Immobilization of phosphortungstic acid on amino-functionalized bimetallic Zr-La-SBA-15 and its highly catalytic performance for acetylation

Article abstract of DOI:10.1016/j.molcata.2014.04.011

Phosphotungstic acid (PW) catalysts supported on amino-functionalized Zr and La incorporated SBA-15 mesoporous materials (PW/H₂N-ZLS) were prepared by an impregnation procedure and their physicochemical properties were characterized by FT-IR, X

Full text of DOI:10.1016/j.molcata.2014.04.011

Accepted Manuscript
Title: Immobilization of phosphortungstic acid on
amino-functionalized bimetallic Zr-La-SBA-15 and its highly
catalytic performance for acetylation
Author: Jing Liu Yan Liu Wu Yang Hao Guo Fang Fang
Zhonghua Tang
PII:
S1381-1169(14)00149-6
DOI:
Reference:
http://dx.doi.org/doi:10.1016/j.molcata.2014.04.011
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To appear in:
Journal of Molecular Catalysis A: Chemical
Received date:
Revised date:
Accepted date:
16-11-2013
4-4-2014
4-4-2014
Please cite this article as: J. Liu, Y. Liu, </sup>,Wu Yang, H. Guo, F. Fang, Z. Tang,
Immobilization of phosphortungstic acid on amino-functionalized bimetallic Zr-La-
SBA-15 and its highly catalytic performance for acetylation, Journal of Molecular
Catalysis A: Chemical (2014), http://dx.doi.org/10.1016/j.molcata.2014.04.011
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Immobilization of phosphortungstic acid on amino-functionalized bimetallic
Zr-La-SBA-15 and its highly catalytic performance for acetylation
a, c
b
a*
a
a
a
Jing Liu , Yan Liu ,Wu Yang , Hao Guo , Fang Fang , Zhonghua Tang
a. College of Chemistry and Chemical Engineering, Key Lab of Bioelectrochemistry and
Environmental Analysis of Gansu Province, Northwest Normal University, Lanzhou 730070,
PR China.
b. Department of Data Traffic, Tianshui Subsidiary, Gansu Mobile Communication Limited
Company, Tianshui 741000, PR China.
c. Gansu College of Agriculture Technology, Lanzhou 730020, PR China.
Abstract: Phosphotungstic acid (PW) catalysts supported on amino-functionalized Zr and La
incorporated SBA-15 mesoporous materials(PW/H
procedure and their physicochemical properties were characterized by FT-IR, XRD, TEM, TG and
adsorption-desorption isotherm techniques. It was found that the modified materials still
2
N-ZLS) were prepared by an impregnation
N
2
preserved a desirable ordered two-dimensional P6 mm hexagonal structure and possessed high
specific surface area, large pore volume and narrow pore size distribution and meanwhile the
Keggin structure of heteopolyaniona could be retained. Moreover, these catalysts were found to be
efficient heterogeneous catalysts for acetylation of anisole with acetic anhydride under microwave
irradiation. High yields, short reaction times, easy work-up, easy availability and handling,
eco-friendliness and reusability of the catalysts were the main aspects of the present method.
2
Keywords: PW; H N-ZLS; mesoporous materials; supported catalysts; microwave irradiation;
acetylation
1
.
Introduction
The Friedel–Crafts acetylation reaction is a classical method for the preparation of aromatic
ketones and it has been one of the most important basic reaction types in organic chemistry. It is a
key step in the synthesis of numerous pharmaceuticals, natural products and versatile synthetic
intermediates [1]. Traditionally, various homogeneous catalysts including Lewis or Brønsted acids,
2 4 3 3 3
such as, H SO , BF , HF, AlCl or FeCl , zirconia sulphated, have been used in this reaction, [2].
*
Correspondence author. Email:xbsfda123@126.com, Tel:+869317971216
1
Page 1 of 28

However, most catalysts suffer from drawbacks of difficult separation after the reaction, therefore,
they are incapable of recycling and reusing. Furthermore, some of them are corrosive and volatile
and often cause the environment problems. Many efforts have been made to exploit the
environmental-friendly catalytic technology for the target reaction. In recent years, use of
heterogeneous catalysts in liquid phase reactions has received great attention due to their
advantages such as high activity, selectivity, reusability, ease of separation, no corrosion or
disposal of effluent problems, etc.
The applications of heteropoly acids (HPA) catalysts have attracted extensive interest in the
last decade as solid acid catalyst [3-7]. Heteropoly acids (HPA), especially phosphotungstic acid
(
PW), have received great attention among the acid catalysts because of their high acid strength
and selectivity properties [8, 9]. However, the main disadvantage of bulk PW is their very low
2
-1
surface area (< 10 m ·g ) and hence it becomes necessary to disperse PW on supports that possess
large surface area. The use of SBA-15 mesoporous materials is attractive because it possesses
well-ordered pore structures, high thermal stability and high surface area [10]. This would make
the material become a suitable host for acid catalysts. There are some reports available on the
modification of SBA-15 with HPA and its applications [11-20]. However, weak interaction
between the PW and the support resulted in its leaching in polar media [21]. The reaction
stabilities of the catalysts are still not satisfactory. Thus, it is necessary to further develop novel
and facile methods to prepare supported PW catalysts, which could be applied in acetylation of
organic compounds with high performance. Some important issues are considered, e.g. to improve
the dispersion of the active species and the interaction between the active species and the
supporter, to minimize the leaching of active species and to boost the reusability of catalysts.
In this present work, zirconium and lanthanum elements, at first, have been successfully
incorporated into SBA-15 mesoporous material framework by a direct synthesis method. Then,
PW was successfully anchored to amino- functionalized Zr and La incorporated SBA-15
mesoporous material (PW/H
catalytic performance for the acetylation of anisole with acetic anhydride. PW of various loadings
supported on H N-ZLS were prepared by an impregnation method and characterized by
Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron
2 2
N-ZLS). The prepared catalyst (PW/H N-ZLS) showed a high
2
microscopy (TEM), N
2
adsorption-desorption isotherm and thermo gravimetry (TG).
2
Page 2 of 28

2
2
2
. Experimental
.1 Catalyst preparation
.1.1 Mesoporous materials ZLS preparation
The catalytic ZLS materials were synthesized by the following procedures. 2 g of pluronic
P123, as a template agent, was dissolved in 100 g of deionized water under vigorous stirring at
5 for 2h. The appropriate amount of tetraethyl orthosilicate TEOS (silica source), ZrOCl ·8H
and La(NO ·6H O (precursors) were added into above solution under vigorous stirring. The
molar ratio of P123/TEOS/H O/ ZrOCl ·8H O/ La(NO ·6H O was maintained as 0.01: 1: 170:
.05: 0.05. The mixed solution was continuously stirred for 20h, and finally crystallized in a
3
2
2
O
)
3 3
2
2
2
2
)
3 3
2
0
teflon-lined autoclave at 100 for 24h. The white product was filtered, washed abundantly with
deionized water and absolute ethanol to pH 7 respectively, and then dried at 60 in vacuum oven
for 8h. The template agent was removed from the as-synthesized product through solvent
extraction using HCl/EtOH solution (1g of sample in 5mL/150mL) for 24h. The obtained sample
was dried at 60 in vacuum oven for 6h. For comparison, conventional SBA-15 was also
prepared according to Zhao’s synthesis procedure [10].
2
.1.2 Different amino-functionalized ZLS (H
The preparation of amino-functionalized mesoporous materials H
post-grafting procedure. Two different aminosilanes were used: 3-(trimethoxysilyl)propylamine
(H N-(CH -Si(OCH )](APTS), N-[3-(trimethoxysilyl)propyl]ethylenediamine [(H N-(CH
NH-(CH -Si(OCH )](AAPTS). Typically, 1 g of ZLS sample was suspended in 60 mL of dried
2
N-ZLS) preparation
2
N-ZLS was performed by
[
2
2
)
3
3
)
3
2
2 2
) -
)
2 3
3 3
)
-
1
toluene and then 8 mmol·g of organosilane (APTS or AAPTS) was added under the strong
stirring. This suspension system was then stirred under refluxing at 75 for 24 h. The resulting
solid material was filtered and washed abundantly with dried toluene and isopropyl alcohol. After
drying at 80 in vacuum oven overnight, the resulting solid was re-suspended in 0.2M HCl for 6
h at room temperature for protonation followed by filtering and vacuum drying at 50 for 12 h.
The obtained samples were named as H
.1.3 Immobilization of PW on H N-ZLS (PW/H
The supported PW catalyst was prepared by a method of incipient wetness. A typical process
was as follows: 2 g of amino-functionalized mesoporous material (H N-ZLS-N or H N-ZLS-NN)
2 2
N-ZLS-N and H N-ZLS-NN, respectively.
2
2
2
N-ZLS)
2
2
-
4
was stirred in 5 mL of deionized aqueous solution containing 6.5×10 mol (1.87g) of PW at 60
3
Page 3 of 28

for 8h. The resulting solid catalysts, PW/H
washed with methanol three times to remove unanchored PW and dried at 95 for 3h. The
catalyst loading capacity of H N-ZLS was calculated to be about 30wt%. The obtained samples
were denoted as 30%PW/H N-ZLS-N and 30%PW/H N-ZLS-NN, respectively. The supported
catalysts PW/H N-ZLS-N and PW/H N-ZLS-NN with 20% and 40% loading capacity were
prepared according to the above steps. They were denoted as 20%PW/H N-ZLS-N,
0%PW/H N-ZLS-N ， 20%PW/H N-ZLS-NN and 40%PW/H N-ZLS-NN, respectively. PW
2 2
N-ZLS-N or PW/H N-ZLS-NN, were then filtered and
2
2
2
2
2
2
4
2
2
2
supported on unmodified ZLS was also synthesized through incipient wetness under similar
conditions, the resulting material was denoted by 30%PW/ZLS. The preparation process of the
catalyst was showed as Scheme 1.
2
.2 Catalysts characterization
FT-IR spectra were recorded on a Digilab FTS3000 FT-IR spectrometer using the KBr wafer
technique. XRD patterns were obtained with an X’Pert/PRO diffractometer in the reflection mode
using Cu Kα radiation source with a resolution of 0.02° and scanning speed of 0.5°/min. N
2
adsorption–desorption isotherms were measured on a Micromeritics ASAP 2020 analyzer. The
samples were first degassed at 110 for 5h before adsorption measurements. TEM images of the
samples deposited on carbon–copper grids were taken on a JEM 1200EX microscope. TGA were
performed by means of a PerkinElmer PE6300 series instrument, in the temperature range from 25
to 800 , with a heating rate of 10 /min under nitrogen atmosphere.
2
.3 Catalytic tests
In a round-bottomed flask (50mL), anisole (1.08g, 10mmol), acetic anhydride (2.04g, 20mmol),
dichloromethane (10mL) and PW/H
2
N-ZLS or PW/ZLS (0.6g) were added respectively. Then the
flask was transferred into the modified microwave oven fitted with a condenser and subjected to
microwave irradiation at the power of 450W for 8 min. The progress of the reaction was
monitored by TLC (petroleum ether:ethyl acetate=5:1 as eluent). After completion of the reaction,
the catalyst was filtered off and the filtrate was evaporated to remove the solvent under reduced
pressure. Finally, the selectivities and conversions were determined by a shimadzu GC 2010
equipped 15m-0.5mm, RTX-1 capillary column and FID detector.
3
3
3
. Results and discussion
.1 Characterization of the catalysts
.1.1 XRD patterns
4
Page 4 of 28

Fig. 1 showed small angle XRD patterns of the 3-aminopropyl-functionalized ZLS
N-ZLS-N and H N-ZLS-NN) and heterogeneous catalysts with different PW loading
PW/H N-ZLS-N, PW/H N-ZLS-NN and PW/ZLS) in the 2θ range of 0.6-5°. Three XRD peaks
(
(
H
2
2
2
2
corresponding to (100), (110) and (200) reflections were exhibited, which can be indexed to a
two-dimensional hexagonal lattice of the mesoporous material ZLS. Although the relative
intensities of the reflections had slight decrease, the well-resolved reflections at (110) and (200) of
H
2
N-ZLS-N and the PW-supported H
structural characterizations. Generally, the appearance of the main reflection (100) suggested the
existence of mesopore in PW/H N-ZLS-N sample. Therefore, this finding demonstrated that the
2
N-ZLS-N indicated that they remained mesoporous
2
mesoporous structure of ZLS was not destroyed after the aminosilylation and immobilization of
PW. In contrast, the intensities of all the peaks of the N-[3-(trimethoxysilyl)propyl]
ethylenediamine modification (H
decreased obviously. It indicated that the regularity of the structure H
N-ZLS-NN became rather poorer. The channels in the ordered hexagonal arrangement were
2 2
N-ZLS-NN) and PW immobilization (PW/ H N-ZLS-NN)
2
N-ZLS-NN and PW/
H
2
partially collapsed, in some degree, into disordered and wormhole-like packings. These findings
demonstrated that the long-range mesoporous ordering of the parent support ZLS was much
affected by the N-[3-(trimethoxysilyl)propyl]ethylenediamine modification (H
2
N-ZLS-NN) and
PW immobilization (PW/ H N-ZLS-NN). The immobilization of PW inside ZLS (PW/ZLS)
2
channels resulted in a slight decrease in the intensity of all diffractions, which was probably
attributed to the pore filling of the host material with PW.
3
.1.2 Nitrogen sorption isotherms
For the N adsorption-desorption isotherms of the ZLS, 3- aminopropyl-functionalized ZLS
N-ZLS-N and H N-ZLS-NN), 3- aminopropyl-functionalized ZLS loaded PW catalysts (PW/
N-ZLS-N, PW/H N-ZLS-NN) and PW/ZLS (Fig. 2a), typical irreversible type IV adsorption
2
(
H
2
2
H
2
2
isotherms with a H1 hysteresis loop as defined by IUPAC [22] were observed. As we can see, the
surface modified and PW immobilized samples retained the same shape of the isotherms as that of
ZLS and the adsorption isotherm showed a sharp inflection of the relative pressure between 0.65
and 0.85, which was a characteristic capillary condensation for mesoporous materials. On the
other hand, the BJH pore size distribution was showed in Fig. 2b. The corresponding textural
2
parameters calculated by N adsorption-desorption isotherms were presented in Table 1. The
results showed that aminosilylation of the surface and follow-up immobilization of PW accounted
for the decrease in pore volume and surface area. This loss of specific surface area can be the
result of strong adsorption of PW that did not block the pores and did not contribute to the surface
area of the supports. The surface area of the samples up to 30% loaded PW was more than
5
Page 5 of 28

2
-1
3
-1
1
23m .g and the pore volume was 0.44cm ·g (Table 1), which was sufficient for catalytic
performance. The above characterization results confirmed that PW were located inside the
channels and the mesoporous channels were still preserved. In all cases, correlation coefficients
above 0.999 were obtained.
3
.1.3 FT-IR analysis
FT-IR spectra could be used to investigate the structure characteristics of the samples and to
monitor the essence of surface interaction between PW and H
patterns of ZLS (a), H N-ZLS-N (b), PW/H N-ZLS-N (c) and PW/ZLS (d). ZLS showed IR bands
at ca. 457 cm , 795 cm , 1074 cm corresponding to the rocking, bending (or symmetric
2
N-ZLS or ZLS. Fig. 3 showed IR
2
2
-
1
-1
-1
stretching) and asymmetric stretching of the inter-tetrahedral oxygen atoms in SiO
2
of ZLS,
-1
-1
2
respectively. In the spectrum of H N-ZLS-N, the bands approximately at 2933 cm and 1486 cm
could be assigned to CH stretching vibration and asymmetric stretching vibration of the methylene
-1
-1
groups. Two other IR bands at 1512 cm and 687 cm belonged to N-H deformation vibration and
bending vibration of protonated amino groups, which indicated that part of the amino groups of
3
2
0%PW/H N-ZLS-N were protonated. From the FT-IR analysis, it was found that no structural
collapse of pore structures occurred by the incorporation of PW into Si-O bonds. The IR bands at
-
1
-1
-1
approximate 987 cm (terminal W=O), 890 cm and 808 cm (W–O–W) were clearly observed
for 30%PW/H N-ZLS-N catalyst. This indicated that the primary structure of PW was preserved
even after being supported on H N-ZLS-N, which was in accordance with the XRD analysis.
.1.4 TEM morphologies
TEM images provided further evidence of the stability of the mesostructure samples after
modification of ZLS. In Fig. 4, the exemplified TEM images of the 30%PW/H N-ZLS-N further
2
2
3
2
demonstrated that the hexagonal ordered channel structure of ZLS had no significant change after
aminosilylation of ZLS and immobilization of PW into the channels. The polyoxometalates filled
in the pores of ZLS were shown by the highly contrast lines in comparison with pure ZLS. Fig.4(d)
was a TEM image of deactivated 30%PW/H
structure of 30%PW/H N-ZLS-N became disordered to some extent and wormhole-like packings.
However, porestructure was still preserved.
.1.5 TGA profiles
2
N-ZLS-N. It illustrated that the regularity of the
2
3
6
Page 6 of 28

The thermal stability of 30%PW/H
mesoporous materials was determined by TGA and their TG curves were illustrated in Fig. 5. The
weight loss of H N-ZLS-N was about 7.5% from 150 to 350 , which was caused by the complete
decomposition and combined combustion of protonated amino groups. It was obvious that
0%PW/H N-ZLS-N possessed a higher thermal stability than 30%PW/ZLS. The weight losses
above 300 s in 30%PW/H N-ZLS-N and H N-ZLS-N were possibly due to further framework
2 2
N-ZLS-N, H N-ZLS-N and 30%PW/ZLS, ZLS
2
3
2
2
2
condensation, as observed in other mesoporous silica [23]. The synthesized sample possessed a
weight loss about 13.8% in the range of 100-800 that was attributed to the decomposition of
organic groups incorporated in the material. The obtained results were in good agreement with the
organic content determined by elemental analysis.
3
.2 Catalytic performance
Catalytic activities of the materials in acetylation of anisole and acetic anhydride with
microwave irradiation were given in Table 4. The detailed reaction scheme was shown in Scheme
. Lately, the use of microwave irradiation in synthesis organic chemistry has become more
2
popular [24] and microwave irradiation has been used for many organic reactions. The
acceleration of the reactions by microwave mainly resulted from two effects: thermal effect and
specific microwave effect [25, 26]. Thermal effect (dielectric heating) resulting from
material-microwave interaction allowed fast and uniform distribution and conversion of
microwave energy into heat. Specific microwave effect can be expected for the polar mechanism,
when the polarity was increased during the reaction from the ground state (GS) towards the
transition state (TS). For the reactions under investigation, it seemed that stabilization of the
transition state was more effective than that of the ground state and therefore, the reactivity was
enhanced as a result of decreased activation energy.
In order to select approximate microwave power, the reaction was conducted at different
power level from 65 W to 650 W (Fig. 6). It was observed that 455 W of power level was the most
promising for the reaction because lower power level gave poor yield and higher power lead to
destroy of the substrate. In this work, we could find that the oil-bath heating method took much
longer to complete the reactions and the selectivities were often lower than the corresponding
microwave irradiation reactions. These clearly showed that microwave irradiation improved the
results.
7
Page 7 of 28

The solvent effect on the acetylation was also investigated (Table 2). Several solvents were
tested for the reaction such as CH CN, DMF, CH Cl and THF. For CH CN, the conversion was
very low though selectivity was better. The reaction can not proceeded in DMF. CH Cl and THF
Cl was
3
2
2
3
2
2
could exhibit higher selectivity and conversion. Considering the environment effect, CH
2
2
chosen in the experiment.
The optimal reaction time was also investigated. It was found that the acetylation of anisole
with acetic anhydride could be completed within 8 min under microwave irradiation to give the
corresponding p-methoxy acetophenone in excellent yield.
The effect of anisole to acetic anhydride mole ratio was studied at 1:1, 1:1.5, 1:2 1:2.3,1:2.5
and 1:2.8 by keeping the catalysts loading constant. The conversion of anisole increased with an
increase of the amount of acetic anhydride, whereas, selectivity towards p-methoxy acetophenone
was found to decrease with an increase in concentration of acetic anhydride. 1:2 was found to be
the optimal mole ratio of anisole to acetic anhydride for the acetylation (Fig. 7). Therefore, all
further experiments were studied by keeping a mild anisole: acetic anhydride mole ratio of 1:2.
The results of acetylation with different catalysts were shown in Table 3. The catalytic
3
activities of Lewis acids such as AlCl /SBA-15 was first tested, but little product was observed.
The PW/H N-ZLS-N could efficiently catalyze Fries-Crafts reaction to give the satisfying
2
selectivity and high yield compared with the data of literature [27-30]. In contrast, the PW
exhibited an intermediate level of activity, which was significantly lower than the
2
PW/H N-ZLS-N. Thus, the current catalysts were much better than others.
2
As listed in Table 4, the 30%PW/H N-ZLS-N sample exhibited the highest product yield and
good selectivity, meaning that suitable concentration of PW was advantageous to the reaction. In
this case, a significant difference was found among these catalysts as a function of the PW loading.
The p-methoxy acetophenone yield decreased in the following order: 30%PW/H
86.4%)>40%PW/H N-ZLS-N (82.9%)>20%PW/H N-ZLS-N (68.8%). This increase in yield can
be ascribed to their higher acidity. Due to the less amounts of active site in the sample,
0%PW/H N-ZLS-N showed less product yield. In the case of 40%PW/H N-ZLS-N the product
yield was found to be less compared to 30%PW/H N-ZLS-N catalyst, which was probably due to
the blocking of active sites by the dense Keggin structure, thereby giving diffusional constraints
2
N-ZLS-N
(
2
2
2
2
2
2
[
31]. It was noteworthy that in all the reactions the region-selectivity and conversion using the
8
Page 8 of 28

H
2
N-ZLS-N supported PW catalytic system were the highest, whereas, 30%PW/ZLS, as a catalyst,
which contained mainly Brønsted acidic sites, only showed moderate yield (81.4%) and lower
selectivity than that of the H N-ZLS-N-based catalyst. It was intriguing that introducing
2
protonated amino groups into ZLS framework would promote the reaction between anisole and
acetic anhydride in terms of higher yield and high selectivity. The reaction with the present
H
2
N-ZLS-N based catalysts was improved effectively as compared to PW/ZLS catalysts. From
these reasons, it can be deduced that high dispersion of PW onto H N-ZLS-N and the large surface
2
area with suitable pore size might account for the high catalytic activity. In addition, the
introduction of lanthanum and zirconium into SBA-15 framework to create a lot of new activity
sites, which can also enhance the catalytic activity and selectivity of the current
catalysts[32,33].Since 30%PW/H
acetophenone yield in our experiments, this sample was chosen for the further study.
In addition, it could be found that when a higher content of PW/H N-ZLS-NN was used, the
2
N-ZLS-N catalyst exhibited the highest p-methoxy
2
total nitrogen content increased, but the BET surface area decreased (Fig. 2 and Table 1). The
higher packing of aminated organosilanes prevented the interaction of amino groups and nearby
chains, and consequently decreased the efficiency of the process (Table 4).
The reuse ability of catalysts was also studied. The catalyst could be so easily separated by
filtering that the recovery and reuse of the catalyst could be very convenient. The selectivity and
conversion with the current catalyst only decreased a little as shown in Fig. 8. This is because that
the protonated amino group on ZLS effectively improved the stability of the immobilizing PW. As
a comparison, even though PW supported unmodified ZLS catalyst showed the same anisole
2
conversion and p-methoxy acetophenone yield as 30%PW/H N-ZLS-N in the first run, the
leaching of PW from 30%PW/ZLS was significant. 30%PW/ZLS after the fourth run almost
showed no catalytic activity.
4
. Conclusion
Phosphotungstic acid supported bimetallic mesoporous material Zr-La-SBA-15 was
successfully synthesized with a simple impregnation method and this material maintained a good
inherent ordered hexagonal channel structure of SBA-15. Under microwave irradiation, the
prepared material showed a high catalytic activity and selectivity for the acetylation of anisole and
acetic anhydride. Besides, this new methodology still had some outstanding advantages, such as
9
Page 9 of 28

the reusability of the catalysts, the operational simplicity, fast reaction and green synthesis
avoiding toxic reagents. Thus, it provided a better and more practical alternative to the existing
methodologies for the synthesis of p-methoxy acetophenone.
Acknowledgements
The authors gratefully acknowledged the financial support from the National Nature Science
Foundation of China (No. 20873101) and Key Lab of Eco-Environment Related Polymer
Materials of MOE, China.
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9-108.
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19] S. Rana, S. Mallick, D. Rath, K. M. Parida, J. Chem. Sci. 124 (2012) 1117-1125.
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Mol. Catal. A: Chem. 223 (2004) 231-235.
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11
Page 11 of 28

Figure captions
Scheme 1 The preparation scheme of the mesoporous materials PW/H N-SBA-15
2
Scheme 2 Catalytic acetylation of anisole with acetic anhydride by phosphotungstic acid
supported on amino-functionalized Zr-La-SBA-15
Fig. 1. Small angle XRD patterns of (a) H
2
N-ZLS-N, 30%PW/H
N-ZLS-N and 30%PW/ZLS (b) N-ZLS-NN, 30%PW/H
N-ZLS-NN and 40%PW/ H N-ZLS-NN
adsorption-desorption isotherms and (b) pore size distributions of ZLS, H
N-ZLS-N, 30%PW/H N-ZLS-NN and 30%PW/ZLS
Fig. 3. FT-IR spectra of ZLS, H N-ZLS-N, 30%PW/H N-ZLS-N, 30%PW/ZLS
Fig. 4. TEM Images of 30%PW/H N-ZLS-N (a) perpendicular channel, (b) parallel channel (c)
2
N-ZLS-N, 20%PW/H
2
N-ZLS-N,
4
2
0%PW/
H2
H2
2N-ZLS-NN,
0%PW/H
2
2
Fig. 2. (a) N
2
2
N-ZLS-N,
3
0%PW/ H
2
2
2
2
2
live FFT and (d) deactivated 30%PW/ZLS-N
Fig. 5. TG curves of (a) ZLS and 30%PW/ZLS and (b) H
2
N-ZLS and 30%PW/ H N-ZLS
2
Fig. 6. Effect of microwave power on the yield of acetylation of anisole with acetic anhydride
catalyzed by 30%PW/H N-ZLS-N
Fig. 7. The effect of mole ratio of acetic anhydride to anisole on yield of p-methoxy acetophenone
Fig. 8. Comparison the reuse ability of 30%PW/H N-ZLS-N and 30% PW/ZLS in acetylation of
anisole with acetic anhydride
2
2
1
2
Page 12 of 28

Table 1 Textural properties of the samples.
BET surface
Pore size
diameters
(nm)
Pore
d
100
a
b
Sample name
area
volume
(nm)
2
3
(
m /g)
(cm /g)
1.34
0.62
0.44
0.57
1.4
ZLS
898
346
123
16
6.65
6.64
5.67
5.09
3.54
6.93
H
2
N-ZLS-N
0%PW/H N-ZLS-N
0%PW/H N-ZLS-NN
PW/ZLS
5.86
3
2
5.16
3
2
3.45
932
6.95
2
a, b. Calculated from the N adsorption branch of the isotherms by the BJH method with
Halsey equation.
1
3
Page 13 of 28

2
Table 2 PW/H N-ZLS-N catalyzed the acetylation of anisole with acetic anhydride in different
a
solvents .
Selectivity of p-methoxy
Entry
Solvent
Conversion(%)
b
acetophenone (%)
1
2
3
4
CH
DMF
CH Cl
THF
3
CN
50.0
30.0
88.2
88.0
85.1
50.2
96.5
95.2
2
2
a. All reactions of anisole (10mmol), acetic anhydride (20mmol) were carried out under
microwave irradiation for 8 min.
b. Conversion and selectivity were measured by GC.
1
4
Page 14 of 28

a
Table 3 The acetylation of anisole with acetic anhydride catalyzed by different catalysts .
Amount of
Time
Yield of p-methoxy
Entry
Catalyst
b
Catalyst(mmol%)
(min)
acetophenone (%)
1
2
3
4
5
AlCl
3
/SBA-15
PW
PW/NH -ZLS-N
0.5K/Beta [29]
19-WO /ZrO [30]
10
10
10
8
8
8
44.2
62.5
86.4
32.2
82.0
2
3
2
a. All reactions of anisole (10mmol), acetic anhydride (20mmol) were carried out in a solution of
CH
2 2
Cl under microwave irradiation.
b. Yields refered to the isolated products and were measured by GC.
1
5
Page 15 of 28

Table 4 Catalytic performances of various catalysts for acetylation of anisole with acetic
anhydride with microwave irradiation method.
Anisole
conversion(%)
54.2
p-methoxy acetophenone
Reaction conditions
Time
a
a
Selectivity (%)
30%PW/H
30%PW/H
30%PW/H
30%PW/H
20%PW/H
40%PW/H
2
N-ZLS-N
2
N-ZLS-N
2
N-ZLS-N
2
N-ZLS-N
2
N-ZLS-N
2
N-ZLS-N
4min
81.2
87.8
98.7
96.5
95.2
98.3
88.5
90.4
90.1
93.2
6min
8min
10min
8min
8min
8min
8min
8min
8min
70.3
87.5
88.2
72.3
84.3
2
0%PW/H
0%PW/H
0%PW/H
2
N-ZLS-NN
2
N-ZLS-NN
2
N-ZLS-NN
28.7
3
4
43.2
40.3
3
0%PW/ ZLS
87.3
Anisole conversion and p-methoxy acetophenone selectivity were determined by GC.
1
6
Page 16 of 28

Highlights：
1
2
3
4
2
. PW/H N-ZLS is synthesized with a simple impregnation method.
. The material has a good inherent ordered hexagonal channel and Keggin structure.
. The acetylation of anisole with acetic anhydride was studied under MW condition.
. The material shows superior catalytic activity.
1
7
Page 17 of 28

*Graphical Abstract (for review)
Page 18 of 28

Figure 1
4
4
3
3
2
2
1
1
5
0
5
0
5
0
5
0
5
0
5
H N-ZLS-N
2
100
3
2
4
3
0% PW/H N-ZLS-N
2
0% PW/H N-ZLS-N
2
0% PW/H N-ZLS-N
2
0% PW/ZLS
1
10
2
00
-
0
1
2
3
4
5
6
2Theta/deg.
(a)
4
4
3
3
2
2
1
1
5
0
5
0
5
0
5
0
5
0
5
H N-ZLS-N-N
2
100
3
2
4
0% PW/H N-ZLS-NN
2
0% PW/H N-ZLS-NN
2
0% PW/H N-ZLS-NN
2
1
10
2
00
-
0
1
2
3
4
5
6
2Theta/deg.
(b)
Page 19 of 28

Figure 2
800
700
600
500
400
300
200
100
0
3
ZLS
H N-ZLS-N
0% PW/ZLS
2
30% PW/H N-ZLS-N
2
30% PW/H N-ZLS-NN
2
0.0
0.2
0.4
0.6
0.8
1.0
Relative Preesure(p/p )
o
(a)
3
0% PW/ZLS
0% PW/H N-ZLS-N
1.0
0.8
0.6
0.4
0.2
0.0
3
2
30% PW/H N-ZLS-NN
2
ZLS
H N-ZLS-N
2
-
4 -2
0
2
4
6
8 10 12 14 16 18 20 22 24 26 28 30
Pore diamter(nm)
(b)
Page 20 of 28

Figure 3
90
80
70
60
50
40
30
20
10
0
4
ZLS
6
87
H N-ZLS-N
2
1486
1512
3
3
0% PW/H N-ZLS-N
2
0% PW/ZLS
3
451
8
08
90
8
2933
9
87
000
3500 3000
2500 2000
1500 1000
500
-1
Wavenumber/cm
Page 21 of 28

Figure 4
(a)
(b)
(c)
(d)
Page 22 of 28

Figure 5
100
95
90
85
80
75
70
PW/ZLS
ZLS
0
100 200 300 400 500 600 700 800
o
Temperature/ C
(a)
100
95
90
85
80
75
70
3
0% PW/H N-ZLS-N
2
H N-ZLS-N
2
0
100 200 300 400 500 600 700 800
o
Temperature/ C
(b)
Page 23 of 28

Figure 6
90
85
80
75
70
65
60
0
100
200
300
400
500
600
700
Microwave power/W
Page 24 of 28

Figure 7
90
85
80
75
70
65
60
0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0
Mole ratio of acetic anhydride to anisole
Page 25 of 28

Figure 8
100
PW/H N-ZLS-N
2
PW/ZLS
80
60
40
20
0
0
1
2
3
4
5
Recycle reaction
Page 26 of 28

Scheme 1
Page 27 of 28

Scheme 2
OCH3
OCH3
COCH3
OCH3
cat.,CH Cl2
2
+
(CH CO) O
+
3
2
MW, 8min
COCH3
Page 28 of 28