pubs.acs.

org/IECR Article

From Core−Shell to Yolk−Shell: Improved Catalytic Performance

toward CoFe2O4@ Hollow@ Mesoporous TiO2 toward Selective
Oxidation of Styrene
Liang Liu, Wei He, Zheng Fang, Zhao Yang,* Kai Guo, and Zhixiang Wang
Cite This: Ind. Eng. Chem. Res. 2020, 59, 19938−19951 Read Online

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ABSTRACT: Developing catalysts with structural characteristics,

reusability, cost-effectiveness, environmental friendliness, and
preferable catalytic performance is challenging for the selective
oxidation of alkenes. In this article, we report the synthesis of
magnetically separable CoFe2O4@ hollow@ mesoporous TiO2
with yolk−shell structure, which could be used as a selectivity
variable and stable catalyst for the selective oxidation of styrene,
yielding different oxidation products. With oxygen as the oxidant,
epoxidation of styrene occurred, affording an epoxy group. With
hydrogen peroxide as the oxidant, oxidative cleavage of double
bonds in the styrene and further oxidation were conducted,
affording a carboxylic acid group. Compared with pristine
CoFe2O4, TiO2, and CoFe2O4/TiO2 core−shell structure, the
CoFe2O4@ hollow@ mesoporous TiO2 with yolk−shell structure was found to be a more efficient catalyst for the oxidation of
styrene. Meanwhile, the kinetic analysis and activation energies of different catalysts were investigated to illustrate the relationship
between the performance and the structure of catalysts. Active radical scavenging experiments were conducted to figure out the
dominant radicals in the oxidation reaction. The corresponding possible reaction mechanisms of the oxidation reaction were also
proposed.

■ INTRODUCTION
Selective oxidation of styrene to corresponding epoxides,
catalysts,14−16 hydrotalcites,11 and Ga-Co-HMS-X,17 have
been developed to catalyze the oxidation of styrene due to
mild reaction conditions, easy separation, and reusability.2
aldehydes, or carboxylic acids is of great interest for both
Although high activity (>98%) and selectivity (>68%) could be
industrial production and academic research due to that the
achieved, most of the catalysts involved precious metals. In
oxidation products, such as tyrene oxide (SO), benzaldehyde
addition, peroxides were used to initiate the reaction, which
(BzA), and benzoic acid (BA), are key organic intermediates
was considered hazardous and environmentally unfriendly.18,19
for pharmaceuticals and fine chemicals.1−3 Notably, SO and
On the other hand, these oxidation reactions are limited by
BA are considered as starting materials for various industrial
uneconomical, harsh conditions or complicated preparation
products, such as plasticizer, epoxy resins, and perfumes.2,4
procedures. Thus, it is necessary to develop efficient
Traditionally, SO is synthesized through cyclization process or
heterogeneous catalysts in the oxidation of styrene.
epoxidation process.2,5 However, basic or acidic catalysts are
Spinel ferrites, MFe2O4 (M = Fe, Mn, Co, Ni, Cu, Zn), have
necessary in these processes, resulting in the generation of
recently attracted tremendous attention in magnetic resonance
enormous waste water. Similarly, BA is mainly produced by
imaging,20 controlled drug release,21 superparamagnetic
direct oxidation of toluene in liquid−gas reaction system with materials,22 electrocatalytic energy conversion,23,24 biosens-
high temperature and pressure. More efficient green oxidants ing,25 and organic pollutant degradation26−28 owing to their
such as hydrogen peroxide, molecular oxygen, and tert-butyl environmental compatibility and stability as well as easy
hydroperoxide6−8 have been applied in this liquid−gas
oxidation reaction to realize the oxidation process at relatively
low temperatures and pressures. Homogeneous and heteroge- Received: August 7, 2020
neous catalysts have also been designed in the oxidation of Revised: October 18, 2020
styrene.6,9−11 However, homogeneous catalysts have received Accepted: October 19, 2020
less attention because of the difficulty in separating catalysts Published: October 28, 2020
from the reaction mixture. Various heterogeneous catalysts,
such as Au supported by metal oxides,12,13 Ag-doped

© 2020 American Chemical Society https://dx.doi.org/10.1021/acs.iecr.0c03884

19938 Ind. Eng. Chem. Res. 2020, 59, 19938−19951
Industrial & Engineering Chemistry Research
synthesis.29 Especially, they have been widely used as
heterogeneous catalysts in many organic reactions due to the
synergistic intermetallic interactions and magnetic recovery
properties.30,31 Ding et al.32 developed spinel CoMn2O4
hollow spheres with a high selectivity (100%) and conversion
(41.6%) for the oxidation of 5-hydroxymethylfurfural. In
addition, these catalysts could be separated from a liquid
reaction by simply placing a magnet on the outside of the flask.
Among all of these spinel ferrites, CoFe2O4, was used as an
efficient catalyst for many oxidation reactions. Nano-CoFe2O4
catalysts were fabricated through the bio-gel template method.
The results revealed that the maximum conversion of
cyclohexane oxidation reached 16.43% and the selectivity for
KA oil was 90.3%.33 Alarcon et al.34 found that Au
nanoparticles deposited at the surface of magnetic CoFe2O4
presented high performance and enhancement in the oxidation
of dimethylphenylsilane. CoFe2O4 nanoparticles with an
average particle size of 4 nm presented high conversion
(80%) in the selective oxidation of 2-propanol.35 Thus,
CoFe2O4 has displayed excellent catalytic activity toward
oxidation reaction.
Recently, CoFe2O4 displayed certain catalytic activity
towards the oxidation of alkene, yielding epoxide products.36,37
However, relatively expensive reagents, such as tert-butyl
hydroperoxide, were applied in the oxidation process. In
addition, single oxidation product was obtained in these
oxidation processes of alkene. Double bonds with high reaction
activity in the alkene could react with various substrates,
affording numerous products involved in pharmaceuticals,
materials, and chemical industry. Thus, development of novel
catalysts based on CoFe2O4 toward the oxidation of alkene was
necessary for the selective and accurate synthesis of various
oxidation products. Complex catalysts including CoFe2O4 and
other active components have been identified as more active
catalysts. On the one hand, catalytic performance would be
enhanced due to the synergistic effects in the ferrites.38,39 On
the other hand, the active components with inherent catalytic
activity would promote the uniform dispersion of active sites,
avoiding catalyst deactivation caused by aggregation of active
sites. In our previous study, metal oxides, such as TiO2, have
displayed excellent catalytic activity toward oxidation reaction
due to the existence of Ti4+. Metal-alkylperoxy intermediate
would be formed to promote the oxidation of alkene.40 Thus,
the integration of CoFe2O4 and TiO2 might promote the
oxidation of alkene. More importantly, the constitution form of
two different components played a vital role in the perform-
ance of the resulting hybrid compound.41,42 However, there
has been no study concerning the relationship between
constitution form of complex catalyst and catalytic activity in
the oxidation of alkene.
In this study, two different complex catalysts including
yolk−shell structure and core−shell structure based on
CoFe2O4 were prepared through the integration of a facile
coprecipitation method and a sol−gel method. A comparison
between the yolk−shell structure and the normal core−shell
structure was made to reveal the role of internal structure in
the catalytic activity. Different oxidants (O2 and hydrogen
peroxide) were applied in the study to investigate the selective
oxidation of styrene. The reaction parameters including
reaction temperature, catalyst amount, molar ratio, reaction
time, solvent, and the amount of urea were investigated in
detail. In addition, the kinetic analysis and activation energies
of different catalysts were studied. The reaction mechanism
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was proposed for a better understanding of the reaction
process.
■ MATERIALS AND METHODS
Materials. Absolute ethanol (C 2 H 6 O), 1,4-dioxane
(C4H8O2), concentrated ammonia aqueous (NH3·H2O), and
cetyltrimethylammonium bromide (C19H42BrN) were ob-
tained from Adamas-Beta (Shanghai, China). Ferric chloride
(FeCl 3 ·6H 2 O), cobalt chloride (CoCl 2 ·6H 2 O), poly-
(vinylpyrrolidone) (PVP), and tetraethyl orthosilicate
(TEOS) were purchased from Macklin (Shanghai, China).
Sodium hydroxide (NaOH) was supplied by Sinopharm
Chemical Reagent (Shanghai, China). Styrene was purchased
from J&K Scientific (Beijing, China). All chemicals used in this
study were of analytical grade and used without further
purification. Ultrapure water (18.2 MΩ·cm) from a Millipore
system (ELGA, U.K.) was employed throughout the experi-
ments.
Catalyst Preparation. Synthesis of CoFe2O4. Spinel ferrite
CoFe2O4 was prepared by a facile coprecipitation method.43 In
a typical synthesis, 2.5 mmol of CoCl2·6H2O and 5 mmol of
FeCl3·6H2O were dissolved in 40 mL of DI water. Then, 0.75 g
of poly(vinylpyrrolidone) (PVP) K30 was added to the above
solution under magnetic stirring and maintained at 90 °C.
Afterward, the pH of the solution was adjusted to 12 by
dropwise addition of 2 M NaOH and kept for 2 h under
stirring conditions before cooling down to room temperature
naturally. The resulting black precipitate was collected by a
magnet and washed with DI water and ethanol repeatedly.
Finally, the products were dispersed in 100 mL of deionized
water for further use.
Synthesis of CoFe2O4/SiO2 Core−Shell Structure. The
interlayer of SiO2 was prepared through a modified Stöber
method.44 In a typical process, 20 mL of the as-prepared
CoFe2O4 suspension was added in 60 mL of absolute ethanol.
Then, the suspension was dispersed under ultrasound for 15
min. Meanwhile, 1 mL of tetraethyl silicate solution was added
dropwise. After that, the mixture solution was mechanically
stirred at 50 °C. Then, 2 mL of concentrated ammonia
aqueous solution was added dropwise. After stirred for 12 h,
the precipitate was washed alternately with absolute ethanol
and deionized water, and then dried under vacuum at 60 °C
for further use.
Synthesis of CoFe2O4/SiO2/Mesoporous TiO2 Core−Shell
Structure. The obtained CoFe2O4/SiO2 composite and 0.116
g of cetyltrimethylammonium bromide were dispersed in 75
mL of absolute ethanol under ultrasound. After forming a
homogeneous dispersion, 0.635 mL of titanium tetraisopropa-
nolate was introduced under mechanical stirring and
maintained at 50 °C. Then, 0.85 mL of concentrated ammonia
aqueous solution was added dropwise. After stirred for 24 h,
the precipitate was washed alternately with absolute ethanol
and DI water and then dried under vacuum at 60 °C for 12 h.
Finally, the precipitate was calcined in air atmosphere at 600
°C for 2 h.
Synthesis of CoFe2O4@ Hollow@ Mesoporous TiO2 Yolk−
Shell Structure. A CoFe2O4@ hollow@ mesoporous TiO2
yolk−shell structure was prepared by etching silica inter-
mediate layer.44 Typically, the obtained CoFe2O4/SiO2/
mesoporous TiO2 composite was dispersed in NaOH solution
(2 M, 60 mL). The reaction mixture was stirred in 60 °C for 5
h. Then, the resulting participate was washed with deionized
water after filtration. Finally, the CoFe2O4@ hollow@
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Scheme 1. Overall Procedure for the Synthesis of CoFe2O4@ Hollow@ Mesoporous TiO2 Yolk−Shell Structure and CoFe2O4/
TiO2 Core−Shell Structure
mesoporous TiO2 yolk−shell catalyst was obtained by drying
at 60 °C for 12 h.
Synthesis of CoFe2O4/TiO2 Core−Shell Structure. For a
better comparison, a CoFe2O4/TiO2 core−shell structure
without silica intermediate layer was prepared as well under
similar conditions. Typically, 20 mL of the as-prepared
CoFe2O4 suspension was dried under vacuum at 60 °C
overnight. Then, the dried black powder and 0.116 g of
cetyltrimethylammonium bromide were dispersed in absolute
ethanol (75 mL) under ultrasound. After that, 0.635 mL of
titanium tetraisopropanolate was added into the solution under
mechanical stirring and maintained at 50 °C. Then,
concentrated ammonia aqueous solution (0.850 mL) was
added dropwise. The reaction was conducted for 24 h. After
the reaction, the precipitate was washed alternately with
absolute ethanol and DI water, and then dried under vacuum
at 60 °C for 12 h. Finally, the precipitate was calcined in air
atmosphere at 600 °C for 2 h. In addition, the overall
procedure for the synthesis of the CoFe2O4@ hollow@
mesoporous TiO2 yolk−shell structure and CoFe2O4/TiO2
core−shell structure is presented in Scheme 1.
Catalyst Characterization. X-ray powder diffraction
(XRD) analysis was conducted on an Ultima IV diffractometer
with Cu Kα-radiation in the 2θ range of 10−80° with a scan
rate of 2°/min. Fourier transform infrared (FTIR) spectros-
copy was carried out on a Bruker Tensor II. Scanning electron
microscopy (SEM) images and energy-dispersive X-ray
spectrum (EDX) mapping were obtained from a Quanta
FEG 250 equipped with an energy-dispersive X-ray spec-
trometer. Transmission electron microscopy (TEM) and high-
resolution TEM (HRTEM) images were recorded using an
HT7800 microscope equipped with an energy-diffusive X-ray
spectroscopy (EDS) attachment. X-ray photoelectron spec-
troscopy (XPS) measurements were characterized on a
Thermo Scientific K-Alpha+ spectrometer with an Al Kα
microfocus monochromatic source. The N2 adsorption−
desorption isotherms were collected on a Quantachrome
Autosorb-iQ3 at 77 K.
Catalytic Test. When molecular oxygen was selected as the
oxidant, a 25 mL Schlenk tube was used. In a typical reaction, a
certain amount of catalyst was added into the tube. Afterward,
the system was evacuated and then filled with molecular
oxygen three times. Especially, a balloon filled with molecular
oxygen was inserted on the stopper to meet the consumption
of molecular oxygen in the system. After adding the mixture of
styrene and solvent into the tube, the reaction mixture was
heated to the desired temperature.
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When hydrogen peroxide was selected as the oxidant, a 15
mL glass flask was used. In a typical reaction, certain amounts
of styrene, solvent, and catalyst were added into the flask under
stirring. After heating the reaction mixture to the desired
temperature, a certain amount of hydrogen peroxide (30%)
was added dropwise into the reaction mixture to initiate the
reaction.
For the recycling test, the used catalyst was magnetically
separated and washed with absolute ethanol three times. Then,
the obtained catalyst was dried at 100 °C for 4 h and applied in
the next run. After the reaction, 0.1 mL of the suspension was
extracted and analyzed. The content of SO and the conversion
of styrene were determined by a gas chromatograph equipped
with an HP-5 column.
Liquid chromatography equipped with C18 column was
used to quantify the content of BA. The styrene conversion
and the selectivities of SO and BA were calculated by the
following equations:
styrene conversion (%)
= (converted styrene in molar/initial styrene in molar)
× 100% (1)
SO selectivity (%) = (SO in the product in molar
/converted styrene in molar) × 100%
(2)
BA selectivity (%) = (BA in the product in molar
/converted styrene in molar) × 100%
(3)
■ RESULTS AND DISCUSSION
Catalyst Characterization. The XRD patterns of
CoFe 2 O 4 , CoFe 2 O 4 /TiO 2 core−shell structure, and
CoFe2O4@ hollow@ mesoporous TiO2 yolk−shell catalysts
are displayed in Figure 1. The characteristic diffraction peaks
observed at 18.2, 30.1, 35.5, 43.5, 53.9, 57.2, and 62.7°
corresponded to the (111), (220), (311), (400), (422), (511),
and (440) planes of the spinel CoFe2O4 (PDF card no. 22-
1086). The peaks at 25.3, 37.8, 48.1, 54.0, 55.1, 62.7, 68.8,
70.3, and 75.1° could be assigned to the (101), (004), (200),
(105), (211), (204), (116), (220), and (215) planes of the
anatase TiO2, respectively (PDF card no. 84-1286). As
expected, the characteristic peaks of pure CoFe2O4 and TiO2
were clearly displayed in CoFe2O4@ hollow@ mesoporous
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The TEM image combined with EDS elemental mapping

allowed a direct view of the surface features and elemental
distribution in the CoFe2O4@ hollow@ mesoporous TiO2
(Figure 3). The HRTEM image in Figure 3b suggested a clear

Figure 1. XRD patterns of CoFe2O4, CoFe2O4/TiO2 core−shell

structure, and CoFe2O4@ hollow@ mesoporous TiO2 yolk−shell
structure.

TiO2 yolk−shell catalysts, indicating that the TiO2 shell had no

effect on the lattice structure of CoFe2O4 core. The strong and
sharp peaks of pristine CoFe2O4 catalyst suggested high
crystallinity. However, when coupled with CoFe2O4 directly,
the diffraction peaks of TiO2 became weak. It could be
attributed to the unexpected reaction between CoFe2O4 and
TiO2 in calcination process with high temperature, which
might result in the generation of Fe2TiO5, CoTi2O5, and
Fe2CoTi3O10.45,46 Thus, it was necessary to introduce an inert
silicon interlayer before the calcination process to prevent the
interaction between CoFe2O4 and TiO2.
The representative SEM image of the CoFe2O4@ hollow@ Figure 3. TEM image (a), HRTEM image (b), and the corresponding
mesoporous TiO2 catalyst was obtained to investigate the EDS mapping images (c−g) of CoFe2O4@ hollow@ mesoporous
TiO2.
surface morphology of the samples (Figure 2a). The elemental
distribution in the catalyst was evaluated by EDS elemental
mapping. The even distribution of Co, Fe, Ti, and O elements
in the catalyst is displayed in Figure 2c−f. In addition, the lattice fringe, further confirming a high crystallinity of the
distribution of different elements in Figure 2b demonstrated catalyst. The lattice fringe spacing of 0.25 nm in the spherical
the overlap of different elements, indicating the formation of particles was assigned to the (311) plane of CoFe2O4.47 In
the core−shell structure. EDX scanning of CoFe2O4@ addition, an interplanar distance of 0.35 nm was exhibited by
hollow@ mesoporous TiO2 (Figure S1) also confirmed the the TiO2 layer, which was consistent with the (101) plane of
elementary composition with 7.95 wt % Co, 15.13 wt % Fe, anatase TiO2.48 The EDS mapping images (Figure 3c−g)
30.0 wt % Ti, and 31.85 wt % O (Table S1). showed the elemental composition and distribution of Co, Fe,

Figure 2. SEM image of the CoFe2O4@ hollow@ mesoporous TiO2 (a) and EDS elemental mapping (b−f) of the CoFe2O4@ hollow@
mesoporous TiO2 samples: Ti (c), Fe (d), O (e), and Co (f).

19941 https://dx.doi.org/10.1021/acs.iecr.0c03884
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Figure 4. FTIR spectrum (a), XPS survey (b), high-resolution Co 2p spectrum (c), Fe 2p spectrum (d), O 1s spectrum (e), and Ti 2p spectrum (f)
of CoFe2O4@ hollow@ mesoporous TiO2.
Ti, and O in the CoFe2O4@ hollow@ mesoporous TiO2,
which also confirmed the yolk−shell structure.
The FTIR spectra of CoFe2O4, CoFe2O4/SiO2/mesoporous
TiO2, and CoFe2O4@ hollow@ mesoporous TiO2 in the range
of 500−4000 cm−1 are given in Figure 4a. A broad stretching
band at 3000−3500 cm−1 in these three curves represented the
stretching vibration of hydroxyl groups (−OH) and hydrogen
bonds owing to the ambient water from the surrounding
atmosphere.49,50 The characteristic peak of CoFe2O4 was
detected in the CoFe2O4/SiO2/mesoporous TiO2 and
CoFe2O4@ hollow@ mesoporous TiO2 samples. In addition,
a new weak band at 793.7 cm−1 was observed in these two
samples. It was generally believed that the infrared spectrum at
400−900 cm−1 was attributed to Ti−O vibrations.51 Mean-
while, from the curves of these three samples, two specific
peaks of spinel ferrites could be detected in the range 500−750
cm−1. The low band at about 535 cm−1 and the high band at
about 580 cm−1 were attributed to the vibration of metal−
oxygen bond at tetrahedral site and octahedral site,
respectively.52 In addition, the characteristic peak of Si−O
was observed at 1065.6 cm−1 in the curve of CoFe2O4@SiO2@
mesoporous TiO2 sample,44 indicating the existence of SiO2.
Especially, the sharp peak at 1065.6 cm−1 only existed in the
CoFe2O4@SiO2@ mesoporous TiO2 sample. No correspond-
ing peak of Si−O was observed in the CoFe2O4@ hollow@
mesoporous TiO2 sample, further proving the successful
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removal of the silicon interlayer. This phenomenon further
demonstrated the existence of yolk−shell structure.
XPS analysis was carried out to further investigate the
surface elemental composition and the chemical state of
individual elements in the CoFe2O4@ hollow@ mesoporous
TiO2 catalyst with yolk−shell structure. As shown in Figure 4b,
the XPS survey confirmed the presence of the elements Co, Fe,
O, and Ti in the CoFe2O4@ hollow@ mesoporous TiO2,
which was consistent with the results of EDS analysis. The
high-resolution spectra of Co 2p, Fe 2p, O 1s, and Ti 2p are
displayed in Figure 4c−f, respectively. In the Co 2p spectrum
(Figure 4c), two main signals of Co 2p3/2 and Co 2p1/2 were
observed at 779.2 eV (with a shakeup satellite peak at 785.7
eV) and 794.9 eV (with a shakeup satellite peak at 802.0 eV),
respectively.53,54 Figure 4d shows the high-resolution XPS
spectrum of Fe 2p, in which two spin−orbit doublets were
attributed to Fe 2p3/2 and Fe 2p1/2. Especially, the fitted two
peaks at 709.6 and 723.1 eV could be assigned to the
contributions from Fe3+ in the octahedral sites. In addition, the
two peaks at 711.8 and 725.2 eV belonged to the contributions
from Fe3+ in the tetrahedral sites,55 and the other two peaks
were attributed to shakeup satellites.56 In the O 1s spectrum
(Figure 4e), two peaks were fitted: one at 529.5 eV could be
assigned to surface lattice oxygen in the metal−oxygen bond,
and the other one at 531.5 eV could be assigned to the
adsorbed with the intrinsic oxygen vacancies on the sur-
face.57,58 With respect to the Ti 2p spectrum (Figure 4f), two
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Figure 5. Nitrogen adsorption−desorption isotherms (a) and the corresponding BJH pore size distributions (b) of the CoFe2O4@ hollow@
mesoporous TiO2 sample.

Scheme 2. Schematic Illustration of the Selectivity Preparation of BA (a) and SO (b)a

a
Reaction conditions: (a) 3 mmol of styrene, 8 mg of CoFe2O4@ hollow@ mesoporous TiO2, 2 mL of H2O, styrene/H2O2 = 1:3, 90 °C, 12 h; (b)
3 mmol of styrene, 8 mg of CoFe2O4/mesoporous TiO2, 2 mL of 1,4-dioxane, molecular oxygen, 90 °C, 8 h.

Figure 6. Effects of reaction temperature (a) and catalyst amount (b) on the catalytic performance of the CoFe2O4@ hollow@ mesoporous TiO2
yolk−shell catalyst. Reaction conditions: (a) 3 mmol of styrene, 8 mg of CoFe2O4@ hollow@ mesoporous TiO2, 2 mL of 1,4-dioxane, molecular
oxygen, 8 h; (b) 3 mmol of styrene, 2 mL of 1,4-dioxane, molecular oxygen, 90 °C, 8 h.

obvious fitted peaks were observed at 458.3 and 464.0 eV,
which corresponded to Ti 2p3/2 and Ti 2p1/2 of TiO2.59,60
To further investigate the structure of the as-prepared
CoFe2O 4@ hollow@ mesoporous TiO2 sample, the N 2
adsorption−desorption isotherms were carried out. As shown
in Figure 5a, the CoFe2O4@ hollow@ mesoporous TiO2
catalyst presented a type IV isotherm with a narrow hysteresis
loop, which was the characteristic curve in mesoporous
materials.36 The surface area obtained by the Brunauer−
Emmett−Teller method61 was 141.7 m2 g−1 for the CoFe2O4@
hollow@ mesoporous TiO2, which was 2.2 times higher than
that of pure CoFe2O4 (65.5 m2 g−1) in the previous study.36
The high surface area of the CoFe2O4@ hollow@ mesoporous
TiO2 sample might be attributed to the novel yolk−shell
structure. On the one hand, high surface area could facilitate
the diffusion of reactants toward active sites. On the other
hand, high surface area would be beneficial to the uniform
distribution of catalytically active sites.2,62 Furthermore, the
mean pore size obtained by the Barrett−Joyner−Halenda
(BJH) method63 from the desorption branches of the
isotherms (Figure 5b) was 3.1 nm for the CoFe2O4@ hollow@
mesoporous TiO2.
19943
Selective Oxidation of Styrene. Initially, the CoFe2O4@
hollow@ mesoporous TiO2 yolk−shell catalyst was tested in
the oxidation of styrene with either molecular oxygen or
hydrogen peroxide as the oxidant (Scheme 2). Interestingly,
SO was found to be the main product with a styrene
conversion of 81.3% and a SO selectivity of 67.3% in the
presence of molecular oxygen. When hydrogen peroxide was
used as the oxidant, 96.3% styrene conversion and 46.6%
selectivity for BA could be achieved.
Molecular Oxygen Oxidation Route. To investigate the
effect of reaction temperature on catalytic performance,
different temperatures in the range of 70−100 °C were
evaluated. The results are summarized in Figure 6a. Usually,
increased conversion was observed with higher reaction
temperatures.64 However, the conversion of styrene exhibited
a volcano-type relationship with respect to the reaction
temperature. On the one hand, high temperature would
promote the proceeding of side reaction, such as ring-opening
reaction of epoxides.65 On the other hand, high temperature
was also unfavorable for the dissolution of molecular oxygen
into the reaction mixture. For the SO selectivity versus reaction
temperature, it displayed the same trend with styrene
conversion. More side reactions with the generation of more
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unwanted byproducts could occur with high temperatures.1,66 Table 1. Effect of the Addition of Urea on Catalytic
Taking both the catalytic selectivity and activity into Performancea
consideration, 90 °C was selected as the optimal reaction
selectivity (%)
temperature for further investigations.
The amount of catalyst from 0 to 12 mg was used to study entry urea (g) conversion (%) SO BzA BA others
the effect of catalyst amount on the SO selectivity and styrene 1 0 97.7 65.8 15.1 10.5 8.6
conversion. When the catalyst amount was increased from 0 to 2 0.025 96.3 66.7 19.9 10.2 3.2
8 mg, the conversion of styrene could be remarkably increased 3 0.05 98.7 65.9 17.3 13.1 3.7
from 13.7 to 81.3% due to more accessible active sites for the 4 0.075 87.2 70.2 21.4 8.4
oxidation reaction (Figure 6b). And the conversion showed a 5b 0.075 89.7 70.4 19.4 10.2
slight increase when the catalyst amount was further increased 6c 0.075 96.8 71.7 13.4 12.3 2.6
to 12 mg. However, the variation trend in the conversion of a
Reaction conditions: 3 mmol of styrene, 8 mg of CoFe2O4@
styrene was not similar to that in the selectivity for SO. The hollow@ mesoporous TiO2, 2 mL of 1,4-dioxane, molecular oxygen,
plotting of SO selectivity with respect to the catalyst amount 90 °C, 12 h. bThe reaction time was 18 h. cThe reaction time was 24
exhibited a volcano-shaped curve. The highest selectivity was h.
obtained when the amount of catalyst was 8 mg. This
phenomenon might be attributed to the increased magnetic
agglomeration of the catalyst with the increase in the amount Hydrogen Peroxide Oxidation Route. The influence of
of catalysts,64 leading to reduced interaction between reactants reaction temperature on the oxidation of styrene was evaluated
and active sites. Therefore, 8 mg of catalyst was chosen as the in the range of 70−100 °C. The results are listed in Figure 7a.
optimum amount of catalyst for the following research. It could be seen that high temperature did not favor high
Different solvents might interact with or modify the catalyst selectivity for BA. The selectivity for BA increased quickly from
surface, thus playing a vital role in the accessibility of active 0 to 46.6% when the temperature was increased from 70 to 90
sites.7 For this reason, various types of solvents were used to °C. With higher temperatures, the selectivity decreased to
study the effect of different solvents on the oxidation of 41.2%. With an increase in reaction temperature from 70 to 90
styrene. The results are illustrated in Table S2. Among all of °C, the conversion of styrene could be remarkably increased
these solvents, 1,4-dioxane was found to give the best catalytic from 12.9 to 96.3%. Subsequently, no obvious increase was
performance with a styrene conversion of 97.7% and a SO detected with a further increase in the temperature. Taking
selectivity of 65.8%. Other solvents, such as acetonitrile, both the catalytic activity and selectivity into consideration, 90
ethanol, tetrahydrofuran, and dimethylformamide, showed low °C was selected as the optimal reaction temperature for further
conversion of styrene (<35%) and selectivity for SO (<50%). research.
To our surprise, the oxidation of styrene was suppressed when Similar to the molecular oxygen route, the amount of
some solvents were applied in the reaction (entries 2−4). catalyst from 0 to 12 mg was evaluated. As expected, the
Considering the relatively low boiling point of these solvents, conversion of styrene increased rapidly when the amount of
we performed the same experiments at a lower temperature catalyst ranged from 0 to 6 mg. Then, the conversion remained
(60 °C, entries 7−9). The results showed lower conversion. As constant even if the catalyst increased from 6 to 12 mg.
a kind of ether solvent, 1,4-dioxane could undergo autoxidation Interestingly, the BA selectivity exhibited a volcano-type
to produce unstable and dangerous hydroperoxide and relationship with respect to the catalyst amount. The highest
peroxides products.67 Therefore, 1,4-dioxane was considered selectivity was obtained when the amount of catalyst was 8 mg
to be the suitable solvent in the molecular oxygen oxidation (Figure 7b). The variation trend for the selectivity was similar
route. to the molecular oxygen route. The magnetic agglomeration
Liu et al.36 found that the basicity of acetonitrile might phenomenon might be the cause for this phenomenon.64 Thus,
promote the improvement in the SO selectivity, which inspired 8 mg was selected as the optimum amount of catalyst in the
researchers to introduce urea into the reaction system. To following investigations.
further increase the SO selectivity, various amounts of urea Table S3 shows the effect of different solvents on the
were added to the reaction mixture. The results are conversion of styrene and products distribution over the
summarized in Table 1. As observed, the addition of urea CoFe2O4@ hollow@ mesoporous TiO2 catalyst. H2O was
reduced the conversion of styrene inevitably (entry 4) due to found to give the highest conversion of styrene and selectivity
the stabilization effect of urea on the peroxides. Thus, extended for BA owing to the fact that the solvent with a high dielectric
reaction time was necessary to obtain high conversion (entries constant favored the oxidation of styrene.64 Other solvents
5 and 6). However, a slight increase in the SO selectivity was displayed low selectivity for BA (<25%) with high conversion
observed with the addition of urea. After further increasing the (>85%).
reaction time to 24 h, the yield of SO could reach 69.4% with a The effect of molar ratio of styrene to H2O2 on the catalytic
styrene conversion of 96.8% and SO selectivity of 71.7% (entry performance was investigated. The amount of styrene
6). remained constant when the amount of H2O2 was altered.
After systematically investigating the effects of reaction The selectivity for BA increased from 44 to 68.7% when the
parameters on the catalytic performance in the oxidation styrene/H2O2 molar ratio was altered from 1:2 to 1:4 (Figure
reaction of styrene, the optimal reaction conditions were listed 7c). However, the selectivity for BA dropped to 61.0% when
as follows: reaction temperature, 90 °C; reaction time, 24 h; 8 the molar ratio of styrene/H2O2 was further decreased to 1:5.
mg of CoFe2O4@ hollow@ mesoporous TiO2 catalyst; 0.075 g In addition, the conversion was almost 100%. When excessive
of urea; 1,4-dioxane as the solvent. Under these reaction H2O2 was added as the oxidant, large occupation of the active
conditions, the conversion of 96.8% was obtained with a sites by H2O2 would take place, resulting in few accessible
selectivity of 71.7%. active sites for styrene.36 Therefore, the ratio of 1:4 was
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Figure 7. Effects of reaction temperature (a), catalyst amount (b), and molar ratio of styrene/H2O2 (c) on the catalytic performance of the
CoFe2O4@ hollow@ mesoporous TiO2 catalyst. Reaction conditions: (a) 3 mmol of styrene, 8 mg of CoFe2O4@ hollow@ mesoporous TiO2, 2
mL of H2O, styrene/H2O2 = 1:3, 12 h; (b) 3 mmol of styrene, 2 mL of H2O, styrene/H2O2 = 1:3, 90 °C, 12 h; (c) 3 mmol of styrene, CoFe2O4@
hollow@ mesoporous TiO2, 2 mL of H2O, 90 °C, 24 h.

Figure 8. Recycling performance of the CoFe2O4@ hollow@ mesoporous TiO2 yolk−shell catalyst: (a) molecular oxygen oxidation route, reaction
conditions: 3 mmol of styrene, 8 mg of catalyst, 2 mL of 1,4-dioxane, molecular oxygen, 90 °C, 12 h; (b) hydrogen peroxide oxidation route,
reaction conditions: 3 mmol of styrene, 8 mg of CoFe2O4@ hollow@ mesoporous TiO2, 2 mL of H2O, styrene/H2O2 = 1:4, 90 °C, 24 h.

Figure 9. Evaluation of the catalytic performance of the CoFe2O4, CoFe2O4/TiO2 core−shell structure, TiO2, and CoFe2O4@ hollow@
mesoporous TiO2 yolk−shell structure. Reaction conditions: 3 mmol of styrene, 8 mg of catalyst, 2 mL of 1, 4-dioxane, molecular oxygen, 90 °C, 12
h.

selected as the optimal molar ratio in hydrogen peroxide
oxidation route.
To further investigate the influence of reaction time on the
oxidation of styrene with hydrogen peroxide as the oxidant, the
reaction time was increased from 12 to 30 h. As shown in
Table S3, the selectivity for BA increased from 46.0 to 52.6%
when the reaction time was increased from 12 to 24 h, which
was attributed to further oxidation of benzaldehyde. And the
BA selectivity further showed a slight decrease when the
reaction time was further increased to 30 h. Thus, 24 h was
selected as the optimum reaction time.
Last but not least, the effect of silicate residue in the etched
sample was also a factor that could not be ignored. Different
amounts of sodium silicate were selected to add into the
reaction system. The results are summarized in Table S4.
Regardless of the oxygen oxidation route or the hydrogen
peroxide oxidation route, the silicate residue in the etched
sample might have little effect on the reaction efficiency.
19945
Recycling Performance of the Catalyst. Catalyst
recyclability is an important parameter for heterogeneous
catalysis.68 The CoFe2O4@ hollow@ mesoporous TiO2 with
yolk−shell structure could be easily separated from the
reaction mixture by applying a magnetic field to the surface
of the tube. The magnetic separation made the recovery of the
CoFe2O4@ hollow@ mesoporous TiO2 catalyst easier. As
shown in Figure 8a, both the catalytic activity and SO
selectivity changed slightly after five consecutive runs with the
catalyst from the same batch, suggesting the good stability and
recyclable applicability of the CoFe2O4@ hollow@ mesopo-
rous TiO2 catalyst.
The recyclability of the catalyst was also tested with
hydrogen peroxide as the oxidant. Using the same recycle
method in molecular oxygen oxidation route, the CoFe2O4@
hollow@ mesoporous TiO2 catalyst with yolk−shell structure
was subjected to five consecutive runs. As shown in Figure 8b,
the conversion of styrene and the selectivity for BA changed
slightly after five runs. The decrease in the selectivity of BA
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Industrial & Engineering Chemistry Research
could be attributed mainly to unavoidable loss of the catalyst
during the process of collection.
The TEM image (Figure S2) of the spent catalyst displayed
no obvious changes with those of fresh catalyst. All of these
results demonstrated that the CoFe2O4@ hollow@ meso-
porous TiO2 catalyst with yolk−shell structure displayed good
stability and recyclable applicability for the oxidation of styrene
under optimal conditions.
Comparison between Core−Shell Structure and
Yolk−Shell Structure. Reaction Efficiency. The
CoFe2O4@ hollow@ mesoporous TiO2 yolk−shell catalyst
was tested in the oxidation of styrene with molecular oxygen as
the oxidation. For comparison, CoFe2O4 nanoparticles,
CoFe2O4/TiO2 core−shell catalysts, and TiO2 were also tested
under the same reaction conditions. SO was found to be the
main product. Figure 9a shows the plot of styrene conversion
versus reaction time. For all of the four catalysts, the
conversion of styrene increased with extended reaction time.
Especially, the CoFe2O4@ hollow@ mesoporous TiO2 catalyst
with yolk−shell structure exhibited the highest initial activity.
The conversion of styrene quickly reached 58.3% in the first 4
h. Then, the conversion increased continuously to nearly 100%
within a total reaction time of 16 h. Interestingly, the
conversion of styrene catalyzed by CoFe2O4@ hollow@
mesoporous TiO2 displayed the highest level compared with
other three catalysts. However, the selectivity for SO in Figure
9b did not show the same trend as the conversion of styrene.
For CoFe2O4@ hollow@ mesoporous TiO2 catalyst with
yolk−shell structure, the selectivity for SO remained constant
(60−65%). However, the selectivity for SO increased rapidly in
the first 4 h and then decreases when other three catalysts were
applied in the oxidation reaction. The decrease in the
selectivity for SO was mainly due to the overoxidation of SO
and the hydrolysis of SO into 1-phenyl-1,2-ethanediol.36,66
This phenomenon indicated that CoFe 2O4@ hollow@
mesoporous TiO2 displayed better catalytic activity toward
the epoxidation. The yolk−shell structure was beneficial to the
formation of epoxides. On the contrary, the catalysts in the
control experiments showed catalytic activity toward epox-
idation reaction and ring-opening reaction, which was the
common phenomenon in the design of catalysts for
epoxidation reaction. When TiO2, CoFe2O4, and CoFe2O4/
TiO2 were used as the catalyst, process optimization was
necessary for the high SO selectivity. Correspondingly, the
yield of SO increased with extended reaction time and reached
the platform after 12 h (Figure 9c). Taking the reaction time
into consideration, the high yield of SO for CoFe2O4@
hollow@ mesoporous TiO2 yolk−shell catalyst was 64.3% with
a styrene conversion of 97.7% and SO selectivity of 65.8%.
For the hydrogen peroxide route, CoFe2O4, CoFe2O4/TiO2,
and TiO2 (8 mg) were also tested under the same reaction
conditions (Table 2, entries 2−4), which also showed lower
catalytic activity compared to CoFe2O4@ hollow@ meso-
porous TiO2.
Reaction Kinetics. Kinetics studies of the CoFe2O4@
hollow@ mesoporous TiO2 catalyst with yolk−shell structure
at various temperatures showed that pseudo-first-order kinetics
could be applied for the evaluation of the catalytic rate (Figure
10a,c). The kinetic equation for the reaction could be
expressed as follows
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Table 2. Effect of Different Catalysts on Catalytic
Performance
selectivity (%)
entry time (h) conversion (%) BA BzA SO
1a 24 94.6 52.6 3.1
2b 24 96.2 45.5 4.2
3c 24 95.8 35.5 14.0
4d 24 97.0 36.4 6.9
a
Reaction conditions: 3 mmol of styrene, 8 mg of CoFe2O4@
hollow@ mesoporous TiO2, 2 mL of H2O, styrene/H2O2 = 1:3, 90
°C. bThe same reaction conditions with (a), but using 8 mg of
CoFe2O4 as the catalyst. cThe same reaction conditions with (a), but
using 8 mg of CoFe2O4/TiO2 as the catalyst. dThe same reaction
conditions with (a), but using 8 mg of TiO2 as the catalyst.
ij C yz
−lnjjj zzz = kt
j C0 z
k {
(4)
where t is the reaction time; k is the apparent rate constant;
and C0 and C are the initial concentration of styrene and the
concentration of styrene at the time t, respectively.36 From the
slopes of these fitted lines, the k values for the reaction
performed at 70, 80, 90, and 100 °C could be calculated to be
0.1873, 0.2968, 0.3487, and 0.2002 h−1, respectively (molec-
ular oxygen oxidation route). The k value at 100 °C decreased
significantly since the temperature was close to the boiling
point of 1,4-dioxane, making it difficult for molecular oxygen to
interact with 1,4-dioxane. For the hydrogen peroxide oxidation
route, the k values could be calculated to be 0.110, 0.2385, and
1.0639 h−1 with respect to 80, 90, and 100 °C, respectively.
Due to the low conversion of styrene at 80 °C in the hydrogen
peroxide oxidation route, reaction time from 6 to 10 h was
chosen to investigate the apparent rate constant (Figure 10c,d,
inset). All of the k values are collected in Table S5.
Further, the apparent activation energy (Ea) could be
calculated by the Arrhenius equation
Ea
ln k = ln A −
RT (5)
where R is the molar gas constant, T is the reaction
temperature, and A is the preexponential factor. From the
slope of the fitted line with respect to ln k versus 1000/T
(Figure 10e), the Ea value for the oxidation reaction of styrene
using molecular oxygen oxidation route could be calculated to
be 32.3 kJ/mol, which was lower than the previously reported
data (42.4 and 36.4 kJ/mol, respectively).2,36 And the Ea value
for the oxidation reaction of styrene using hydrogen peroxide
oxidation route is 39.9 kJ/mol (Figure 10e).
In addition, the apparent activation energies of CoFe2O4/
TiO2 were also calculated to be 67.9 and 66.7 kJ/mol,
respectively (Figure 10f). An obvious decrease in the activation
energies was observed when the CoFe2O4@ hollow@
mesoporous TiO2 yolk−shell structure was formed (Table
3). On the one hand, CoFe2O4@ hollow@ mesoporous TiO2
yolk−shell structure with a large specific surface area was
obtained through etching of silicon layer, promoting the
interaction between catalysts and reactants. On the other hand,
the interaction between active oxygen species and metal
cations would be realized in the CoFe2O4@ hollow@
mesoporous TiO2, resulting in the selective oxidation of
styrene and the improvement in the catalytic activity.
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Figure 10. ln (C/C0) versus reaction time and Arrhenius plot of the styrene oxidation reactions performed at different temperatures: molecular
oxygen oxidation route (a, b, e, f); hydrogen peroxide oxidation route (c, d, e, f).

Table 3. Apparent Activation Energies of Different Catalysts peroxy radical. The hydroperoxide was formed when the
Using Different Oxidants peroxy radical abstracted a hydrogen atom from another 1,4-
dioxane molecule. Subsequently, the metal (Co, Fe, and Ti)
oxidation Ea
entry route catalysts (kJ/mol) sites coordinated with the activated hydroperoxide molecules,
1 molecular CoFe2O4/TiO2 67.9
yielding a metal-peroxo species (I) and 1,4-dioxane. The
2 oxygen CoFe2O4@ hollow@ mesoporous TiO2 32.3
complex (I) would attack the CC bonds of the styrene
route molecules to give an intermediate (II). Migratory insertion of
3 hydrogen CoFe2O4/TiO2 66.7 the intermediate (II) would afford metal-peroxo metallocycles
4 peroxide CoFe2O4@ hollow@ mesoporous TiO2 39.9
route (III). Four-membered cyclic peroxide radical (IV) was
generated along with the simultaneous release of metal species.
Reaction Mechanism. Depending on the reaction data and The obtained peroxide intermediate (IV) further reacted with
previous studies,2,5,36,62 mechanistic research of the oxidation another styrene to form styrene oxide. In addition, thermal
reaction was investigated. Superoxide radical scavenger decomposition of unstable peroxide intermediate (IV) also
molecules, benzoquinone (BQ) and 4-hydroxy-2,2,6,6-tetra- could occur to afford benzaldehyde.
methyl-piperidinooxy (TEMPOL), were used to check if For the hydrogen peroxide oxidation route, the mechanism
superoxide radical (O·− 2 ) was involved in the reaction. As
proposed here was similar to the mechanism proposed by
expected, introduction of radical scavengers suppressed the Ghosh et al.15 First, active Ti4+ centers interacted with H2O2,
reaction obviously whether it was molecular oxygen oxidation affording a metal-peroxo intermediate (named as Intermediate-
route or hydrogen peroxide oxidation route (Table S6). These I). Then, two types of oxametallacycle intermediates (named
results suggested that a superoxide radical intermediate was Intermediate-IIa and Intermediate-IIb) were formed through
involved in the reaction pathway. the reaction between styrene and Intermediate-I. With the
The possible reaction pathways for the two different transfer of oxygen to the double bond of styrene, styrene oxide
oxidation routes catalyzed by CoFe2O4@ hollow@ mesopo- was formed. In addition, benzaldehyde would be formed
rous TiO2 catalyst with yolk−shell structure were proposed through the breakage of C−C bond of Intermediate-IIb.
and are illustrated in Scheme 3. In the molecular oxygen Further oxidation of benzaldehyde would promote the
oxidation route, an active hydrogen atom in 1,4-dioxane was formation of benzoic acid.
abstracted, affording a 1,4-dioxane radical. Then, the resulting Comparison Our Method with Other Reported
1,4-dioxane radical reacted with molecular oxygen to yield the Methods for the Oxidation of Styrene. To give a
19947 https://dx.doi.org/10.1021/acs.iecr.0c03884
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Industrial & Engineering Chemistry Research pubs.acs.org/IECR Article

Scheme 3. Schematic Illustration of the Possible Reaction Mechanism for the Styrene Oxidation Reaction with the CoFe2O4@
Hollow@ Mesoporous TiO2 Yolk−Shell Catalysta

a
(a) Molecular oxygen oxidation route; (b) hydrogen peroxide oxidation route.

Table 4. Catalytic Oxidation of Styrene into SO or BA Using Various Methods

yield
entry catalyst oxidant T (°C) styrene conversion (%) SO (%) BA (%) references
1 Pd@Co TBHP 50 100 75 69
2 Co-Y-ZrO2 air 120 >99 68 70
3 MnFe-based hydrotalcite H2O2 50 19.6 10.6 71
4 CoFe2O4 TBHP 80 96.4 82.7 36
5 CoFe2O4@ hollow@ mesoporous TiO2 oxygen balloon 90 96.8 69.4 11.9 this work
6 nano-HKUST-1 TBHP 80 99 75 72
7 [3-ampH]4[{Zn(3-ampy)(H2O)4}Mo7O24]·4H2O H2O2 80 100 3.8 69 73
8 CoFe2O4@ hollow@ mesoporous TiO2 H2O2 90 94.5 68.7 this work

reasonable evaluation of our developed method for the
synthesis of SO and BA from styrene, the developed method
in this work was compared with other recently reported
methods. As shown in Table 4, various green oxidants, such as
TBHP, H2O2, and air, have been reported for the catalytic
oxidation of styrene into SO or BA. Although higher styrene
conversion and SO yield could be obtained (entry 1), Pd-based
catalysts may not be applied on a large scale in industry. Other
non-noble catalysts also had some distinct drawbacks such as
the need for high temperature (entry 2) and low catalytic
activity (entry 3). Owing to the stronger oxidation of TBHP,
pure CoFe2O4 catalyst gave a yield of 82.7% for SO (entry 4).
In this study, molecular oxygen or hydrogen peroxide at
ambient pressure, accompanying medium reaction temper-
ature, was used (entries 5 and 8), avoiding noble metal and
high temperature. Furthermore, the used catalyst could be
quickly separated from the reaction system with an external
magnetic field. Importantly, SO and BA could be selectively
19948
obtained by adjusting oxidant and the reaction solvent when
the same catalyst was used.
■ CONCLUSIONS
In conclusion, a novel catalyst CoFe2O4@ hollow@ meso-
porous TiO2 catalyst with yolk−shell structure has been
developed and applied in the selective oxidation of styrene.
With molecular oxygen as the oxidant, styrene oxide was
selectively obtained. With hydrogen peroxide as the oxidant,
benzoic acid was selectively synthesized. Under the optimum
reaction conditions, the yield of SO could reach 69.4% with a
styrene conversion of 96.8% and a SO selectivity of 71.7%.
Furthermore, the yield of BA reached 64.9% with a styrene
conversion of 94.5% and a BA selectivity of 68.7%. In addition,
the yolk−shell structure displayed higher reaction conversion
and selectivity compared with the normal core−shell structure.
Through calculation, yolk−shell CoFe2O4@ hollow@ meso-
porous TiO2 displayed lower Ea values in the oxidation of
styrene compared with core−shell CoFe2O4/TiO2. Interest-
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Ind. Eng. Chem. Res. 2020, 59, 19938−19951
Industrial & Engineering Chemistry Research
ingly, the Ea values of yolk−shell CoFe2O4@ hollow@
mesoporous TiO2 was approximately half of the Ea values of
core−shell CoFe2O4/TiO2 in two oxidation routes. The
addition of superoxide radical scavenger molecules revealed
that superoxide radical was involved in the oxidation reaction.
Corresponding mechanisms in these two routes were
proposed. With the attractive catalytic activity and product
selectivity, magnetic separation and reusability of the catalyst
would promote broad application in the chemical trans-
formation.
■
ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.iecr.0c03884.
EDX information of CoFe2O4@ hollow@ mesoporous
TiO2, TEM image of the used CoFe2O4@ hollow@
mesoporous TiO2, effect of different solvents on catalytic
performance, effect of sodium silicate on catalytic
performance, a list of the apparent rate constants of
different catalysts, and the effect of radical scavenger on
catalytic performance (PDF)
■
AUTHOR INFORMATION
Corresponding Author
Zhao Yang − College of Engineering, China Pharmaceutical
University, Nanjing 211198, P. R. China; orcid.org/0000-
0003-1283-1947; Phone: +86-18013895668;
Email: yzcpu@cpu.edu.cn
Authors
Liang Liu − College of Engineering, China Pharmaceutical
University, Nanjing 211198, P. R. China
Wei He − College of Biotechnology and Pharmaceutical
Engineering, Nanjing Tech University, Nanjing 211816, P. R.
China
Zheng Fang − College of Biotechnology and Pharmaceutical
Engineering, Nanjing Tech University, Nanjing 211816, P. R.
China
Kai Guo − College of Biotechnology and Pharmaceutical
Engineering and State Key Laboratory of Materials-Oriented
Chemical Engineering, Nanjing Tech University, Nanjing
211816, P. R. China; orcid.org/0000-0002-0013-3263
Zhixiang Wang − College of Engineering, China Pharmaceutical
University, Nanjing 211198, P. R. China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.iecr.0c03884
Author Contributions
L.L. and W.H. contributed equally to this work. The
manuscript was written through contributions of all authors.
All authors have given approval to the final version of the
manuscript.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This research was supported by The National Natural Science
Foundation of China (21776130 and 21908094); the State
Key Laboratory of Materials-Oriented Chemical Engineering
(KL19-01); and the Top-notch Academic Programs Project of
Jiangsu Higher Education Institutions.
19949
■
pubs.acs.org/IECR Article
ABBREVIATIONS
SO styrene oxide
BzA benzaldehyde
BA benzoic acid
■
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