The supported sulphated La2O3-ZrO2 on SBA-15 as a promising mesoporous solid superacid catalyst for alkenylation of p-xylene with phenylacetylene

Article abstract of DOI:10.1016/j.catcom.2017.02.001

The well-dispersed supported sulphated La₂O₃-ZrO₂(SLZ) superacid catalysts on SBA-15 with loadings were prepared and applied in alkenylation of p-xylene with phenylacetylene. The amount of acidic sites increases with the e

Full text of DOI:10.1016/j.catcom.2017.02.001

Accepted Manuscript
The supported sulphated La2O3-ZrO2 on SBA-15 as a promising
mesoporous solid superacid catalyst for alkenylation of p-xylene
with phenylacetylene
Zhongkui Zhao, Yongle Guo
PII:
DOI:
Reference:
S1566-7367(17)30046-8
doi: 10.1016/j.catcom.2017.02.001
CATCOM 4929
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Catalysis Communications
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14 October 2016
20 January 2017
1 February 2017
Please cite this article as: Zhongkui Zhao, Yongle Guo , The supported sulphated
La2O3-ZrO2 on SBA-15 as a promising mesoporous solid superacid catalyst for
alkenylation of p-xylene with phenylacetylene. The address for the corresponding author
was captured as affiliation for all authors. Please check if appropriate. Catcom(2017), doi:
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ACCEPTED MANUSCRIPT
The supported sulphated La2O3-ZrO2 on SBA-15 as a promising mesoporous solid superacid
catalyst for alkenylation of p-xylene with phenylacetylene
Zhongkui Zhao*, Yongle Guo
State Key Laboratory of Fine Chemicals,
Department of Catalysis Chemistry and Engineering, School of Chemical Engineering, Dalian
University of Technology, 2 Linggong Road, Dalian 116024, China, E-mail: zkzhao@dlut.edu.cn
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Abstract
The well-dispersed supported sulphated La2O3-ZrO2 (SLZ) superacid catalysts on SBA-15 with
loadings were prepared and applied in alkenylation of p-xylene with phenylacetylene. The amount
of acidic sites increases with the enlarged loading, it reaches maximum at the loading of 25%, and
then decreases while the loading is further increased. The increasing loading leads to a continuous
decrease in specific surface area and pore volume. The optimized 25% SLZ/SBA-15 catalyst shows
the outstanding catalytic performance, attributed to the more acidic sites and the not too low surface
area and pore volume. The developed well-ordered mesoporous sulphated La2O3-ZrO2 solid
superacid catalyst may be extended to diverse transformations.
Keywords: Well-ordered mesoporous solid superacid, Supported type catalyst, Alkenylation,
Heterogeneous catalysis, Clean synthesis
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1. Introduction
The alkenylation of arenes with alkynes is a useful protocol for alkenyl aromatics production in
organic synthesis. This is an alternative to the classical methods like the Heck-Mizoroki,
* Corresponding Author. Tel.: +86-411-84986354; Fax.: +86-411-84986354
E-mail: zkzhao@dlut.edu.cn
Suzuki-Miyaura, Stille, and Negishi reactions for synthesizing alkenyl aromatics [1]. Compared
with the traditional cross coupling methods, this approach avoids the use of prefunctionalized
substrates, and thereby provides a facile and clean route for the preparation of the desired alkenyl
aromatics that extensively applied in many fields such as pharmaceuticals, agrochemicals, natural
products, flavors, and dyes [2-4]
Homogeneous metal complex catalysis demonstrated satisfactory activity and selectivity for
alkenyl aromatics production [5-8]. However, owing to the existing disadvantage in terms of
expensive, low recyclability, and purification of the desired products from traces of a metal
contaminant, it is highly desirable for developing a cheap and clean method. Heterogeneous
catalysis provides clean and economical alternative to homogeneous catalysis in terms of its clean,
easy-separation, catalyst reusability [9-11]. Up to now, just a few reports on alkenylation over solid
acid catalysts can be found, although extensive reports on alkylation can be found [12,13]. Sartori
made a pioneering work on alkenylation of aromatics over HSZ-360 zeolite. Unfortunately, the
catalytic results are not satisfactory, and an irreconcilable contradiction between the selectivity and
the catalytic activity exists [14]. The low catalytic efficiency would be observed while HY was used
as catalyst for the alkenylation. Therefore, the improvement in the catalytic efficieny is desirable
[15,16]. Mesoporous solid acids have shown a great prospect for alkenylation of diverse aromatics.
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Haldar demonstrated that the Fe-containing mesoporous alluminosilicate exhibited very high
activity for the Friedel-Crafts alkenylation of phenols with aryl-substituted alkynes under mild
conditions [17], but the improvement in selectivity is still required. The H3PW12O40/MCM-41 as a
fascinating mesoporous solid acid catalyst for alkenylation of diverse aromatics was developed [18].
Unfortunately, the recovery of spent H3PW12O40/MCM-41 catalyst requires the usage of a large
amount of polar and evaporable solvent, which can lead to economic and environmental issues,
besides the possible H3PW12O40 leaching. Therefore, it is highly desirable for developing a more
efficient and robust mesoporous solid acid catalyst for alkenylation.
Sulfonated ZrO2 has been extensively employed as a solid superacid catalyst to catalyze diverse
reactions [19,20]. However, rare report on alkenylation can be found. We developed a novel and
2−
efficient SO4 /meso-La2O3-ZrO2 catalyst for alkenylation [21,22]. Although the usage of volatile
organic solvent can be avoided for regenerating spent catalyst, the preparation of a well-ordered
mesoporous La2O3-ZrO2 is required for accelerating mass transfer. But it still remains a challenge,
besides the cost of La and Zr is relatively high. Therefore, the preparation of a highly-ordered
mesoporous La2O3-ZrO2 based superacid catalyst for alkenylation is highly desirable. Supported
sulfonated ZrO2 catalysts on SBA-15 have been prepared and used in some acid-catalyzed reactions
but not in alkenylation [23-25]. From our previous report [22], the addition of La remarkably
improved the acidic properties and alkenylation catalytic performance of sulfonated ZrO2.
Therefore, in this work, we prepared highly-ordered mesoporous SLZ/SBA-15 solid superacid
catalysts by supporting different amount of La2O3-ZrO2 with La/(La+Zr) molar fraction of 0.1 on
SBA-15 by incipient wetness impregnation (IWI), which overcomes the challenge for synthesizing
well-ordered mesoporous La2O3-ZrO2 based solid superacids, besides the required amount of
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relatively high cost La and Zr becomes lowering. The 25% SLZ/SBA-15 with optimized SLZ
loading shows outstanding catalytic performance in alkenylation. N2 adsorption–desorption, X-ray
diffraction (XRD and NH3 temperature-programmed desorption (NH3-TPD) characterization
techniques were employed to reveal the relationship between the nature and catalytic properties of
the developed highly-ordered mesoporous solid superacid catalyst.
2. Experimental
2.1. Catalyst Preparation
The preparation of SBA-15 material was performed according to the procedure described by
Zhao et al [26]. 4.0 g of P123 purchased from Sigma-Aldrich Co. was dissolved in the mixture of
o
30 g of de-ionized water and 120 g of 2 M HCl solution with stirring at 35 C. Then, 8.50 g of
tetraethylorthosilicate (TEOS) was added into the above solution with stirring at 35 oC for 20 h. The
o
resulting mixture was aged at 80 C overnight. The obtained solid product was recovered, washed,
and then dried at room temperature. The final product was obtained by calcination at 500 oC for 6 h.
The catalyst precursors La2O3-ZrO2/SBA-15 with diverse La2O3-ZrO2 loadings were prepared
by IWI method (x% LZ/SBA-15, x=20, 25, 30) by using the mixed aqueous solution containing
zirconium nitrate (Sinopharm Group, AR) and lanthanum nitrate (Tianjin Guangfu Institute, AR)
with 0.1 of molar fraction of La/(La+Zr) as an impregnant with a subsequent calcination process at
550 °C for 6 h. The highly ordered mesoporous solid superacid x% SLZ/SBA-15 catalysts were
o
prepared by a wetness impregnation in 1 M H2SO4 followed by drying at 105 C and calcination
o
process at 500 C. For comparison, the physically mixed mesoporous solid acid containing 20%
2-
mesoporous SO4 /La2O3-ZrO2 and 80% SBA-15 (20% SLZ/SBA-15 (PM)) was prepared. The
2-
traditional mesoporous SO4 /La2O3-ZrO2 solid superacid was prepared on the basis of references
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[21,22]. Moreover, for comparison, the H2SO4-treated SBA-15 sample (SA-SBA-15) was also
prepared by soaking SBA-15 into 1M H2SO4 solution with the same calcination process as above.
2.2. Catalyst Characterization
XRD patterns of the samples were recorded in the 2 Theta range of 20-80o with a step of 0.02o
on a Rigaku D/max-2400 apparatus using Cu Kα radiation. Nitrogen adsorption experiments at -196
oC were carried out on a Beishide 3H-2000PS1 instrument to measure the specific surface area and
o
pore volume. The samples were degassed at 130 C for 6 h prior to N2 adsorption experiment.
NH3-TPD measurements were performed on an in-house constructed system equipped with a
thermal conductivity detector (TCD) to measure the desorbed NH3. 50 mg sample was loaded in
quartz reactor between two quartz wool plugs, and then was pretreated in Ar at 300 oC (a ramp rate
o
of 10 C min-1) for 0.5 h, followed by cooling to room temperature. The pretreated sample was
o
saturated with ammonia at 100 C via the pulse injection of NH3. NH3 desorption process was
carried out from 100 to 600 oC at a heating rate of 10 oC min-1 with an Ar flow of 30 ml min-1.
2.3. Catalytic Performance Measurement
The catalytic performance test on the SLZ/SBA-15 catalysts for alkenylation of p-xylene with
phenylacetylene was performed in a stainless steel fixed-bed flow reactor. 1.0 g of catalyst
suppressed into tablets and sieved into 20-60 mesh was loaded into the reactor for all performance
tests. The remaining space of the reactor was filled with 20–60 mesh quartz granules. Before the
introduction of feedstock, the catalyst was in situ pre-activated for 1 h in N2 flow at 30 ml min−1.
The liquid feed was introduced into the fixed-bed reactor by a syringe measuring pump. N2 (99.999%
purity) was used to maintain reaction system pressure to keep the liquid phase of reaction mixture.
o
The reaction was performed at 140 C. Quantitative analysis of the effluent was performed on a
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FULI 9790 II GC equipped with a HP-5 column (30 m × 0.32 mm × 0.25 μm ) and a FID detector.
The GC chromatogram of products can be found in our previous papers [21,22]. As an evaluation
standard of alkenylation reaction, the phenylacetylene conversion was calculated by weight
percentage of the transformed phenylacetylene in the total amount of introduced phenylacetylene in
the feed. The molecular structure of alpha-(2, 5-dimethylphenyl) styrene (I) was further identified
by 1H NMR (Fig. S1). The catalyst stability and regeneration performance (calcination regeneration
from previous report [21, 22]) were measured. No extra fresh catalyst was added for the
regeneration performance test.
3. Results and discussion
It was previously demonstrated that the ZrO2 loading has a significant influence on the
properties of acidic sites on the supported ZrO2/SBA-15 catalysts [23-25], and subsequently affects
the catalytic performance of solid acid catalysts. Therefore, the effect of La2O3-ZrO2 loading on the
catalytic performance of x% SLZ/SBA-15 catalysts in Friedel-Crafts alkenylation of p-xylene with
phenylacetylene has been investigated. Table 1 presents the reaction results, and 20 % SLZ/SBA-15
(PM) and SA-SBA-15 are included for comparison.
From Table 1, 20 % SLZ/SBA-15 catalyst shows ca. 3.5 times much higher conversion
towards phenylacetylene than 20 % SLZ/SBA-15 (PM) although they containing the same amount
of SLZ (in the physically mixed 20 % SLZ/SBA-15 (PM), the traditional mesoporous SLZ
prepared by soft template method [21,22] was used), suggesting the promoting role of supporting
SLZ on highly-ordered mesoporous SBA-15. SA-SBA-15 shows a very low catalytic activity and
quite low selectivity (a large amount of oligomers on SA-SBA-15 can be observed), implying the
activity of 20 % SLZ/SBA-15 originating from the well-dispersed SLZ. It was also found that the
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catalytic activity and selectivity of x% SLZ/SBA-15 catalysts for alkenylation are strongly
dependent on the SLZ loading on SBA-15. The conversion rises along with the increase in SLZ
loading from 20 to 25%, but a decreased conversion can be observed as the SLZ loading is further
increased up to 30%. The 25% SLZ/SBA-15 catalyst shows the highest catalytic activity with
medium selectivity among the three x% SLZ/SBA-15 solid superacid catalysts. The decreasing
selectivity along with the increase in SLZ loading is originated from the increasing side-products
with respect to acetophenone and oligomers (Table 1). 25% of the optimum SLZ loading is required
for alkenylation. Furthermore, the supported SLZ catalyst with 25% loading shows much superior
catalytic activity to the neat mesoporous SLZ, suggesting the significantly enhancing role of
supporting. The structure-performance relationship of the as-prepared well-ordered SLZ/SBA-15
solid acid catalysts for alkenylation p-xylene with phenylacetylene was revealed by correlating the
reaction results to the nature of catalysts obtained by N2 adsorption-desorption, NH3-TPD, and
XRD characterizations.
Fig. 1 shows the N2 adsorption-desorption isotherm and the pore-size distribution (inset). The
specific surface area (SBET) and pore volume (Vtotal) are also listed in Fig. 1. From Fig. 1, the
characteristic of type IV with a clear H1 hysteresis loop for all samples can be observed, suggesting
the well-ordered mesoporous structure of the samples can be maintained after they are suffered
from loading La2O3-ZrO2 and H2SO4 treatment [27-29]. However, the addition of La2O3-ZrO2 leads
to a remarkable decrease in both SBET and Vtotal. The continuously decreased SBET and pore volume
can be observed as the SLZ loading is increased from 20 to 30%. Especially, a significant decrease
in SBET and Vtotal takes place while the loading increases from 25 to 30%. The decrease in SBET and
Vtotal is unfavorable for the catalytic reaction.
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NH3-TPD technique was used to investigate the acidic properties of the as-prepared x %
SLZ/SBA-15 catalysts with different x values and the 20 % SLZ/SBA-15 (PM) and SA-SBA-15.
The NH3-TPD profiles are presented in Fig. 2. Based on the previous reports [21-25], the NH3-TPD
o
profiles can be divided into three regions, which can be assigned as weak (150-300 C), medium
(300-450 oC), and strong (450-600 oC) acid sites. From Fig. 2, the x % SLZ/SBA-15 catalysts show
o
three types of acid sites with the peak center at around 216, 360, and 480 C. The 20 %
SLZ/SBA-15 (PM) and SA-SBA-15 also show three types of acidic sites but with lower strength in
comparison with x % SLZ/SBA-15. The x % SLZ/SBA-15 solid acids show much higher acidic
sites than 20 % SLZ/SBA-15 (PM) and SA-SBA-15, which endows then with much higher catalytic
activity that shown in Table 1. It is understandable that the x % SLZ/SBA-15 solid acids show much
higher amount of acidic sites. However, it is interesting that 20 % SLZ/SBA-15 shows much higher
amount of acidic sites than 20 % SLZ/SBA-15 (PM), although they have the same content of SLZ.
In order to discover the origin, we performed the XRD experiments on the x % SLZ/SBA-15 and
20 % SLZ/SBA-15 (PM) samples, and the XRD patterns are presented in Fig. 3. From Fig. 3, the
well-resolved XRD peaks corresponding to the tetragonal La-Zr-O composite can be observed on
the 20 % SLZ/SBA-15 (PM) [21,22], but no peak on x % SLZ/SBA-15 samples can be observed.
This suggests the high dispersion of SLZ on SBA-15 for x % SLZ/SBA-15 catalysts, which endows
them with much more acidic sites in comparison with 20 % SLZ/SBA-15 (PM). From Fig. 2, with
the increase in SLZ loading from 20 to 30%, the sum of weak and medium acidic sites increases,
and reaches the maximum (989.0 μmol.g-1) at 25% loading, and then decreases up to 974 μmol.g-1.
The 25 % SLZ/SBA-15 shows the highest amount of weak and medium acidic sites among the three
x % SLZ/SBA-15 catalysts with diverse SLZ loadings, which endows it with highest catalytic
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activity.
The high amount of strong acidic sites of SA-SBA-15 leads to the formation of many
oligomers. The amount of strong acidic sites increases from 18.4 to 180.4 μmol.g-1 as the SLZ
loading increases from 20% to 30%, which results in the increasing amount of oligomers (Table 1).
In summary, the weak and medium strong acids are main active sites for alkenylation, but the strong
acidic sites will promote the formation of oligomers, which is in consistent with the previous
reports [21, 22].
From Fig. S2, no visible XRD peak at low angle can be well-resolved on the supported SLZ
catalysts, suggesting that the mesopores are disordered after loading SLZ. From Fig. 1, the
mesopores of the supported SLZ catalysts definitely appear. Table 1 shows that the supported SLZ
catalysts, especially the 25% SLZ/SBA-15, exhibit outstanding catalytic performance, although the
loading of SLZ deteriorates the degree of order of the mesopores. Therefore, we can safely say that
the more weak and medium acidic sites and the mesopore of the developed solid acid catalysts
allow them to show promising catalytic performance for production of alpha-arylstyrene through
alkenylation of aromatics with phenylacetylene. The 25% of optimum SLZ loading is required for
achieving superior catalytic performance.
As an industrially important catalytic reaction process, the stability and regeneration of solid
acid catalyst is of great significance. Fig. 4 shows the catalytic performance vs. time on stream in
alkenylation over fresh and regenerated 25% SLZ/SBA-15 solid superacid catalyst. No fresh
catalyst was compensated for regeneration performance test. From Fig. 4, 72.1% conversion can be
maintained for up to 480 min of time on stream on the 25% SLZ/SBA-15 solid superacid catalyst,
2-
while less than conversion over our previously reported catalyst SO4 /meso-La0.1Zr0.9Oδ can be
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observed. Moreover, the spent 25% SLZ/SBA-15 solid superacid catalyst can be basically
recovered by a facile calcinations process.
4. Conclusions
2-
In summary, the highly-ordered mesoporous SO4 /La2O3-ZrO2/SBA-15 with diverse SLZ
loadings were prepared and used in the production of alpha-arylstyrene through Friedel-Crafts
alkenylation. The catalytic performance of x% SLZ/SBA-15 solid superacid catalysts are
remarkably dependent on the acidic and textural properties that strongly affected by SLZ loading.
The 25% SLZ/SBA-15 solid superacid catalyst shows outstanding catalytic performance and good
regeneration behavior in alkenylation. Owing to the much superior acidic properties and ordered
mesoporous structures, the SLZ/SBA-15 solid superacid could be considered as a promising solid
acid catalyst for clean synthesis of many fine chemicals through diverse catalytic transformations.
Acknowledgements
This work is financially supported by the National Natural Science Foundation of China (grant no.
21276041) and the Chinese Ministry of Education via the Program for New Century Excellent
Talents in University (grant no. NCET-12-0079).
Appendix A. Supplementary material
Supplementary data to this article can be found online at doi:10.1016/j.catcom.2016.xx.xxx.
B. Supplementary material
Supplementary Figures
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List of Figure Captions:
Fig. 1. Nitrogen adsorption-desorption isotherms and pore size distributions from adsorption branch
of the SLZ/SBA-15 catalysts with different SLZ loadings. SA-SBA-15 is included for comparison.
Fig. 2.NH3-TPD profiles of the SLZ/SBA-15 catalysts prepared by IWI with different SLZ loadings.
(a) 20 %, (b) 25 %, (c) 30 %. The 20% SLZ/SBA-15 (PM) (d) and SA-SBA-15 (e) are included for
comparison.
Fig. 3. XRD patterns of the SLZ/SBA-15 catalysts with diverse SLZ loadings. The 20%
SLZ/SBA-15 (PM) is included for comparison.
Fig. 4. The catalytic stability and regeneration performance of the developed supported sulphated
La2O3-ZrO2 on SBA-15 (25% SLZ/SBA-15) for the alkenylation of p-xylene with phenylacetylene.
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Tables:
Table 1.
Reaction results for the alkenylation of p-xylene with phenylacetylene over SLZ-based solid
superacid catalysts with diverse preparation methods and SLZ loadings.
Product distribution (%)
Catalyst
Conversion (%)
Ⅰ
Ⅱ
3.1
0.6
0.9
0
Ⅲ
0.5
0.1
0.0
0.1
0.4
0.0
Ⅳ
2.3
3.8
4.7
5.1
3.6
3.0
Ⅴ
3.9
4.1
12.2
3.3
5.3
6.1
20% SLZ/SBA-15 (PM)
20% SLZ/SBA-15
SA-SBA-15
22.6
78.5
11.2
89.6
99.5
92.3
90.3
91.4
82.2
90.5
90.0
89.8
2-
SO4 /La2O3-ZrO2
25% SLZ/SBA-15
30% SLZ/SBA-15
0.7
1.1
o
Reaction conditions: m (cat.)= 1.0 g, np-xylene/Phen= 25:1, Tr= 140 C, Ps = 1.0 MPa, TOS = 4 h,
VHSV = 6 ml g-1 h-1 cat.
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Figures:
Fig. 1. Nitrogen adsorption-desorption isotherms and pore size distributions from adsorption branch
of the SLZ/SBA-15 catalysts with different SLZ loadings. SA-SBA-15 is included for comparison.
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Fig. 2.NH3-TPD profiles of the SLZ/SBA-15 catalysts prepared by IWI with different SLZ loadings.
(a) 20 %, (b) 25 %, (c) 30 %. The 20% SLZ/SBA-15 (PM) (d) and SA-SBA-15 (e) are included for
comparison.
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Fig. 3. XRD patterns of the SLZ/SBA-15 catalysts with diverse SLZ loadings. The 20%
SLZ/SBA-15 (PM) is included for comparison.
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Fig. 4. The catalytic stability and regeneration performance of the developed supported sulphated
La2O3-ZrO2 on SBA-15 (25% SLZ/SBA-15) for the alkenylation of p-xylene with phenylacetylene.
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Graphical Abstract
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Highlights
2-


Well-ordered mesoporous SO4 /La2O3-ZrO2/SBA-15 solid superacid is prepared.
SO4 /La2O3-ZrO2/SBA-15 shows outstanding catalytic performance in alkenylation.
2-


The catalytic performance is strongly dependent on acidic and textural properties.
The acidic and textural properties are notably affected by La2O3-ZrO2 Loading.

The developed mesoporous solid superacid has a great prospect in clean synthesis.
21