Journal of Solid State Chemistry 233 (2016) 303–310

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Journal of Solid State Chemistry

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

Heteropoly acid encapsulated into zeolite imidazolate framework

(ZIF-67) cage as an efficient heterogeneous catalyst for Friedel–Crafts
acylation
Muhammad Ammar, Sai Jiang, Shengfu Ji n
State Key Laboratory of Chemical Resource Engineering Beijing University of Chemical Technology, 15 Beisanhuan Dong Road, P.O.Box 35, Chaoyang District,
Beijing 100029, China

art ic l e i nf o a b s t r a c t

Article history: A new strategy has been developed for the encapsulation of the phosphotungstic heteropoly acid
Received 15 May 2015 (H3PW12O40 denoted as PTA) into zeolite imidazolate framework (ZIF-67) cage and the PTA@ZIF-67(ec)
Received in revised form catalysts with different PTA content were prepared. The structure of the catalysts was characterized by
5 November 2015
XRD, BET, SEM, FT-IR, ICP-AES and TG. The catalytic activity and recovery properties of the catalysts for
Accepted 6 November 2015
the Friedel-Crafts acylation of anisole with benzoyl chloride were evaluated. The results showed that
Available online 7 November 2015
14.6–31.7 wt% PTA were encapsulated in the ZIF-67 cage. The PTA@ZIF-67(ec) catalysts had good catalytic
Keywords: activity for Friedel-Crafts acylation. The conversion of anisole can reach
100% and the selectivity of the
Heteropoly acid production can reach
94% over 26.5 wt% PTA@ZIF-67(ec) catalyst under the reaction condition of
Encapsulate
120 °C and 6 h. After reaction, the catalyst can be easily separated from the reaction mixture by the
Zeolite imidazolate framework
centrifugation. The recovered catalyst can be reused five times and the selectivity can be kept over 90%.
Catalyst
Friedel–Crafts acylation & 2015 Elsevier Inc. All rights reserved.

1. Introduction nts employ for the Friedel–Crafts acylation of aromatic compounds.

However, there is ambit to develop heterogeneous acid catalysts for
The production of various pharmaceutical, pesticides, dyes and the Friedel–Crafts acylation reaction. Solid catalysts are secure, rea-
agrochemicals at industrial scale involves the synthesis and fur- sonable and benign. Furthermore the methods using solid catalysts
ther transformation of aromatic ketones. The Friedel–Crafts acy- have advantages for instance better selectivity, moderate reaction
lation of aromatic compounds is an essential route for the synth- conditions, minimize waste and cheap construction of material [9,10].
esis of the aromatic ketones that are intermediates in the manu- Acetic acid, acetic anhydride and acetyl chloride as acylating agents
facturing of fine and special chemicals as well as pharmaceuticals have been utilized for the acylation of activated aromatic compounds
[1]. Traditionally Lewis acid catalysts i.e. ZnCl2, AlCl3, FeCl3 and in presence of zeolites [10], acid-treated metal oxides [11] and het-
Brönsted acid catalysts i.e. HCl, HF and H2SO4 had been sig- eropoly acids [12]. However, heteropoly acids (HPAs) have been used
nificantly used for the acylation of aromatic compounds [2]. Uti- in excess of organic reactions [9,12]. Nevertheless heteropoly acids in
lization of homogeneous acid catalyst for the acylation reactions unsupported form present poor stability, fast deactivation and low
caused a number of issues such as produced impurities along with efficiency. A variety of supports, as mesoporous alumina silicate, me-
soporous silica, carbon, alumina, zirconia and metal-organic frame-
desired products, production of large amounts of toxic waste, in-
works (MOFs) have been employed to build up the stability and ef-
crease in expenditures, and utilization of catalyst more than stoi-
fectiveness of heteropoly acids [13]. Indeed, the catalytic activity and
chiometric quantity, and difficulty in recovery. For Friedel–Crafts
acidity of the supported heteropoly acids rely mainly on the loading
reactions, incessant investigation for appropriate heterogeneous
and the nature of carrier, i.e. strong interaction with activated carbons
catalyst had led to growth of catalysts for example Re–Br(CO)5,
cause low catalytic activity than that of the heteropoly acid itself, while
LiClO4-acyl anhydride complex [3], acid-treated clays [4], HZSM-5
dramatic leaching cause by low interactions of heteropoly acid with
zeolite [5], cation exchange resins [6], Ln-(OTf)3-LiClO4 [7], and
support. Direct synthesis of the Keggin structures inside the zeolite
heteropoly acids supported catalyst [8,9]. cavities (FAU) has been used to achieve the encapsulation of hetero-
The literatures until now supply an array of catalysts and reage- poly acids. This method is revealed to solve the leaching problem,
since the windows of the zeolitic cavities are smaller than the het-
n
Corresponding author. Fax: þ 86 10 64419619 eropoly acid clusters, but only very low loadings can be utilized
E-mail addresses: [email protected], [email protected] (S. Ji). (o5 wt%) if diffusion limitations are to be avoided [14].

http://dx.doi.org/10.1016/j.jssc.2015.11.014
0022-4596/& 2015 Elsevier Inc. All rights reserved.
304 M. Ammar et al. / Journal of Solid State Chemistry 233 (2016) 303–310

Metal-organic frameworks (MOFs) consist of metallic nodes 2.2.2. PTA@ZIF-67(ec) Preparation

bonded by organic linker, are currently receiving significant at- The encapsulation of the phosphotungstic acid in ZIF-67 has
tention because of their versatile properties [15–17].They have been done by the same procedure as follow in the synthesis of ZIF-
been extensively utilized as gas storage [18], separation [19], ion 67 with same synthesis mixture. But the phosphotungstic acid
exchange [20], sensor drug delivery [21] and catalysis [22,23]. (PTA) was dissolved in 11 mL deionized water and added to Co
MOFs as compared to traditional microporous and mesoporous (NO3)2  6H2O solution. Different loadings of phosphotungstic acid
inorganic materials reveal advantages such as tunable pore sizes, in ZIF-67 structure were achieved (14.6 wt% to 46.4 wt% according
high surface area, structural diversity, flexibility and geometrical to ICP-AES), depending on the amount of phosphotungstic acid
control by the functionalization and controlling the size of organic introduced into the synthesis mixture.
linkers [24,25]. However, MOFs used in catalysis are limited be-
cause of limited thermal and moisture stability including often 2.3. Catalyst characterization
completely blocked metal sites by the organic linker or solvent,
leaving no free position available for substrate chemisorption’s The power X-ray diffraction patterns of all samples were re-
[26]. Zeolite imidazolate frameworks (ZIFs) classified as a novel corded at room temperature using a Cu Kα radiation source
subclass of MOFs, have fascinated important attention as they (λ ¼1.54056 Å), operating at 40 kV and 50 mA using a Rigaku D/
unite advantages from both zeolite and conventional MOFs Max 2500 VB2þ/PC diffractometer. The BET surface areas and pore
[27,28]. In the past decade, research works have directed on syn- size distributions were obtained from N2 adsorption–desorption
thesizing new ZIFs and utilizations in different fields. In the lit- isotherms measured on the Micrometrics ASAP 2020 adsorption
erature, there are a small number of applications of ZIFs as catalyst analyzer at 77 K. Structure and morphology of samples were
or catalyst supports for transformation of organic compounds as characterized by scanning electron microscopy (SEM) on a Zeiss
compare to conventional MOFs [29–31]. Supra55. Fourier transform infrared (FT-IR) spectra of the samples
In this work, we wish to report a direct, synthetic encapsulation were collected on a Bruker Tensor 27, by dispersing the samples on
of active species such as phosphotungstic acid (PTA) into MOFs. KBr pellets in the range of 600–4000 cm  1. Thermogravimetric
We demonstrate that incorporation of highly dispersed PTA into analysis (TGA) measurements were collected on a SETSYS Evolu-
zeolite imidazolate frameworks-67 (ZIF-67) cage is possible to tion from Setaram Instrumentation with a heating rate of 10 °C
achieve by following the one-pot synthesis approach. As far as we /min in air up to 800 °C. Elemental analysis was performed by
know, the Friedel–Crafts acylation reaction catalyzes by PTA en- means of Inductively Coupled Plasma Atomic Emission Spectro-
capsulated in ZIF-67 are not previously mentioned in the litera- scopy (ICP-AES). The samples were investigated with SPECTRO
ture. The novel composite material PTA@ZIF-67(ec) has been uti- Analytical Instruments GmbH in order to calculate the amount of
lized as an efficient heterogeneous catalyst for Friedel–Crafts PTA encapsulated into the ZIF-67 structure. Gas chromatographic
acylation reaction of anisole with benzoyl chloride. High conver- (GC) analyses were carried out using a Beijing Beifenruili SP-2100
sions have been achieved with PTA@ZIF-67(ec) catalyst without an with flame ionization detector (FID). GC–MS analyses were carried
inert atmosphere. PTA@ZIF-67(ec) catalyst was easily separated out using a Shimadzu GCMS-QP5000.
from the reaction mixture and reused without significant de-
gradation in activity. 2.4. Catalytic performance testing

The Friedel–Crafts acylation of anisole with benzoyl chloride

2. Experimental using PTA@ZIF-67(ec) catalyst was carried out in the magnetically
stirred round-bottom flask. In a typical reaction, a mixture of an-
2.1. Materials isole and benzoyl chloride with molar ratio 1:2, n-Dodecane as an
internal standard was charged into a 50 mL flask containing the
Cobalt nitrate hexahydrate (99%), 2-methylimidazole (98%) and PTA@ZIF-67(ec) catalyst. The reaction mixture was then heated to
phosphotungstic acid were purchased from Aladdin Chemical Co., 120 °C with continuously stirring for 6 h. After 6 h, the reaction
Ltd., China. Anisole ( Z98%) was purchased from Sinopharm mixture was quenched with an aqueous NaOH solution (1%,
Chemical Reagent Co., Ltd., China. Benzoyl Chloride (98%) was 0.15 mL). The organic components were extracted using diethyl
purchased from Tianjin Fuchen Chemical Reagents, China. Diethyl ether (2 mL), dried over anhydrous Na2SO4 and the product was
ether and methanol were purchased from Beijing Yili Fine Che- analyzed by GC. The structure of the product was defined by GC–
mical Co. Ltd., China. Hydrogen gas and nitrogen gas were pur- MS. For the investigating the reusability of the catalyst, the
chased from HaiPu Gas Industry Co. Ltd., China. All these reagents PTA@ZIF-67(ec) catalyst was separated by simple centrifugation
were used as received without further purification. from the reaction mixture, washed with abundant amounts of
dichloromethane (DCM), dried under vacuum at room tempera-
2.2. Catalyst Preparation ture for 6 h and reused in reaction.

2.2.1. Zeolite imidazolate framework (ZIF-67) preparation

For the synthesis of ZIF-67, 0.722 g of Co (NO3)2  6H2O (2.48 mmol) 3. Results and discussion
was dissolved in 25 mL methanol and 1.629 g of 2-methylimidazole
(19.84 mmol) was dissolved in 25 mL methanol separately, were stir- 3.1. XRD and BET
red until dissolved. When both reagents were entirely dissolved in
methanol, the solution consists of 2-methylimidazole was slowly ad- Fig. 1 illustrates the XRD patterns of bare ZIF-67 and PTA@ZIF-
ded to the solution of Co (NO3)2  6H2O. The solution became purple 67(ec) samples. The XRD patterns of synthesized samples in this
immediately, and the resultant mixture was stirred for 2 h at room work were in good agreement with simulated single crystal
temperature. The solids were collected by centrifugation for 10 min structure patterns in the Cambridge Structural Database (CCDC
and were washed with methanol for several times to remove excess code¼ GITTOT). In the bare ZIF-67 sample, a very sharp peak was
2-methylimidazole present on the surface and pores. Then solids were detected at 7.3° on the XRD pattern, demonstrating that the ma-
dried overnight in air oven, at room temperature. Finally, the sample terial was obtained, is highly crystalline material.
was dried under vacuum at 130 °C for 2 h. In fact, whenever MOF-based materials are synthesized, highly
 M. Ammar et al. / Journal of Solid State Chemistry 233 (2016) 303–310 305

67 as shown in Fig. 2B. With the inclusion of PTA, the pore size and
(011)
pore volume were substantially decreased. The result is evidence
that the highly accessible structure of the ZIF-67 is maintained,
even at high PTA loading.
(f) Table 1 presents the results of BET surface area, pore size and
Intensity (a.u.)

total pore volume. The BET surface area of the ZIF-67 encapsulated

(224)

(244)
(112)

phosphotungstic acid decreases from 1390.45 to 600.27 m2/g with

(044)
(222)
(013)
(002)

(134)
(233)
(022)

(114)

(334)
addition of PTA. The total pore volume of the ZIF-67 encapsulated

(235)
(e) phosphotungstic acid also decreases from 0.71 to 0.29 cm3/g.
(d)
3.2. Structure and morphology
(c)
(b) Fig. 3 shows the SEM micrographs of ZIF-67 and different
(a) PTA@ZIF-67(ec) samples, synthesized at room temperature. Ac-
cording to SEM micrographs, ZIF-67 revealed that well-shaped,
hexagonal nano-crystals were obtained having an average particle
10 20 30 40 50 size of about 200 nm (Fig. 3a) and as the amount of PTA en-
2 Theta (degree) capsulated into the cage of ZIF-67 (14.6–31.7 wt%) keep up the
crystal shape and structure (Fig. 3b and c). But the higher amount
Fig. 1. XRD patterns of simulated ZIF-67 obtained from Cambridge Structural Da-
of PTA about 46.4 wt% could not encapsulate PTA in the cage and
tabase(a), ZIF-67 synthesized in this work(b), 14.6 wt% PTA@ZIF-67(ec)(c), 26.5 wt%
PTA@ZIF-67(ec)(d), 31.7 wt% PTA@ZIF-67(ec)(e) and 46.4 wt% PTA added in synth- demolished the crystal structure as shown in Fig. 3d.
esis mixture caused to demolish the crystal structure(f).
3.3. FT-IR spectroscopy
crystalline material is always expected. However, the PTA@ZIF-67
(ec) sample patterns showed hardly any difference and good FT-IR spectroscopic studies were carried out to confirm whe-
agreement with the peaks of bare ZIF-67 up to a certain amount of ther PTA and ZIF-67 structures were preserved in the novel com-
PTA added in the synthesis mixture (14.6–31.7 wt% PTA@ZIF-67 posite materials PTA@ZIF-67(ec). FT-IR spectra of bare ZIF-67 and
(ec)). While, the presence of higher amount of PTA (46.4 wt% PTA different PTA@ZIF-67(ec) samples are shown in Fig. 4.
added in synthesis mixture) caused to lower the pH of the The bands at 693 and 753 cm  1 in the spectral region are as-
synthesis mixture. Low pH prevented ligand from coordination sociated with out-of-plane bending of the imidazole ring, while
with metal due to protonation and resulted into demolishing the peaks in the region of between 900 and 1350 cm  1 are assigned as
crystal structure. Apart from the fact that the crystal structure in-plane bending. The peaks at 1576 and 1663 cm  1 are attributed
appeared to remain unchanged during the PTA encapsulation to the stretching and bending N–H vibration of the imidazole ring,
while the intensity of the peak at 7.3° decreased for the PTA en- respectively. The intense and convoluted bands at 1350–1500 cm  1
capsulated samples. are associated with the entire ring stretching, whereas two peaks at
Fig. 2A shows the N2 adsorption–desorption isotherms of bare 2922 and 3131 cm  1 are attributed to the aliphatic and the aro-
ZIF-67 and PTA@ZIF-67(ec). The isotherms revealed type-I with matic C–H stretch of the imidazole, respectively. As one can judge
sharply increased adsorption at low relative pressure, which is from the FT-IR spectra of bare ZIF-67 and PTA@ZIF-67(ec) presented
typical for microporous materials. No indication of pore blocking in Fig. 4, the most intensive peaks belong to ZIF-67 and the matrix
was observed in the isotherms. The pore size distribution curves of structure certainly retained upon PTA encapsulation in ZIF-67. The
bare ZIF-67 and PTA@ZIF-67(ec) were transformed using the presence of strongly bonded water in the PTA@ZIF-67(ec) samples
Horvath–Kawazoe (HK) method, which further supported the can easily be observed as shown in Fig. 4(A) (range between 800
presence of two kinds of micropore in bare and encapsulated ZIF- and 4000 cm  1), from a broad absorption band between 3200 and

500
Quantity Adsorbed (cm?g STP)

4 (a)
dV/dw (cm3/g.nm )

400 (b)
(c)
3
(d)
300
2
200
(a) 1
100 (b)
(c)
(d)
0
0
0.0 0.2 0.4 0.6 0.8 1.0 0.5 1.0 1.5 2.0
Relative Pressure (P/Po)
Pore Width (nm)
Fig. 2. N2 adsorption–desorption isotherms(A) and pore size distribution curves(B) of ZIF-67 synthesized in this work(a), 14.6 wt% PTA@ZIF-67(ec)(b), 26.5 wt% PTA@ZIF-67
(ec)(c) and 31.7 wt% PTA@ZIF-67(ec)(d).
306 M. Ammar et al. / Journal of Solid State Chemistry 233 (2016) 303–310

Table 1
Structural characteristics of ZIF-67 and PTA@ZIF-67(ec) samples.

Samples BET Surface area (m2/g) Pore size (nm) Total pore volume (cm3/g) PTA (wt%) ZIF-67 (wt%)

ZIF-67 1390.45 2.04 0.71 – 100.00

14.6 wt%PTA@ZIF-67(ec) 994.85 2.21 0.55 14.60 85.40
26.5 wt%PTA@ZIF-67(ec) 647.42 1.98 0.32 26.50 73.50
31.7 wt%PTA@ZIF-67(ec) 600.27 1.95 0.29 31.70 68.30

Fig. 3. SEM micrographs of ZIF-67 synthesized(a), 14.6 wt% PTA@ZIF-67(ec)(b), 26.5 wt% PTA@ZIF-67(ec)(c) and 46.4 wt% PTA added in synthesis mixture caused to demolish
the crystal structure(d).

(a)
(a)
Transmittance

Transmittance

(b) (b)
(c) (c)
(d) (d)
(e) (e)
(1663)

(1382)
(2922)

(1576)

(1171)
(3131)

(1060)
(992)
(1305)

(1455)

(888)

(693)
(956)
(1141)
(1423)

(823)
(753)

4000 3500 3000 2500 2000 1500 1000 1800 1600 1400 1200 1000 800
-1 -1
Wavenumber (cm ) Wavenumber (cm )
Fig. 4. FTIR spectra of the phosphotungstic acid (PTA)(a), ZIF-67 synthesized(b), 14.6 wt% PTA@ZIF-67(ec)(c), 26.5 wt% PTA@ZIF-67(ec)(d) and 31.7 wt% PTA@ZIF-67(ec)(e).
 M. Ammar et al. / Journal of Solid State Chemistry 233 (2016) 303–310 307

100 100 (c)

(d) (b)
80 (e)

Conversion (%)
98
Weight (%)

(c) 60 (d)
96 (a)
(b)
40
94
(a) 20

92 0
100 200 300 400 500 600 700 800 0 2 4 6 8 10
Temperature (oC) Catalyst Content (wt%)
Fig. 5. TGA analysis of the ZIF-67 synthesized(a), 14.6 wt% PTA@ZIF-67(ec)(b),
Fig. 6. Effect of catalyst content on the reaction conversion in the presence of
26.5 wt% PTA@ZIF-67(ec)(c) and phosphotungstic acid (PTA)(d).
catalyst: ZIF-67 synthesized(a), 14.6 wt% PTA@ZIF-67(ec)(b), 26.5 wt% PTA@ZIF-67
(ec)(c), 31.7 wt% PTA@ZIF-67(ec)(d), and 46.4 wt% PTA added in synthesis mixture
3700 cm  1 and the broad band centered at 1305 cm  1 [32]. The caused to demolish the crystal structure(e).
stretching band at 1305 cm  1 is also present in the bare ZIF-67
sample; however the width and intensity is increased in PTA en- 3.5. Catalytic performance testing
capsulated samples.
When focusing on the 800–1100 cm  1 range (Fig. 4(B)), after 3.5.1. Screening of catalysts
subtraction the bare ZIF-67 FT-IR spectra from PTA@ZIF-67(ec) The performance of the PTA@ZIF-67(ec) as a heterogeneous
sample spectra. The FT-IR spectra of novel composite materials catalyst in the Friedel–Crafts acylation of anisole with benzoyl
PTA@ZIF-67(ec) exhibit the principal stretching modes of the PTA chloride was assessed (Scheme 1). The benzoyl chloride was used
Keggin units such as W–O–W, W ¼O and PO4. The PO4 stretching as an acylating agent to form p-benzoylanisole as the major pro-
appeared at 1060 cm  1. The bands at 956 and 888, 823 cm  1, duct and o-benzoylanisole as the minor product.
clearly present in all PTA@ZIF-67(ec) samples, are related to the In this work, it was achieved that the Friedel–Crafts acylation of
W¼ O and W–O–W stretching, respectively. This definitely in- anisole with benzoyl chloride can take place in the presence of
dicated that the heteropolyanion structure was maintained after bare ZIF-67 and PTA@ZIF-67(ec) as a catalyst. The reaction was
encapsulation. carried out at 120 °C for 6 h with anisole:benzoyl chloride molar
ratio 1:2 and the results were graphically summarized in Fig. 6.
The bare ZIF-67 gave hardly 45% conversion with higher
3.4. Thermal stability analysis amount of catalyst. PTA@ZIF-67(ec) samples were found much
more active catalysts as compared to bare ZIF-67 under the same
Thermal degradation of solid materials has significant im- condition. A conversion of 100% was achieved in the presence of
portance for their application because most of them depend on 26.5 wt% PTA@ZIF-67(ec) catalyst under reaction condition with-
their thermal stability. Fig. 5 shows the TGA curves of PTA, ZIF-67 out an inert atmosphere. As it can be observed from Fig. 6, the bare
and PTA@ZIF-67(ec) samples. It can be seen that PTA revealed a ZIF-67 did not reveal good catalytic activity, most probably caused
one-step degradation process; bare ZIF-67 and PTA@ZIF-67(ec) by the lack of active sites on which the Friedel-Crafts acylation
samples followed two-step degradation process. The TGA curve of reaction could take place. On the other hand, the encapsulated PTA
PTA only illustrated a weight loss at about 160 °C, perhaps as a into the ZIF-67 cage gave dramatic increment of strongly active
result of dehydration of water from crystalline structure, and no sites on PTA@ZIF-67(ec), which resulted in a boost in the reaction
more considerable weight loss was observed until 800 °C. conversion.
The TGA curve of bare ZIF-67 revealed that only tiny weight Furthermore, it was also observed that the catalytic activities of
loss up to 350 °C, concerning to the removal of guest molecules 26.5 wt% PTA@ZIF-67(ec) and 14.6 wt% PTA@ZIF-67(ec) catalysts were
and un-reacted species, while the thermal stability of PTA@ZIF-67 better than the 31.7 wt% PTA@ZIF-67(ec) catalyst under the same
(ec) samples were reduced in the range 200–350 °C owing it to the conditions, that can be caused by active sites strongly bonded with
introduction of PTA. Therefore, when comparing the residual carrier and could not take part in the reaction efficiently in 31.7 wt%
content of bare ZIF-67 and PTA@ZIF-67(ec) samples, it can be PTA@ZIF-67(ec) catalyst. The demolish sample of ZIF-67 caused by the
observed that TGA curves showed high residual content system- PTA, showed higher conversion than 31.7 wt% PTA@ZIF-67(ec) catalyst
atically with the increase of PTA content. From TGA, it can be seen may be because of some trace amount of PTA present with demol-
that encapsulation of the PTA into ZIF-67 structure did not badly ishing structure after washing. But, further investigation would be
damage the thermal stability. required to examine the mechanism thoroughly.

Scheme 1. Friedel–Crafts acylation of anisole with benzoyl chloride using PTA@ZIF-67(ec) catalyst.
308 M. Ammar et al. / Journal of Solid State Chemistry 233 (2016) 303–310

Table 2
Effects of 26.5 wt% PTA@ZIF-67(ec)catalyst content on reaction conversion and
100 Conversion p-isomer
yielda.

26.5 wt% PTA@ZIF- PTA Con- ZIF-67 Conversion Selectivity Yield 80

67(ec) Content tent Content (%) (%) (%)
(wt%) (wt%) (wt%)
60

(%)
2 0.53 1.47 44.31 92.53 40.99
4 1.06 2.94 82.14 93.51 76.81
6 1.59 4.41 95.75 93.03 89.08
8 2.12 5.88 99.21 93.88 93.14
40
10 2.65 7.35 99.99 94.47 94.46

a
Reaction condition: anisole, 0.006 mol; benzoyl chloride, 0.012 mol; tem- 20
perature, 120 °C; time, 6 h.

0
3.5.2. Effect of catalyst content 100 110 120 130 140
Table 2 shows the effect of PTA@ZIF-67(ec) catalyst content on o
reaction conversion, selectivity and yield. In the literature, it was
Temperature ( C)
reported that the Friedel-Crafts acylation reaction can be needed Fig. 7. Effect of temperature on the reaction conversion and p-isomer selectivity
an extra stoichiometric amount of the Lewis acid due to complex over 26.5 wt% PTA@ZIF-67(ec) catalyst. Reaction condition: anisole, 0.006 mol;
formation with the oxygen atom of aroyl products [33,34]. The benzoyl chloride, 0.012 mol; catalyst amount, 0.1 g; time, 6 h.

catalyst concentration can be diminished dramatically with var-

ious solid catalysts for the Friedel–Crafts acylation reaction such as
beta zeolite [35,36], metal triflate loaded SBA-15 [37], hybrid able to give a significant increase in reaction conversions at 130
zeolite-mesostructured material [38] and mesoporous superacid and 140 °C (Fig. 7) because the reaction reached almost the equi-
catalyst [39,40]. In fact, the Friedel–Crafts acylation reaction can librium under 140 °C. The reaction selectivity was found almost
need less than 1 wt% to more than 10 wt% catalyst, depending on unchanged at
94% to p-benzoylanisole (Fig. 7).
Whenever a solid catalyst is used, a vital issue is the risk that
the nature of the catalyst as well as the substrate.
some active sites can transfer to the liquid phase from the solid
In this work, it was observed from the preliminary investiga-
support and so on; these leached species can be a significant factor
tions that catalyst content is a significant factor that can con-
for the reaction conversion [45]. In order to find out either
siderably influence the reaction conversion as well as yield of
leaching of active sites occurred in Friedel–Crafts acylation reac-
product. The reaction rate was found directly proportional to the
tion using PTA@ZIF-67(ec) catalyst or not. An experiment was
26.5 wt% PTA@ZIF-67(ec) catalyst content. 44% to 100% conver-
accomplished to assess the contribution of leached active species
sions were achieved in the presence of 2 wt% to 10 wt% of
to the reaction conversion. A simple centrifugation was carried out
26.5 wt% PTA@ZIF-67(ec) catalyst. Moreover, the reaction conver-
during the conduct of the reaction to separate the solid catalyst
sion observed for the 26.5 wt% PTA@ZIF-67(ec) catalyst was higher
from the reaction mixture. If the catalytic reaction still carried on
than several previously reported Lewis acid catalysts, where
after the separation of solid catalyst, this would indicate that the
higher catalyst loading and/or longer reaction time was needed for
real active species was leached acid rather of the solid PTA@ZIF-67
the same reaction [41]. The selectivity was found almost the same
(ec) catalyst. Within experimental error, after the solid catalyst
for all cases with
94% for p-benzoylanisole.
was separated from the organic phase, no further reaction was
Previously, Firouzabadi and co-workers used aluminum dode-
found. Consequently, it can be concluded that there were no lea-
catungstophosphate for Friedel–Crafts acylation of anisole with ched active species in the organic phase, and reaction could only
benzoyl chloride, as heterogeneous catalyst and achieved 80% se- be carried out in the presence of PTA@ZIF-67(ec) catalyst.
lectivity to the p-benzoylanisole [42].Chourdhary and co-workers Choudhary and co-workers previously investigated by using a
used zeolite based catalyst for the same reaction and ameliorated zeolite-based catalyst and reported that the rate of the Friedel–
the selectivity of p-isomer to 90% [43]. Kemnitz and co-workers Crafts acylation reaction was drastically enhanced in the presence
utilized borate zirconia solid acid as a heterogeneous catalyst and of new Brönsted acid sites developed by the interaction of the
enhanced the selectivity to 93-95%, but the reaction was carried Lewis acid sites of the catalyst with moisture [43]. Lewis acid sites
out in the presence of nitrobenzene as solvent [44]. Therefore, the combine with Brönsted acid sites could devote to the catalytic
selectivity of 26.5 wt% PTA@ZIF-67(ec) catalyst in the Friedel- activity of solid catalyst in the Friedel–Crafts acylation reaction.
Crafts acylation of anisole with benzoyl chloride was comparable
with those previously reported in the literature. 3.5.4. Effect of electron donors and withdraws as substitution group
The study was then expanded to investigate the effect of dif-
3.5.3. Effect of reaction temperature ferent substrates on the Friedel–Crafts acylation reaction using
With such results in hand, we then decided to investigate the PTA@ZIF-67(ec) catalyst. The reaction was accomplished by using
effect of reaction temperature on conversion. The Friedel–Crafts 4 wt% of 26.5 wt% PTA@ZIF-67(ec) catalyst with substrate:benzoyl
acylation reaction was performed using 4 wt% of 26.5 wt% PTA@- chloride molar ratio 1:2 for 6 h. Fernandes and co-workers re-
ZIF-67(ec) catalyst at 140, 130, 120, 110 and 100 °C, respectively. ported that the most excellent yields of Friedel–Crafts acylation
Aliquots from the reaction mixtures were withdrawn after 6 h and were observed in the presence of electron donor groups in the
analyzed by GC to provide kinetic data for the course of the re- aromatic ring [33]. In this work, the results illustrated that the
action. After 6 h, a conversion of 82% was achieved at 120 °C re- addition of an electron donor group on the aromatic ring increased
action temperature. A considerable drop in the reaction rate was the acylation reaction conversion as well as yield while the addi-
observed by decreasing the reaction temperature, with 71% and tion of an electron withdraw groups significantly decreased them.
57% conversions being achieved after 6 h at 110 and 100 °C, re- The acylation reaction of anisole with benzoyl chloride gave 82%
spectively. In fact, increasing the reaction temperature was not conversion at 120 °C after 6 h, whereas 73% and 69% conversions
 M. Ammar et al. / Journal of Solid State Chemistry 233 (2016) 303–310 309

Table 3 4. Conclusion
Effect of electron donating and withdraw substitution group on acylation reactiona.
The Friedel–Crafts acylation of anisole with benzoyl chloride is
Conversion (%) Selectivity (%) Yield (%)
Substrate investigated over novel PTA@ZIF-67(ec) catalyst. The PTA@ZIF-67
p-isomer o-isomer (ec) catalyst has been synthesized by direct addition of phospho-
tungstic acid to the synthesis mixture of ZIF-67 at room tem-
R ¼OCH3 82.14 93.51 6.49 76.81
perature. An excellent dispersion of phosphotungstic acid over the
R ¼CH3 73.04 88.54 11.46 64.67
R ¼C2H5 69.11 87.63 12.37 60.56 ZIF-67 sample is achieved. Different amount of phosphotungstic
R ¼Br 45.64 69.75 30.25 31.83 acid has been encapsulated in a ZIF-67 structure (14.6–31.7 wt%)
R ¼CHO 40.41 74.43 25.57 30.08 depending on the amount of phosphotungstic acid introduced in
a
the synthesis mixture. Among the various (14.6–31.7 wt%) PTA@-
Reaction condition: substrate, 0.006 mol; benzoyl chloride, 0.012 mol; cata-
lyst amount, 0.1 g; temperature, 120 °C; time, 6 h.
ZIF-67(ec) catalyst, 26.5 wt% PTA@ZIF-67(ec) catalyst reveals high
activity, stability and reusability for acylation reaction. The effects
of catalyst content, reaction temperature and electron donor and
100 Conversion p-isomer withdraw as substitution group on reaction conversion and yield
have been discussed in detail. In conclusion, we have utilized ZIF
structure as a support for heteropoly acid and develop a highly
80 active, stable, reusable and environmentally friendly hetero-
geneous catalyst for the Friedel–Crafts acylation.
60
(%)

Acknowledgment
40
This work was carried out with financial support from
the National Natural Science Foundation of China (Grant nos.
20 21136001 and 21173018).

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