoacetate (7 mmol), Cat. 0.10 g (corresponding to 0.31 mmol amino groups),
solvent: DMF (5 ml), 40 C. The conversion is based on ethyl cyanoacetate.
Fig. 5. (a) Catalyst recycling studies. Conditions: benzaldehyde (5 mmol), malonon-
itrile (10 mmol), solvent: DMF (5 ml), Cat. 0.144 g, 40 C, 1 h. (b) IR spectra of the fresh
and used catalysts.
203
Fig. 6. (a) Knoevenagel condensation with different catalysts. Conditions: benzal-
dehyde (5 mmol), ethyl cyanoacetate (10 mmol), solvent: EtOH (5 ml), 80 C, Cat.
0.45 mmol Zr or NH2 , 2 h. (b) The reactions of benzaldehyde (1 mmol) with DMBDC-
NH2 (1.2 mmol) in EtOH (6 ml, 80 C) in the absence/presence of UiO-66 (0.014 g).
demonstrated by XRD measurements (see Fig. 2a). The intactness
of the catalyst is also conrmed by the fact the FT-IR spectra of the
catalyst shows no appreciable difference after catalytic reactions
(Fig. 5b).
3.2.4. Mechanism considerations
To determine the role of the amine group in the catalyst, the
amine-free MOF (UiO-66) prepared and activated by similar proce-
dures was tested as catalyst for the reaction between benzaldehyde
and ethyl cyanoacetate. As can be seen from Fig. 6a, under the
same catalytic conditions, the amino-free MOF led to much lower
conversion than UiO-66-NH2 . Since the two MOFs are isostruc-
tural, the superior performance of UiO-66-NH2 indicates that the
basic amine group is important in promoting the Knoevenagel
reaction, as is normally expected for NH2 -tagged catalysts. It has
been demonstrated that the introduction of amino groups into
the linkers of UiO-66 leads to an appreciable increase in basicity
[28]. The organic analog of UiO-66-NH2 , dimethyl 2-amine-1,4-
benzenedicarboxylate (DMBDC-NH2 ), was also tested under the
same conditions. The homogeneous reaction showed a low conver-
sion of 29%, which is only slightly higher than the reaction without
any catalysts and much lower than the heterogeneous reaction
using UiO-66-NH2 (see Fig. 6a), though the amount of amino groups
204 Y. Yang et al. / Journal of Molecular Catalysis A: Chemical 390 (2014) 198205

was set to be equal in two catalytic reactions. This could indicate

that the catalytic activity of amine is enhanced in the MOF struc-
ture or that the reaction is promoted by other sites besides amine.
The Knoevenagel reactions with aniline as homogenous catalyst
have also been reported to give much lower conversion than those
with IRMOF-3 as heterogeneous catalyst [45,46]. The high activity
of IRMOF-3 compared to aniline was attributed to the increased
basicity of the aromatic amino group when incorporated within
the MOF structure. It was proposed that the increase of basicity
could be due to the intramolecular hydrogen bonding interaction
between the amino group and an carboxylate oxygen (coordinated
to Zn(II)) [45]. However, this explanation fails for DMBDC-NH2 ,
which could have similar hydrogen interactions but does not show
signicant catalytic activity. A DFT study [59] suggested that the
basicity of the aromatic amine (Ar-NH2 ) and the aldimine derivative
(Ar-N = CHC6 H5 ) indeed increases in going from aniline to DMBDC-
NH2 and that the increase is more signicant in going further to
the amine embedded in IRMOF-3. The increase has been related to
the stabilization of the protonated aminium and iminium species,
which are hydrogen bonded to a carboxylate oxygen to generate
a 6-membered planar ring. The theoretical study also indicated
that the aldimine intermediates are the most basic species in the
reaction systems and should be the active species that deproto-
nate ethyl cyanoacetate. However, the DFT energetic study on the
catalytic cycles of Knoevenagel condensation indicated that the
increased catalytic activity of IRMOF-3 seems to be unrelated to
its increased basicity but could be explained by its adsorption abil-
ity for the water by-product which would otherwise poisons the
catalytic amino sites.
It should be noted that the theoretical study was based on the
hypothesis that the amine groups are the only catalytic sites in
the MOF, not considering the possibility of the existence of other
active sites. A recent reinvestigation of IRMOF-3 for Knoevenagel
condensation suggested that the MOF behaves as an unexpected Scheme 2. (a) Mechanism for amine-catalyzed Knoevenagel condensation. (b)
Aldimine formation promoted by the Lewis acid site in close proximity to the amine
bifunctional acidbase catalyst [15]. The unintentional acid sites
group.
come from a defective origin, either ZnOH species formed upon
partial hydrolysis of the framework or ZnO particles entrapped
inside the cavities during the synthesis. in Fig. 6a, ZrO2 and DMBDC-NH2 show very low activity (the con-
As already mentioned, UiO-66 is much less active than UiO- versions are higher than the blank test by only 8% and negligibly
66-NH2 , but it is noteworthy that the NH2 -free MOF still shows 2%, respectively), while the mixture show enhanced activity (15%
signicant catalytic activity (50% after 2 h, See Fig. 6a) when com- higher than the blank test), indicating the presence of some coop-
pared with the blank non-catalytic reaction. This suggests that the eration, although weak. The much higher activity of UiO-66-NH2
Knoevenagel reaction could also be promoted by Zr(IV) centers than UiO-66 may indicate much stronger cooperation in the porous
(Lewis acid sites), so UiO-66-NH2 could be a bifunctional acidbase framework. Probably, the framework arranges Zr and amino sites
catalyst for Knoevenagel condensation. The bifunctional charac- in close proximity on the inner surface so that the two sites can
ter has recently been proposed to explain the high activity of the cooperate more efciently.
material for the cross-aldol condensation between heptanal and Knoevenagel condensation, as a modication of aldol conden-
benzaldehyde [24]. The acid sites in UiO-66 and UiO-66-NH2 could sation, may proceed via different mechanisms that depend on the
be the open Zr(IV) sites generated by dehydration of the Zr6 O4 (OH)4 nature of the catalyst used. A Lewis acid site usually interacts
cluster to give Zr6 O6 . It has been shown that the dehydration begins with the carbonyl oxygen of benzaldehyde, thus the C O bond is
at about 100 C for UiO-66 and even below the temperature for further polarized to facilitate the nucleophilic attack at the car-
UiO-66-NH2 [24]. Therefore, the activation procedure (heating at bon atom. Strong bases would cause direct deprotonation of the
150 C) that we applied before catalytic reactions could induce par- methylene group, generating the carbanion that attacks the car-
tial dehydration. Another origin of the Lewis acid site could be the bonyl carbon atom of benzaldehyde. For amino-based catalysts, it
presence of defects. Since the UiO-66 MOFs are much stable than is generally accepted that the reaction proceeds via aldimine inter-
MOF-5 and IRMOF-3, one would not expected that the Zr MOFs con- mediates [45,59]. Two nucleophilic addition-elimination processes
tains a large density of defects of similar origin to those in the Zn are involved, as illustrated in Scheme 2a. The rst is the formation
MOFs. However, recent studies have demonstrated the presence of an aldimine intermediate (and water) from aldehyde and the
of linker vacancies (defects due to the missing of organic linkers amine group at the catalyst surface. The aldimine intermediate is
between Zr6 clusters) even in well-crystallized UiO-66 materials more basic than the original amine and also more reactive than the
[26,57,58]. The defects could generate open metal sites upon heat- original aldehyde [36]. Thus, the methylene compound is activated
ing. Whatever the origin of the acid sites is, the presence of both (deprotonated) by aldimine rather than by amine, and meanwhile
acid and base sites could explain the superior performance of UiO- the aldimine group is also activated by the proton transfer. There-
66-NH2 . fore, the second addition-elimination process is facilitated, which
Comparisons among ZrO2 , DMBDC-NH2 and their mixture may occurs between methylene and aldimine (rather than aldehyde)
give some information about the acidbase cooperation. As shown groups to give the product and to regenerate the amine catalyst.
 Y. Yang et al. / Journal of Molecular Catalysis A: Chemical 390 (2014) 198205
Spectroscopic evidences for the formation of intermediate aldimine
have been recently reported for amino-tagged silicas and IRMOF-3
[45,60].
According to this mechanism, the formation of the aldimine
intermediate is important. We have studied the formation by reac-
ting benzaldehyde with DMBDC-NH2 under the conditions used for
the Knoevenagel reaction. As can be seen from Fig. 6b, the forma-
tion of aldimine in the absence of any catalyst is much slower than
in the presence of UiO-66. The results clearly suggest the catalytic
role of the Zr MOF for aldimine formation. The promotion is most
likely due to the activation of carbonyl groups by Zr sites.
Based on the above considerations, the cooperative acidbase
bifunctional catalysis of UiO-66-NH2 can be speculated as follows
(Scheme 2b). The Zr site serves to activate benzaldehyde so that
the amino group in close proximity the Zr site can readily attack
the carbonyl group to generate the aldimine intermediate, which
serves not only as a base (the N atom) to extract proton from methy-
lene but also as an acid (the C atom) to couple with methylene.
This synergic process is a little different from that proposed for
the cross-aldol condensation between heptanal and benzaldehyde
[24], where the reaction was supposed to occur between benz-
aldehyde activated by Zr(IV) and the heptanal methylene group
activated by amine.
4. Conclusions
In this work, we reported the use of UiO-66-NH2 as solid
catalyst for Knoevenagel condensation. It has been demonstrated
that the catalyst shows better performance in highly polar solvents
such as DMF, DMSO and ethanol. It can efciently catalyze the
condensation reactions of aromatic aldehydes with cyanoacetate
and malononitrile, the conversion easily reaching more than 90%
under mild conditions within a short time (dependent on the
substrates). The catalytic process is heterogeneous and shows
size effects, characteristic of a porous catalyst with active sites
inside the pores. The catalyst can be recycled without losing its
framework integrity and catalytic activity. Compared with the
homogeneous amino precursor (2-aminoterephthalate) and the
isostructural amino-free MOF (UiO-66), the superior performance
of UiO-66-NH2 has been attributed to the acidbase bifunctional
character. It was proposed that the Zr site in close proximity to
the amino group facilitates the formation of aldimine interme-
diates, which are the active species reacting with the methylene
compounds. This study further demonstrates that MOFs can offer
extraordinary opportunity of achieving site-isolated acidbase
catalysts, which are desirable for more efcient and more facile
organic synthesis. Working along this line, we are exploring such
catalysts for multi-component reactions.
Acknowledgements
This work is supported by the National Science Foundation of
China (NSFC nos. 21173083 and 91022017) and the Research Fund
for the Doctoral Program of Higher Education of China.
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