A novel green process for the synthesis of glutaraldehyde by WS 2@HMS material with aqueous H2O2

Article abstract of DOI:10.1039/c2ra22194b

A novel and green route is reported for the selective oxidation of cyclopentene oxide to glutaraldehyde by using aqueous H₂O₂ as the oxidant and WS₂@hexagonal mesoporous silica (WS2@HMS) material as the catalyst, which shows a very large surface area, high efficiency, excellent selectivity and outstanding reusability.

Full text of DOI:10.1039/c2ra22194b

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A novel green process for the synthesis of
glutaraldehyde by WS @HMS material with aqueous
2
Cite this: RSC Advances, 2013, 3, 1744
H O 3
2
2
Received 18th September 2012,
Accepted 3rd December 2012
Quanjing Zhu, Xiaofeng Chu, Zhaoyan Zhang, Wei-Lin Dai* and Kangnian Fan
DOI: 10.1039/c2ra22194b
www.rsc.org/advances
8
A novel and green route is reported for the selective oxidation of
cyclopentene oxide to glutaraldehyde by using aqueous H as
the oxidant and WS @hexagonal mesoporous silica (WS2@HMS)
effective catalyst in hydrodesulfurization and hydrogenation.
2
O
2
Chiranjeevi and co-workers have reported that HMS and Al–
HMS mesoporous material supported WS2 catalysts showed
outstanding activities in catalyzing thiophene hydrodesulfuriza-
tion and cyclohexene hydrogenation in comparison with WS
2
material as the catalyst, which shows a very large surface area,
high efficiency, excellent selectivity and outstanding reusability.
2
8
b
supported on c-Al O . Recently, by sonication of a slurry
2
3
During this decade, the catalytic oxidation of organic compounds
using aqueous hydrogen peroxide (H O ) as the oxidant has
containing SBA-15 and W(CO)
sulfidation with dimethyldisulfide, Vradman et al. have obtained
the high loading of layered nanoslabs of a WS phase with a well-
6
–sulfur–diphenylmethane and then
2
2
1
attracted much attention from the viewpoint of green chemistry.
In particular, an enormous amount of effort has been devoted to
the development of efficient methods for the oxidation of alkenes
2
defined hexagonal crystalline structure inside SBA-15, which is
promoted with nickel and showed good performance in hydro-
desulfurization of dibenzothiophene and hydrogenation of
2
3
4
to their corresponding epoxides, aldehydes and acids. Among
these green methods, the selective oxidation of cyclopentene (CPE)
8c
toluene. However, to the best of our knowledge, WS -containing
2
to glutaraldehyde (GA) with H
2
O
2
has been widely investigated
catalysts have been rarely studied as a catalyst in the selective
because GA is used extensively as a disinfecting and sterilizing
oxidation of epoxides to aldehydes.
Herein, for the first time, we report a green and novel process
in the synthesis of GA from CPO using WS @HMS as an efficient
3
agent in many areas, and cyclopentene oxide (CPO) has been
5
often considered as the intermediate in the reaction. Therefore,
2
catalytic oxidation of CPO should be an attractive alternative to
synthesize GA, bearing in mind that CPO has a much higher
boiling point (102 uC) than CPE (46 uC), leading to its convenience
in transport and industrial handling, and there have been few
reports about this reaction.
and reusable catalyst with aqueous H O as the oxidant in a
tributyl phosphate (TBP) system. The catalyst was simply
2
2
synthesized by sonication of HMS and commercial WS , and the
2
reaction was carried out under mild conditions and enjoyed high
selectivity. The catalysts can be easily removed by filtration after
the reaction. The GA product can be easily obtained with high
purity through rectification, due to the big difference in boiling
point between GA and the solvent TBP.
Tungsten-containing mesoporous silica materials with large
surface areas and uniform pore sizes have been reported as
effective and selective catalysts for the synthesis of GA in recent
3
years. Although the influence of the nature of supports and WOx
The chemical nature and structural morphology of the
WS @HMS materials were characterized by N adsorption–
species on the selectivity of GA has been widely studied, the yield
2
2
3
of GA is still not very high (,85%). Hence, the development of a
desorption, transmission electron microscopy (TEM), scanning
electron microscopy (SEM) and X-ray diffraction (XRD). Fig. 1
novel efficient tungsten-containing catalyst to synthesize GA
utilizing H
2
O
2
as the sole oxidant is of highly actual significance.
shows that the N adsorption–desorption isotherms of HMS and
2
WS , well-known for its application as a solid lubricant, has
2
20% WS @HMS were of type IV and exhibited hysteresis of type
2
attracted tremendous attention due to its application as a counter
H1, corresponding to a typical large-pore mesoporous material
with a 1D cylindrical channel. Compared with the HMS support
6
electrode in dye-sensitized solar cells, as a novel hydrogen
7
2
21
evolution catalyst for water decomposition, and especially as an
(SBET: 864 m g ), it is not surprising to find that the S
of
BET
2
21
2
0%WS
2
@HMS decreased (SBET: 675 m
g ). This finding
Department of Chemistry & Shanghai Key Laboratory of Molecular Catalysis and
Innovative Material, Fudan University, Shanghai 200433, P. R. China.
indicated that the mesoporous structure was preserved in the
WS @HMS material under sonication, despite the fact that a
2
E-mail: wldai@fudan.edu.cn; Fax: (+86-21) 55665572; Tel: (+86-21) 55664678
2
1
2
small amount of pores of HMS were blocked by WS (SBET: 2 m
3
Electronic Supplementary Information (ESI) available: Experimental section, H-
2
g
1
NMR and XRD data. See DOI: 10.1039/c2ra22194b
). TEM results showed that HMS possesses the typical
1
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2 2
Fig. 3 XRD patterns of WS , 20%WS @HMS and HMS.
2 2
Fig. 1 Nitrogen adsorption–desorption isotherms for HMS, WS @HMS and WS .
the selective oxidation of CPO to GA. The activity test was
performed at 308 K with magnetic stirring in a closed regular glass
wormhole structures of an HMS material assembled from long
alkyl chain neutral amines as the surfactant (Fig. 2b), and
9
reactor (25 mL) using 76% aqueous H
TBP as the solvent. In a typical experiment, 0.696 g of the
WS @HMS material (20%), 7.5 mL of TBP and 0.52 mL of 76 wt.%
aqueous H O (14.6 mmol) were introduced into the regular glass
2 2
O as the oxygen-donor and
compared with WS
encapsulated by WS
that sonication could be an environmentally friendly approach to
combine WS with HMS. SEM images of HMS and
0%WS @HMS also confirm that no agglomerated WS could
2
(Fig. 2a) and HMS (Fig. 2b), HMS was partly
2
in WS @HMS (Fig. 2c and 2d), indicating
2
2
2
2
2
reactor at 308 K with vigorous stirring. The reaction was started by
adding 1.00 mL of CPO (11.2 mmol) into the above mixture and
was maintained for 1 h. The quantitative analysis of the reaction
products was performed by the GC method and the different
products in the reaction mixture were identified by means of GC-
MS on a HP 6890GC/5973 MS. It should be noted that the reaction
cannot be carried out smoothly with an obvious GA yield without
any catalysts or only with pure HMS as the catalyst.
According to the GC-MS analysis, the products of the catalytic
oxidation of CPO, as shown in Scheme 1, comprise the main
product GA and a small amount of cyclopentane-1,2-diol (CPDL).
The catalytic performance and the optimization of the reaction
conditions are based on the yield of GA.
2
2
2
be observed on the surface of 20%WS @HMS and that the
2
WS @HMS materials retained a morphology similar to that of
2
pristine HMS, as shown in Fig. S1.
commercial WS , as-synthesized 20%WS
presented in Fig. 3. It is shown that the commercial WS
hexagonal phase (JCPDS No. 08-0237) and the as-prepared HMS is
amorphous. For WS @HMS, the (002) peak appeared at a 2h of
3
The XRD patterns of
@HMS and HMS are
is of
2
2
2
2
u
10
1
4.3 , characteristic of the layer stacking along the c direction,
which decreased and became broader after sonication with HMS,
suggesting that WS was dispersed into small slices on HMS and
2
the degree of crystallization of WS
phase of WS was retained.
Having established the chemical nature of the WS
materials, the catalytic performance of the catalyst was studied in
2
decreased while the crystalline
2
The effect of WS
WS @HMS materials in the oxidation of CPO to GA is illustrated
in Fig. 4. As can be seen from Fig. 4, it is important to disperse the
WS on the HMS for the reason that all of the supported WS
catalysts showed better catalytic activities than bulk WS in this
reaction. This is likely related to the large surface areas and
mesoporous structure of the WS @HMS materials and the fact
that WS was dispersed into small slices. The conversion of CPO
2
loadings on the catalytic activity of
2
@HMS
2
2
2
2
2
2
was enhanced from 98.3% to 99.4% when WS
from 10% to 20%, and was retained with further increasing WS
loadings. In addition, it was found that the selectivity of GA was
also strongly dependent on the content of WS in the supported
catalysts. The selectivity decreased with an increase in the loading
of WS on the HMS-supported WS catalysts, while all of them
2
loading increased
2
2
2
2
Fig. 2 TEM images of (a) WS
2
, (b) HMS and (c, d) 20%WS
2
@HMS.
2
Scheme 1 The oxidation products of CPO by H O2 in TBP.
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Fig. 5 The effect of the molar ratio of WS
2
in the catalysts to CPO in the reaction.
Fig. 4 The catalytic performance of the oxidation of CPO to GA over bulk WS
WS @HMS with different WS loadings. Reaction conditions: reaction temperature
08 K, CPO 1.00 mL, H 0.52 mL, TBP 7.5 mL, reaction time 1 h, molar ratio of
WS : CPO = 5 : 100.
2
and
2 2
Reaction conditions: reaction temperature 308 K, CPO 1.00 mL, H O 0.52 mL,
2
2
reaction time 1 h, TBP 7.5 mL.
3
2 2
O
2
th
the 4 run demonstrated that WS
2
on the catalyst was not
were higher than 91.0%. As a result, the best yield of GA (94.7%) is
achieved in the present reaction catalyzed by 20%WS @HMS, and
is much higher than that reported previously using WO –HMS,
oxidized by H
2
O
2
during this reaction. The little decrease,
2
compared to the second run, of the conversion of CPO and the
selectivity to GA in runs 3 and 4 could be attributed to the loss in
weight of the catalyst by washing. The catalyst could be reused
more times without deactivation if a little amount of fresh catalyst
was added. It is implied that the catalyst is reusable in the
synthesis of GA from CPO and could be considered as a promising
alternative for the GA synthesis in industry.
In addition, the hot catalyst filtration test was carried out in
this work. It was found that the conversion of cyclopentene oxide
continued to increase but was much lower than the one with the
3
2
+
2
WO –SBA-15 and PW –NH –SBA-15 (PW : 12-tungstophosphoric
3
3
3
heteropolyacid) as the catalysts, as shown in Table 1. Particularly,
the specific reaction rate value based on the GA yield of
21
WS
higher (y3 times) than the reported W-containing mesoporous
silica materials (see Table 1), implying that the WS @HMS catalyst
2
@HMS (entry 1 in Table 1) in this work was 18.9 h , much
2
showed excellent catalytic performance in the synthesis of GA.
The reaction conversion and selectivity as a function of the
molar ratio of WS to CPO in the 20%WS @HMS catalyst were
catalyst after the removal of the WS –HMS catalyst. However, after
2
2
2
also investigated (see Fig. 5). It is obvious that an efficient catalytic
performance is reached when the molar ratio of WS to CPO is
only 2.0%, implying that the WS @HMS material was a highly
the reaction, the catalyst was removed by filtration and the filtrate
was examined by the ICP method. The result showed that there
was a negligible amount of W species in the filtrate, suggesting
2
2
effective catalyst for the present reaction. Additionally, increasing
the molar ratio is beneficial for this reaction, however, the
conversion of CPO and the selectivity to GA was slightly decreased
when the molar ratio was higher than 5.0%. The 5.0% molar ratio
that the present WS
catalyst. In order to avoid the effect of sonication, we have studied
the activity of bulk WS after the sonication treatment. It was
2
@HMS was a real heterogeneous oxidation
2
found that there was no obvious difference, indicating that
of WS to CPO is used in the following studies considering that the
without the presence of HMS, bulk WS cannot be dispersed to
2
2
best yield of GA is reached under this condition.
small slices only by sonication.
To further confirm the practical reusability of the WS
2
–HMS
In summary, a simple, efficient and eco-friendly process for the
catalyst in the oxidation of CPO to GA, the recycling test of the
catalyst was studied, as shown in Fig. 6. After each cycle, the
catalyst was separated by simple filtration, washed with TBP twice
and acetone twice, and reused in the next run. There was no
synthesis of GA from CPO with aqueous H
using WS @HMS, a kind of mesoporous structural material with
large surface areas prepared by sonication of HMS and
commercial WS , as the catalyst. With the high specific reaction
2 2
O has been developed
2
2
21
decrease in the catalytic activity and selectivity of 20%WS @HMS
rate value (18.9 h ), the GA yield reached 94.7% with
2
in runs 1 and 2. XPS results (not shown here) of the catalyst after
20%WS @HMS, much higher than those reported previously,
2
a
Table 1 Catalytic performance of various catalysts for the selective synthesis of GA
b
c
21
Entry
1
2
3
4
Catalyst
Reaction time (h)
Conversion (%)
Selectivity (%)
Yield (%)
Rate (h
)
WS
W–HMS (30)
WO –SBA-15(OA)
2
@HMS
1
24
24
24
99.4
100
100
95.3
76.3
85.0
81.0
94.7
76.3
85.0
81.0
18.9
4.47
0.88
5.40
3
3
3
a
b
c
3
2
+
PW –NH
3
–SBA-15
100
a
Reaction conditions: reaction temperature 308 K, CPO 1.00 mL, H
: 100. The substrate is CPE (entries 2, 3 and 4). Calculated as rate = moles of GA per mole of W per hour.
2
O
2
0.52 mL, reaction time 1 h, TBP 7.5 mL, molar ratio of WS
2
: CPO =
b
c
5
1
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O
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2
6
7
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Acknowledgements
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Financially supported by the Major State Basic Resource
Development Program (Grant No.2012CB224804), NSFC
(
Project 20973042, 21173052), and the Natural Science
Foundation of Shanghai Science and Technology Committee
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RSC Adv., 2013, 3, 1744–1747 | 1747