Reac Kinet Mech Cat

https://doi.org/10.1007/s11144-018-1429-6

Highly selective oxidation of styrene to benzaldehyde

over Fe3O4 using H2O2 aqueous solution as oxidant

Lulu Xie1 • Hongxia Wang1 • Bin Lu1 • Jingxiang Zhao1 •

Qinghai Cai1

Received: 16 February 2018 / Accepted: 3 June 2018

Ó Akadémiai Kiadó, Budapest, Hungary 2018

Abstract Fe3O4 was prepared by an alternative method using the dropwise addition
of FeCl3 and FeSO4 precursor solutions into a NaOH solution, as proved by XRD,
TEM and magnetic measurements. The Fe3O4 material was confirmed to be well-
crystallized magnetite with an average size of about 21.5 nm and stronger super-
paramagnetic with a saturation magnetization of 57.04 emu/g and it was found to be
an effective catalyst for liquid-phase oxidation of styrene to benzaldehyde (BzH)
with H2O2 as oxidant, getting ca. 100% selectivity to BzH with 40.4% conversion of
styrene. This catalyst can be easily recovered by a simple magnetic separation and
effectively reused. However, the reaction mechanism was confirmed by in situ
DRIFTS spectra analysis and according to literature reports.

Keywords Styrene  Iron oxide  H2O2  Oxidation  Magnetic separable

catalyst

Introduction

Selective oxidation of styrene at side chains is a very important reaction because the
products styrene oxide and benzaldehyde are versatile synthetic intermediates in
chemical industries [1]. Especially, benzaldehyde has widespread applications in

Electronic supplementary material The online version of this article (https://doi.org/10.1007/s11144-

018-1429-6) contains supplementary material, which is available to authorized users.

& Qinghai Cai

caiqinghai@yahoo.com
1
Key Lab for Photonic & Electronic Bandgap Materials, Ministry of Education, School of
Chemistry and Chemical Engineering, Harbin Normal University, No. 1 Shida Road Limin
Development Zone, Harbin 150025, People’s Republic of China

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perfumery, pharmaceuticals, dyestuffs and agrochemicals [2]. However, the

oxidation of styrene is somewhat difficulty because it is a terminal olefin. Many
efforts have been developed to increase in the controllable conversion of styrene to
benzaldehyde [3–5], including various homogeneous and heterogeneous catalysis
processes. The former faces a huge challenge of removing catalysts from the
reaction mixture and some cases represent rather poor catalytic activity [3, 6]; and
the latter is considered as more efficient and environment friendly system for green
chemistry principles and thus various kind of catalysts in this trend have been
employed for catalyzing the oxidation of alkene, involving Ce0.3Co0.7Fe2O4 [7], Ag-
WO3 [8], V-MCM-48 [9], Ti-MCM-41 [10], V/SBA-15 [11], W/SiO2 [12], Fe/SBA-
15 [13] and H3PW12O40/SBA-15 [14] etc. Although these liquid-phase oxidation
systems using H2O2 oxidant exhibited good catalytic activity, these reactions are
usually allowed to proceed in organic solvents such as acetonitrile, acetone and 1,4-
dioxane. A significant mass loss of solvents is inevitable by the evaporation or over-
oxidation to CO2 during the oxidation reaction, which lead to environmental
pollution. Besides, these catalysts are also limited by complicated preparation
procedures with high cost. Therefore, the oxidation of styrene to BzH now depends
on the way to effective transfer terminal olefin into aldehyde using highly efficient,
low cost and environmentally-friendly heterogeneous catalyst. Iron oxides or/and
supported iron oxide catalysts could meet the above need, taking into account their
benign nature in terms of cost, toxicity, availability and environmental compati-
bility. Iron oxide actually has a long demonstrated high efficiency as a catalyst for a
variety of alcohol oxidations, partial oxidation of olefins to olefin oxide and
aldehyde [15–18]. Iron oxide nanoshells are active and selective catalysts for the
oxidation of styrene with molecular oxygen [19]. However, c-Fe2O3 represents low
catalytic activity and selectivity with prolonged reaction time (12 h) for the
oxidation of styrene [15, 16]. As part of our interest in green or sustainable catalysis
in organic synthesis, here we wish to report efficient and selective procedure for
solvent-free oxidation of styrene over Fe3O4 in H2O2 aqueous medium. This
catalytic progress using highly efficient and environment friendly iron oxide
catalysts with simply prepared technology has always been pursued by green or
sustainable chemistry.

Experimental

Preparation and characterization of iron oxide

Iron oxide was prepared by the following procedure: pre-prepared 84 g of NaOH

aqueous solution (1.25 mol/L) was added to a three-necked flask fitted with a
condenser and a stirrer. The flask was put in tank with ultrasonics and 65.41 g of
FeCl3 aqueous solution (5.41 g of FeCl36H2O in 60 mL distilled water) was added
to the NaOH solution dropwise under ultrasonics. After the completion of the
addition, the reaction mixture was continuously carried out under the same
conditions for 40 min, and then the mixture was heated in a water bath to 80 °C,
followed by adding 62.78 g of FeSO4 aqueous solution (2.78 g of FeSO47H2O in

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60 mL distilled water) to this mixture and stirring at this temperature for 2 h to

reach at about pH 12. After cooling down, the sol solution was filtered to remove the
filtrate. The obtained gel was washed with distilled water and anhydrous ethanol
three times. Thereafter, it was dried at 50 °C to afford Fe3O4.
The XRD pattern of the sample was performed on a Bruker-D8 advance X-ray
diffractometer with Cu Ka radiation (40 kV and 36 mA). The morphology and
particle size of the samples were observed by a FEI Tecnai F20 transmission
electron microscope (TEM). The magnetic measurement was performed on a
vibration sample magnetometer (Lake Shore 7410).
In situ DRIFTS spectra were measured by an FT-IR spectrometer (Bruker
TENSOR II) equipped with a diffuse reflectance optics accessory (Harrick Scientific
products Inc.). To clean the catalyst surface, the iron oxide sample was thermally
pretreated by heating at 50 °C for 2 h in vacuo prior to acquisition of DRIFTS
spectra. Thereafter, The build-up of the styrene and H2O2 onto the catalyst surface
was performed by taking them along by high purity N2 gas, followed by evacuating
from the system to about 9.8 9 10-4 Pa. After that, the DRIFTS spectra at 80 °C
were measured half an hour under vacuo condition.

Catalytic test

2 mL (17.5 mmol) of styrene and 0.15 g of the catalyst (Fe3O4) were added into a
25 mL three-necked flask fitted with a reflux condenser and a mechanical stirrer.
The reactor was heated to 80 °C in a water bath with electric heater, and then 8 mL
of 11% H2O2 (28.5 mmol, 2.9 mL of 30% H2O2 solved in 5.1 mL of distilled water)
was slowly dropped in. The resulting mixture was stirred at 80 °C for 2 h. At the
end of the reaction, the mixture solution was cooled down to room temperature and
extracted with 10 mL of toluene. The catalyst was separated by a magnet, washed
with water and ethanol, dried at 50 °C, and then reused in the next run. The upper
organic liquid in the reaction mixture was analyzed by GC (Agilent GC7820) and
GC–MS (Agilent GC7890A-MS5975C) using HP-5 column (30 m 9 0.32 mm 9
0.25 um) and FID detector (GC) with the temperature programming as following:
54–110 °C at heating rate of 15 °C/min and holding at 110 °C for 1 min; 110–
280 °C at heating rate of 25 °C/min and holding at 280 °C for 3 min. The bottom
aqueous solution in the mixture was analyzed by the iodometric method to
determine the concentration of surplus H2O2, and further to calculate the reaction
rate represented by the consumed millimoles of H2O2 per hour (mmol/h). Besides,
the conversion and selectivity was calculated by the following formula:
Conversion ¼ mt =m0  100%;
mt is the converted styrene mass, m0 is the initially added styrene mass.
Selectivity ¼ mb =mi  100%;
mb is the produced BzH mass, mi is the total mass of BzH and other by-products.

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Results and discussions

Preparation and characterization

Generally, Fe3O4 material is prepared using co-precipitation method by NaOH or

NH3H2O aqueous solution added to the solution of Fe2? and Fe3?, as shown in
Eq. (1) [20].
Fe2þ + 2Fe3þ þ 8OH ¼ Fe3 O4 þ 4H2 O ð1Þ
On basis of the reaction thermodynamics, complete precipitation of Fe3O4 should be
expected at pH between 8 and 14 [21]. As seen from Eq. (1), Fe3O4 is stable under
basic medium. Otherwise, Fe3O4 can be converted into c-Fe2O3 in the acidic
medium as shown in Eq. (2).

Fe3 O4 þ 2Hþ ¼ c  Fe2 O3 þ Fe2þ þ H2 O ð2Þ

As in our previously reported work [22], Fe3O4 was prepared by an alternative

way, using acid pickling waste added to the basic solution to ensure the pH ] 8
during the preparation process. Unlike our previous preparation procedure, Fe3?
(FeCl3) and Fe2? (FeSO4) solutions were used as precursors in the absence of
dispersant and the precipitation pH was adjusted to reach at pH 12, falling between
8 and 14 after FeSO4 solution added to the mixture solution. As a result, Fe3O4
nanoparticles were successfully prepared by the simple method.
The XRD pattern of as-prepared Fe3O4 material was depicted in Fig. 1. It was
clear that the Fe3O4 product was well crystallized and the characteristic diffraction
at 2h of 30.3°, 35.7°, 43.2°, 53.6°, 57.2° and 62.9°, corresponding to (220), (311),
(400), (422), (511) and (440) planes, could be readily identified as the cubic phase
of Fe3O4 (magnetite JCPDS 19-0629). Moreover, the average crystallite size of the
311
Intensity (a. u.)

440
511
220

400

422

10 20 30 40 50 60 70 80
2 Theta (o)

Fig. 1 XRD pattern of the product

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product was estimated to be 21.5 nm from Debye–Scherrer equation, which was

basically in agreement with one observed in TEM image (Fig. 2a). As seen from the
image, about 20 nm particles and 20 nm diameter of nanorods were clearly
observed although the aggregate of these particles and rods was remarkable. The
nanostructured material was further examined with high-resolution TEM. A typical
HRTEM image of nanostructured Fe3O4 was obtained as shown in Fig. 2b and the
lattice fringes in the image corresponding to a set of atomic planes within the
particles were obviously observed, exhibiting that the nanoparticle or rod is a single
crystal.
The magnetic property of the synthesized Fe3O4 particles was analyzed by
vibrating sample magnetometry. The field-dependent magnetization curve shown in
Fig. 3 exhibited the magnetization as a function of applied magnetic field. The
hysteresis was remarkably found because of M-H loop produced in the curve during
the external field cycle scanning from - 6 kOe to 6 kOe. The magnetic hysteresis
indicated superparamagnetic with the highest magnetization saturation M(s) of
57.04 emu/g, the coercivity value H(c) of 66.68 Oe, and the remanence value M(r) of

Fig. 2 Low- (TEM) and high-resolution transmission electron microscopy (HRTEM) images of Fe3O4

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60

40

M (emu/g)
20

0
-6000 -4000 -2000 0 2000 4000 6000
H (Oe)
-20

-40

-60

Fig. 3 Magnetic hysteresis curve for Fe3O4 nanoparticles

7.52 emu/g. This suggested that the Fe3O4 particles possess stronger magnetic
properties.

Catalytic activity

The oxidation of styrene under solvent-free condition was conducted at 80 °C. As

shown in Fig. 4, the conversion of styrene was increased with increasing the dose of
the catalyst up to maximum value of 40.4% when using 0.15 g of Fe3O4; and then it
was rapidly decreased during continuous increase in dose of the catalyst from 0.20
to 0.30 g. Obviously, the selectivity to BzH remained at ca. 100% all the time and
the abnormal decline of catalytic activity was probably ascribed to decomposition

100

90
Conversion/Selectivity (%)

80

70
Conversion
Selectivity
60

50

40

30

20

10
0.00 0.05 0.10 0.15 0.20 0.25 0.30
Amount of catalyst (g)

Fig. 4 Dependence of catalytic activity on dose of the catalyst. Reaction conditions: reaction
temperature 80 °C, time 2 h, molar ratio of H2O2 to styrene 4:1

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of H2O2 catalyzed by excess catalyst. For that reason, the surplus concentration of
H2O2 in these cases was monitored by iodometry and the experiment results as
shown in Fig. 5 exhibited that the consumed rate of H2O2 is greatly increased with
the amount of the catalyst. Moreover, the conversion calculated on the basis of
H2O2 was estimated to be 62.7% at the catalyst dose of 0.15 g and reaction time of
2 h, which is remarkably higher than that based on styrene. This phenomenon
indicated that the oxidation of styrene was likely carried out via first interaction
between H2O2 and Fe3O4 to produce OH or/and OOH, followed by OOH or OH
radicals oxidizing styrene to form BzH [23]. This process for the production of OH
or/and OOH radicals proceeded through the following equations [24]:
Fe2þ þ H2 O2 ¼ Fe3þ þ OH þ OH ð3Þ

Fe3þ þ H2 O2 ¼ Fe3þ þ Hþ þ OOH ð4Þ

Fe3þ þ OOH ¼ Fe2þ þ Hþ þ O2 ð5Þ

Also, the produced OOH could interact with Fe3? to release O2 gas, leading to extra
consuming H2O2, that is decomposition H2O2.
According to the proposed pathway for styrene oxidation [7], the highest
selectivity to BzH was possibly due to further rapid oxidation of styrene oxide
formed in the step 1, as shown in Scheme 1. In our experiments, no styrene oxide
and other oxidized products were detected in the reaction mixture (Fig. 4), implying
that the step 2 in Scheme 1 for further oxidation of styrene oxide to BzH was so fast
that it was immediately consumed away once the styrene oxide was produced. On
the other hand, it was reported that Brønsted acidic sites could greatly promote
overoxidation of BzH to benzoic acid or COx, while the catalysts with stronger

15

14
Consumed rate of H 2O2 ( mmol/h)

13

12

11

10

9
0.15 0.20 0.25 0.30
Amount of catalyst (g)

Fig. 5 Dependence of consumed rate of H2O2 on dose of the catalyst. Reaction conditions: reaction
temperature 80 °C, time 2 h, molar ratio of H2O2 to styrene 4:1

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O O
H
C CH2 CH CH2 C
H 2O 2 H
Step 1 Step 2

Scheme 1 Oxidation process of styrene

Lewis acidity on the surface represented better selectivity to aromatic aldehyde

[25, 26]. Iron oxide possesses higher Lewis acidity on its surface, and thus exhibits
high selectivity to BzH during the oxidation of toluene through inhibiting BzH
further oxidation into benzoic acid [27]. These reported results supported the high
selectivity to BzH obtained by oxidation of styrene in this case.
The dependence of the reactivity on reaction temperature was represented in
Fig. 6. The conversion of styrene was sharply increased as the temperature raising.
Expectedly, the selectivity to BzH was independent on the reaction temperature
with holding at ca. 100% in the temperature range from 60 to 80 °C. Thereafter, the
selectivity was greatly decreased when the temperature increased to 90 and 100 °C.
The decrease in selectivity to BzH was confirmed to be relative to polymerization of
styrene at high temperature because polystyrene was obtained via separated from
the reaction mixture. The FT-IR and 1H NMR spectra of the polystyrene were
measured and represented in Figs. S1 and S2 in the Supplementary Information.
As the used amount of styrene kept constant, the dependence of H2O2/styrene
molar ratio on the catalytic activity was investigated, and the results were depicted
in Fig. 7. It could be seen that the conversion was increased with increasing the
ratio. At the same time, the increase in the molar ratio led the selectivity to BzH to
falling down when the ratio was exceeding 4:1, showing that excess H2O2 was
disadvantageous to selective synthesis of BzH. Thus, lower concentration of H2O2
(11%) solution was feasible to the process of styrene oxidation.

100
Conversion/Selectivity (%)

80

60 Conversion
Selectivity

40

20

60 70 80 90 100
Reaction temperature ( oC)

Fig. 6 Dependence of catalytic activity on reaction temperature. Reaction conditions: catalyst 0.15 g,
time 2 h, molar ratio of H2O2 to styrene 4:1

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100

90

Conversion/Selectivity (%)
80

Conversion
70
Selectivity

60

50

40

30

2 3 4 5 6
Molar ratio of H2O2 /Styrene

Fig. 7 Dependence of catalytic activity on molar ratio of H2O2 to styrene. Reaction conditions: reaction
temperature 80 °C, time 2 h, catalyst 0.15 g

The catalytic performance-time profile of the oxidation of styrene by H2O2 at

80 °C using Fe3O4 as catalyst was shown in Fig. 8. The conversion was increased in
the time range from 1 to 3 h, giving 40.4% conversion with ca. 100% selectivity to
BzH at 2 h and 70.8% conversion with 90.0% selectivity at 3 h. As the reaction
proceeded beyond 3 h, the conversion of styrene remained unchanged with the
reaction proceeding from 3 to 5 h, which was possibly due to decomposition of
H2O2 on the catalyst surface. Moreover, as the time was beyond 2 h, the selectivity
to BzH remarkably fell down.

100

90
Conversion/Selectivity (%)

80

70

60

50 Conversion
Selectivity
40

30

20

10
1 2 3 4 5
Reaction time (h)

Fig. 8 Dependence of catalytic activity on reaction time. Reaction conditions: reaction temperature
80 °C, catalyst 0.15 g, molar ratio of H2O2 to styrene 4:1

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In situ DRIFTS spectra of the styrene and H2O2 and the reaction
mechanism

In situ DRIFTS spectra of the styrene and H2O2 at 80 °C and different time were
displayed in Fig. 9. As compared with FT-IR spectrum of Fe3O4 catalyst (Fig. 10),
The characteristic peak at 586.7 cm-1 corresponding to stretching vibration of Fe–
O bond shifted to 668.2 cm-1 due to adsorption of the reactants styrene and H2O2
on the catalyst surface by means of interacting with Fe2? or Fe3? species. The
intensity of the peak was greatly weaken as the adsorption time prolonging until the
peak basically disappeared at the time of 3 h, and a new peak appeared at
678.5 cm-1 at that time (Fig. 9a). This finding indicated stronger interaction
between the reactants and active sites Fe2? or Fe3? species on the catalyst surface.
Synchronously, Fig. 9b represented that the characteristic peak at 1652.9 cm-1
assigned to C=C vibration in styrene molecule was also weaken as the adsorption
proceeded and it almost disappeared at 3 h. However, a peak around 1700 cm-1
corresponding to carbonyl group was not found, which implied that the conversion
of styrene into styrene oxide on the catalyst surface was possibly carried out, just
like description in Scheme 1. Furthermore, abundant hydroxyl groups, attributed to
OH or/and OOH radicals produced by interaction between H2O2 and Fe2? or Fe3?
species on the catalyst surface were found at 3500–3800 cm-1. As the reaction
proceeded the intensity of these peaks was remarkably decreased, meaning that the
OH or OOH radicals were consumed for oxidizing styrene to styrene oxide. Based
on these results and literature reports [28, 29], the reaction mechanism was proposed
as shown in Scheme 2.
Firstly, H2O2 and styrene were adsorbed on the surface of the catalyst via
interaction with the active sites of Fe2? or Fe3?. The adsorbed H2O2 molecule is
reduced by Fe2? to form OH radicals or OH- ions on the surface and the
interaction between H2O2 and Fe3? could produce OOH radicals [24, 30]; then the
adsorbed styrene interacted with adsorbed OOH or OH to form phenyl
hydroperoxyl intermediate, followed by the intermediate converted into styrene
oxide on the surface. Thereafter, the styrene oxide was continuously oxidized by
OOH or OH on the interface between the catalyst and the mixture solution to
produce BzH according to the DRIFT analysis.

Reusability of the catalyst

The recovery and recycle of the used catalyst is one of the most important criteria
for industrial based catalyst system, which gives useful information about the
catalytic stability along the catalytic cycle. To address the concern, the catalyst was
trapped with a magnet after the reaction, washed with water and ethanol, dried at
50 °C, and then reused for the next run under the same conditions. The results
(Fig. 11) indicated that the activity of the reused catalyst was almost unaffected
even at the seventh run, exhibiting 40.0% conversion and ca. 100% selectivity to
BzH. This finding implies that the catalyst can be efficiently recovered and recycled
via magnetic separation.

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0.30
(a)
668.2
0.25
0.5 h

Diffuse Reflectance
1.0 h
0.20
1.5 h
2.0 h

678.5
682.7
0.15 2.5 h
3.0 h

0.10

0.05

0.00
800 750 700 650 600

Wavenumber (cm-1)

1485.5
(b)
0.030

0.025
0.5 h
Diffuse Reflectance

1.0 h
0.020 1.5 h
2.0 h
1589.2

0.015 2.5 h
3.0 h
1652.9

0.010

0.005

0.000

1700 1600 1500 1400 1300

-1
Wavenumber (cm )

0.0025
(c)
0.5 h
0.0020 1.0 h
Diffuse Reflectance

1.5 h
2.0 h
0.0015 2.5 h
3.0 h

0.0010

0.0005

0.0000
4000 3900 3800 3700 3600 3500 3400 3300 3200

Wavenumber (cm-1)

Fig. 9 In situ DRIFTS spectra of Fe3O4 catalyzing oxidation of styrene at temperature of 80 °C

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1.00

0.95

Abs 0.90

0.85

0.80

586.7
0.75

4000 3500 3000 2500 2000 1500 1000 500

Wavebumber (cm-1)

Fig. 10 IR spectrum of Fe3O4 sample

OH OOH
H H Fe3O4
O O OOH
Fe3O4
O Fe3O4 OH

Fe3O4
Fe3O4
OOH Fe3O4 OH
(bulk phase) O
O

Scheme 2 Proposed oxidation mechanism

Conclusions

In conclusion, the preparation of Fe3O4 nanocrystals with super paramagnetism and

average 20 nm nanosize was successfully realized by an alternative method. The
obtained nanomaterial was found to be active and efficient for the oxidation of
styrene with H2O2 oxidant, getting 40.4% conversion of styrene and ca. 100%
selectivity to BzH at reaction temperature of 80 °C and reaction time of 2 h. The
catalytic activity was mainly ascribed to interaction between Fe3O4 nanocrystals
and H2O2 to produce OH or OOH radicals on the surface. The highest selectivity to
BzH has been related to inhibiting action of Lewis sites on the Fe3O4 surface for
further oxidation of BzH to benzoic acid and using diluent H2O2 solution (11%).
The oxidation reaction mechanism was proposed by in situ DRIFTS spectra of the

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Conversion
Selectivity
100

Conversion/Selectivity (%)
80

60

40

20

0
1 2 3 4 5 6 7
Recycle times

Fig. 11 Reusability of the catalyst

styrene and H2O2 on the catalyst. The catalyst was easily separated from the
reaction mixture by a magnet and possessed excellent reusability.

Acknowledgements We make a great acknowledgment for the financial support of this work by the
National Natural Science Foundation of China (No. 21671050), Discipline Leader Foundation of Harbin
(No. 2013RFXXJ009) and the Natural Science Foundation of Heilongjiang Province (No. B201119).

References
1. Dhakshinamoorthy A, Alvaro M, Garcia H (2011) Aerobic oxidation of styrenes catalyzed by an iron
metal organic framework. ACS Catal 1:836–840
2. Nemanashi M, Meijboom R (2013) Dendrimer derived titania-supported Au nanoparticles as
potential catalysts in styrene oxidation. Catal Lett 143:324–332
3. Das BK, Clark JH (2000) A novel immobilised cobalt(III) oxidation catalyst. Chem Commun
605–606
4. Adam F, Iqbal A (2010) The oxidation of styrene by chromium-silica heterogeneous catalyst pre-
pared from rice husk. Chem Eng J 160:742–750
5. Liu C, Huang J, Sun D, Zhou Y, Jing X, Du M, Wang H, Li Q (2013) Anatase type extra-framework
titanium in TS-1: a vital factor influencing the catalytic activity toward styrene epoxidation. Appl
Catal A 459:1–7
6. Wang J, Lu J, Yang J, Chen R, Zhang Y, Yin D, Wang J (2013) Ti containing mesoporous silica
submicrometer-sphere, with tunable particle size for styrene oxidation. Appl Surf Sci 283:794–801
7. Tong J, Li W, Bo L, Wang H, Hu Y, Zhang Z, Mahboob A (2016) Selective oxidation of styrene
catalyzed by cerium-doped cobalt ferrite nanocrystals with greatly enhanced catalytic performance.
J Catal 344:474–481
8. Ghosh S, Acharyya SS, Kumar M, Bal R (2015) One-pot preparation of nanocrystalline Ag-WO3
catalyst for the selective oxidation of styrene. RSC Adv 5:37610–37616
9. Wang H, Qian W, Chen J, Wu Y, Xu X, Wang J, Kong Y (2014) Spherical V-MCM-48: the
synthesis, characterization and catalytic performance in styrene oxidation. RSC Adv 4:50832–50839
10. Chen D, Li N, Sun P, Kong Y (2009) Catalytic performance of Ti-MCM-41 for styrene oxidation.
Chin J Catal 30:643–648

123
 Reac Kinet Mech Cat

11. Zhang Y, Shen J, Zhu J, Sun Y (2012) Study on preparation process of benzaldehyde by catalytic
oxidation of styrene on catalyst V-SBA-15. Petrochem Tech Appl 30:124–128
12. Adam F, Iqbal A (2011) The liquid phase oxidation of styrene with tungsten modified silica as a
catalyst. Chem Eng J 171:1379–1386
13. Zhang L, Hua Z, Dong X, Li L, Chen R, Shi J (2007) Preparation of highly ordered Fe-SBA-15 by
physical-vapor-infiltration and their application to liquid phase selective oxidation of styrene. J Mol
Catal A 268:155–162
14. Sun W, Hu J (2016) Oxidation of styrene to benzaldehyde with hydrogen peroxide in the presence of
catalysts obtained bby the immobilization of H3PW12O40 on SBA-15 mesoporous material. Reac
Kinet Mech Cat 119:305–318
15. Shi F, Tse M-K, Pohl M, Brükner A, Zhang S, Beller M (2007) Tuning catalytic activity between
homogeneous and heterogeneous catalysis: improved activity and selectivity of free nano-Fe2O3 in
selective oxidations. Angew Chem Int Ed 46:8866–8868
16. Shi F, Tse M-K, Pohl M, Radnik J, Brükner A, Zhang S, Beller M (2008) Nano-iron oxide-catalyzed
selective oxidations of alcohols and olefins with hydrogen peroxide. J Mol Catal A 292:28–35
17. González-Arellano C, Campelo JM, Macquarrie DJ, Marinas JM, Romero AA, Luque R (2008)
Efficient microwave oxidation of alcohols using low-loaded supported metallic iron nanoparticles.
ChemSusChem 1:746–750
18. Rajabi F, Karimi N, Saidi MR, Primo A, Varma RS, Luque R (2012) Unprecedented selective
oxidation of styrene derivatives using a supported iron oxide nanocatalyst in aqueous medium. Adv
Synth Catal 354:1707–1711
19. Rak MJ, Lerro M, Moores A (2014) Hollow iron oxide nanoshells are active and selective catalysts
for the partial oxidation of styrene with molecular oxygen. Chem Commun 50:12482–12485
20. Laurent S, Orge D, Port M, Roch A, Robic C, Elst LV, Muller RN (2008) Magnetic iron oxide
nanoparticles: synthesis, stabilization, vectorization, physicochemical characterizations, and bio-
logical applications. Chem Rev 108:2064–2110
21. Jolivet JP, Chaneac C, Tronc E (2004) Iron oxide chemistry. From molecular clusters to extended
solid networks. Chem Commun 5:481–487
22. Zhang W, Lu B, Tang H, Zhao J, Cai Q (2015) Reclamation of acid pickling waste: a facile route for
preparation of single-phase Fe3O4 nanoparticle. J Magn Magn Mater 381:401–404
23. Tasca J, Lavat A, Nesprias K, Barreto G, Alvarez E, Eyler N, Canizo A (2012) Cyclic organic
peroxides thermal decomposition in the presence of CuFe2O4 magnetic nanoparticles. J Mol Catal A
363–364:166–170
24. Xing M, Xu W, Dong C, Bai Y, Zeng Y, Zhou Y, Zhang J, Yin Y (2018) Metal sulfides as excellent
co-catalysts for H2O2 decomposition in advanced oxidation processes. Chem 4:1–14
25. Brückner A (2000) A new approach to study the gas-phase oxidation of toluene: probing active sites
in vanadia-based catalysts under working conditions. Appl Catal A 200:287–297
26. Kumar S, Sinha AK, Hegde SG, Sivasanker S (2000) Influence of mild dealumination on physico-
chemical, acidic and catalytic properties of H-ZSM-5. J Mol Catal A 154:115–120
27. Fan S, Pan Y, Wang H, Lu B, Zhao J, Cai Q (2017) Effect of acidic and red-ox sites over modified
ZSM-5 surface on selectivity in oxidation of toluene. Mol Catal 442:20–26
28. Walker KL, Dornan LM, Zare RN, Waymouth RM, Muldoon MJ (2017) Mechanism of catalytic
oxidation of styrenes with hydrogen peroxide in the presence of cationic palladium(II) complexes.
J Am Chem Soc 139:12495–12503
29. Adam W, Corma A, Martinez A, Renz M (1996) The mechanism of the double bond cleavage in the
titanium zeolite-catalyzed oxidation of alpha-methylstyrene by hydrogen peroxide: the & b-hy-
droperoxy alcohol as intermediate. Chem Ber 129:1453–1455
30. Wróblewska A, Makuch E, Młodzik J, Koren Z, Michalkiewicz B (2017) Fe/nanoporous carbon
catalysts obtained from molasses for the limonene oxidation process. Catal Lett 147:150–160

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