Mn-MIL-100 heterogeneous catalyst for the selective oxidative cleavage of alkenes to aldehydes

Article abstract of DOI:10.1016/j.catcom.2017.08.017

Four MIL metal organic framework materials with large surface area and high stability were utilized as heterogeneous catalysts in the selective oxidation of styrene with tert-butylhydroperoxide (70% aqueous) as an oxidant in acetonitrile. Mn-MIL-100 exhib

Full text of DOI:10.1016/j.catcom.2017.08.017

Accepted Manuscript
Mn-MIL-100 heterogeneous catalyst for the selective oxidative
cleavage of alkenes to aldehydes
Ying Ha, Manman Mu, Qingling Liu, Na Ji, Chunfeng Song,
Degang Ma
PII:
DOI:
Reference:
S1566-7367(17)30348-5
doi: 10.1016/j.catcom.2017.08.017
CATCOM 5166
To appear in:
Catalysis Communications
Received date:
Revised date:
Accepted date:
19 May 2017
9 August 2017
9 August 2017
Please cite this article as: Ying Ha, Manman Mu, Qingling Liu, Na Ji, Chunfeng Song,
Degang Ma , Mn-MIL-100 heterogeneous catalyst for the selective oxidative cleavage of
alkenes to aldehydes. The address for the corresponding author was captured as affiliation
for all authors. Please check if appropriate. Catcom(2017), doi: 10.1016/
j.catcom.2017.08.017
This is a PDF file of an unedited manuscript that has been accepted for publication. As
a service to our customers we are providing this early version of the manuscript. The
manuscript will undergo copyediting, typesetting, and review of the resulting proof before
it is published in its final form. Please note that during the production process errors may
be discovered which could affect the content, and all legal disclaimers that apply to the
journal pertain.

ACCEPTED MANUSCRIPT
Mn-MIL-100 heterogeneous catalyst for the selective oxidative
cleavage of alkenes to aldehydes
Ying Haa, Manman Mub, Qingling Liua,c,*,Na Jia,c, Chunfeng Songa,c, Degang Maa,c
aTianjin Key Laboratory of Indoor Air Environmental Quality Control, School of
Environmental Science and Engineering, Tianjin University, No. 135, Yaguan Road, Haihe
Education Park, Tianjin, 300350, China
bSchool of Science, Tianjin University, No. 135, Yaguan Road, Haihe Education Park, Tianjin,
300350, China
cState Key Laboratory of Engines, Tianjin University, No. 135, Yaguan Road, Haihe
Education Park, Tianjin, 300350, China
1

ACCEPTED MANUSCRIPT
Abstract
Four MIL metal organic framework materials with large surface area and high
stability were utilized as heterogeneous catalysts in the selective oxidation of styrene
with tert-butylhydroperoxide (70% aqueous) as an oxidant in acetonitrile.
Mn-MIL-100 exhibits excellent styrene conversion (89%) and benzaldehyde
selectivity (85%) under optimized conditions. Furthermore, Mn-MIL-100 displays
superior catalytic activity in the selective oxidation of aryl-olefins and is reused at
least three times without significant deactivation. It appears that this specific material
would open up a new pathway for MOFs towards the selective catalytic oxidation of
aryl-olefins to the corresponding aldehydes.
Keywords: MOFs; Mn-MIL-100; Selective oxidation; Styrene; Benzaldehyde.
2

ACCEPTED MANUSCRIPT
1. Introduction
Benzaldehyde is one of the important chemical materials that can be widely
applied in perfumes, pharmaceuticals, dyes and fine chemicals industry [1].
Traditionally, benzaldehyde is produced via toluene or benzoyl alcoholoxidation,
benzoic acid hydrogenolysis and benzoyl chloride hydrolysis [2-4]. Owing to complex
procedures, harsh conditions and toxic waste disposal, these methods are gradually
eliminated and the selective oxidation of styrene is considered as a desirable process.
Recently, a series of heterogeneous catalysts, such as metal oxides, transition metal
coordination polymers and metal nanoparticles supported on porous materials (e.g.,
metal oxides or zeolites) [5-7], have been explored for the oxidation of styrene using
tert-butylhydroperoxide as an oxidant. However, most of them have been studied for
the selective oxidation of alkenes to epoxides and relative few studies were focused
on the corresponding aldehydes as the main reaction product.
In recent years, metal-organic frameworks (MOFs) have been received
considerable attention worldwide as a new class of porous materials built from metal
nodes and organic ligands. Compared to the traditional porous materials (zeolite),
MOFs are provided with certain predominant features, such as large surface area,
controllable pore size and suitable functionalization, which render them ideal
candidates for various applications, such as gas storage, chemical sensors, separation
and catalysis [8-11]. Nevertheless, MOFs still exhibit some drawbacks such as low
thermal and chemical stability, which restrict their applications in catalysis. Férey and
co-workers [12] reported on the mesoporous chromium and iron terephthalates,
3

ACCEPTED MANUSCRIPT
Cr-MIL-101 and Fe-MIL-101, which have a rigid zeotype crystal structure. These two
kinds of MOFs revealed good resistance to air, water, common solvents and thermal
treatments (e.g., Fe-MIL-101 is stable up to 150 °C while Cr-MIL-101 maintains its
structure up to 300 °C). In addition, a crystalline iron trimesate (Fe-MIL-100)
discovered by Férey and co-workers [13] also possess high chemical and thermal
stability (up to 300 °C). In 2013, Reinsch and co-workers [14] have proposed the
formation of Mn-MIL-100 that can be obtained in a methanolic solution of trimesic
acid and manganese nitrate in short reaction times (2 h). The chemical stability of
Mn-MIL-100 is analogous to that of other MIL materials, but its thermal stability is
relatively higher (ca. stable up to 400 °C). Furthermore, after the removal of the
terminal water molecules from MIL framework by heating in vacuum, coordinatively
unsaturated sites are provided and can be utilized as catalytic active sites in various
reactions [15]. So far, Fe-MIL-101 and Cr-MIL-101 have been employed in the
selective oxidation of alkenes with oxygen, H2O2 and tert-butyl hydroperoxide (TBHP)
as oxidants, respectively, but the main products obtained are epoxide compounds
[16-18]. To the best of our knowledge, there are rare reports on the selective oxidative
cleavage of styrene to benzaldehyde over MOFs.
Based on the above consideration, in the present work we describe four MIL
materials (Mn-MIL-100, Fe-MIL-100, Fe-MIL-101, Cr-MIL-101) as catalysts for the
selective oxidation of styrene to benzaldehyde using TBHP (70% aqueous) as an
oxidant. In particular, the effects of solvents and reaction conditions: temperature,
reaction time, catalyst dosage and mole ratio have been investigated. It was clearly
4

ACCEPTED MANUSCRIPT
observed that Mn-MIL-100 exhibits excellent styrene conversion and benzaldehyde
selectivity for this selective oxidation reaction. Finally, the selective oxidation of
various alkenes over the Mn-MIL-100 catalysts and its recyclability were also
tested.
2. Experimental
All chemicals and solvents were purchased from Tianjin Jiangtian Chemical
Technology (China) Co. and used without further purification except for otherwise
noted.
2.1 Catalysts preparation
All the MOFs materials were prepared by the solvothermal method. The
Mn-MIL-100 was prepared according to the literature [14] with some modifications.
An ethanolic solution of trimesic acid and manganese nitrate was heated in a
Teflon-lined steel autoclave without stirring to produce Mn-MIL-100 in high yield.
Zhang and co-workers [19] vaguely mentioned the similar synthetic method. It was
eco-friendly for the synthetic process to use ethanol instead of methanol as solvent.
Specifically, manganese nitrate (Mn(NO3)2·4H2O, 2 mmol) and trimesic acid (H3BTC,
1.9 mmol) were dissolved in ethanol (18 ml) under ultrasonic conditions to form a
clear solution. Then, the clear reaction solution was transferred into a Teflon-lined
steel autoclave and heated at 125 °C for 2 h. After cooled down to room temperature,
the brown product was obtained by centrifugation and washed with ethanol for three
5

ACCEPTED MANUSCRIPT
times. Finally, the resulting solid was dried at 70 °C in vacuum overnight.
Fe-MIL-100, Fe-MIL-101 and Cr-MIL-101 were synthesized according to the
methodology described in Huo et al. [20], Maksimchuk et al. [18] and Férey et al.
[12] , respectively.
2.2 Catalysts characterization
Powder X-ray diffraction (XRD) patterns were measured on a D8-Focus X-ray
diffractometer equipped with Cu Kα radiation (1.54 Å) in the range of 3-30° 2theta.
Scanning electron microscopy (SEM) images were obtained using a HitachiS-4800
scanning electron microscope. FT-IR spectra were collected on a Nicolet 22 AVATAR
-1
370 FT-IR spectrometer in the 4000-550 cm region. Thermogravimetric analyses
(TGA) were performed on an STA 409PC thermal analyzer at the heating rate of
10 °C min-1from room temperature to 800 °C. Nitrogen adsorption-desorption
isotherms were measured at 77 K (liquid N2) using a NOVA 2000e surface and
porosity analyzer (Quantachrome, USA).
2.3 Selective oxidative cleavage of styrene
The selective oxidation of styrene to benzaldehyde was carried out in a 25 mL
round bottom flask equipped with a magnetic stirrer and reflux condenser. Generally,
styrene (1 mmol) and an appropriate amount of tert-BuOOH (TBHP, 70% aqueous)
were dispersed in acetonitrile (1 mL) and an appropriate amount of catalyst (5 wt%)
was then added in the solution. The resulting mixture was heated up to 70 °C and
6

ACCEPTED MANUSCRIPT
stirred for 6 h. After cooled to room temperature, the mixture was filtered and the
filtrate was analyzed by gas chromatography with an OV-1701 capillary column (30
m × 0.25 mm, 0.2 μm film thickness) and a flame ionization detector (FID).
Scheme 1. The synthetic route of selective oxidation of styrene.
3. Results and discussion
As it is well known, the selective oxidation of styrene mainly generates
benzaldehyde (Bza), styrene oxide (So), benzonic acid and phenylacetaldehyde.
Compared to traditional porous materials, MOFs containing metal ions as active sites
may enhance the catalytic performance of this oxidation. Thus, in order to further
investigate the influence of various metal sites or organic ligands, four different
MOFs (e.g., Mn-MIL-100, Fe-MIL-100, Fe-MIL-101, Cr-MIL-101) were selected.
Initially, a blank experiment in the absence of catalyst was performed. The oxidation
reaction occurs at a low rate and only a low conversion of styrene was estimated.
The catalytic performance of the selective oxidation of styrene over the four MOFs
materials is presented in Table 1. It is obviously seen that the main product is
benzaldehyde, resulting from the direct oxidative cleavage of the styrene side chain
C=C bond. The results indicate that styrene conversion is higher but the selectivity of
benzaldehyde is lower over Fe-MIL-101 compared to Cr-MIL-101. When
Fe-MIL-100 linked with trimesic acid was used as catalyst, the styrene conversion and
7

ACCEPTED MANUSCRIPT
the selectivity of benzaldehyde obtained are 73.87% and 76.31%, respectively. This
demonstrates that Fe-MIL-101 exhibits superior styrene conversion but benzaldehyde
selectivity is distinctly reduced. It is worth noting that styrene conversion and
benzaldehyde selectivity obtained over Mn-MIL-101 are 72.52% and 81.81%,
respectively. The catalytic performance results of the selective oxidation of styrene
over four MOFs under different reaction conditions are presented in Table S2. When
o
the reaction time is reduced to 4 h or reaction temperature is increased to 75 C, the
tendency in the catalytic activity behavior remains the same. Thus, it was concluded
that Mn-MIL-100 with manganese as metal site and trimesic acid as organic ligand
exhibits superior catalytic performance than the other three MOFs. Based on the
above consideration, Mn-MIL-100 was selected as the optimum catalyst which was
further investigated.
Table 1. The selective oxidation of styrene over four different MOFs.
Selectivity (%)
Styrene oxide
12.01
Conversion
(%)
Catalyst
Benzaldehyde
81.81
Other
6.18
10.25
7.45
-
Mn-MIL-100
Fe-MIL-100
Fe-MIL-101
Cr-MIL-101
72.52
73.87
83.72
46.79
76.31
13.45
67.94
24.61
91.20
8.80
Reaction conditions: n(70% TBHP): n (Styrene) = 3:1; reaction temperature = 70 °C; time =
6 h; catalyst dosage = 5 wt%; solvent: CH3CN.
8

ACCEPTED MANUSCRIPT
3.1 Characterization of materials
In order to verify the chemical structure of the four MIL MOFs, powder XRD,
SEM and FT-IR techniques were used. The XRD patterns of Mn-MIL-100 and
Fe-MIL-100 are illustrated in Fig S1. It is observed that the XRD patterns of the
synthesized Fe-MIL-100 matches the simulated one, indicating that Fe-MIL-100 is
successfully synthesized. The same result is also observed for the Mn-MIL-100
material. Furthermore, the XRD pattern of Mn-MIL-100 is similar to that of
Fe-MIL-100, further indicating that the structures of Mn-MIL-100 and Fe-MIL-100
are analogous.
The SEM images obtained for the Mn-MIL-100 and Fe-MIL-100 solids are
shown in Fig S2. It is observed that Mn-MIL-100 and Fe-MIL-100 both show cubic
shape with an average secondary crystal size ~ 0.5 μm [21, 22]. It can be also
observed that the structure of Mn-MIL-100 is less regular than that of Fe-MIL-100.
Thus, Mn-MIL-100 is expected to present more crystal defects than Fe-MIL-100.
To further prove the incorporation of trimesic acid into the framework, FT-IR
spectra of Mn-MIL-100 and Fe-MIL-100 are presented in Fig S3. Strong absorption
-1
bands at ~1640 and 3400 cm confirm the presence of water molecules within the
frameworks. It is clearly shown that the presence of vibrational bands (O-C-O) at
-1
1390 and 1470 cm indicate the coordination of the tricarboxylate within two MOFs
[23]. These results further verify that the two Mn-MIL-100 and Fe-MIL-100 MOFs
materials were prepared.
Thermogravimetric analyses of Mn-MIL-100 and Fe-MIL-100 solids were
9

ACCEPTED MANUSCRIPT
performed to study their thermal stability and results are presented in Fig. S4. The
main weight loss can be observed at ~350 °C for the Fe-MIL-100 because of the
collapse of the framework. In the case of Mn-MIL-100, the main weight loss occurred
at 400 °C as the result of the collapse of the framework. Moreover, Fe-MIL-100 and
Mn-MIL-100 were respectively calcinated in different temperatures (100, 200, 300,
350, 400 or 500oC) at the rate of 10°/min in a muffle furnace for 30 min. The obtained
XRD patterns of these samples are shown in Fig. S5. It is found that the characteristic
peaks of Fe-MIL-100 and Mn-MIL-100 are still preserved when the calcination
o
temperature is below 300 C. When Fe-MIL-100 is calcinated at 350oC, the
characteristic peaks disappear, indicating that the framework of Fe-MIL-100 has
collapsed. When Mn-MIL-100 is also calcinated at 350oC, the characteristic peaks
still exist but the intensities become weaker. The framework of Mn-MIL-100 is
destroyed once the calcination temperature is raised to 400oC. Based on these
investigations, it could be concluded that Mn-MIL-100 is more stable than
Fe-MIL-100.
The surface area and porosities of Mn-MIL-100 and Fe-MIL-100 solids are
further examined by N2 adsorption-desorption isotherms at 77 K (Table S1). It is
found that the two MOFs present type-I isotherm. It is observed that the surface area
and pore volume of Mn-MIL-100 are 1133 m2/g and 0.49 cm3/g, respectively. The
synthesized Fe-MIL-100 gave larger BET surface area (1215 m2/g) and pore volume
(0.64 cm3/g) than the Mn-MIL-100 solid.
10

ACCEPTED MANUSCRIPT
3.2 Effect of solvent
As it is well known, the solvent has a significant influence on the yield and
by-product formation in an oxidation reaction. . To examine the solvent’s influence in
the selective oxidation of styrene, polar and nonpolar solvents, such as acetonitrile
(CH3CN), 1,2-dichloromethane (CH2ClCH2Cl), carbon tetrachloride (CCl4) and
tetrahydrofuran (THF) were tested and experimental results are listed in Table 2. It
is seen that the styrene conversion in other solvents are higher than that in CH3CN.
However, due to the excessive oxidation of benzaldehyde to benzoic acid, the
benzaldehyde selectivity in the other solvents is relatively lower. When the reaction
temperature was decreased, the benzaldehyde selectivity is still not high. Thus,
CH3CN is considered to be the optimum solvent.
Table 2. Effect of various solvents on the selective oxidation of styrene.
Selectivity (%)
Solvent
Conversion (%)
Benzaldehyde
81.81
Styrene oxide
Other
6.18
CH3CN
CH2ClCH2Cl
CCl4
72.52
98.78
100
12.01
18.30
-
50.92
30.78
51.11
51.80
48.79
THF
83.66
36.40
11.80
Reaction conditions: n(70% TBHP): n (Styrene) = 3:1; reaction temperature = 70 °C; time =
6h; catalyst dosage = 5 wt%.
11

ACCEPTED MANUSCRIPT
3.3 Effect of various reaction conditions
The effect of various reaction conditions, such as temperature, reaction time,
catalyst dosage and mole ratio have been tested and results are presented in Fig 1. The
effect of reaction temperature on the selective oxidation of styrene using 5 wt%
Mn-MIL-100 as the catalyst and 3 equiv. TBHP (70 wt% aqueous) as the oxidant for 6
h is presented in Fig. 1A. It is clearly observed that styrene conversion rapidly
increases but the benzaldehyde selectivity decreases with the increase of reaction
temperature. Meanwhile, the amount of by-product benzoic acid also increases. Thus,
the temperature of 70 °C was promising to be the optimum temperature. Figure 1B
presents the effect of reaction time on selective oxidation at 70 °C. With increasing
reaction time, the conversion apparently increases, while the selectivity to
benzaldehyde remains unchanged after 6 h of reaction. The 88.99% conversion of
styrene and 84.97% selectivity of benzaldehyde were obtained at t=10 h. Based on
this, 10 h reaction time was selected as the optimum one. The effect of catalyst dosage
on the selective oxidation using Mn-MIL-100 and TBHP at 6 h is also presented (Fig.
1C). When the amount of Mn-MIL-100 was raised from 2.5 to 5 wt%, the conversion
of styrene increases from 55.89 to 72.52% and the reaction selectivity to
benzaldehyde is also enhanced (from 75.99 to 81.81%). However, the amount of
Mn-MIL-100 continues to increase, whereas the selectivity to benzaldehyde rapidly
decreases. This behavior indicates that the addition of excess catalyst was not
beneficial to the selective oxidation of styrene. Thus, 5 wt% was considered as the
optimum catalyst dosage. Finally, Fig. 1D describes the effect of 70% TBHP/styrene
12

ACCEPTED MANUSCRIPT
molar ratio on the selective oxidation of styrene. When the molar ratio of n(70%
TBHP)/ n(styrene) was raised from 1:1 to 3:1, the styrene conversion increases from
68.45 to 72.52% and the selectivity to benzaldehyde increases from 59.44 to
81.81%. When the molar ratio was further increased to 5:1, the conversion suddenly
declines to 48.21%. Thus, when the molar ratio of n (70% TBHP)/ n (styrene) is 3:1,
maximum yield of benzaldehyde is attained.
(A) 140
140
(B)
Conversion of styrene
Selectivity of bza
Selectivity of so
Conversion of styrene
Selectivity of bza
Selectivity of so
120
120
100
80
60
40
20
0
100
80
60
40
20
0
Slectivity of other
Selectivity of other
65
70
75
80
4
6
8
10
Temperature (
℃
)
Time (h)
(D) 140
(C)140
Conversion of styrene
Selectivity of bza
Selectivity of so
Conversion of styrene
Selectivity of bza
Selectivity of so
120
120
100
80
60
40
20
0
100
80
60
40
20
0
Selectivity of other
Selectivity of other
2.5
5.0
7.5
10.0
1： 1
3： 1
5： 1
Catalyst dosage (wt %)
n
: n
(70% TBHP) (styrene)
Fig. 1. Effect of (a) temperature, (b) reaction time, (c) catalyst dosage and (d) reactants molar
ratio on the selective oxidation of styrene.
3.4 Possible mechanism of the selective oxidation of styrene
The possible mechanism of the selective oxidation of styrene over the present
catalysts was investigated. A radical scavenger, butyl hydroxy toluene (BHT) was
13

ACCEPTED MANUSCRIPT
added after the Mn-MIL-100-catalyzed reaction proceeded for 2 h. It was observed
that the reaction terminated immediately with the addition of BHT, demonstrating that
the reaction proceeded via radical intermediates [24]. Thus, the radical mechanism for
the formation of benzaldehyde, styrene oxide and other products could be proposed
(see Scheme S1), which is similar to that for Co(II)-MOF, Cu(II)-MOF [25] and
CPO-27-Mn [26]. First, TBHP reacts with Mn-MIL-100 to form a Mn(III)-peroxy
adduct by the removal of terminal water. Then, Mn(III)-peroxy adduct releases a
t-butylperoxy radical and regenerates Mn-MIL-100. The t-butylperoxy radical reacts
with styrene to generate a benzylic radical derivative, which further reacts with
t-butylperoxy radical to afford benzaldehyde via C-C oxidative cleavage (route II). In
addition, the benzylic radical derivative undergoes oxygen migration to form styrene
oxide and t-BuOH product (route I). Benzaldehyde could be obtained through the
ring-opening reaction of styrene oxide with TBHP followed by C-C oxidative
cleavage (route III). Besides, phenylacetaldehyde and benzoic acid might be formed
by the Lewis acid catalyzed ring-opening isomerization of styrene oxide (route IV) or
over-oxidation of benzaldehyde (route V).
3.5 Catalytic selective oxidation of various alkenes
To determine the general scope of reaction, the selective oxidation of various
alkenes such as α-styrene, diphenylethene, cyclohexene and cyclooctene over
Mn-MIL-100 are performed under the optimum condition identified in the case of
styrene and results are shown in Table S3. Apparently, phenyl-substituted olefins
14

ACCEPTED MANUSCRIPT
underwent oxidative cleavage and efficiently produced aldehydes or ketones. It is also
clearly observed from Table S3 that the reaction rate of cyclic olefins is lower than
that of phenyl-substituted olefins. In the case of cyclic olefins, there is competition
between oxidation of the allylic position and oxidation of the double bond.
Cyclohexene was converted to the corresponding epoxide (59.07% yield) with no
other product, whereas cyclooctene was converted to the corresponding epoxide with
low yields (only 8.95%).
In addition, the catalytic properties of various materials [27] previously reported
are shown in Table S4. Compared with a series of porous materials, such as
Cr-ZSM-5,
SBA-Fe(acac:salen),
MoO2(acac)–POM,
hierarchical
ZSM-5,
[Cu2(bipy)2(btec)], MOF-525-Mn, MOF-74(Cu), MOF-74(Co) and MOF-74(Cu/Co),
it is obvious that Mn-MIL-100 has an excellent conversion and benzaldehyde
selectivity.
3.6 Recyclability of the catalyst
The recyclability of catalyst is one of the most important criteria for commercial
applications. The recyclability of Mn-MIL-100 was tested towards the selective
oxidation of styrene. This catalytic system could be easily recovered from the
reaction mixture by centrifugation and it was ready for reuse after washing with
acetonitrile twice. As summarized in Fig. S6, the styrene conversion was only slightly
reduced (< 4%) but the benzaldehyde yield remained practically constant in three
consecutive runs, implying high recyclability for the Mn-MIL-100 catalyst.
15

ACCEPTED MANUSCRIPT
4. Conclusions
Mn-MIL-100 is synthesized by a modified solvothermal method and utilized as
a heterogeneous catalyst for the selective oxidation of styrene. Compared to
Fe-MIL-100, Fe-MIL-101 and Cr-MIL-101, Mn-MIL-100 exhibits excellent styrene
conversion and benzaldehyde selectivity, which is probably due to the presence of
manganese ion as metal sites. Moreover, the characterization results of XRD and TGA
indicate that the structures of Fe-MIL-100 and Mn-MIL-100 are analogous but
Mn-MIL-100 possesses higher thermal stability than Fe-MIL-100. An 88.99%
conversion of styrene and 84.97% reaction selectivity to benzaldehyde were obtained
using 5 wt% Mn-MIL-100 and 3:1 molar ratio of 70% TBHP/styrene at 70 °C for 10 h.
Mn-MIL-100 not only has high chemical stability and recyclability but also exhibits
superior catalytic activity in the selective oxidation of aryl-olefins. Thereby, this work
provides a new pathway for the selective oxidation of aryl-olefins to the
corresponding aldehydes.
Acknowledgements
This work was financially supported by the National Natural Science Foundation of
China (No. 21406165), the National Key Basic Research Program (No.
2016YFC0205300) and the Tianjin Research Program of Application Foundation and
Advanced Technique.
References
16

ACCEPTED MANUSCRIPT
1. Weinheim, Ullmann’s Encyclopedia of Industrial Chemistry, fifth ed., Wiley-VCH,
Germany, 1985.
2. (a) A. S. Burange, S. R. Kale, R. Zboril, M. B. Gawande, R. V. Jayaram, RSC Adv.
4 (2014) 6597-6601; (b) Z. Chen, P. Zou, R. Zhang, L. Dai, Y. Wang, Catal Lett.
145 (2015) 2029-2036. (c)V. Ravat, I. Nongwe, N. J. Coville, Micro. Meso. Mater.
225 (2016) 224-231.
3. Y. Sakata, V. Ponec, Appl. Catal. A Gen. 1 (1998) 173-184.
4. J. S. Cha, D. Y. Lee, Bull. Kor. Chem. Soc. 21(2000) 1260-1262.
5. (a) N. T. Thao, L. T. K. Huyen, Chem. Eng. J. 279 (2015) 840-850. (b) J. Tong, W.
Li, L. Bo, H. Wang, Y. Hu, Z. Zhang, A. Mahboob, J. Catal. 344 (2016) 474-481.
6. (a) H. Su, S. Wu, Z. Li, Q.Huo, J. Guan, Q. Kan, Appl. Organometal. Chem. 29
(2015) 462-467; (b) L. Paul, B. Banerjee, A. Bhaumik, M. Alia, J. Solid State
Chem. 237 (2016) 105-112; (c) X. Wang, S. Wu, Z. Li, X. Yang, H. Su, J. Hu, Q.
Huo, J. Guan, Q. Kan, Micro. Meso. Mater. 221 (2016) 58-66.
7. (a) N. E. Thornburg, A. B. Thompson, J. M. Notestein, ACS Catal. 5 (2015)
5077-5088; (b) Z. Wang, X. Hou, J. Shen, T. Li, RSC Adv. 6 (2016),
89503-89509.
8. (a) Y. Y. Liu, J. L. Zeng, J. Zhang, F. Xua, L. X. Sun, Inter. J. Hydrogen Energy.
32 (2007) 4005-4010; (b) Q. Liu, L. Ning, S. Zheng, M. Tao, Y. Shi, Y. He, Sci.
Rep. 3 (2013) 2916.
9. (a) X. Li, L. Yang, L. Zhao, X.L. Wang, K.Z. Shao, Z.M. Su, Cryst. Growth Des.
16 (2016) 4374-4382; (b) F. Y. Yi, D. Chen, M. K. Wu, L. Han, H. L. Jiang,
17

ACCEPTED MANUSCRIPT
ChemPlusChem. 81 (2016) 675-690; (c)X. Lian, B. Yan, Inorg. Chem. 55 (2016)
11831-11838.
10. (a) J. R. Li, Y. Ma, M. C. McCarthy, J. Sculley, J. Yu, H. K. Jeong, P. B. Balbuena,
H. C. Zhou, Coordin. Chem. Rev. 255 (2011) 1791-1823; (b) N. A. Khan, S. H.
Jhung, J. Hazar. Mater. 325 (2017) 198-213.
11. (a) Y. Wang, X. Chen, Q. Lin, A. Kong, Q. G. Zhai, S. Xie, P. Feng, Nanoscale. 9
(2017) 862-868; (b) J. Liang, R. P. Chen, X.Y. Wang, T. T. Liu, X. S. Wang, Y. B.
Huang, R. Cao, Chem. Sci. 8 (2017) 1570-1575.
12. (a) G. Férey, C. Mellot-Draznieks, C. Serre, F. Millange, J. Dutour, S. Surblé, I.
Margiolaki, Science. 309(2005) 2040-2042; (b)N. V. Maksimchuk, K. A.
Kovalenko, V. P. Fedinbc, O. A. Kholdeeva, Chem. Commun. 48(2012)
6812-6814.
13. P. Horcajada, S.Surblé, C. Serre, D.Y. Hong, Y. K. Seo, J. S. Chang, J. M.
Grenèche, I. Margiolakid, G. Férey, Chem. Commun. 48 (2007) 2820-2822.
14. H. Reinsch, N. Stock, CrystEngComm.15 (2013) 544-550.
15. (a) M. Banerjee, S. Das, M. Yoon, H. J. Choi, M. H. Hyun, S. M. Park, G. Seo, K.
Kim, J. Am. Chem. Soc. 131 (2009) 7524-7525; (b)B. Li, Y. Zhang, D. Ma, L. Li,
G. Li, G. Li, Z. Shi, S. Feng, Chem. Commun.48 (2012) 6151-6153.
16. Z. Saedi, S. Tangestaninejad, M. Moghadam, V. Mirkhani, I.
Mohammadpoor-Baltork, Catal. Commun. 17 (2012) 18-22.
17. J. Sun, G. Yu, Q. Huo, Q. Kana, J. Guan, RSC Adv. 4 (2014) 38048-38054.
18. N. V. Maksimchuk, K. A. Kovalenko, V. P. Fedin, O. A. Kholdeeva, Chem.
18

ACCEPTED MANUSCRIPT
Commun. 48 (2012) 6812-6814.
19. W. Zhang, Y. Shi, C. Li, Q. Zhao, X. Li, Catal Lett. 146 (2016) 1956-1964.
20. S. H. Huo, X.P. Yan, J. Mater. Chem. 22 (2012) 7449-7455.
21. B. Zhang, S. Hao, D. Xiao, J. Wu, Y. Huang, Mater. and Design 98 (2016)
319-323.
22. Y.-Y. Fu, C.-X. Yang, X.-P. Yan, J. Chromatography A 1274 (2013) 137-144.
23. H. Lv, H. Zhao, T. Cao, L. Qian, Y. Wang, G. Zhao, J. Mol. Catal. A: Chem. 400
(2015) 81-89.
24. J. Zhang, A.V. Biradar, S. Pramanik, T.J. Emge, T. Asefa, J. Li, Chem. Commun.
48 (2012) 6541-6543.
25. C. Chen, P. Shen, M. Wan, N. Ding, X. Shi, X. Wang, N. Zhang, Micro. Meso.
Mater. 232 (2016) 167-173.
26. H. Yao, Y. Yang, H. Liu, F. Xi, E. Gao, J. Mol. Catal. A: Chem. 394 (2014)
57-65.
27. (a) P. Cancino, V. Paredes-García, P. Aguirre, E. Spodine, Catal. Sci. Technol. 4
(2014) 2599-2607. (b) J. W. Brown, Q. T. Nguyen, T. Otto, N. N.
Jarenwattananon, S. Glöggler, L.-S. Bouchard, Catal. Commun. 59 (2015) 50-54.
(c) Y. Fu, L. Xu, H. Shen, H. Yang, F. Zhang, W. Zhu, M. Fan, Chem. Eng. J. 299
(2016) 135-141. (d) C. Sauxa, L. B. Pierella, Appl. Catal. A: Gen 400 (2011)
117-121. (e) N. Anand, K. H. P. Reddy, V. Swapna, K. S. R. Rao, D. R. Burri,
Micro. Meso. Mater. 143 (2011) 132-140. (f) M. Moghadam, V. Mirkhani, S.
Tangestaninejad, I. Mohammadpoor-Baltork, M. M. Javadi, Inorg. Chem.
19

ACCEPTED MANUSCRIPT
Commun. 13 (2010) 244-249. (g) S. Narayanan, J. J. Vijaya, S. Sivasanker, C.
Ragupathi, T. M. Sankaranarayanan, L. J. Kennedy, J. Porous Mater. 23 (2016)
741-752.
20

ACCEPTED MANUSCRIPT
Graphical Abstract
21

ACCEPTED MANUSCRIPT
Highlights
1. Mn-MIL-100 is synthesized by a modified solvothermal method.
2. Mn-MIL-100 exhibits excellent styrene conversion and benzaldehyde
selectivity.
3. Mn-MIL-100 has superior catalytic activity in the selective oxidation
of aryl-olefins.
4. Mn-MIL-100 exhibits high chemical stability and recyclability.
Keywords: MOFs, Mn-MIL-100, Selective oxidation, Styrene,
Benzaldehyde
28.
22