Fast-synthesis and catalytic property of heterogeneous Co-MOF catalysts for the epoxidation of α-pinene with air

Article abstract of DOI:10.1039/d0nj03269g

In the past decades, many methods have been developed for synthesizing MOFs, including solvothermal synthesis, mechanical synthesis, electrochemical synthesis, and microwave synthesis. Based on the existing research, a method is proposed for synthesizing Co-MOF by rapidly rotating hydrothermal crystallization, which largely shortens the crystallization time of Co-MOF. When the rotation speed was 150 rpm, only 2 h of crystallization time was needed to synthesize Co-MOF-150-2 with high crystallinity and stability. The optimal Co-MOF-150-2 manifested remarkable activity and selectivity for the epoxidation of α-pinene under mild conditions. The catalytic conversion of α-pinene reached the highest over the Co-MOF-150-2 catalyst, in which the conversion of α-pinene was 99.5% and the yield of 2,3-epoxypinane was 95.7%. The Co-MOF materials synthesized by the rotary method also had excellent stability and highly catalytic activity in recycling experiments. This journal is

Full text of DOI:10.1039/d0nj03269g

View Article Online
View Journal
NJC
New Journal of Chemistry
Accepted Manuscript
A journal for new directions in chemistry
This article can be cited before page numbers have been issued, to do this please use: H. Zhang, J. He, X.
Lu, L. Yang, C. Wang, F. Yue, D. Zhou and Q. Xia, New J. Chem., 2020, DOI: 10.1039/D0NJ03269G.
Volume 42
Number
March 2018
Pages 3963-4776
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
6
21
NJC
New Journal of Chemistry
rsc.li/njc
A journal for new directions in chemistry
Accepted Manuscripts are published online shortly after acceptance,
before technical editing, formatting and proof reading. Using this free
service, authors can make their results available to the community, in
citable form, before we publish the edited article. We will replace this
Accepted Manuscript with the edited and formatted Advance Article as
soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes to the
text and/or graphics, which may alter content. The journal’s standard
Terms & Conditions and the Ethical guidelines still apply. In no event
shall the Royal Society of Chemistry be held responsible for any errors
or omissions in this Accepted Manuscript or any consequences arising
from the use of any information it contains.
ISSN 1144-2546
PAPER
Chechia Hu, Tzu-Jen Lin et al.
Yellowish and blue luminescent graphene oxide quantum dots
prepared via a microwave-assisted hydrothermal route using
H2O2 and KMnO4 as oxidizing agents
rsc.li/njc

Page 1 of 22
New Journal of Chemistry
1
2
3
4
5
6
7
8
9
View Article Online
DOI: 10.1039/D0NJ03269G
Fast-synthesis and catalytic property of heterogeneous Co-MOF
catalysts for the epoxidation of α-pinene with air
Haifu Zhang, Jie He, Xinhuan Lu*, Lu Yang, Chenlong Wang, Fanfan Yue, Dan
Zhou, Qinghua Xia*
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Ministry-of-Education Key Laboratory for the Synthesis and Application of Organic
Functional Molecules & Ministry-of-Education Key Laboratory for Green Preparation
and Application of Functional Materials, Hubei University, Wuhan 430062, P. R.
China.
Abstract
In the past decades, many methods for synthesizing MOFs have been developed,
such as solvothermal synthesis, mechanical synthesis, electrochemical synthesis and
microwave synthesis method. Based on the existing researches, a method was
proposed for synthesizing Co-MOF by rapidly rotating hydrothermal crystallization,
which largely shortened the crystallization time of Co-MOF. When the rotation speed
was 150 rpm, only 2 h of crystallization time was needed to synthesize
Co-MOF-150-2 material quickly with high crystallinity and stability. The optimal
Co-MOF-150-2 manifested remarkable activity and selectivity for the epoxidation of
α-pinene under mild conditions. Catalytic conversion of α-pinene reached the highest
over the catalyst of Co-MOF-150-2, in which the conversion of α-pinene was 99.5%
and the yield of 2,3-epoxypinane was 95.7%. The Co-MOF materials synthesized by
rotary method also had excellent stability and highly catalytic activity in recycling
experiments.
Keywords: Co-MOF-150-2, rota-crystallization, fast-synthesis, α-pinene, epoxidation
* Corresponding authors.
E-mail: xinhuan003@aliyun.com (X.H. Lu); xiaqh518@aliyun.com (Q.H. Xia)

New Journal of Chemistry
Page 2 of 22
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
View Article Online
DOI: 10.1039/D0NJ03269G
1
. Introduction
With the rapid development of materials science, metal-organic frameworks
MOFs) have attracted extensive researches as a new type of porous materials. It was
(
a multi-dimensional network crystal material formed by metal ions or metal clusters
and self-assembled by mono- or multi-dentate organic ligands contain O, N, S, P,
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1-4
etc. Compared with traditional porous framework materials such as zeolite and
activated carbon, metal organic framework materials have the characteristics of
adjustable pore size, ultra-high aperture ratio, ultra-high specific surface area and
varied components. In addition, MOFs material can be adjusted by changing the metal
species and ligand size to synthesize porous materials with different properties and
different pore structure. Therefore, in recent years, MOFs have been widely used in
5
-7
8-10
gas storage and separation,
molecular sensors and identification,
liquid
11
12
13
14-16
17-20
separation and adsorption, light, electromagnetic, biomedical,
and other fields.
catalysis
In 1995, the Yaghi team first reported the synthesis of MOFs using solvothermal
synthesis. This more common method puts a homogeneous mixture of inorganic salts
and organic ligands in a closed reaction kettle, and then heats up to produce
self-pressure in the container, thereby promoting the growth of precipitates into frame
2
1,22
crystals. This method was widely used in the synthesis of MOFs materials,
but
this synthesis method usually required a longer crystallization time or higher
temperature. The mechanical synthesis method also could use to synthesize MOFs.
When Xu et al. synthesized MIL-101 (Cr) by mechanical synthesis, the zirconium salt
and terephthalic acid were ball-milling at room temperature for 30 minutes without
adding hydrofluoric acid and solvent, and then transferred to a high pressure reactor
23
and crystallized at 220 °C for 4 h. It was difficult to adjust the synthesis conditions
to control the structure, because mechanical synthesis method required more stringent
conditions. The electrochemical synthesis method had the advantage of mild synthesis
conditions, short crystallization time and continuous synthesis of MOFs. Gascon and
Dryfe have successfully synthesized a series of typical MOFs materials in a short
period of time, including ZIF-8, MIL-53, MIL-100 (Al), ZIF-4, ZIF-14, ZIF-67,

Page 3 of 22
New Journal of Chemistry
1
2
3
4
5
6
7
8
9
View Article Online
2
4-25
etc.
However, the electrochemical synthesis method has low yield. In rece
D
n
O
t
I:
y
1
e
0.
a
10
r
39/D0NJ03269G
s,
microwave synthesis method has also been developed for synthesizing MOFs. As a
new heating method, microwave could also be applied to the synthesis of MOFs. The
heat energy from microwave synthesis could be transferred directly to the reaction
liquid, which can be heated directly, so the temperature could rise rapidly. It can
promote the occurrence of coordination reaction sharply, accelerate the nucleation and
growth rate of crystals, and finally form small-sized crystals with intact crystal forms
in a short time. Jhung et al. reported the successful synthesis of MIL-100 (Cr) by
microwave method, and obtained perfectly structured MIL-100 (Cr) under microwave
heating for 4 h at 220 °C ; compared with the original 4 days of crystallization time,
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
2
6
the crystallization time was significantly shortened by the microwave method.
2
7-29
Catalytic epoxidation of olefins has attracted much attention in recent years.
Among the various oxidants, molecular oxygen was undoubtedly the most ideal
oxidant in epoxidation. However, the use of molecular oxygen efficiency and
dissociation problems limited the widespread use of molecular oxygen in epoxidation
3
0-32
reaction.
study of heterogeneous catalyst for epoxidation reaction.
proven that rotary method could quickly synthesize heterogeneous catalytic materials
In recent years, MOFs materials have attracted much attention in the
3
3-36
Our previous works had
3
7,38
with excellent properties.
In this work, Co-MOF materials were rapidly
synthesized by rotary method. Compared with the traditional static hydrothermal
method, the rotary method could significantly shorten the crystallization time from 24
h to 2 h. At the same time, as-prepared material showed excellent catalytic activity for
the epoxidation of α-pinene with 99.5% conversion and 95.7% yield of epoxide
(
2,3-epoxypinane), accompanied by highly repeated use performance.
2
. Experimental section
2.1. Materials
The materials included terephthalic acid (H BDC) (98%, Aladdin),
2
Co(Ac) ·4H O (≥99.0%, Aladdin), hydrofluoric acid (HF, ≥40%, Sinopharm), cumene
2
2

New Journal of Chemistry
Page 4 of 22
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
View Article Online
hydroperoxide (CHP, ≥72%, Sinopharm), tert-butyl hydroperoxide (TBHP
D
,
O
≥
I: 1
6
0
5
.1
%,
039/D0NJ03269G
Sinopharm), H O (≥30%, Sinopharm), DMF (≥98.5%, Sinopharm), acetone (≥98%,
2
2
Sinopharm), 1,4-dioxane (≥99.5%, Aladdin), cyclohexanone (≥98%, Aladdin),
cyclohexane (≥99.5%, Sinopharm), α-epoxypinane (≥95%, Tokyo Kasai), α-pinene
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
(
≥98.0%, Macklin), styrene (≥98.5%, Sinopharm), β-pinene (≥98.0%, Macklin),
-decene (≥95%, Macklin), 1-dodecene (≥95%, Macklin). All reagents and materials
were used without further purification.
1
2
.2. Preparation of catalytic materials
2
.2.1. Synthesis of Co-MOF-S
The static hydrothermal synthesis method was used for synthesizing Co-MOF. In
a typical experiment, 6 mmol of cobalt acetate tetrahydrate (Co(Ac) ·4H O), 6 mmol
2
2
of terephthalic acid (H BDC) and 6 mmol of hydrophoric acid (HF, 40%) were
2
dissolved in deionized water (60 mL), then stirred well and transferred into the 100
mL reactor lined with a Teflon liner. After static crystallization at 200 °C for 24 h, it
was cooled to room temperature. The product was recovered by filtration and washed
with water many times. The obtained solid samples were washed by DMF for 12 h
under heating at 60 °C , then filtered and separated. The samples were dried in an
80 °C vacuum oven for 12 h. The pink catalytic material was named as Co-MOF-S.
2
.2.2. Synthesis of Co-MOF-R-t
The rotary method was used for synthesizing Co-MOF. In a typical experiment, 6
mmol of cobalt acetate tetrahydrate (Co(Ac) ·4H O), 6 mmol of terephthalic acid
2
2
(
H BDC) and 6 mmol of hydrophoric acid (HF, 40%) were dissolved in deionized
2
water (60 mL), then stirred well and placed in a 100 mL reactor lined with a Teflon
liner. After being sealed, the hydrothermal synthesis was conducted in a rotating
crystallization reactor, which was then crystallized at different speeds (56-150 rpm)
and different time (2-24 h) with the crystallization temperature of 200 °C . After the
crystallization reaction, the solution was cooled down to room temperature and
filtered. The solid samples were washed with deionized water several times. Then the
solid samples were washed with DMF for 12 h at 60 °C . The samples were filtered
and dried in an 80 °C vacuum oven for 12 h. Thus-obtained samples were denoted as

Page 5 of 22
New Journal of Chemistry
1
2
3
4
5
6
7
8
9
View Article Online
DOI: 10.1039/D0NJ03269G
Co-MOF-R-t（R = 56, 80, 100, 120, 150 rpm, t = 24, 12, 6, 3, 2 h, where t is the
synthesis time required at different speeds.)
2
.3. Characterizations
Powder X-ray diffraction (XRD) was performed on a Bruker D8A25
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
diffractometer with CuKα radiation (λ = 1.54184 Å) operating at 25 mA and 30 kV.
Scanning electron image (SEM) was collected on a JEOL (JSM6700F) at an
accelerating voltage of 15 kV. Fourier transform infrared (FTIR) spectrum was
analyzed on an OPUS Fourier Transform Infrared Spectrophotometer with a scanning
-1
range of 400-4000 cm . ICP analysis was conducted by inductively coupled
plasma-atomic emission spectroscopy (Plasma-Spec-II spectrometer). The test
instrument for solid UV-visible spectroscopy was the Shimadzu UV-2550 UV
−
1
spectrophotometer with a scanning wavelength of 800-200 cm . Thermal gravimetric
analysis (TGA) was carried out with a Perkin Elmer thermo analyzer under nitrogen
atmosphere, the heating rate was 10 °C/min and the test range was 30-800 °C . The
samples were dried prior to testing and 5-10 mg samples were taken for testing.
2.4. Catalyst performance evaluation
In a typical reaction, 3 mmol α-pinene, 0.3 mmol CHP, 30 mg catalyst and 10 g
DMF solvent were in turn added to 50 mL double-port flask, for which dry air was
then pumped into the flask at a flow rate of 40 mL/min. The flask was heated and
stirred in a water bath pot at a certain temperature. After the reaction was completed,
the mixture was extracted and centrifuged to remove solvent and solid catalyst. The
content of product and substrate was analyzed by gas chromatography (FL9720) using
flame ionization detector (FID).
3
. Results and discussion
3
.1 Structure description
The preparation route and structural characteristics of the Co-MOF material were
shown in Scheme 1 and Fig. 1. Fig. 1(a) was the powder diffraction pattern of the
Co-MOF material synthesized by the rotary hydrothermal crystallization method at
different rotation speeds and the static hydrothermal crystallization method. The

New Journal of Chemistry
Page 6 of 22
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
View Article Online
039/D0NJ03269G
e
characteristic signal peak of the diffraction peaks was completely consistent
D
w
O
i
I:
t
1
h
0.1
t
h
3
9-41
literature,
it showed that the crystalline structure of the synthesized materials was
identical to that reported in the literature. It can be seen from the figure that the
materials synthesized by different methods maintain the crystal structure of Co-MOF
and had the same characteristic diffraction peaks, which indicated that the MOF
material with better crystal form could be successfully synthesized by the rotary
method. It can be found that when the rotation speed was 150 rpm, only 2 h was
required to synthesize Co-MOF-150-2 material with complete crystal form. Fig. 1(b)
was a powder XRD pattern of the Co-MOF-150-t material synthesized at different
time. It can be seen from the figure that the Co-MOF material was synthesized in a
shorter time of 0.5 h, but the crystallinity was poor. With the extension of
crystallization time, the crystallinity of MOF materials gradually increased; when the
crystallization time was extended to 2 h, the MOF material with high crystallinity
could be obtained. Therefore, the rotation speed of 150 rpm and the crystallization
time of 2 h were the most appropriate synthesis conditions.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Scheme. 1 Preparation route of Co-MOF catalyst by different methods.

Page 7 of 22
New Journal of Chemistry
1
2
3
4
5
6
7
8
9
View Article Online
DOI: 10.1039/D0NJ03269G
(a)
(b)
Co-MOF-150-2
Co-MOF-150-2
Co-MOF-120-3
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Co-MOF-100-6
Co-MOF-80-12
Co-MOF-150-1.5
Co-MOF-56-24
Co-MOF-S
Co-MOF-150-1
Co-MOF-150-0.5
5
10
15
20
25
30
5
10
15
20
25
30
2 ()
2 ()
Fig. 1. XRD patterns of Co-MOF: a) different hydrothermal crystallization methods,
b) different crystallization time at 150 rpm.
The infrared spectra also proved that the rotary crystallization method
successfully synthesized Co-MOF with good crystallinity in a short time. Fig. 2 was
the IR spectra of ligand H BDC and Co-MOF material synthesized under different
2
-1
rota-crystallization methods. The absorption peak at 1685 cm in the Fig. 2 was
attributed to the -COOH characteristic peak of the ligand H BDC. It can be found that
2
-1
the absorption peak at 1685 cm was not found in the materials synthesized by static
hydrothermal method and rota-crystallization method. At the same time, it was found
that the MOF materials synthesized by different crystallization methods showed the
-
1
same characteristic vibration absorption peaks in the range of 1300~1700 cm .
-1
-1
Among those, 1583 cm and 1500 cm belonged to the asymmetric stretching
vibration peak of the MOF skeleton structure -(O-C-O)- group, and the absorption
-1
-1
peaks at 1404 cm and 1365 cm belonged to -(O-C-O)- based symmetrical
stretching vibration peak of the mass. These results indicated that the carboxyl group
of H BDC had a strong coordination with metallic cobalt, and that the Co-MOF
2
material synthesized by the rotary method had the same chemical composition as the
static hydrothermally synthesized material. Fig. S1 showed the UV spectra of
Co-MOF materials synthesized by static hydrothermal and rota-crystallization method.
The broad peak at 504 nm and the shoulder peak at 624 nm were assigned to the UV
2
+
characteristic peak of the six-coordinated Co . The materials synthesized under

New Journal of Chemistry
Page 8 of 22
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
View Article Online
039/D0NJ03269G
o
different synthesis conditions had the same spectrum, and the UV results w
D
e
O
r
I
e
: 10
a
.1
l
s
consistent with the results of IR analysis.
1583
1365
Co-MOF-150-2
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Co-MOF-120-3
Co-MOF-100-6
Co-MOF-80-12
Co-MOF-56-24
Co-MOF-S
H BDC
2
2000
1800
1600
1400
1200
1000
-1
Wavenumber (cm )
Fig. 2. IR spectra of Co-MOF synthesized by different hydrothermal crystallization
methods.
Fig. 3 showed the thermal stability curves of the Co-MOF materials synthesized
under different crystallization conditions. It can be clearly seen from the figure that
the weight loss occurring at 30-200 °C was the first stage, mainly due to the weight
loss of water and DMF molecules. There was no significant weight loss at 200-400 °C ,
indicating that the MOF material was stable in this temperature range. In the second
stage of weight loss, the apparent weight loss (49.2%) occurred at 400-520 °C , which
was attributed to the weight loss of the ligand, it was indicated that the skeleton of the
MOF material collapsed. No significant weight loss occurred at the temperature above
5
20 °C . At the same time, it was found that the thermogravimetric curves of the
synthesized MOF materials under different crystallization conditions were the same,
which indicated that the synthesized materials with different crystallization methods
had the same stability.

Page 9 of 22
New Journal of Chemistry
1
2
3
4
5
6
7
8
9
View Article Online
DOI: 10.1039/D0NJ03269G
1
00
90
8
7
6
5
0
0
0
0
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
40
Co-MOF-150-2
3
0
Co-MOF-120-3
Co-MOF-100-6
Co-MOF-80-12
Co-MOF-56-24
Co-MOF-S
100 200 300 400 500 600 700 800
Temperature (C)
Fig. 3. TG curves of Co-MOF synthesized by different hydrothermal crystallization
methods.
Fig. 4 showed the SEM images of Co-MOF material synthesized at different
rotation speed and crystallization time. On the whole, the samples all showed a strip
shape. Among them, the shape of the sample synthesized under static condition was
not uniform, and the surface of the material synthesized by the rota-crystallization
method was more flat and more uniform. At relatively low speed (56 rpm), the width
of the strip sample was approximately 4 μm (Fig. 4b). At relatively high rotation
speeds (100-150 rpm), the width of the resulting MOF material becomes smaller and
the thickness becomes thinner, the Co-MOF-150-2 (Fig. 4f) synthesized at 150 rpm
for 2 h was between 0.5 and 2.5 μm wide. The above results showed that the
rota-crystallization method affected the morphology of the material, and the rotary
method could also make the material size smaller and the dispersion more uniform.
The elemental composition of the two synthesized materials was shown in Table 1. It
can be seen from the Table 1 that the proportions of elements in Co-MOF materials
synthesized by the rotary method and the static hydrothermal method were similar,
and the Co content in the Co-MOF-150-2 material was the lowest (28.9%).

New Journal of Chemistry
Page 10 of 22
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
View Article Online
DOI: 10.1039/D0NJ03269G
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Fig. 4. SEM images of Co-MOF (a: Co-MOF-S, b: Co-MOF-56-24, c:
Co-MOF-80-12, d: Co-MOF-100-6, e: Co-MOF-120-3, f: Co-MOF-150-2).
Table 1 Characterization results of the materials.
a
b
C
Co
Sample
content
wt%)
content
(wt%)
(
Co-MOF-S
30.9
31.2
32.2
31.6
31.5
30.9
29.2
29.5
29.4
29.7
29.6
28.9
Co-MOF-56-24
Co-MOF-80-12
Co-MOF-100-6
Co-MOF-120-3
Co-MOF-150-2
a
b
Measured by elemental analysis; Measured by ICP-AES.
The compositions and elemental oxidation states of Co-MOF-150-2 were
characterized by XPS spectrum (Fig. S2). XPS survey spectrum (Fig. S2a) proved the
presence of C, O, and Co elements. Obviously, Co-MOF-150-2 was mainly composed
of C (283.8 eV), O (532.8 eV) and Co (781.3 eV) elements. Fig. S2b showed a high
resolution XPS spectrum of Co 2p for Co-MOF-150-2. The binding energies of Co
2
p and Co 2p in Co-MOF-150-2 were 781.3 and 797.2 eV, which was attributed
3/2 1/2
2+
to characteristic peaks of Co , indicating that all cobalt in Co-MOF-150-2 existed in
2
+
42
the form of Co -coordinated state.

Page 11 of 22
New Journal of Chemistry
1
2
3
4
5
6
7
8
9
View Article Online
DOI: 10.1039/D0NJ03269G
3
.2 Aerobic epoxidation of α-pinene
As a heterogeneous catalytic material, Co-MOF materials were used in the
epoxidation of α-pinene to detect the catalytic activity. Fig. S3 and Fig. S4 present the
corresponding NMR data of the main epoxy product 2,3-Epoxypinane. Table 2
showed the epoxidation results of α-pinene over Co-MOF prepared by different
methods. It can be seen from the table that the Co-MOF catalyst showed excellent
catalytic activity for the epoxidation reaction, in which the Co-MOF-150-2 material
synthesized by rotary method had the best catalytic activity. The MOF materials
prepared by static crystallization (24 h, entry 1) and rotary crystallization at 150 rpm
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
(
2 h, entry 6) showed superior catalytic activity to other materials. The substrate
α-pinene (entry 6) was almost converted completely, and the yield of epoxide was
high (99.5% and 95.7%, respectively). At the same time, it can be clearly seen from
Fig. S5 that the catalytic efficiency of Co-MOF-150-2 was always higher than that of
Co-MOF-S in different reaction periods. The reason may be that when the rotating
speed was 150 rpm and the crystallization time was 2 h, the lamellar layer was thinner
and more uniform, much beneficial to the exposure of active sites, thus to the
enhancement of the catalytic activity. .
Table 2 Results of the catalytic epoxidation of α-pinene over various catalysts.
Conversion
%)
Selectivity
(%)
Yeild
(%)
Entry
Catalyst
(
1
2
Co-MOF-S
93.3
94.8
90.3
Co-MOF-56-24
90.7
96.3
87.3
3
4
5
6
Co-MOF-80-12
Co-MOF-100-6
Co-MOF-120-3
Co-MOF-150-2
90.1
90.5
90.8
99.5
95.0
91.9
92.1
96.2
85.6
83.2
83.6
95.7
Reaction conditions: catalyst (30 mg), α-Pinene (3 mmol), CHP (0.3 mmol), DMF (10
g), flowrate of air (40 mL/min), temperature (90 C), time (5 h).
Table 3 showed the epoxidation results of α-pinene catalyzed by Co-MOF-150-t
prepared at different crystallization time. It can be seen from the table that the
Co-MOF-150-t catalyst had highly catalytic activity for α-pinene epoxidation.
However, the catalytic activity of the MOF materials prepared at 150 rpm and 2 h

New Journal of Chemistry
Page 12 of 22
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
View Article Online
(
entry 4) was superior to that of the other materials. The substrate α-pin
D
e
O
n
I
e
: 10
w
.1039/D0NJ03269G
as
basically converted completely, and the yield of epoxide was as high as 95.7%. The
XRD result in Fig. 1 (b) also showed that when the crystallization time was less than
2
h, the crystallinity of the Co-MOF material obtained at 150 rpm was significantly
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
lower than that of the material at 2 h, indicating that the crystallization of Co-MOF
material was incomplete at this time.
Table 3 Results of the catalytic epoxidation of α-pinene over MOF-150-t.
Conversion
Selectivity
Yield
(%)
Entry
Catalyst.
(%)
(%)
1
2
3
4
Co-MOF-150-0.5
Co-MOF-150-1.0
Co-MOF-150-1.5
Co-MOF-150-2.0
82.8
88.5
90.1
99.5
89.8
90.1
89.5
96.2
74.4
79.7
80.6
95.7
(a)
5
Co-MOF-150-2.0
88.4
77.5
68.5
Reaction conditions: catalyst (30 mg), α-Pinene (3 mmol), CHP (0.3 mmol),
DMF (10 g), flowrate of air (40 mL/min), temperature (90 C), time (5 h).
(a)
Substrate (6 mmol).
Conversion (%)
Yield (%)
100
8
6
4
2
0
0
0
0
0
5
0
60
70
80
90
100
110
Reaction temperature (C)
Fig. 5. Effect of reaction temperature on the epoxidation of α-pinene. Reaction
conditions: catalyst (Co-MOF-150-2, 30 mg), α-pinene (3 mmol), CHP (0.3 mmol),
DMF (10 g), flowrate of air (40 mL/min), time (5 h).
The effect of the reaction temperature on the epoxidation of α-pinene over
Co-MOF-150-2 was studied as shown in Fig. 5. It can be seen when the reaction
temperature was raised from 60 to 80 °C , the conversion of α-pinene increased rapidly,
in which the conversion increased from 13.4% to 90.9%; at the same time, the yield
of the epoxide compound was also increased from 11.6% to 84.1%. When further
increasing the reaction temperature to 90 °C, the conversion of α-pinene increased

Page 13 of 22
New Journal of Chemistry
1
2
3
4
5
6
7
8
9
View Article Online
from 90.9% to 99.5%, and the yield of the target product increased to 95.7%
reaction temperature continued to rise to 100 °C, the yield of epoxide decreased to
1.3%, possibly due to the increase of side reaction during the reaction process.
D
.
O
A
I: 1
s
0.1
t
039/D0NJ03269G
h
e
7
Therefore, the optimal reaction temperature was 90 °C.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Fig. 6 showed the effect of reaction time on the epoxidation of α-pinene. In the
initial stage of the reaction (the reaction time was less than 2 h), the conversion of
α-pinene was low. After one hour of the reaction, only 29.2 % of α-pinene was
converted. The epoxidation reaction began to accelerate while extending the reaction
time. When reaction time was extended to 5 h, 99.5% of α-pinene conversion and
9
5.7% of epoxide yield was obtained. As the reaction time was further extended to 7 h,
the conversion of α-pinene remained unchanged, but the yield of epoxide decreased
sharply from 95.7% to 72.2%. This indicated that as the reaction time was further
extended, the epoxide was further transformed into other by-products (enol and
enone), which led to the decrease in the yield of the epoxide. Therefore, the optimal
reaction time for α-pinene epoxidation was 5 h.
Conversion (%)
Yield (%)
1
00
8
6
4
2
0
0
0
0
0
0
1
2
3
4
5
6
7
8
Reaction time (h)
Fig. 6. Effect of reaction time on the epoxidation of α-pinene. Reaction conditions:
catalyst (Co-MOF-150-2, 30 mg), α-pinene (3 mmol), CHP (0.3 mmol), DMF (10 g),
flowrate of air (40 mL/min), temperature (90 C).
The results in Fig. S6 have reflected the effect of catalyst amount on the
epoxidation reaction. It can be seen from the results that when the amount of catalyst
was increased from 5 to 30 mg, the conversion of α-pinene rapidly increased from
3
8.8% to 99.5%, and the yield of epoxide increased from 36.6% to 95.7%. As

New Journal of Chemistry
Page 14 of 22
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
View Article Online
increasing the amount of catalyst to 40 mg, the conversion remainedDO
a
I:
l
1
m
0.1
o
0
st
39/D0NJ03269G
unchanged, but the yield of epoxide dropped rapidly from 95.7% to 83.5%. This was
because the excess catalyst caused side reactions at the same time. It indicated that an
appropriate amount of catalyst contributed to the progress of the catalytic reaction and
product distribution, the optimum catalyst amount was 30 mg. The effect of the
initiator CHP amount on the epoxidation of α-pinene was studied in Fig. S7. With the
increased of the initiator amount, the conversion of α-pinene increased, and the yield
of epoxide product first increased and then decreased. When no initiator was added,
only 70.2% of α-pinene was converted. As the amount of CHP was increased to 0.3
mmol, the conversion was 99.5%, and the yield of the epoxide was 95.7%. With
increasing the amount of CHP to 0.6 mmol, the yield of the epoxide was reduced to
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
7
9.8%, because excessive initiators also caused the occurrence of side reactions.
Solvents had a great influence on the epoxidation reaction of α-pinene. The
reaction results were shown in Fig. S8. When polar solvents such as 1,4-dioxane and
methyl isobutyl ketone (MIBK) were used as the reaction solvent, the conversion of
α-pinene was 46.4% and 23.2%, respectively. When toluene was used as the reaction
solvent, the amount of oxygen molecules involved in the epoxidation reaction
decreased due to its weak capacity of dissolution oxygen, which eventually led to the
low conversion of α-pinene. When the strong polar solvents DMF and cyclohexanone
were used as the reaction solvents, they had higher conversion of α-pinene than other
solvents, for which the conversion of α-pinene was 99.5% and 91.5%, respectively.
However, the selectivity of the latter target epoxide was only 8.2% when
cyclohexanone used as the solvent. When DMF used as the reaction solvent, the
active center formed by Co ion coordination with DMF in the catalyst could activate
oxygen molecules in the air, it could promoted the dispersion of the catalyst in the
reaction system, thereby facilitating the smooth progress of olefin epoxidation.
The effect of the substrate amount on the epoxidation of α-pinene was shown in
Fig. S9. When the molar amount of the substrate was increased from 1.0 to 3.0 mmol,
the reaction substrate also could be completely converted. When the molar amount of
the substrate was increased to 6.0 mmol, the conversion of α-pinene and the yield of

Page 15 of 22
New Journal of Chemistry
1
2
3
4
5
6
7
8
9
View Article Online
epoxide decreased to 88.4% and 68.5%, respectively. With increasing the amDO
o
I
u
: 1
n
0.
t
10
o
39/D0NJ03269G
f
substrate to 8.0 mmol, the conversion of α-pinene and the yield of epoxide were
greatly reduced to 52.1% and 35.3%. The above research results indicated that when
the molar amount of the substrate was less than 6.0 mmol, both the conversion of
α-pinene and the yield of epoxide were high.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Under the same reaction conditions, the effects of different oxidants on the
catalytic epoxidation of α-pinene were investigated, as shown in Table 4. It was found
that the epoxidation reaction did not occur when no oxidizing agent was added (entry
1
). When air was used as the oxidizing agent (entry 2), the conversion of α-pinene
was 75.6 %, much higher than those of pure oxygen (22.9 %, entry 4), pure hydrogen
peroxide (15.9 %, entry 5), cumene hydroperoxide (28.7 %, entry 6) and tert-butyl
hydroperoxide (20.5 %, entry 7). When the flowrate of air increased to 50 ml/min, the
conversion of α-pinene was 78.5%, and the selectivity of epoxide dropped to 84.7%
(entry 3). In order to improve the conversion of α-pinene, different initiators were
introduced into the reaction system. When an appropriate amount of hydrogen
peroxide was added to the reaction system, the conversion of α-pinene was 81.7%
(entry 8) and the yield of epoxide was 75.4%. The use of hydrogen peroxide did not
significantly promote the reaction, possibly due to the fact that hydrogen peroxide
was easily decomposed at 90 °C. When CHP and TBHP (entry 9-10) were used as the
initiators, the conversion of α-pinene was further improved, which reached 99.5% and
9
3.5%, respectively. When CHP was used as initiator in oxygen system, the
conversion of α-pinene was only 34.2% (entry 11) and the yield of epoxide was
8.2%. It can be concluded that when air was used as the oxidant, the addition of
2
small amounts of CHP or TBHP would beneficially promote the epoxidation reaction
of α-pinene.
Table 4 Results of the catalytic epoxidation of α-pinene with different oxidants.
Selectivity
Yield
(%)
Entry
Oxidant
Conversion (%)
(%)
1
2
3
4
None
Air



75.6
78.5
22.9
95.6
84.7
83.5
72.3
66.5
19.1
a
Air
b
O2

New Journal of Chemistry
Page 16 of 22
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
c
View Article Online
13.4 DOI: 10.1039/D0NJ03269G
5
6
H O
15.9
28.7
20.5
81.7
99.5
93.5
34.2
84.2
79.8
85.9
92.3
96.2
96.5
82.4
2
2
c
CHP
22.9
17.6
75.4
95.7
90.2
28.2
c
7
TBHP
Air+H O
8
2
2
9
Air+CHP
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
10
Air+TBHP
b
11
O +CHP
2
Reaction conditions: catalyst (Co-MOF-150-2, 30 mg), α-pinene (3 mmol),
α-pinene/initiator=10; DMF (10g), flowrate of air (40 mL/min), temperature (90

C), time (5h).
a
flowrate of air: 50 mL/min.
flowrate of O : 40 mL/min.
b
2
c
α-pinene/initiator=1.
In order to evaluate the stability of the catalyst, we performed catalyst recycling
tests under the optimal reaction conditions, as shown in Fig. 7. After each reaction,
the catalyst was separated from the reaction system by centrifugation, and then
washed several times with acetone, dried in an oven overnight, and finally subjected
to the next epoxidation reaction under the same reaction conditions. The results of the
recycling performance test showed that there was no significant decrease in catalytic
activity after the catalyst was reused 5 times. The results of recycling tests indicated
that the catalyst had high reusability, as proven by the XRD pattern. Fig. 8 shows that
the crystal phase and peak intensity did not change significantly after repeated use,
meaning high stability of the catalyst. The recycling stability experiments of
Co-MOF-150-2 and Co-MOF-S for the epoxidation of α-pinene (6 mmol) were also
conducted. It can be seen from Fig. S10a that the Co-MOF-150-2 material had good
catalytic activity and the conversion rate and yield were basically maintained during
the recycling process, indicative of high stability of the Co-MOF-150-2 material.
However, Fig. S10b presents that the catalytic activity of the Co-MOF-S material
decreased significantly during the recycling process. The reason may be that the
lamellar layer of Co-MOF-150-2 material was thinner and more uniform, much
beneficial to the enhancement of the catalytic stability.

Page 17 of 22
New Journal of Chemistry
1
2
3
4
5
6
7
8
9
View Article Online
DOI: 10.1039/D0NJ03269G
Conversion (%)
Yield (%)
1
00
80
6
0
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
40
2
0
0
1
2
3
4
5
Numbers of cycles
Fig. 7. Recycling tests of catalyst. Reaction conditions: catalyst (Co-MOF-150-2),
α-pinene (3 mmol), α-pinene/initiator=10; DMF (10g), flowrate of air (40 mL/min),
temperature (90 C), time (5 h).
1
0000
8000
Used 5 times
6
000
000
4
2000
0
Fresh
25
5
10
15
20
30
2()
Fig. 8. Powder X-ray diffraction patterns of fresh and used catalysts.
Finally, the applicability of Co-MOF-150-2 in the epoxidation of other olefins
was discussed (Table 5). When the substrates were styrene and β-pinene, the catalyst
also showed good catalytic activity, the conversion was 78.5% and 70.2% (entry 1).
At the same time, the catalyst also showed highly catalytic activity when catalyzing
other cyclic olefins. After 5 h of reaction, the conversion of cyclooctene was 78.5%.
Compared with cyclooctene, cyclododecene showed low catalytic activity (with
1
9.6% conversion at 12 h) under the same conditions. It was found from Table 5 that
the catalyst exhibited good catalytic activity for linear olefin 1-decene. After 12 h of
reaction, 87.2% of 1-decene was transformed into epoxide product (entry 5). However,

New Journal of Chemistry
Page 18 of 22
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
View Article Online
further increasing the length of the carbon chain to 1-dodecene led to a quickDO
d
I
r
:
o
10
p
.10
o
39/D0NJ03269G
f
olefin conversion to 15.8% (entry 6).
Table 5 The epoxidation of other olefins with air over Co-MOF-150-2.
Reaction time Conversion
Epoxide
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Entry
1
Substrate
(%)
Yield (%)
(h)
5
70.8
42.5
2
3
4
5
78.5
19.6
78.5
99.5
79.8
70.0
12
5
5
6
12
12
87.2
15.8
99.4
97.2
Reaction conditions: catalyst (Co-MOF-150-2, 30 mg), olefin (3 mmol), CHP (0.3
mmol), DMF (10 g), flowrate of air (40 mL/min), temperature (90 C), time (5 h).
4
. Conclusion
In summary, Co-MOF materials with high crystallinity and catalytic activity
were rapidly synthesized by the rotary method. In this work, the effects of different
synthesis methods and conditions on the activity were discussed. It was found that
Co-MOF materials could be successfully synthesized in 2 h at 150 rpm. The
Co-MOF-150-2 catalyst was used to catalyze the epoxidation of α-pinene, showing
excellent catalytic activity, for which the conversion of α-pinene and the yield of
epoxide were higher than 95%. Thus-synthesized Co-MOF material had excellent
recyclable stability and could recycle 5 times without significant decrease in catalytic
activity. This work has developed a novel method for synthesizing MOFs materials
with highly catalytic activity, which not only broadens the synthesis method, but also
provides a broad application prospect for other fields.
Conflicts of interest
There are no conflicts of interest to declare.

Page 19 of 22
New Journal of Chemistry
1
2
3
4
5
6
7
8
9
View Article Online
DOI: 10.1039/D0NJ03269G
Acknowledgments
Financial supports from the National Natural Science Foundation of China
21673069, 21503074), Hubei University Student Innovation and Entrepreneurship
(
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Foundation of China (S201910512016), and Applied Basic Frontier Project of Wuhan
Science and Technology Bureau (2019010701011415).
References
1
2
3
4
O.M. Yaghi, G.M. Li, H.L. Li, Nature. 1995, 378, 703-706.
M. Eddaoudi, H.L. Li, O.M. Yaghi, J. Am. Chem. Soc. 2000, 122, 1391-1397.
S. Kitagawa, R. Kitaura, S.I. Noro, Angew. Chem. Int. Edit. 2004, 43, 2334-2375.
H.C. He, L. Hashemi, M.L. Hu, A. Morsali, Coordin. Chem. Rev. 2018, 376,
3
19-347.
5
6
E.J. Carrington, C.A. McAnally, A.J. Fletcher, S.P. Thompson, M. Warren, L.
Brammer, Nature Chem. 2017, 9, 882-889.
C.X. Chen, Z.W. Wei, J.J. Jiang, S.P. Zheng, H.P. Wang, Q.F. Qiu, C.C. Cao, D.
Fenske, C.Y. Su, J. Am. Chem. Soc. 2017, 139, 6034−6037.
7
8
A.J. Rieth, Y. Tulchinsky, M. Dinca, J. Am. Chem. Soc. 2016, 138, 9401-9404.
N.D. Rudd, H. Wang, E.M.A. Fuentes-Fernandez, S.J. Teat, F. Chen, G.S. Hall,
Y.J. Chabal, J. Li, ACS Appl. Mater. Interfaces. 2016, 8, 30294-30303.
A. Ranft, F. Niekiel, I. Pavlichenko, N. Stock, B.V. Lotsch, Chem. Mater. 2015,
27, 1961-1970.
9
1
1
1
0 W.P. Lustig, S. Mukherjee, N.D. Rudd, A.V. Desai, J. Li, S.K. Ghosh, Chem. Soc.
Rev. 2017, 46, 3242-3285.
1 R. Ameloot, A. Liekens, L. Alaerts, M. Maes, A. Galarneau, B. Coq, G. Desmet,
B.F. Sels, J.F.M. Denayer, D.E.D. Vos, Eur. J. Inorg. Chem. 2010, 24, 3735-3738.
2 L. Sun, C.H. Hendon, M.A. Minier, A. Walsh, M. Dincă, J. Am. Chem. Soc. 2015,
1
37, 6164-6167.

New Journal of Chemistry
Page 20 of 22
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
View Article Online
DOI: 10.1039/D0NJ03269G
13 D. Maspoch, D. Ruiz-Molina, K. Wurst, C. Roviraa, J. Veciana, Chem. Commun.
004, 10, 1164-1165.
4 J. Yang, X.J. Chen, Y.S. Li, Q.X. Zhuang, P.F. Liu, J.L. Gu, Chem. Mater. 2017,
9, 4580-4589.
5 K.Y. Zeng, M.K. Zhang, M.Y. Peng, D. Gong, X.Z. Zhang, Adv. Funct. Mater.
018, 28, 1705451.
2
1
1
1
1
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
2
2
6 Y. Zhang, F.M. Wang, E.G. Ju, Z. Liu, Z.W. Chen, J.S Ren, X.G. Qu, Adv. Funct.
Mater. 2016, 26, 6454-6461.
7 B.L. Chen, L.B. Wang, Y.Q. Xiao, F.R. Fronczek, M. Xue, Y.J. Cui, G.D. Qian,
Angew. Chem. Int. Edit. 2009, 48, 500-503.
18 I. Liang, Z.B. Liang, R.Q Zou, Y.L. Zhao, Adv. Mater. 2017, 29, 1701139.
19 B.W. Anson, S. Ghosh, S. Hammes-Schiffer, S.S. Stahl, J. Am. Chem. Soc. 2016,
138, 4186-4193.
2
0 M.L. Hu, S.A.A. Razavi, M. Piroozzadeh, A. Morsali, Inorg. Chem. Front. 2020,
, 1598-1632.
7
2
2
2
1 Y.Y. An, L.P. Lu，M.L. Zhu, Acta Cryst. 2018, C74, 418-423.
2 N. Stock, S. Biswas, Chem. Rev. 2012, 112, 933-969.
3 K.Y. Leng, Y.Y. Sun, X.L. Li, S. Sun, W. Xu, Cryst. Growth. Des. 2016, 16,
1168-1171.
2
4 A.M. Joaristi, J.J. Alcañiz, P.S. Crespo, F. Kapteijn, J. Gascon, Cryst. Growth.
Des. 2012, 12, 3489-3498.
2
5 S.D. Worrall, H. Mann, A. Rogers, M.A.Bissett, M.P. Attfield, R.A.W. Dryfe,
Electrochim Acta. 2016, 197, 228-240.
26 S.H. Jhung, J.H. Lee, J.S. Chang, B. Korean, Chem. Soc. 2005, 26, 880-881.
27 Q.H. Xia, H.Q. Ge, C.P. Ye, Z.M. Liu, K.X. Su, Chem. Rev. 2005, 105,
1
603-1662.
2
8 R. Neumann, M. Dahan, Nature. 1997, 388, 353.

Page 21 of 22
New Journal of Chemistry
1
2
3
4
5
6
7
8
9
View Article Online
DOI: 10.1039/D0NJ03269G
29 C.L. Hill, Nature. 1999, 401, 436.
3
0 R.K. Castellano, D.M. Rudkevich, J. Rebek, J. Am. Chem. Soc. 1996, 118,
319-1329.
1
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
3
1 A.T. Gallagher, J.Y. Lee, V. Kathiresan, J.S. Anderson, B.M. Hoffman, T. David
Harris, Chem. Sci. 2018, 9, 1596-1603.
3
2 Y.S. Raupp, C. Yildiz, W. Kleist, M.A.R. Meier, Appl. Catal. A Gen. 2017, 546,
1
-6.
33 A.P. Zhang, L.Q. Li, J. Li, Y. Zhang, S. Gao, Catal. Commun. 2011, 12,
1183-1187.
3
3
3
4 J. Zhang, A.V. Biradar, S. Pramanik, T.J. Emge, T. Asefa, J. Li, Chem. Commun.
012, 48, 6541-6543.
2
5 G.J. Zhang, H. Li, F.F. Zhao, H.L. Hu, H. Huang, H.T. Li, X. Han, R.H. Liu, H.
Dong, Y. Liu, Z.H. Kang, Dalton. Trans. 2013, 42, 9423-9427.
6 J.F. Hui, H. M. Chu, W.L. Zhang, Y. Shen, W.Z. Chen, Y. Hu, W. Liu, C. Gao,
S.H. Guo, G.W. Xiao, S. Li, Y. Fu, D.D. Fan, W.N. Zhang, F.W. Huo,
Nanoscale. 2018, 10, 8772-8778.
37 H.F. Zhang, G.Q. Li, R.F. Nie, X.H. Lu, Q.H. Xia, J. Mater. Sci. 2019, 54,
7529-7540.
38 D. Zhou, T,J. Zhang, Q.H. Xia, Y.R. Zhao, K.X. Lv, X.H. Lu, R.F. Nie, Chem. Sci.
2
016, 7, 4966-4972.
3
9 M. Anbia, S. Sheykhi, J. Ind. Eng. Chem. 2013, 19, 1583-1586.
0 T. Rodenas, I. Luz, G. Prieto, B. Seoane, H. Miro, A. Corma, F. Kapteijn, F.X.
Llabrés i Xamena, J. Gascon, Nat. Mater. 2015, 14, 48-55.
4
4
4
1 S.L. Zhao, Y. Wang, J.C. Dong, C.T. He, H.J. Yin, P.F. An, K. Zhao, X.F. Zhang,
C. Gao, L.J. Zhang, J.W. Lv, J.X. Wang, J.Q. Zhang, A.M. Khattak, N.A. Khan,
Z.X. Wei, J. Zhang, S.Q. Liu, H.J. Zhao, Z.Y. Tang, Nat. Energy. 2016, 1, 16184.
2 P.P Tao, X.H. Lu, H.F. Zhang, R. Jing, F.F. Huang, S. Wu, D. Zhou, Q.H. Xia,
Mol. Catal. 2019, 463, 8-15.

New Journal of Chemistry
Page 22 of 22
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
View Article Online
DOI: 10.1039/D0NJ03269G
Graphical Abstract
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
A method was proposed for synthesizing Co-MOF by rapidly rotating
hydrothermal crystallization. When the rotation speed was 150 rpm, only 2 h of
crystallization time was needed to synthesize Co-MOF-150-2 material quickly with
high crystallinity and stability. Catalytic conversion of α-pinene reached the highest
over the catalyst of Co-MOF-150-2, in which the conversion of α-pinene was 99.5%
and the yield of 2,3-epoxypinane was 95.7%.