Epoxide hydrolysis and alcoholysis reactions over crystalline Mo-V-O oxide

Article abstract of DOI:10.1039/c6ra10212c

Crystalline Mo-V-O oxides have been used as a catalyst for the hydrolysis and alcoholysis of propylene oxide to diols and ethers, respectively. Relationships between the active crystal facet, the acidity of Mo-V-O catalysts and the activity have been established. Our results indicate that the a-b plane is the active facet for the hydrolysis reaction.

Full text of DOI:10.1039/c6ra10212c

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Epoxide hydrolysis and alcoholysis reactions over
crystalline Mo–V–O oxide†
Cite this: RSC Adv., 2016, 6, 70842
Xiaochen Zhang,a Min Wang,a Chaofeng Zhang,ab Jianmin Lu,a Yehong Wanga
a
*
and Feng Wang
Received 20th April 2016
Accepted 11th July 2016
DOI: 10.1039/c6ra10212c
www.rsc.org/advances
Crystalline Mo–V–O oxides have been used as a catalyst for the These materials have a layered structure in the direction of the
hydrolysis and alcoholysis of propylene oxide to diols and ethers, c-axis and consist of uniform ve-, six-, and seven-membered
respectively. Relationships between the active crystal facet, the acidity rings on the a–b plane.21
of Mo–V–O catalysts and the activity have been established. Our results
In view of their unique structures, more interest has been
indicate that the a–b plane is the active facet for the hydrolysis reaction. paid to the catalytic applications of Mo–V–O materials in the
selective oxidation of hydrocarbons. For example, the ammox-
idation of propane to acrylonitrile and propane oxidation to
acrylic acid,1–3,11,13,21–32 selective oxidation of isobutane14,19,33–37
Mo–V–O oxides represent rare zeolite-like oxides with crystal-
line structure but containing transition metals. These oxides
have received increasing attention in recent years,1–8 focusing
on the structure and properties of metal doped Mo–V–O oxides,
such as Ni, Zn, Cu, Fe, Te, Ta, Ga, Sb, Zr, Sr, W, Bi, and Ln.9–20
Table 1 Hydrolysis reaction of propylene oxide over different crys-
talline catalysta
Catalyst
Conv./%
Sel./%
1
2
3
4
None
0
0
Orthorhombic
Tetragonal
Trigonal
27.1
41.5
53
>99
97
97
a
Reaction conditions: 0.01 g catalyst, 3 mmol propylene oxide, 1 mL
H2O, 2 h, 40 ꢀC.
Fig. 1 XRD patterns of different crystalline Mo–V–O. A: orthorhombic,
B: tetragonal, C: trigonal (milling time-10 min), D: trigonal (milling
time-5 min), E: trigonal (milling time-3 min).
aState Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy,
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023,
Liaoning, China. E-mail: wangfeng@dicp.ac.cn; Fax: +86-411-84379762; Tel: +86-
411-84379762
bGraduate University of Chinese Academy of Sciences, Beijing 100049, China
† Electronic supplementary information (ESI) available: Details of the materials,
synthesis procedure, characterization techniques, catalytic experimental
methods, GC-MS spectra of some products, 1H NMR and 13C NMR spectra of
some products, alcoholysis of propylene oxide in different conditions, XRD
patterns of fresh and used trigonal catalyst, the scheme with the structure of
the trigonal material and the morphology of the used catalyst. See DOI:
10.1039/c6ra10212c
Fig. 2 The reaction time profiles over trigonal Mo–V–O in propylene
oxide hydrolysis. Reaction conditions: 0.01
propylene oxide, 1 mL H2O.
g catalyst, 3 mmol
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through chemisorption method. The applications of Mo–V–O
materials mostly used in vapour phase reactions. Recently, we
reported the oxidation of alcohols in liquid phase.49–52 Sergio
Castillon et al.53 reported epoxidation/alcoholysis and
´
epoxidation/hydrolysis of glucal and galactal derivatives by Mo
catalyst. These studies expand the application of Mo–V–O-based
materials into broad catalytic processes.
As it is well known, epoxides are important organic chem-
icals and intermediates. Ring-opening of epoxides is an
important route to dihydric alcohol derivatives which are the
precursors for cosmetics, pharmaceuticals and other prod-
ucts.54–56 Generally, the procedure can be catalyzed by basic or
acid conditions.
On the basis of the special performance of Mo–V–O mate-
rials, we here aim to correlate the feature with the ring-opening
of epoxides. The Mo–V–O materials were employed as the
catalyst in the hydrolysis and alcoholysis of propylene oxide and
gave a good conversion and selectivity. The apparent activation
energy was calculated to be 50.3 kJ molÀ1. We veried the a–b
Fig. 3 (a) The kinetic analysis of propylene oxide hydrolysis in the
presence of the trigonal Mo–V–O catalyst. (b) Arrhenius plot. The
X-axis is multiplied by 1000.
and ethane,9,12,28,38–44 and the oxidation of acrolein to acrylic
acid.5,28,45–47 Moreover, Guliants et al.31,48 investigated the cata-
lytic behaviors of Mo–V–O in the vapor phase oxidation reaction
Table 2 Hydrolysis of various epoxides
Entry
Substrate
Time/h
4
Temp./ꢀC
25
Product
Conv./%
99
Sel./%
>99
1
2
3
4
5
4
4
4
6
25
80
80
80
>99
>99
84
95
>99
90
94
89
6
4
3
3
3
100
150
180
180
5
>99
>99
>99
>99
7
42
42
25
8
9a
10a
24
180
55
>99
a
Reaction conditions: 0.01 g trigonal Mo–V–O, 0.2 mL substrate, 1 mL H2O. a: 0.02 g catalyst, 1.5 mmol substrate, 1 mL H2O.
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plane possess the most amount of acid sites and is an active acid. The crystalline structure of the materials was studied by
crystal facet. A wide range of epoxides were converted to the XRD characterization (Fig. 1). The XRD peaks around 10ꢀ for all
corresponding dihydric alcohol derivatives with moderate to the materials are ascribed to the structure of a–b plane.
excellent yields.
Diffraction peaks at 22ꢀ and 45ꢀ indicates that the catalysts are
We synthesized the Mo–V–O materials by hydrothermal a kind of layered-type material in the c axis. These two peaks
method according to literature38 rstly. The orthorhombic, were ascribed to (001) and (002) plane reections.38
trigonal and tetragonal Mo–V–O materials were synthesized
Then the hydrolysis reaction (see the ESI†) of propylene
from a reaction mixture of aqueous solution of (NH4)6Mo7O24, oxide was used as the model reaction to investigate the catalytic
and VOSO4$nH2O under some conditions. By controlling the pH performance of crystalline Mo–V–O catalyst. The reaction did
value of the precursor solution, the orthorhombic or trigonal not happen in the absence of catalyst (Table 1, entry 1). The
Mo–V–O was selectively synthesized. The tetragonal material Orthorhombic, trigonal and tetragonal Mo–V–O were used as
was prepared by heat-treatment of the orthorhombic material. catalyst for this reaction. Trigonal Mo–V–O showed highest
The obtained crude materials was puried with aqueous oxalic activity in the propylene oxide hydrolysis reaction.
Table 3 Alcoholysis of propylene oxide with different alcoholsa
Entry
Substrate
Product
Conv./%
>99
Sel./%
39/54
1
MeOH
2
3
4
5
6
7
EtOH
94
82
34
76
74
64
40/50
30/55
35/42
31/61
30/62
29/63
n-BuOH
t-BuOH
n-Pentanol
n-Hexanol
n-Octanol
8
Cyclohexanol
Benzyl alcohol
57
58
32/57
37/53
9
a
Reaction conditions: 3 mmol propylene oxide, 1 mL alcohol, 0.015 g trigonal Mo–V–O, 100 ꢀC, 12 h.
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Using the trigonal Mo–V–O as the catalyst, the optimization cmÀ1 for Mo–O–Mo and 599 cmÀ1 for V–O–Mo were observed in
of propylene oxide hydrolysis condition was investigated both the fresh and used catalyst.18 And, there is no change in the
(Fig. 2). The conversion of propylene increases with reaction diffraction peaks for the fresh and used catalysts. Besides, the
time. 88% conversion was obtained at 25 ꢀC for 12 h. When the catalyst aer the reaction still keep the morphology of rod
reaction increases to 40 ꢀC and 55 ꢀC, 95% conversion were crystal, and there is no obvious change in the average particle
obtained at 8 h and 3 h, respectively. The selectivity is above size (Fig. S2†). This indicated that the catalyst crystal structure
95% at the range of temperature.
was not changed during the reaction.
Basꢀed on above results, the reaction kinetics was studied at
To ascertain the active crystal facet, a series of experiment
were carried. Milling the Mo–V–O materials was used to create
more a–b plane. The morphology of trigonal with different
milling time was shown in the SEM images (Fig. 5). The rod
crystal in the c-axis was grinded into shorter rod, the average
particle size decreased from 1300 nm to 280 nm, thus exposing
more a–b planes. The diffraction peaks of the trigonal Mo–V–O
corresponding to the crystal at 4.9ꢀ, 8.4ꢀ, and 9.6ꢀ, were ascribed
to the plane of (100), (110), and (200), respectively (Fig. 1). It can
be seen that the crystalline structure did not change signi-
cantly aer grinding, which indicated that grinding did not
destroy the crystal structure. As reported, the a–b crystal mainly
consists of 6- or 7-member rings (6MRs and 7MRs) where highly
dense unsaturated metal cation centers and oxygen anions may
function as catalytic active sites for many reactions.50 The
Mo : V atoms ratio of trigonal Mo–V–O was determined by
inductively coupled plasma atomic emission spectroscopy (ICP-
AES) and was about 2.4 : 1. The structure of trigonal Mo–V–O
25–55 C (Fig. 3). The hydrolysis reaction is shown as follows:
The total volume of the reaction mixture in all kinetic
experiments was 1 mL. The concentration of water and the
amount of catalyst remained constant through the reaction. The
kinetic study indicates a pseudo-rst-order reaction (Fig. 3a).
ꢀ
The apparent reaction rate constants at 25, 40, and 55 C were
calculated from the slopes of plots to be 9.3 Â 10À5, 1.82 Â
10À4, 5.86 Â 10À4 molÀ1 LÀ1 sÀ1, respectively. From the Arrhe-
nius plot shown in Fig. 3b, the activation energy Ea was evalu-
ated to be 50.3 kJ molÀ1
.
In light of the results of the propylene oxide hydrolysis
above, the catalytic properties of Mo–V–O catalyst for hydrolysis
of other epoxides were investigated as listed in Table 2. During
these studies, the catalyst exhibit 99% conversion and above
95% selectivity to corresponding ring-opening reaction for
styrene oxides and cyclohexene oxides within 4 h at room
temperature (Table 2, entries 1–2). Higher temperature and
longer reaction time are needed for the hydrolysis of 2-buty-
loxirane and chloropropylene oxide (Table 2, entries 3–5).
Besides, 1,3-dioxane show 42% conversion. And there is no
obvious increase with the temperature rise from 150 ꢀC to
180 ꢀC which may due to the symmetrical structure (Table 2,
entries 7–8). 4-Methyl-1,3-dioxane exhibit 55% conversion at
ꢀ
180 C within more long time.
In addition, considering the similarity between the hydro-
lysis and the alcoholysis, the alcoholysis of propylene oxide with
a series of alcohols over trigonal Mo–V–O were investigated
(Table 3). We rstly optimized the reaction conditions (see
Table S1†). Increase the catalyst loading, and reaction temper-
ature and time can promote propylene oxide conversion. The
optimized results were provided in Table 3. It is noted that the
catalyst showed a conversion above 90% and a higher selectivity
of two main products in the methanol and ethanol alcoholysis,
respectively (Table 3, entries 1–2). But, the conversion decreased
with increasing the carbon chain of the alcohols. The conver-
sion for octanol is 64% (Table 3, entry 7). On the other hand,
compared to the 1-butanol (94% conversion), a 34% conversion
was obtained for t-butanol (Table 3, entry 4). The lower
conversion may be due to the steric hindrance. For cyclohexanol
and benzyl alcohol, 57% and 58% conversion of propylene oxide
were obtained (Table 3, entries 8–9).
Fig. 4 The IR spectra of the fresh and used catalysts.
To verify the structure of the catalyst material aer the
reaction, the FT-IR spectrum and XRD characterization were
carried out (Fig. 4 and Fig. S1†). The bands at 906 cmÀ1
ascribable for V]O, 870 cmÀ1 for Mo]O, 810, 712 and 646
Fig. 5 The SEM images (a–d) and the average particle size (e) of
trigonal Mo–V–O with different milling time.
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Conclusions
In conclusion, the new application of Mo–V–O materials in the
ring-opening of epoxide was developed. It was utilized as a cata-
lyst for the hydrolysis and alcoholysis of propylene oxide and gave
a good conversion and selectivity. A relationship between the
active crystal facet, acidity of Mo–V–O and the yield of product
was built up. The result veried the a–b plane is the active crystal
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