catalysts

Article
Liquid-Phase Catalytic Oxidation of Limonene to
Carvone over ZIF-67(Co)
Yizhou Li, Yepeng Yang, Daomei Chen, Zhifang Luo, Wei Wang, Yali Ao, Lin Zhang,
Zhiying Yan * and Jiaqiang Wang *
National Center for International Research on Photoelectric and Energy Materials, Yunnan Provincial
Collaborative Innovation Center of Green Chemistry for Lignite Energy, Yunnan Province Engineering Research
Center of Photocatalytic Treatment of Industrial Wastewater, The Universities’ Center for Photocatalytic
Treatment of Pollutants in Yunnan Province, School of Chemical Sciences & Technology, Yunnan University,
Kunming 650091, China; [email protected] (Y.L.); [email protected] (Y.Y.);
[email protected] (D.C.); [email protected] (Z.L.); [email protected] (W.W.);
[email protected] (Y.A.); [email protected] (L.Z.)
* Correspondence: [email protected] (Z.Y.); [email protected] (J.W.);
Tel.: +86-871-6503-1567 (Z.Y.); +86-871-6503-1567 (J.W.)




Received: 15 March 2019; Accepted: 16 April 2019; Published: 21 April 2019


Abstract: Liquid-phase catalytic oxidation of limonene was carried out under mild conditions,
and carvone was produced in the presence of ZIF-67(Co), cobalt based zeolitic imidazolate framework,
as catalyst, using t-butyl hydroperoxide (t-BHP) as oxidant and benzene as solvent. As a heterogeneous
catalyst, the zeolitic imidazolate framework ZIF-67(Co) exhibited reasonable substrate–product
selectivity (55.4%) and conversion (29.8%). Finally, the X-ray diffraction patterns of the catalyst before
and after proved that ZIF-67(Co) acted as a heterogeneous catalyst, and can be reused without losing
its activity to a great extent.

Keywords: liquid-phase catalytic oxidation; limonene; carvone; zeolitic imidazolate frameworks

1. Introduction
As we know, the reaction about the allylic oxidation plays a critical role in developing fine
chemicals with high additional value from biomass, and has great value in the synthesis of unsaturated
aldehydes and ketones [1,2]. Carvone is a main ingredient, derived from plant essential oils, used
for cosmetics and food flavors, and is also used in the preservation of meat, fruits, and vegetables
because it has good antioxidant activity, analgesic effects, and antibacterial effects [3,4]. In addition,
carvone is an important intermediate in industrial chemistry, where it can further be used to synthesize
carvone thioether and cyanoacetone [5]. The applicability of traditional methods of transforming
limonene to carvone through catalytic oxidation, such as epoxidation and nitrosochlorination, is limited;
largely because environmentally unfriendly reagents are often used and poisonous secondary products
are produced [6]. Compared with these methods, the use of heterogeneous catalysts has broader
applicability prospects in the allylic oxidation of cycloolefins, due to their remarkable advantages in
catalyst recovery and stability.
However, current research results show that the selectivity of the catalytic oxidation of limonene
to carvone by heterogeneous reaction has not been satisfactory. For instance, 36% substrate
conversion and 25% selectivity for carvone were obtained by using chromium-containing mesoporous
molecular sieves MCM-41 [7]. Lower than 5% selectivity for carvone was obtained by using the
[FeIII (BPMP)Cl(µ-O)FeIII Cl3 ] complex as catalyst [8]. A 21% conversion and 20% selectivity for carvone
were obtained in a reaction using Fe/EuroPh catalysts [9]. In another study, high conversion up to 93%

Catalysts 2019, 9, 374; doi:10.3390/catal9040374 www.mdpi.com/journal/catalysts

Catalysts 2019, 9, 374 2 of 13

of limonene was attained, while the selectivity for carvone was less than 7% [10]. In our previous
study, cobalt-doped mesoporous silica templated by reed leaves exhibited high substrate conversion
(100%) and relatively good product (carvone) selectivity (40.2%) for the allylic oxidation of limonene to
carvone [11].
Metal–organic frameworks (MOFs) have attracted considerable attention in catalysis and
adsorption in recent years, owing to their advantages, such as high surface areas, well-defined
structures, special metal centers, their ease of processing, and their structural diversity [12–16]. Thus,
the performance of MOF materials in this reaction has also been reported [17,18], but their application
is limited by their thermal and chemical stability [19]. However we are sure that it is valuable to use
some MOFs materials in this reaction, and this research has aroused our great interest.
Zeolitic imidazolate frameworks (ZIFs), which are constructed from tetrahedrally coordinated
divalent cations (Zn2+ or Co2+ ) linked by the uninegative imidazolate ligands, are a new class of porous
metal–organic framework (MOF) [20]. They are widely used in organic synthesis [21–25], CO2 capture
of [26], and olefin/paraffin separation [27] because of their excellent thermal and chemical stability.
They benefit from strong interactions between imidazolium salts and metal ions, which make the
frameworks of zeolitic imidazolates maintain their structural integrity even in water, and this is difficult
for other MOFs [28]. Additionally, ZIF-67 has a high-porosity zeolite structure, which is conducive
to catalytic reactions. According to our surveys, ZIFs have been widely used to catalyze different
types of organic synthesis reactions in recent years, such as cyclohexene hydrogenation [29], glycerol
esterification [30], and transesterification reactions [31].To this end, the zeolitic imidazole framework
ZIF-67(Co) was selected because ZIF-67 is easy to prepare at large scale in water under ambient
conditions without using toxic solvents, and the preparation of ZIF-67(Co) has good reproducibility.
In this continuation of our work, we successfully synthesized ZIF-67(Co) by hydrothermal
synthesis, and it displayed good catalytic properties in the catalytic oxidation of limonene. Furthermore,
the application of tert-butyl hydroperoxide (t-BHP) to the allylic oxidation of cycloolefins offers an
alternative to traditional unfriendly oxidants. In this work, the effects of solvents, oxidants, and reaction
temperature on the productivity and reaction time were investigated. Under the optimal conditions,
although the conversion of limonene was only 29.8%, we increased the selectivity for carvone to 55.4%,
which is more than that in all the literature we have been able to refer to. For comparison, the catalytic
activities of more MOFs were also investigated. This is the first report about the oxidation of limonene
to carvone over ZIF-67(Co).

2. Results and Discussion

2.1. Characterization of ZIF-67(Co)

Powder XRD patterns of the ZIF-67(Co) are shown in Figure 1. The diffraction peaks of the 2θ
values at 7.48◦ , 10.42◦ , 12.74◦ , and 18.06◦ , were assigned to the (011), (002), (112), and (222) planes of
ZIF-67, which has been reported by other researchers [20,21,29]. Figure 1 also reflects the fact that
synthetic ZIF-67(Co) is a phase-pure product. Besides, in order to compare the different catalysts’
ability about catalyzed the limonene to carvone, some other MOFs have been synthesized successfully
and their XRD patterns have been revealed in supplementary material (Figures S1–S5)
The N2 sorption experiments for the ZIF-67(Co) yielded the typical type I isotherms in Figure 2.
The Brunauer–Emmett–Teller (SBET ) and Langmuir surface areas of ZIF-67 were 1378 and 1805 m2 /g,
and the pore volume was 0.62 cm3 /g, which are near to the previously reported values [32,33]. At lower
relative pressures, the micropore in the material makes the adsorption capacity increase rapidly,
while at higher relative pressures, due to the existence of spin/large porosity nanoparticles structure,
the enhancement of adsorption capacity is lower. The pore size distribution curve was calculated by
the Horvath–Kawazoe (HK) method, which clearly showed that there were two kinds of micropores in
ZIF-67(Co). This result is similar to an earlier work [22].
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83
84 Figure 1. XRD patterns of the zeolitic imidazolate framework ZIF-67(Co).

85 The N2 sorption experiments for the ZIF-67(Co) yielded the typical type I isotherms in Figure 2.
86 The Brunauer–Emmett–Teller (SBET) and Langmuir surface areas of ZIF-67 were 1378 and 1805 m2/g,
87 and the pore volume was 0.62 cm3/g, which are near to the previously reported values [32,33]. At
88 lower relative pressures, the micropore in the material makes the adsorption capacity increase
89 rapidly, while at higher relative pressures, due to the existence of spin / large porosity nanoparticles
90 structure, the enhancement of adsorption capacity is lower. The pore size distribution curve was
91
83 calculated by the Horvath–Kawazoe (HK) method, which clearly showed that there were two kinds
92 of micropores in ZIF-67(Co).
Figure 1. XRDThis resultofisthe
patterns similar
zeolitictoimidazolate
an earlier framework
work [22]. ZIF-67(Co).
84 Figure 1. XRD patterns of the zeolitic imidazolate framework ZIF-67(Co).

85 The N2 sorption experiments for the ZIF-67(Co) yielded the typical type I isotherms in Figure 2.
86 The Brunauer–Emmett–Teller (SBET) and Langmuir surface areas of ZIF-67 were 1378 and 1805 m2/g,
87 and the pore volume was 0.62 cm3/g, which are near to the previously reported values [32,33]. At
88 lower relative pressures, the micropore in the material makes the adsorption capacity increase
89 rapidly, while at higher relative pressures, due to the existence of spin / large porosity nanoparticles
90 structure, the enhancement of adsorption capacity is lower. The pore size distribution curve was
91 calculated by the Horvath–Kawazoe (HK) method, which clearly showed that there were two kinds
92 of micropores in ZIF-67(Co). This result is similar to an earlier work [22].

93
Figure 2. N2 adsorption/desorption isotherms of ZIF-67(Co) samples at 77 K and Horvath–Kawazoe
94 Figure 2. Nsize
(HK) pore 2 adsorption/desorption isotherms of ZIF-67(Co) samples at 77 K and Horvath–Kawazoe
distribution curve.
95 (HK) pore size distribution curve.
The morphology and particle size of the samples revealed by scanning electron microscopy
96 (SEM) The
aremorphology and particle
shown in Figure 3. Thesize
SEMof the samples
picture revealed
reveals by particles
that the scanningwere
electron microscopy
submicroscopic
97 (SEM) are shown in Figure 3. The SEM picture reveals that the particles were submicroscopic
crystals with polyhedral shapes, each surface was a homogeneous quadrilateral, and the particle sizes
98 crystals with 200
ranged from polyhedral shapes,
to 500 nm. This each surfacethat
also proves wasthe
a homogeneous
as-synthesizedquadrilateral,
ZIF-67(Co) wasandcomposed
the particle
of
99 sizes ranged from
submicroscopic 200 to 500 nm. This also proves that the as-synthesized ZIF-67(Co) was composed
crystals.
100 of submicroscopic
FT-IR and TGAcrystals.
were employed to obtain further structural information about the ZIF-67(Co).
93 Figure 4 presents FT-IR spectra of ZIF-67(Co) between 400 and 4000 cm−1 . The peak at 3420 cm−1 is
a contribution of the asymmetric characteristic absorption peaks of O–H bonds in hydroxyl groups
94 Figure
adsorbed on2.the
N2 adsorption/desorption isotherms
surface of materials. There of also
were ZIF-67(Co) samples
some peaks at 77 K and
between 1500 cm−1 caused
Horvath–Kawazoe
500 and
95 (HK) pore size distribution
by plane-bending vibrations curve.
and stretching vibrations of the imidazole ring. Meanwhile, the two
small peaks at 758 and 534 cm−1 were attributed to the stretching vibration peak of the Co–N bond.
96 The morphology
In addition, there were andtwoparticle
bands size of the
at 3134 andsamples
2931 cmrevealed
−1 causedby by
scanning electron microscopy
the asymmetric absorption
97 (SEM) are shown in Figure 3. The SEM picture
vibrations of the C–H bond in the methyl groups. reveals that the particles were submicroscopic
98 crystals with polyhedral shapes, each surface was a homogeneous quadrilateral, and the particle
99 sizes ranged from 200 to 500 nm. This also proves that the as-synthesized ZIF-67(Co) was composed
100 of submicroscopic crystals.
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101
102 Figure 3. SEM pictures of ZIF-67(Co).

103 FT-IR and TGA were employed to obtain further structural information about the ZIF-67(Co).
104 Figure 4 presents FT-IR spectra of ZIF-67(Co) between 400 and 4000 cm−1. The peak at 3420 cm−1 is a
105 contribution of the asymmetric characteristic absorption peaks of O–H bonds in hydroxyl groups
106 adsorbed on the surface of materials. There were also some peaks between 500 and 1500 cm−1 caused
107 by plane-bending vibrations and stretching vibrations of the imidazole ring. Meanwhile, the two
108 small peaks at 758 and 534 cm−1 were attributed to the stretching vibration peak of the Co–N bond. In
101
109 addition, there were two bands at 3134 and 2931 cm−1 caused by the asymmetric absorption
110
102 vibrations of the C–H bond in theFigure
methyl
Figure
3. SEM pictures of ZIF-67(Co).
groups.
3. SEM pictures of ZIF-67(Co).

103 FT-IR and TGA were employed to obtain further structural information about the ZIF-67(Co).
104 Figure 4 presents FT-IR spectra of ZIF-67(Co) between 400 and 4000 cm−1. The peak at 3420 cm−1 is a
105 contribution of the asymmetric characteristic absorption peaks of O–H bonds in hydroxyl groups
106 adsorbed on the surface of materials. There were also some peaks between 500 and 1500 cm−1 caused
107 by plane-bending vibrations and stretching vibrations of the imidazole ring. Meanwhile, the two
108 small peaks at 758 and 534 cm−1 were attributed to the stretching vibration peak of the Co–N bond. In
109 addition, there were two bands at 3134 and 2931 cm−1 caused by the asymmetric absorption
110 vibrations of the C–H bond in the methyl groups.

111
Figure 4. FT-IR spectra of ZIF-67(Co).
112 Figure 4. FT-IR spectra of ZIF-67(Co).
The synthesized ZIF-67(Co) submicroscopic crystals had high thermostability, which was proved
113 by TGAThe and
synthesized ZIF-67(Co)
differential scanningsubmicroscopic
calorimetry (DSC) crystals had high
as shown thermostability,
in Figure 5. The testwhich was
increased
114 proved by TGA and differential scanning calorimetry (DSC) as shown in Figure 5.
temperature to 873 K from room temperature at 5 K/min. When calcined below 373 K, the total weight The test increased
115 temperature
loss to 873
of the sample was Kvery
fromsmall
room temperature
(about at 5 to
8%), relating K/min. When of
the removal calcined below 373such
guest molecules K, as
thewater.
total
116 weight loss
Between 373of the510
and sample
K, thewas very
curve small (about
remained 8%),
smooth relating
overall, to the removal
indicating that theofskeleton
guest molecules such
of ZIF-67(Co)
117 as water. Between 373 and 510 K, the curve remained smooth overall, indicating
has good thermal stability below 510 K. When the temperature was greater than 520 K, the mass lossthat the skeleton of
118 ZIF-67(Co) has good thermal stability below 510 K. When the temperature was greater
began at the stage of skeletal decomposition. This was attributed to the collapse of the ligands, which than 520 K,
111
119 the mass loss
was caused bybegan at the stage of of
the decomposition skeletal decomposition.The
2-methylimidazole. Thisweight-loss
was attributed to the
process collapse
was completeof the
at
120
112 ligands, which was caused by the
620 K, and the residue was Co3 O4Figure .decomposition of 2-methylimidazole.
4. FT-IR spectra of ZIF-67(Co). The weight-loss process was
121 complete at 620 K, and the residue was Co3O4.
113 The synthesized ZIF-67(Co) submicroscopic crystals had high thermostability, which was
114 proved by TGA and differential scanning calorimetry (DSC) as shown in Figure 5. The test increased
115 temperature to 873 K from room temperature at 5 K/min. When calcined below 373 K, the total
116 weight loss of the sample was very small (about 8%), relating to the removal of guest molecules such
117 as water. Between 373 and 510 K, the curve remained smooth overall, indicating that the skeleton of
118 ZIF-67(Co) has good thermal stability below 510 K. When the temperature was greater than 520 K,
119 the mass loss began at the stage of skeletal decomposition. This was attributed to the collapse of the
120 ligands, which was caused by the decomposition of 2-methylimidazole. The weight-loss process was
121 complete at 620 K, and the residue was Co3O4.
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122
Figure 5. TGA and differential scanning calorimetry (DSC) curves of ZIF-67(Co) submicroscopic crystals.
123 Figure 5. TGA and differential scanning calorimetry (DSC) curves of ZIF-67(Co) submicroscopic
124 crystals. Experiments
2.2. Catalytic

125 2.2. Catalytic

2.2.1. Experiments
The Effect of Various Catalysts on the Reaction
The comparison of the catalytic activities of different catalysts for the oxidation of limonene is
126 2.2.1. The Effect of Various Catalysts on the Reaction
summarized in Table 1. Using t-BHP as oxidant yielded carvone as the main product, and the reaction
127 time The
was comparison
8 h. Besides,of
thethe catalyticmethod
synthetic activities
andofXRD
different catalysts
patterns about for theMOFs
these oxidation
have of limonene
been is
revealed
128 summarized
in in Table
supplementary 1. Using
material t-BHP
(Figures as oxidant yielded carvone as the main product, and the
S1–S5)
129 reaction time was 8 h.
Table 1. Comparison of the catalytic activities of various metal–organic frameworks (MOFs) for the
130 Table 1. Comparison
oxidation of limonene.of the catalytic activities of various metal–organic frameworks (MOFs) for the
131 oxidation of limonene.
Catalysts Conversion (%) Selectivity (%)
Catalysts
MIL-101(Fe) Conversion
50.8 (%) Selectivity20.3 (%)
MIL-101(Fe)
ZIF-8(Zn) 50.8
16.5 20.3
9.2
ZIF-8(Zn)
ZIF-67(Co) 16.5
35.7 9.2
32.6
MIL-101(Cr)
ZIF-67(Co) 44.1
35.7 26.6
32.6
HKUST-1(Cu) 20.4 7.9
MIL-101(Cr) 44.1 26.6
MIL-125(Ti) 18.2 10.1
HKUST-1(Cu)
No catalyst 20.4
26.7 7.9
0.05
MIL-125(Ti) 18.2 10.1
Conditions: limonene: 2 mL, catalyst: 100 mg, solvent: 15 mL acetic acid, oxidant: 15 mL t-BHP (tert-butyl
No85catalyst
hydroperoxide), temperature: 26.7
◦ C, reaction time: 8 h. 0.05
132 Conditions: limonene: 2 mL, catalyst: 100 mg, solvent: 15 mL acetic acid, oxidant: 15 mL t-BHP
133 (tert-butyl
First, hydroperoxide),
the reactivity temperature:
of several common 85 °C, reaction
catalysts time: 8 h. without any condition optimization.
was compared
134 The activity of MIL-101(Fe)(Materials
First, the reactivity of several of Institutecatalysts
common LavoisierwasFrameworks)
comparedwas the most
without anyoutstanding
condition
135 for the oxidation of limonene—the conversion rate was 50.8% after 8 h; followed
optimization. The activity of MIL-101(Fe)(Materials of Institute Lavoisier Frameworks) was the most by MIL-101(Cr),
136 whose conversion
outstanding for therate was 44.1%.
oxidation ZIF-8 showedconversion
of limonene—the the worst activity,
rate waswith50.8%a conversion rate of only
after 8 h; followed by
137 16.5%. However, after the reaction, the filtrates from HKUST-1(Cu)([Cu
MIL-101(Cr), whose conversion rate was 44.1%. ZIF-8 showed the worst 3 (BTC) (H
activity,
2 O) ] ), MIL-101(Fe),
3 n a conversion
2 with

138 and
rate MIL-101(Cr)
of only 16.5%.were light blue,
However, afterdark red, and the
the reaction, yellow-green,
filtrates fromrespectively. This indicates
HKUST-1(Cu)([Cu that metal
3(BTC)2(H2O)3]n),

139 ions, as metal centers, leaked during the reactions with HKUST-1(Cu), MIL-101(Fe),
MIL-101(Fe), and MIL-101(Cr) were light blue, dark red, and yellow-green, respectively. This and MIL-101(Cr).
140 On the other
indicates hand,
that ZIF-67
metal showed
ions, the highest
as metal centers,selectivity,
leaked and
duringthe selectivity
the reactions for carvone reached 36.6%
with HKUST-1(Cu),
141 after 8 h of reaction.
MIL-101(Fe), The high selectivity
and MIL-101(Cr). On the other of ZIF-67(Co)
hand, ZIF-67 mayshowed
be attributed to its selectivity,
the highest unique ion and
centers.
the
142 Heterogeneous catalysis with MOF materials is one of their extensively investigated
selectivity for carvone reached 36.6% after 8 h of reaction. The high selectivity of ZIF-67(Co) may applications [21].
be
143 attributed to its unique ion centers. Heterogeneous catalysis with MOF materials is one of their
144 extensively investigated applications [21].
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145 2.2.2.
2.2.2.The
TheEffect
Effect
ofof
thethe Catalyst
Catalyst Dosage
Dosage onon
thethe Reaction
Reaction
146 TheThe catalyst
catalyst dosage
dosage had
had a significant
a significant effect
effect on the
on the oxidation
oxidation of limonene.
of limonene. FiveFive different
different dosages
dosages of
147 ZIF-67(Co)—35,
of ZIF-67(Co)—35, 60, 85, 110, and 135 mg—were used while keeping all
60, 85, 110, and 135 mg—were used while keeping all the other reaction parameters the other reaction
148 fixed,
parameters
and the fixed, and the results
experimental experimental
are shownresults are shown
in Figure in Figure 6.
6. Conversions ofConversions
4.75%, 13.2%,of28.1%,
4.75%,30.3%,
13.2%,
149 and
28.1%, 30.3%, and 33.5%, corresponding to the 35, 60, 85, 110, and 135
33.5%, corresponding to the 35, 60, 85, 110, and 135 mg catalyst loadings, respectively, weremg catalyst loadings,
150 obtained
respectively,
in the were obtained
experiment. in the
With experiment.
increasing With increasing
ZIF-67(Co) dosage, the ZIF-67(Co)
conversiondosage, the conversion
of limonene increased.of
151 When
limonene increased.
the amount When the
of catalyst wasamount
135 mg,ofthe catalyst was 135
conversion mg, the conversion
of limonene was 33.5%.of Interestingly,
limonene was
152 the33.5%. Interestingly, the selectivity for carvone increased at low catalyst contents
selectivity for carvone increased at low catalyst contents and then decreased, relative to increasing and then
153 content
decreased,
of therelative
catalyst.toWhen
increasing content
the dosage of of
thethe catalyst.
catalyst wasWhen
85 mg, the
thedosage of the
selectivity forcatalyst
carvonewas 85 mg,
reached
154 thethemaximum
selectivityvalue
for carvone reached the maximum value (36.7%). After that, the
(36.7%). After that, the yield of carvone decreased slightly as the amount of yield of carvone
155 catalyst
decreased slightly
continued toas the amount
increase, of catalyst
but the continued
rate of change wasto increase, but the rate of change was small.
small.

156
Figure 6. The effect of the catalyst dosage on the reaction. Conditions: limonene: 2 mL, catalyst:
157 Figure 6. solvent:
ZIF-67(Co), The effect of the
15 mL catalyst
acetic dosage on
acid, oxidant: 15 the
mL reaction. Conditions:85limonene:
t-BHP, temperature: 2 mL,
◦ C, reaction time:catalyst:
8 h.
158 ZIF-67(Co), solvent: 15 mL acetic acid, oxidant: 15 mL t-BHP, temperature: 85 °C, reaction time: 8 h.
2.2.3. The Effects of Various Oxidizing Agents on the Reaction
159 2.2.3. The Effects of Various Oxidizing Agents on the Reaction
Choosing a suitable oxidant is very important for improving the conversion and selectivity of
160 catalytic oxidation,
Choosing becauseoxidant
a suitable oxidantsisare one
very of the keyfor
important factors in catalytic
improving oxidation.and
the conversion We tried to getof
selectivity
161 aircatalytic
in the reaction to use
oxidation, oxygen
because as a reagent.
oxidants are oneInofaddition, hydrogen
the key factors peroxide
in catalytic and t-BHP
oxidation. Wewere
triedused
to get
162 asair
oxidants. The results of these experiments are recorded in Table 2. When t-BHP (70%)
in the reaction to use oxygen as a reagent. In addition, hydrogen peroxide and t-BHP were used was added
163 toasthe system,The
oxidants. the results
conversion of limonene
of these increased
experiments to 28.1%,
are recorded and the
in Table selectivity
2. When t-BHPfor carvone
(70%) was
was added
164 36.7%.
to theHowever, if hydrogen
system, the peroxide
conversion (30%) was
of limonene used astooxidant,
increased 28.1%, the
andconversion of limonene
the selectivity and the
for carvone was
165 selectivity decreasedif significantly.
36.7%. However, hydrogen peroxide (30%) was used as oxidant, the conversion of limonene and
166 the selectivity decreased significantly.
Table 2. The effect of various oxidizing agents on the reaction.
167 Table 2. The effect of various oxidizing agents on the reaction.
Oxidant Conversion (%) Selectivity (%)
Oxidant
Air Conversion
11.3 (%) Selectivity
30.9 (%)
30% HAir
2 O2 11.3
6.8 30.9
9.9
70% t-BHP
30% H2O2 28.1
6.8 36.7
9.9
Conditions: limonene: 2 mL, catalyst: 85
70% t-BHP mg of 28.1
ZIF-67(Co), solvent: 15 mL 36.7acid, oxidant: 5 mL H2 O2 (30%) or
acetic
5 mL t-BHP, temperature: 85 ◦ C, reaction time: 8 h.
168 Conditions: limonene: 2 mL, catalyst: 85 mg of ZIF-67(Co), solvent: 15 mL acetic acid, oxidant: 5 mL
169 H2O2 (30%) or 5 mL t-BHP, temperature: 85 °C, reaction time: 8 h.
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170 2.2.4.
2.2.4.
TheThe Effect
Effect of the
of the Dosage
Dosage of of
thethe Oxidanton
Oxidant onthe
theReaction
Reaction
171 Experimental
Experimental results
results ononthe
theeffect
effect of
of oxidant
oxidantdosage
dosageononthethe
reaction were
reaction shown
were in Figure
shown 7. We 7.
in Figure
172 We noticed
noticed that the conversion of limonene increased with increasing amounts of t-BHP. Whenthe
that the conversion of limonene increased with increasing amounts of t-BHP. When the
173 amount
amount of t-BHP was 7 mL, the conversion of limonene was 33.1%. Meanwhile, the
of t-BHP was 7 mL, the conversion of limonene was 33.1%. Meanwhile, the selectivity for selectivity for
174 carvone
carvone increased and then decreased with the increase in t-BHP. We also found that the selectivity
increased and then decreased with the increase in t-BHP. We also found that the selectivity for
175 carvone
for carvone reached its maximum (43.5%) when the dosage of oxidant was 3 mL. After that,
reached its maximum (43.5%) when the dosage of oxidant was 3 mL. After that, increasing the
176 increasing the amount of oxidant increased the degree of oxidation, resulting in a decrease of
amount of oxidant increased the degree of oxidation, resulting in a decrease of selectivity and yield.
177 selectivity and yield.

178
179 Figure 7. The effect of the oxidant dosage on the reaction. Conditions: limonene: 2 mL, catalyst:
Figure 7. The effect of the oxidant dosage on the reaction. Conditions: limonene: 2 mL, catalyst:
ZIF-67(Co), solvent: 15 15
mLmLacetic acid, oxidant: ◦ C, reaction time: 8 h.
180 ZIF-67(Co), solvent: acetic acid, oxidant:t-BHP,
t-BHP,temperature:
temperature: 85
85 °C, reaction time: 8 h.
2.2.5. The Effects of Different Solvents on the Reaction
181 2.2.5. The Effects of Different Solvents on the Reaction
The solvent is an important factor affecting heterogeneous catalytic reaction systems. The polarity,
182 The solvent is an important factor affecting heterogeneous catalytic reaction systems. The
acidity, viscosity, and volatility of solvents have a great influence on the performance and reactivity
183 polarity, acidity, viscosity, and volatility of solvents have a great influence on the performance and
184 of the catalyst.
reactivity of Some experiments
the catalyst. Some were carried out
experiments weretocarried
study the
out effects of different
to study the effectssolvents on the
of different
185 catalytic
solvents on the catalytic oxidation of limonene by ZIF-67(Co), and the results are shown in Tablethat
oxidation of limonene by ZIF-67(Co), and the results are shown in Table 3. We found 3.
186 limonene
We foundconversion and carvone
that limonene selectivity
conversion were higher
and carvone whenwere
selectivity benzene
higherwas usedbenzene
when as solvent
wasthan
usedwith
as
187 acetic acid, than
solvent acetic anhydride,
with or acetic
acetic acid, ethyl acetate.
anhydride, or ethyl acetate.

188 Table The

3. 3.
Table effect
The ofofdifferent
effect differentsolvents
solventson
onthe
thereaction.
reaction.

Solvent
Solvent Conversion
Conversion (%) (%) Selectivity
Selectivity
(%)(%)
Acetic
Acetic acidacid 25.9 25.9 33.3
33.3
Acetic anhydride
Acetic 38.1 15.9
38.1 15.9
anhydride
Ethyl acetate 42.6 23.1
EthylBenzene
acetate 42.6 20.3 23.1
49.4
Benzene 20.3 49.4
189 Conditions: limonene: 2 mL, catalyst: 85 mg of ZIF-67(Co), solvent: 15 mL, oxidant: 3 mL t-BHP,
190 Conditions:
◦
limonene:
temperature: 85 °C,2 reaction
mL, catalyst:
time:858 mg
h. of ZIF-67(Co), solvent: 15 mL, oxidant: 3 mL t-BHP, temperature:
85 C, reaction time: 8 h.

191 2.2.6. The Effect of the Temperature on the Reaction

2.2.6. The Effect of the Temperature on the Reaction
192 The oxidation of limonene was examined over the temperature range of 55–95 °C, and the
◦ C, and the results
193 resultsoxidation
The are shown of in
limonene
Figure 8.was
Theexamined over
conversion the temperature
of limonene range
increased of 55–95
quickly from 6.5% to 30.5% for
are shown in Figure 8. The conversion of limonene increased quickly from 6.5% to 30.5% for a reaction
 Catalysts 2019, 9, 374 8 of 13

Catalysts 2019, 9, x FOR PEER REVIEW 8 of 12

Catalysts 2019, 9, x FOR PEER REVIEW 8 of 12
time of 8 h, when the temperature was increased from 55 to 65 ◦ C.
Thereafter, the trend of conversion
194
194 a reaction time of 8 h, when the temperature was increased from 55 to 65 °C. Thereafter, the trend of
a reaction time of 8Interestingly
h, when the temperature
had a slow decline. enough, the was increased
selectivity for from 55 toreached
carvone 65 °C. Thereafter,
its maximum the trend
(48.7%)of at
195
195 conversion
◦
conversion
had a slow decline. Interestingly enough, the selectivity for carvone reached its
had a slow decline. Interestingly enough, the selectivity for carvone reached its
85 C. This might be because the activity of the catalyst definitely increased at the beginning of the
196
196 maximum (48.7%) at 85 °C. This might be because the activity of the catalyst definitely increased at
maximum (48.7%)
temperature rise, so at
the85conversion
°C. This might be because
of limonene the activity
increased of theHowever,
rapidly. catalyst definitely
after theincreased at
temperature
197
197 the beginning of the temperature rise, so the conversion of limonene increased rapidly. However,
the beginning ofvalue,
the temperature rise,activity
so the conversion of limonene increased rapidly. However,
198 reached a certain the catalytic of the material did not increase and
after the temperature reached a certain value, the catalytic activity of the material did not increasethe byproduct
198 after thedid
formation temperature
increase, reached
so a certain for
the selectivity value, the catalytic
carvone activity of the material did not increase
decreased.
199
199 and the byproduct formation did increase, so the selectivity for carvone decreased.
and the byproduct formation did increase, so the selectivity for carvone decreased.

200
200
201
201 Figure
Figure 8.
The
8. 8.
Figure
The
The
effect of temperatureon
effect
effectofoftemperature
on thereaction.
temperature onthe
reaction. Conditions: limonene:
the reaction. Conditions: limonene:22 2mL,
Conditions: limonene:
mL, catalyst:
mL,catalyst:
catalyst:85 mgmg
85 85
mg
202
202 ZIF-67(Co),
ZIF-67(Co), solvent:1212mL
solvent: mLbenzene,
benzene,oxidant:
oxidant: 33 mL
mL t-BHP,
t-BHP, reaction
reaction time:
time:
ZIF-67(Co), solvent: 12 mL benzene, oxidant: 3 mL t-BHP, reaction time: 8 h.
88h.h.

203
203
2.2.7. The
2.2.7. Effect
The Effectofofthe
theReaction
ReactionTimeTimeon onthe
theReaction
2.2.7. The Effect of the Reaction Time on the Reaction
Reaction
204
204 TheThe
The
catalytic
catalytic
catalytic
oxidation of limonene,using
oxidation
oxidationofoflimonene,
using the above conditions
above conditions
limonene, using the above
for
conditionsfor different
fordifferent reaction
differentreaction
reaction times,
times,
times,
was
waswas
205
205 studied.
studied. As Ascan
canbebeseen
seenininFigure
Figure9,9,the
theconversion
conversion of limonene
limonene increased
increased with
with
studied. As can be seen in Figure 9, the conversion of limonene increased with increasing reaction
increasing
increasing reaction
reaction
206
206 time,
time, and
time,
and
and
the
thethe conversion was37.8%
conversion
conversionwas
37.8% at12
was 37.8%at
12 h. Meanwhile,
at 12 h.
Meanwhile, the
h. Meanwhile, the
selectivity
theselectivity for
selectivityfor carvone
forcarvone
carvone increased
increased
increased
first,
first,
first,
207
207 reached
reached
reached
a maximum
a maximum
a maximum
at
at 6 at 6 h (57.7%),
h (57.7%), and
and then
6 h (57.7%),
then decreased.
and decreased.
Owing
OwingOwing
then decreased.
to
to the fact the fact
thatfact
to the t-BHPthat t-BHP
thatist-BHP
is not
not completely
is not
208
208 completely over
decomposed decomposed
short over
times, theshort times,efficiency
oxidation the oxidation
was efficiency was
undesirable, and
completely decomposed over short times, the oxidation efficiency was undesirable, and with
undesirable,
with andreaction
increasing with
209
209 increasing
time, there were
increasing
reaction time,
corresponding
reaction
there were
time, thereincreases
corresponding increases
in the oxidants’
were corresponding
in
oxidation
increases
the oxidants’
in thecapacity
oxidants’
oxidation
asoxidation
well as the capacity as
conversion
capacity as
210
210 well as the conversion rate. However, selectivity of carvone decreased with reaction time increased
rate.
wellHowever, selectivity
as the conversion of However,
rate. carvone decreased
selectivity with reaction
of carvone time increased
decreased because
with reaction timeofincreased
the depth
211
211 because of the depth oxidation of carvone and by-product increased.
oxidation
becauseof of carvone
the depthand by-product
oxidation increased.
of carvone and by-product increased.
212
212

213
213
214
214
Figure The
9. 9.
Figure effect
The
Figure 9. The
ofof
effect
effect12
the
thereaction
ofmL
reactiontime
the benzene,
timeon
reaction time
onthe
thereaction.
on the
reaction. Conditions:
reaction.
limonene:2 2mL,
Conditions: limonene:
Conditions: limonene:
mL,catalyst:
catalyst:
8585
mgmg
◦ C.2 mL, catalyst: 85 mg
215
215
ZIF-67(Co), solvent: oxidant: 3 mL t-BHP, temperature:
ZIF-67(Co), solvent: 12 mL benzene, oxidant: 3 mL t-BHP, temperature: 75 °C.
ZIF-67(Co), solvent: 12 mL benzene, oxidant: 3 mL t-BHP, temperature: 75 °C.
75
 Catalysts 2019, 9, 374 9 of 13

Catalysts 2019, 9, x FOR PEER REVIEW 9 of 12

2.2.8. Study of the Catalyst Stability
216 2.2.8. Study of the Catalyst Stability
Stability is an important parameter of catalyst performance. In order to investigate the stability of
217 StabilityXRD
ZIF-67(Co), is anspectra
important parameterbefore
of ZIF-67(Co) of catalyst
and performance. In order round
after the first reaction to investigate the stability
were obtained and
218 of ZIF-67(Co), XRD spectra of ZIF-67(Co) before and after the first reaction round were obtained
are presented here. As shown in Figure 10, the characteristic peak was still present, but its strength and
219 are presented here. As shown in Figure 10, the characteristic peak was still
decreased slightly. So, we can be sure that the structure of ZIF-67 still existed. present, but its strength
220 decreased slightly. So, we can be sure that the structure of ZIF-67 still existed.

221
222 Figure 10.
Figure XRD spectra
10. XRD spectra of
of ZIF-67(Co)
ZIF-67(Co) as
as synthesized
synthesized and
and after
after the
the first
first recycle.
recycle.

Concurrently, the specific data about repetitive experiments are revealed in Table 4.
223 Concurrently, the specific data about repetitive experiments are revealed in Table 4.
Table 4. The data from reuse experiments.
224 Table 4. The data from reuse experiments.
Times Conversion (%)
Times Conversion (%) Selectivity (%)
Selectivity (%) TON
TON
First round
First round 29.8
29.8 55.4
55.4 18.1
18.1
Second round 33.5 41.6 13
Second round 33.5 41.6 13
Third round 32.5 28.0 8.7
Third round 32.5 28.0 8.7
Conditions: limonene: 2 mL, catalyst: 85 mg of ZIF-67(Co), solvent: 12 mL benzene, oxidant: 3 mL t-BHP,
225 Conditions: 75
temperature: limonene: 2 mL,
◦ C, reaction time:catalyst: 85 mg
8 h. Turnover of ZIF-67(Co),
number solvent:
(TON) = carvone 12 mL
(yield) benzene,
mmol/total oxidant:
Co site mmol.3 mL
226 t-BHP, temperature: 75 °C, reaction time: 8 h. Turnover number (TON) = carvone (yield) mmol / total
227 Co site mmol.
The data in Table 4 reveal the repeatability of ZIF-67(Co) in the catalytic oxidation of limonene.
228 As canThebedata
seeninfrom the4 data
Table in the
reveal Table 4, we found
repeatability ofthat the selectivity
ZIF-67(Co) for carvone
in the catalytic declined
oxidation of slightly
limonene.in
229 the second round. At the same time, the conversion of limonene declined as well. We conclude
As can be seen from the data in Table 4, we found that the selectivity for carvone declined slightly that
230 this
in themay be related
second to At
round. a partial collapse
the same time,ofthe
theconversion
basic structure of ZIF-67(Co).
of limonene declined as well. We conclude
231 that this may be related to a partial collapse of the basic structure of ZIF-67(Co).
3. Materials and Methods
232 3. Materials and Methods
3.1. Materials and Solvents
233 3.1. Materials
Cobaltous andnitrate
Solvents
hexahydrate was supplied by Xilong Chemical Co., Ltd. (Shantou, China)
and 2-methylimidazole was obtained from Sinopharm Chemical Reagent Co., Ltd. (Shanghai,
234 Cobaltous nitrate hexahydrate was supplied by Xilong Chemical Co., Ltd. (Shantou, China) and
China). All other reactants used in the synthesis of the ZIF-67(Co) catalyst samples were supplied
235 2-methylimidazole was obtained from Sinopharm Chemical Reagent Co., Ltd. (Shanghai, China). All
by Xilong Chemical Co., Ltd. Methanol and acetic acid were purchased from Xilong Chemical Co.,
236 other reactants used in the synthesis of the ZIF-67(Co) catalyst samples were supplied by Xilong
Ltd. The tert-butyl hydroperoxide and limonene were obtained from Adamas Reagent Co., Ltd.
237 Chemical Co., Ltd. Methanol and acetic acid were purchased from Xilong Chemical Co., Ltd. The
(Shanghai, China).
238 tert-butyl hydroperoxide and limonene were obtained from Adamas Reagent Co., Ltd. (Shanghai,
239 China).

240 3.2. Catalyst Preparation

241 In a typical preparation process [33], 0.45 g cobaltous nitrate hexahydrate was dissolved in 3 mL
242 of distilled water, and then 5.5 g of 2-methylimidazole was dissolved in 100 mL of distilled water.
Catalysts 2019, 9, 374 10 of 13

3.2. Catalyst Preparation

In a typical preparation process [33], 0.45 g cobaltous nitrate hexahydrate was dissolved in 3 mL
of distilled water, and then 5.5 g of 2-methylimidazole was dissolved in 100 mL of distilled water.
Then the two solutions were mixed evenly and stirred at room temperature for 6 h. The products
obtained were washed with distilled water and methanol, and then dried in at 80 ◦ C for 24 h.

3.3. Catalyst Characterization

ZIF-67(Co) was characterized through a series of techniques. The diffraction patterns of the
materials and the residual catalyst were obtained by powder X-ray diffraction (XRD, Rigaku Co., Tokyo,
Japan) experiments using Cu Kα band radiation on a D/max-3B spectrometer. Scans were made over
the 2θ range of 10–90◦ with a scan rate of 10◦ /min (wide-angle diffraction). Pore size distributions,
pore volumes, and specific surface area were measured by nitrogen adsorption/desorption using a
Micromeritics ASAP 2460(Micromeritics, Norcross, GA, USA) at 77 K. The specific surface areas were
calculated by the Brunauer–Emmett–Teller (SBET ) and Langmuir methods, and the pore volumes
and pore sizes were calculated by the BJH (Barrett–Joyner–Halenda) method. Thermogravimetric
analysis (TGA) curves and differential scanning calorimetry (DSC) determinations were carried out
on a NETZSCH STA 449 F3 synchronous TG-DSC thermal analyzer (Nuremberg, Germany) with
a scanning rate of 5 K/min in a dry nitrogen atmosphere and heating from room temperature to
1073 K. The FT-IR(Fourier transform infrared spectroscopy) measurements were performed on a
Thermo Nicolet 8700 instrument(Wilmington, MA, USA). Potassium bromide pellets were used in
FT-IR experiments at a spectral resolution of 4 cm−1 . Scanning electron microscopy (SEM) images were
taken on a Quanta 200FEG microscope (FEI, Hillsboro, OR, USA) at an accelerating voltage of 15 kV
with the pressure in the sample chamber set to 2.7 × 10−5 Pa. Double-sided adhesive tape was bonded
on the carrier disc, then a small amount of powder sample was placed near the center of the carrier
disc on the adhesive tape. Then, a rubber ball was used to blow the sample outward along the radial
direction of the load plate, so that the powder was evenly distributed on the tape. The tape was then
coated with conductive silver paste to connect the sample to the carrier plate. After the silver paste
was dried, the final gold steaming process could be carried out.

3.4. Catalytic Performance

In a typical reaction, 2 mL limonene with varying amounts of catalyst and solvents were used
as received, without further purification, in a 25 mL three-neck flask. Each set of experiments
was performed at a corresponding temperature, under atmospheric pressure and magnetic stirring,
using an appropriate amount of solvent, e.g., acetic acid, acetic anhydride, ethyl acetate, benzene,
etc. Afterwards, the catalyst was separated by filtration, and the sample solution was dried with
anhydrous magnesium sulfate. A final filtration was carried out, and the samples were qualitatively
and quantitatively analyzed by gas chromatography (GC-9560, HUAAI Chromatography, Shanghai,
China), with a capillary column AE.OV-624, 30 m in length, 0.25 mm i.d., 0.5 µm film thickness, and an
FID (Flame ionization detector).
In order to assess the stability of the ZIF-67(Co), some sets of a repeatability experiment were
performed. After the first reaction, the catalyst was centrifuged and separated from the reaction
system, and after repeated washing with distilled water and anhydrous ethanol, the catalyst was
reactivated at 90 ◦ C in the vacuum drying chamber for 12 h. Thereafter, the reactor was supplied with
the recovered dry catalyst, new reagents, and solvent for the second reaction. We repeated the above
process three times.

4. Conclusions
In conclusion, we proved that the zeolitic imidazolate framework ZIF-67(Co) was an efficient
catalyst for the liquid-phase catalytic oxidation of limonene, under relatively mild reaction conditions,
Catalysts 2019, 9, 374 11 of 13

to carvone. Based on current research, the catalytic oxidation of limonene comprises two parallel
reactions, namely a synergistic reaction and a free-radical reaction. Carvone is the product
of the free-radical reaction of limonene at the allyl group. The synergistic reaction produced
limonene-1,2-oxides and limonene-1,2-diols. Meanwhile, under acidic conditions, the 1,2-oxide
of limonene could be hydrolyzed to produce the 1,2-diol of limonene, and the 1,2-diol of limonene
could be further rearranged and converted to carvone.
This is the first report on catalyzing the oxidation of limonene using ZIF-67(Co) as catalyst. It was
revealed that ZIF-67(Co) was an efficient catalyst, with selectivity of 55.4% for carvone in the catalytic
oxidation of limonene, and could be reused with similar activity.

Supplementary Materials: The following are available online at http://www.mdpi.com/2073-4344/9/4/374/s1,

Figure S1: XRD pattern of MIL-101(Cr), Figure S2: XRD pattern of MIL-125(Ti), Figure S3: XRD pattern of
HKUST-1(Cu), Figure S4: XRD pattern of ZIF-8(Zn), Figure S5: XRD pattern of MIL-101(Fe).
Author Contributions: Conceptualization, J.W. and Y.L.; Data curation, Z.Y. and Y.L.; Formal analysis, Y.L. and
W.W.; Investigation, Y.L., Y.Y., D.C., and Z.L.; Methodology, J.W.; Project administration, J.W. and Z.Y.; Software,
Z.L., Y.A., and L.Z.; Supervision, J.W. and Z.Y.; Writing—original draft, Y.L.; Writing—review and editing, J.W.
and Z.Y.
Funding: This research was funded by National Natural Science Foundation of China (Project 21573193 and
21464016). The authors also thank the Key Projects for Research and Development of Yunnan Province (2018BA065),
the Scientific Research Fund of Department of Yunnan Education (Project 2016CYH04 and 2017ZZX223) for
financial support.
Acknowledgments: The work was supported by National Natural Science Foundation of China (Project
21573193 and 21464016). The authors also thank the Key Projects for Research and Development of Yunnan
Province (2018BA065), the Scientific Research Fund of Department of Yunnan Education (Project 2016CYH04
and 2017ZZX223), and the Program for Innovation Team of Yunnan Province and Key Laboratory of Advanced
Materials for Wastewater Treatment of Kunming for financial support.
Conflicts of Interest: The authors declare no conflict of interest.

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