1. Efficient molybdenum(VI) modified Zr-MOF
catalysts for epoxidation of olefins†
Jia Tang,a
Wenjun Dong,b
Ge Wang,*a
Yuze Yao,a
Leiming Cai,a
Yi Liu,a
Xuan Zhao,a
Jingqi Xua
and Li Tana
Efficient molybdenum(VI) modified Zr-MOF catalysts have been successfully prepared for the epoxidation of
olefins. The stable and porous Zr-MOF (UiO-66(NH2)) was modified with salicylaldehyde, pyridine-2-
aldehyde, or 2-pyridine chloride by the post-synthesis modification (PSM) method, and then the Mo-
based catalyst was loaded by a chelating method. The MOFs not only act as the carriers of the Mo(VI)
catalyst, but also improve the contacting ability between the substrate and the active center of the Mo(VI)
compound. The high dispersion of the Mo catalyst on Zr-MOF and the big pore size of MOF guarantee
sufficient contact between substrate and catalytic active center, thus accelerating the rate of reaction
and providing improved catalytic efficiency for the epoxidation of olefins. The obtained Zr-MOF catalyst
exhibited high activity for the epoxidation of olefins with 70 wt% tert-butyl hydroperoxide (TBHP) or 30%
H2O2 as the oxygen sources. Furthermore, MoO2(acac)2 loaded Zr-MOF was prepared in the same way,
and it also showed good catalytic performance for the epoxidation of olefins.
Introduction
Molybdenum(VI) compounds, such as MoO2(acac)2 and
MoO(O2)2$2DMF, have been extensively used as olen epoxida-
tion catalysts due to their non-toxic nature, low-price and high
catalytic activity in mild conditions.1–4
However, the separation
and reuse of molybdenum(VI) homogeneous catalysts still remains
as a great challenge. Up to now, suitable carriers have been widely
developed to support molybdenum(VI) compounds.5,6
For
example, Shahram Tangestaninejad et al. prepared a silica sup-
ported MoO2(acac)2 catalyst, and the catalytic activity and reus-
ability of this catalyst were improved for the alkene epoxidation.7–9
David C. Sherrington sorted Mo(VI) compounds on a polymer
substrate, which exhibited enhanced catalytic performance,
excellent stability and recycling ability for alkene epoxidation.10–13
However, these catalysts supports show low loading, poor
dispersion rates and low-collision inefficiencies between the
catalyst and the substrate. Especially, the leakage of the catalyst is
a seemingly insurmountable shortcoming. Therefore, a green,
inexpensive, heterogeneous molybdenum catalyst that exhibits
both a homogeneous catalyst's activity and a heterogeneous
catalyst's re-usability still remains a challenge.
As is well known, metal–organic frameworks (MOFs) with
large micropore volume, high specic surface area and adjust-
able structure,14–17
have aroused a lot of interest for catalysts.18–21
The MOFs can not only resolve the difficulties in separating the
products, but also allow for a high level of dispersion and the
high level activity of homogeneous catalysts.22,23
Post-synthesis
modication method improves the interaction of MOF with the
catalyst, which is a potential method to solve the catalyst
leakage problem. For example, Rosseinsky bound V(O)acac2 on
IRMOF-3 by PSM for the oxidation of cyclohexene with
tBuOOH.24
Corm loaded bifunctional iridium-(2-amino-
terephthalate) on Zr-MOF for the synthesis of secondary amines
with a cascade reaction, which displayed high levels of catalytic
efficiency.25
Lin and colleagues prepared a series of metallated
UiO-67 and Ir-containing UiO-67 derivative catalysts with high
catalytic efficiency for water-oxidation catalysis (WOC).26
In this paper, the Zr-MOF (UiO-66(NH2)) was functionalized
with salicylaldehyde,27
pyridine-2-aldehyde, 2-pyridine chloride
by PSM, respectively, and then loaded with the Mo-based cata-
lysts by chelating method. The Mo–Zr-MOF catalysts were used
for olen epoxidation. The MOFs acted as the carrier for Mo(VI)
catalyst to improve the contact between the substrate and the
active center of the Mo(VI) compound. The high dispersion of
Mo catalyst on Zr-MOF and the big pore size of MOF guaranteed
sufficient contact between the substrate and the catalytic active
center, thus accelerating the reaction and improving the cata-
lytic efficiency for the epoxidation of olen. Furthermore,
MoO2(acac)2 loaded on Zr-MOF was prepared in the same way,
which also showed good catalytic performance for the epoxi-
dation of olens.
a
School of Materials Science and Engineering, University of Science and Technology
Beijing, Beijing 100083, P. R. China. E-mail: gewang@mater.ustb.edu.cn; Fax: +86
10 62327878; Tel: +86 10 62333765
b
Center for Optoelectronics Materials and Devices, Zhejiang Sci-Tech University,
Hangzhou 310018, P. R. China
† Electronic supplementary information (ESI) available: Synthesis of 2-pyridine
chloride and MoO(O2)2$2DMF, SEM, 1
HNMR, FT-IR, TGA, XRD and BET tests.
See DOI: 10.1039/c4ra07133f
Cite this: RSC Adv., 2014, 4, 42977
Received 15th July 2014
Accepted 19th August 2014
DOI: 10.1039/c4ra07133f
www.rsc.org/advances
This journal is © The Royal Society of Chemistry 2014 RSC Adv., 2014, 4, 42977–42982 | 42977
RSC Advances
PAPER

2. Experimental
Synthesis methods
All chemicals purchased were of reagent grade and used
without further purication. 2-Pyridine chloride and
MoO(O2)2$2DMF were synthesized according to the reported
literatures.28–30
Synthesis of UiO-66(NH2), UiO-66-sal, UiO-66-PI, and UiO-66-
PC
Synthesis of Zr-BDC-NH2 MOF: UiO-66(NH2) was carried out as
reported previously.25
In order to remove the unreacted 2-amino
terephthalate and ZrCl4, the precipitate was isolated through
centrifugation and washed with DMF two times each day for two
days to activate the MOF. The suspension was isolated and then
washed with methanol for three times in the same way to
replace DMF. In order to modify salicylaldehyde on UiO-
66(NH2), 0.5 g of UiO-66(NH2) and 10 mL of CHCl3 were added
into a ask and ultrasonically dispersed for 10 min, and then
0.5 mL of salicylaldehyde was injected in the mixture and
magnetically stirred at 40
C for three days. Aer the reaction,
the MOFs washed 3–5 times with acetonitrile and dried over-
night at 120
C in a vacuum, to nally obtain the yellow UiO-66-
sal. Using the same method, pyridine-2-aldehyde was modied
on UiO-66(NH2) and named UiO-66-PI. For the preparation of
UiO-66-PC, 0.5 g of UiO-66(NH2), 0.25 g of 2-pyridine chloride,
0.36 mL of pyridine and 10 mL of CHCl3 were added into a ask
and ultrasonically dispersed for 10 min, and then magnetically
stirred at 40
C for three days, washed 3–5 times with acetoni-
trile and dried overnight at 120
C in a vacuum with the UiO-66-
PC product stored in a screw bottle.
Synthesis of UiO-66-sal-MoD, UiO-66-PI-MoD, and UiO-66-PC-
MoD
0.5 g of UiO-66-sal was dispersed into 30 mL of acetonitrile and
0.5 g of MoO(O2)2$2DMF was added into the slurry. The mixture
was magnetically stirred at reux for 24 h. The product was
collected by centrifugation, washed with acetonitrile three
times, washed three times with ethanol and dried in the air at
80
C for 24 h. UiO-66-sal was replaced with UiO-66-PI or UiO-
66-PC, and then UiO-66-PI-MoD and UiO-66-PC-MoD were
obtained.
Characterization and measurement
The phase composition of the sample was investigated by X-ray
powder diffraction (XRD, M21X, Cu Ka radiation, l ¼ 0.154178
nm). The morphology and structures of the as-obtained products
were characterized using scanning electron microscopy (SEM,
ZEISS SUPRA55). The chemical compositions were analysed
using an X-ray photoelectron spectrometer (XPS, ESCALAB 250Xi)
and inductively coupled plasma-atomic emission spectrometry
(ICP-AES, Vavian 715-ES). Thermogravimetric analysis (TG) was
conducted with a TGA instrument (Netzsch STA449F) at a heating
rate of 10
C minÀ1
under an N2 ow. The specic surface areas
were calculated with nitrogen sorption–desorption isotherms
using a Micromeritics ASAP 2420 adsorption analyzer. The pore
size distributions were derived from the adsorption branches of
isotherms by using the Barrett–Joyner–Halenda (BJH) model.
Fourier transform infrared (FTIR) spectra were acquired on a
Nicolet 6700 using the KBr pellet technique. The catalytic results
were analyzed with a gas chromatography-mass spectrum
(GC-MS, Agilent7890/5975C-GC/MSD).
Results and discussion
Characterization
SEM images of the UiO-66(NH2) nanoparticles showed that the
as-prepared MOF was octahedral in structure and the octahe-
dral length was 150–200 nm. Aer the Zr-MOF was modied
with salicylaldehyde,24,31
no morphology change in the UiO-
66(NH2) nanoparticles was observed, which was similar to the
previous reports.25
Fig. 1c shows the SEM image of the Mo(VI)
loaded with UiO-66-sal and almost no change in the
morphology or size was observed in the product. Other modi-
cations on Zr-MOF also maintained the same morphology. In
addition, the octahedral morphology was intact aer the
modication and Mo(VI) loading on the Zr-MOF catalyst, which
displayed its strong stability.
The powder XRD patterns of the UiO-66-NH2 and UiO-66-sal
shown in Fig. 2(a and b) illustrate that the amino-functionalized
Fig. 1 SEM images (a) of UiO-66(NH2), (b) UiO-66-sal and (c) UiO-66-
sal-MoD.
Fig. 2 Powder XRD patterns of UiO-66(NH2) samples: (a) UiO-
66(NH2), (b) UiO-66-sal and (c) UiO-66-sal-MoD.
42978 | RSC Adv., 2014, 4, 42977–42982 This journal is © The Royal Society of Chemistry 2014
RSC Advances Paper

3. UiO-66(NH2) derivatives are tolerant with the functionalized
ligands, which is similar to literatures reports.25,27,32–35
MoO(O2)2$2DMF loaded onto the modied UiO-66(NH2), shown
in Fig. 2c, conrms that the loading of Mo(VI) retains the main
structure crystalline of the Zr-MOF. Similarly, the modication
of pyridine-2-aldehyde or 2-pyridine chloride, and their Mo(VI)
loading on MOF showed the same reections as UiO-66(NH2)
(Fig. S10 and S11†). In addition, the temperature-dependent
XRD of UiO-66-MoD conrmed that the decomposition of the
catalyst was starting from 250
C, which indicated that the
catalyst showed good thermal stability in the catalytic reaction
conditions (80
C) (Fig. S12†).
FT-IR spectra is an effective method to conrm the catalyst
loading Mo(VI) on Zr-MOF supports. FT-IR spectra of UiO-
66(NH2), UiO-66-sal, UiO-66-sal-MoD are shown in Fig. 3. The
NH groups of the UiO-66(NH2) could be easily modied with
the chelating groups by PSM method. The bands of the NH in-
plane deformation were shied from 1618 cmÀ1
to a higher
frequency at 1655 cmÀ1
due to the chemical complexation
with MoO(O2)2. Furthermore, due to a strong coordination
between Mo(VI) and chelating groups of UiO-66-sal,
MoO(O2)2$2DMF was coordinated with chelating groups on
Zr-MOF. The characteristic IR vibration band of the Mo]O
group was present in the Zr-MOF catalyst, which appeared in
the range of 890–905 cmÀ1
.12
In order to evaluate the porosity of the samples, nitrogen
adsorption isotherms were plotted, which conrmed that the
three kinds of MOFs structures were type I isotherms. The
porosity of the UiO-66(NH2) was retained aer functionalization
of the linker and the loading of MoO(O2)2$2DMF (Fig. 4). The
large surface and the porosity conrmed the successful salicy-
laldehyde modication and catalyst loading on the uniform
pore surface of UiO-66(NH2).
BET tests of UiO-66(NH2), UiO-66-sal and UiO-66-sal-MoD
are shown in Table 1. The BET surface area of UiO-66(NH2) was
1263.6 m2
gÀ1
(pore volume ¼ 0.6 cc gÀ1
) (Table 1), which was
larger than the literature reported 800 m2
gÀ1
due to sufficient
exchanging with methanol to activate the MOF.25
The BET
surface area of UiO-66-sal was 994.9 m2
gÀ1
(pore volume ¼
0.44 cc gÀ1
) because the channel surface of Zr-MOF was modi-
ed by salicylaldehyde. When MoO(O2)2$2DMF was loaded on
the UiO-66-sal, the specic surface area (558 m2
gÀ1
) and pore
volume (0.29 cc gÀ1
) conrmed that the channel surface of UiO-
66-sal were further modied with the Mo(VI) catalyst. ICP anal-
ysis also conrmed that about 15.2 wt% Mo was loaded on the
Zr-MOF (Table 1).
The surface modication by PSM was critical for catalyst
loading on MOF. The UiO-66(NH2) functionalized with salicy-
laldehyde, pyridine-2-aldehyde and 2-pyridine chloride
conrmed that salicylaldehyde modied on UiO-66(NH2) was
the most benecial to support catalysis (Table 1 and S2†).
Loading of Mo(VI) catalyst and the maximum pore volume
conrmed that the UiO-66-sal-MoD showed high loading of
Mo(VI) catalyst on it. In the same way, functionalized Zr-MOFs
were also loaded MoO(acac)2 to obtain UiO-66-sal-MoA, UiO-66-
PI-MoA and UiO-66-PC-MoA, respectively. Therefore, six kinds
of Zr-MOF catalysts were successfully obtained.
Fig. 3 Infrared spectra of (a) UiO-66(NH2), (b) UiO-66-sal and (c) UiO-
66-sal-MoD.
Fig. 4 Nitrogen adsorption–desorption isotherms at 77 K of the as-
synthesized UiO-66(NH2), UiO-66-sal, UiO-66-sal-MoD.
Table 1 The BET tests and ICP of UiO-66(NH2), UiO-66-sal and UiO-66-sal-MoD
Catalytic materials SBET (m2
gÀ1
) SLANG (m2
gÀ1
) Pore volume (cc gÀ1
) ICP (Mo) (wt%)
UiO-66(NH2) 1263.6 1337.7 0.60 —
UiO-66-sal 994.9 1040.4 0.44 —
UiO-66-sal-MoD 558 587 0.29 15.2
This journal is © The Royal Society of Chemistry 2014 RSC Adv., 2014, 4, 42977–42982 | 42979
Paper RSC Advances

4. Catalytic studies
Epoxidation of cis-cyclooctene by Mo MOF catalysts
To investigate the catalytic performance of the Zr-MOF-sup-
ported catalytic materials, the epoxidation of olens as a probe
reaction with 70 wt% TBHP or 30 wt% hydrogen peroxide as an
oxygen source in CH3CN was performed. The conversion of cis-
cyclooctene was about 99% aer 24 h, when UiO-66-sal-MoA
and UiO-66-sal-MoD were used as catalysts. When 70 wt% TBHP
was used as an oxidant source (Table 2), Zr-MOF modied with
salicylaldehyde showed better catalytic activity than the other
Zr(IV)-based MOF catalysts modied with pyridine-2-aldehyde or
2-pyridine chloride due to less space occupation of the pore by
salicylaldehyde molecule. On the other hand, salicylaldehyde
ensured a high amount of Mo catalyst loading (see Table 1).
When 30 wt% H2O2 was used as an oxygen source, UiO-66-sal-
MoD, UiO-66-PI-MoD and UiO-66-PC-MoD exhibited higher
catalytic efficiency than UiO-66-sal-MoA, UiO-66-PI-MoA and
UiO-66-PC-MoA for the epoxidation of cis-cyclooctene, which
may be due to an easier coordination of MoO(O2)2$2DMF with
the functional groups.
The inuence of solvents and oxygen sources in the catalytic
efficiency of UiO-66-sal-MoD for the epoxidation of cis-
cyclooctene
UiO-66-sal-MoD exhibited enhanced catalytic performance with
30 wt% H2O2 or 70 wt% TBHP as the oxygen sources; therefore,
its catalytic properties were further examined in detail.
In order to explore the optimal reaction conditions, different
polarity solvents were applied to the epoxidation of cis-
cyclooctene with 30 wt% H2O2 and 70 wt% TBHP as oxygen
sources (Table 3). Due to the dispersion of active catalytic sites
on the high surface area of UiO-66(NH2) and the greater polarity
of the solvent facilitated the dispersion of the oxygen source, the
catalytic effect of UiO-66-sal-MoD was improved in acetonitrile,
which may due to the activity center being highly conducive to
the olen epoxidation reaction. In addition, UiO-66-sal-MoD
also exhibited good catalytic activity in CHCl3 and toluene with
70 wt% TBHP as oxygen source. However, when the catalyst was
used in other solvents with 30 wt% H2O2 as oxygen source, the
desired results were not obtained. By comparison of the results
of the 70 wt% TBHP and 30 wt% H2O2 used in epoxidation of
cis-cyclooctene reaction system, the epoxidation of cis-cyclo-
octene catalyzed by UiO-66-sal-MoD with 70 wt% TBHP in
CH3CN, CHCl3 or toluene solvent was an optimal choice.
Reusability tests and heterogeneity
In order to evaluate the stability of Zr(IV)-based MOFs catalysts,
the epoxidation reaction was tested with the reaction cycle
repeated under the above reaction conditions. Aer each
reaction, the catalyst was recovered and washed with CH3CN
(3 Â 10 mL) for another reaction. The catalyst remained
substantially active over 5 recycles, and the conversion of
epoxidation remained at 99% (Fig. 5). The powder XRD of the
catalyst aer 5 cycles showed that the overall structure of the
material remained intact aer the catalytic experiments
(Fig. S13†), and TEM images (Fig. S17†) for fresh and recovered
catalyst materials also showed that the structure was main-
tained aer the reaction. So the Zr(IV)-based MOFs catalysts are
stable in these reaction conditions.
To conrm that the MOF materials were heterogeneous
catalysts for the epoxidation reaction, two reactions were
carried out on the UiO-66-sal-MoD catalyst (Table 4). Aer two
Table 2 Epoxidation of cis-cyclooctene over Zr(IV)-based MOFs
catalysts with oxygen sourcesa
Entry Catalyst ROOH Conv. (%) Sel.b
(%)
1 — TBHP 34.7 76.5
2 UiO-66-NH2 TBHP 11 68.1
3 UiO-66-sal-MoA TBHP 99 99
H2O2 83 99
4 UiO-66-sal-MoD TBHP 99 99
H2O2 88 99
5 UiO-66-PI-MoA TBHP 91.1 99
H2O2 84 99
6 UiO-66-PI-MoD TBHP 77.5 99
H2O2 85 99
7 UiO-66-PC-MoA TBHP 83.7 99
H2O2 81 99
8 UiO-66-PC-MoD TBHP 90.7 99
H2O2 88 99
a
Reaction conditions: 40 mg cat, 0.5 mmol substrate, 2.5 mmol 30 wt%
H2O2 or 2 mmol 70 wt% TBHP, 4 mL CH3CN, 80
C, 24 h. b
Conversion
(%) and selectivity (%) were determined by GC-MS with an internal
standard method.
Table 3 Results of the epoxidation of cis-cyclooctene by UiO-66-sal-
MoD in different solvents with two oxygen sourcesa
Entry Solvent T (
C) ROOH Conv.b
(%) Sel. (%)
1 DMF 80 TBHP 4.65 99
H2O2 31.9 99
2 CH3CN 80 TBHP 99 99
H2O2 88 99
3 Ethanol 78 TBHP 86.5 99
H2O2 58.8 99
4 1,4-Dioxane 80 TBHP 63.2 99
H2O2 9.0 99
5 THF 66 TBHP 19 99
H2O2 39 99
6 1,2-DCE 80 TBHP 15.8 99
H2O2 2.1 99
7 CHCl3 61 TBHP 95.2 99
H2O2 3.8 99
8 Toluene 80 TBHP 91.7 99
H2O2 2.8 99
a
Reaction conditions: 40 mg cat, 0.5 mmol substrate, 2.5 mmol 30 wt%
H2O2 or 2 mmol 70 wt% TBHP, 4 mL CH3CN, 24 h. b
Conversion (%) and
selectivity (%) were determined by GC-MS with an internal standard
method.
42980 | RSC Adv., 2014, 4, 42977–42982 This journal is © The Royal Society of Chemistry 2014
RSC Advances Paper

5. hours of reaction, the solution was ltered to remove the MOF
catalyst. Aer another 8 hours of reaction, the conversion of
cis-cyclooctene changed from 64.7% to 64.7% + 12.6% (Fig. 4),
and the increase of 12.6% was attributed to the slow oxidation
of the substrate, which was consistent with the blank experi-
ment (Table 2, entry 1).36
Furthermore, it proved that the cata-
lytic activity for epoxidation of cis-cyclooctene was associated
with the UiO-66-sal-MoD catalyst exclusively, and no other
reaction took place when the catalyst was ltered from the
reaction solution.
Epoxidation of different olens in CH3CN catalyzed by the
UiO-66-sal-MoD catalyst
In order to expand the range of the epoxidation reaction, other
olens, such as cyclopentene, cyclohexene and 1,5-cyclo-
octadene, were catalyzed using Mo MOF catalysts (Table 5). The
main products were 1,2-cyclopentanediol, 1,2-cyclohexanediol
and 9-oxabicyclo[6.1.0]non-4-ene, respectively. The products of
cyclopentene and cyclohexene were corresponding diols. This
may be because cyclopentene and cyclohexene were rst
oxidized to epoxides, due to the instability of 1,2-epoxy
cyclopentane and epoxycyclohexane, and these epoxides were
further converted to 1,2-cyclopentanediol and 1,2-cyclo-
hexanediol, respectively. 1,5-Cyclooctadene was epoxidized with
only one double bond and mainly converted into 9-oxabicyclo
[6.1.0]non-4-ene. Hence, it could be concluded that the catalysis
was carried out efficiently and UiO-66-sal-MoD exhibited high
selectivity for catalyzing the epoxidation of olens.
Conclusions
In summary, Mo complexes modied Zr-MOF were successfully
prepared by a PSM method. Firstly, the Zr-MOF was modied
with salicylaldehyde, pyridine-2-aldehyde, or 2-pyridine chlo-
ride, and then MoO(O2)2$2DMF and MoO2(acac)2 was loaded to
obtain the molybdenum(VI) modied Zr-MOF catalysts, respec-
tively. MOFs act not only to carry the Mo(VI) catalysts, but also to
improve the contact between the substrate and the active center
of the Mo(VI) compound. The high dispersion of Mo catalyst on
Zr-MOF and the big pore size of MOF guaranteed the sufficient
contact between substrate and catalytic active center, thus
accelerating the reaction and improving the catalytic efficiency
for epoxidation of olen. Furthermore, this method can be
extended to prepare other catalysts and used for olen epoxi-
dation reaction, which conrmed that it be extended to other
catalysts and reactions for real applications.
Acknowledgements
The work was supported by the Co-building Special Project of
Beijing Municipal Education and the National High Technology
Research and Development Program of China (no.
2013AA031702).
Notes and references
1 A. N. F. R. Fronczek, R. L. Luck and G. Wang, Inorg. Chem.
Commun., 2002, 5, 384–387.
2 S. L. Benjamin and B. Kevin, Chem. Rev., 2003, 103, 2457–
2473.
3 G. Wang, G. Chen, R. L. Luck, Z. Wang, Z. Mu, D. G. Evansa
and X. Duan, Inorg. Chim. Acta, 2004, 357, 3223–3229.
4 F. Adam and A. Iqbal, Microporous Mesoporous Mater., 2011,
141, 119–127.
5 M. Deng, Y. Ling, B. Xia, Z. Chen, Y. Zhou, X. Liu, B. Yue and
H. He, Chem.–Eur. J., 2011, 17, 10323–10328.
6 L. X. Dai, Y. H. Teng, K. Tabata, E. Suzuki and T. Tatsumi,
Microporous Mesoporous Mater., 2001, 44–45, 573–580.
7 S. Tangestaninejad, M. Moghadam, V. Mirkhani,
I. M. Baltork and K. Ghani, Inorg. Chem. Commun., 2008,
11, 270–274.
8 F. Blanc, J. T. Cazat, J. M. Basset, C. Cop´eret, A. S. Hock,
Z. J. Tonzetich and R. R. Schrock, J. Am. Chem. Soc., 2007,
129, 1044–1045.
Fig. 5 The recyclability of UiO-66(NH2)-sal-MoD catalyst in the
epoxidation of cis-cyclooctene.
Table 4 Epoxidation of cis-cyclooctene with UiO-66-sal-MoD and
filtration of UiO-66-sal-MoD at 64.7% conversion
Time (h) 1 2 3 4 6 8 10
Conv.a
(%) 47 64.7 82.4 92 97 98 99
Conv.b
(%) 47 64.7 66.9 70.4 72.7 74.4 77.3
a
Epoxidation of cis-cyclooctene with UiO-66-sal-MoD catalyst.
b
Filtration of UiO-66-sal-MoD at 64.8% conversion. Reaction
conditions: cat (40 mg), cis-cyclooctene (0.5 mmol), 70 wt% TBHP
(2 mmol), CH3CN (4 mL), 80
C.
Table 5 Epoxidation of alkenes with 70 wt% TBHP catalyzed by UiO-
66-sal-MoD under different conditionsa
Run Substrate Conv.e
(%) Sel. (%)
1 Cyclopentene 96.5b
95
2 Cyclohexene 70.3c
95
3 1,5-Cyclooctadene 57.7d
91.1
a
Cat, 40 mg; substrate, 0.5 mmol; 70 wt% TBHP, 2 mmol; CH3CN, 4 mL;
80
C, 24 h. b
The main product is 1,2-cyclopentanediol. c
The main
product is 1,2-cyclohexanediol. d
The main product is 9-oxabicyclo
[6.1.0]non-4-ene. e
The products were analyzed by GC-MS.
This journal is © The Royal Society of Chemistry 2014 RSC Adv., 2014, 4, 42977–42982 | 42981
Paper RSC Advances

6. 9 F. Blanc, R. Berthoud, A. Salameh, J. M. Basset, C. Cop´eret,
R. Singh and R. R. Schrock, J. Am. Chem. Soc., 2007, 129,
8434–8435.
10 R. Mbeleck, K. Ambroziak, B. Saha and D. C. Sherringto,
React. Funct. Polym., 2007, 67, 1448–1457.
11 S. Leinonen, D. C. Sherrington, A. Sneddon, D. McLoughlin,
J. Corker, C. Canevali, F. Morazzoni, J. Reedijk and
S. B. D. Spratt, J. Catal., 1999, 183, 251–266.
12 K. Dallmann, R. Buffon and W. Loh, J. Mol. Catal. A: Chem.,
2002, 178, 43–46.
13 M. M. Miller, D. C. Sherrington and S. Simpsonb, J. Chem.
Soc., Perkin Trans. 2, 1994, 2, 2091–2096.
14 O. M. Yaghi, M. O'Keeffe, N. W. Ockwig, H. K. Chae,
M. Eddaoudi and J. Kim, Nature, 2003, 423, 705–714.
15 M. Li, D. Li, M. O'Keeffe and O. M. Yaghi, Chem. Rev., 2014,
114, 1343–1370.
16 X. Duan, J. Cai, J. Yu, C. Wu, Y. Cui, Y. Yang and G. Qian,
Microporous Mesoporous Mater., 2013, 181, 99–104.
17 H. Furukawa, K. E. Cordova, M. O'Keefe and O. M. Yaghi,
Science, 2013, 341, 974–986.
18 A. Dhakshinamoorthy, M. Alvaro and H. Garcia, Adv. Synth.
Catal., 2009, 351, 2271–2276.
19 J. L. Harding and M. M. Reynolds, J. Mater. Chem. B, 2014, 2,
2530–2536.
20 G. Calleja, R. Sanz, G. Orcajo, D. Briones, P. Leo and
F. Mart´ınez, Catal. Today, 2014, 227, 130–137.
21 Z. H. Li, L. P. Xue, L. Wang, S. T. Zhang and B. T. Zhao, Inorg.
Chem. Commun., 2013, 27, 119–121.
22 R. K. Das, A. Aijaz, M. K. Sharma, P. Lama and
P. K. Bharadwaj, Chem.–Eur. J., 2012, 18, 6866–6872.
23 S. Xiong, S. Li, S. Wang and Z. Wang, CrystEngComm, 2011,
13, 7236–7245.
24 M. J. Ingleson, J. P. Barrio, J. B. Guilbaud, Y. Z. Khimyak and
M. J. Rosseinsky, Chem. Commun., 2008, 2680–2682.
25 M. Pintado-Sierra, A. M. Rasero-Almansa, A. Corma,
M. Iglesias and F. Sanchez, J. Catal., 2013, 299, 137–145.
26 C. Wang, Z. Xie, K. E. deFra and W. Lin, J. Am. Chem. Soc.,
2011, 133, 13445–13454.
27 M. Servalli, M. Ranocchiari and J. A. Van Bokhoven, Chem.
Commun., 2012, 48, 1904–1906.
28 S. M. Cohen, Chem. Rev., 2012, 112, 970–1000.
29 H. Mimoun, I. Scree da Rech and L. Sajus, Bull. Soc. Chim.
Fr., 1969, 5, 1481–1492.
30 W. Winter, C. Mark and V. Schurig, Inorg. Chem., 1980, 19,
2045–2048.
31 L. Liu, X. Zhang, J. Gao and C. Xu, Green Chem., 2012, 14,
1710–1720.
32 M. Kim, J. F. Cahill, K. A. Prather and S. M. Cohen, Chem.
Commun., 2011, 47, 7629–7631.
33 S. J. Garibay and S. M. Cohen, Chem. Commun., 2010, 46,
7700–7702.
34 M. Kandiah, M. H. Nilsen, S. Usseglio, S. Jakobsen,
U. Olsbye, M. Tilset, C. Larabi, E. A. Quadrelli, F. Bonino
and K. P. Lillerud, Chem. Mater., 2010, 22, 6632–6640.
35 C. G. Silva, I. Luz, F. L. Xamena, A. Corma and H. Garc´ıa,
Chem.–Eur. J., 2010, 16, 11133–11138.
36 A. Dhakshinamoorthy, M. Alvaro and H. Garcia, Adv. Synth.
Catal., 2010, 352, 711–717.
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