Hindawi

Advances in Materials Science and Engineering

Volume 2018, Article ID 2716435, 7 pages
https://doi.org/10.1155/2018/2716435

Research Article
Selective Oxidation of Styrene to Benzaldehyde by Co-Ag
Codoped ZnO Catalyst and H2O2 as Oxidant

Abderrazak Aberkouks,1 Ayoub Abdelkader Mekkaoui ,1,2 Brahim Boualy,2

Soufiane El Houssame,2 Mustapha Ait Ali,1 and Larbi El Firdoussi 1
1
Laboratoire de Chimie de Coordination et de Catalyse, Département de Chimie, Faculté des Sciences Semlalia, BP 2390, 40001
Marrakech, Morocco
2
Laboratoire de Chimie et Modélisation Mathématique, Faculté Polydisciplinaire de Khouribga, Université Hassan 1er, BP 145,
25000 Khouribga, Morocco

Correspondence should be addressed to Larbi El Firdoussi; elfi[email protected]

Received 7 November 2017; Revised 20 February 2018; Accepted 25 March 2018; Published 24 April 2018

Academic Editor: Marco Cannas

Copyright © 2018 Abderrazak Aberkouks et al. This is an open access article distributed under the Creative Commons Attribution
License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is
properly cited.

Various ratio of Co-Ag supported on ZnO have been evaluated in the selective catalytic oxidation of styrene to benzaldehyde,
using H2O2 as an oxidant. The catalysts were prepared by a sol-gel process and were characterized using XRD, FT-IR, TG-DTG,
BET, and SEM/EDX. The performance of the prepared catalyst was investigated under different parameters such as solvent,
temperature, substrate/oxidant molar ratios, reaction time, and doping percent. The Zn1−x−yAgxCoyO catalysts exhibit a good
activity and a high selectivity towards benzaldehyde (95%) with the formation of only 5% of acetophenone.

1. Introduction in the presence of activated carbon (AC) and H2O2 as the

oxidant, the styrene was selectively converted to benzal-
Benzaldehyde is an important intermediate in the industrial dehyde [12].
fine chemical synthesis for fragrances, flavorings, pharma- The main objective of this work was the preparation of
ceuticals, and in the organic synthesis [1, 2]. Conventional heterogeneous supported catalysts (Zn1−x−yAgxCoyO) by a
preparation of benzaldehyde is based on the hydrolysis of sol-gel method and their evaluation in the oxidation of
benzyl chloride, and it can be obtained as an intermediate of styrene to benzaldehyde (supplementary data 1).
the oxidation of toluene to benzoic acid [3, 4]. This process
was not environmentally friendly because of using organic 2. Experimental Details
solvents and producing traces of chlorine [5]. The devel-
opment of recyclable catalysts, to simply separate from the 2.1. Materials. Zinc acetate dihydrate (Zn(CH3COO)2·2H2O),
reaction mixture, has attracted an economic and ecological cobalt nitrate hexahydrate (Co(NO3)2·6H2O), silver nitrate
interest [6]. In this context, there are two categories of (Ag(NO3)), citric acid (HOC(COOH)(CH2COOH)2), hy-
catalysts: transition metal immobilized or constituted mo- drogen peroxide (H2O2 30 wt.%), ethanol, styrene, aceto-
lecular sieves, such as NbCo-MCM-41 [7], VSB-5 [8], and nitrile, acetone, and methanol were purchased from Sigma-
Co-ZSM-5 [9], and application of metal oxides or com- Aldrich chemical reagent grade and used as received.
plexes, such as MgxFe3−xO4 [1] and TiO2/SiO2 [10]. Recently,
Long et al. [11] have developed magnetic microparticles 2.2. Characterization. Thermogravimetric analysis (TGA)
immobilizing palladium acetate as heterogeneous coordi- was recorded on a TA Instrument Q500 apparatus in flowing
nation catalysts for selective oxidation of styrene allowing air at a heating rate of 10°C·min−1. BET specific surface areas
mainly to prepare acetophenone. Earlier, it was shown that and average pore diameter of the prepared catalyst were
2 Advances in Materials Science and Engineering

Co (NO3)2∙6H2O + EtOH Zn(CH3COO)2∙2H2O + EtOH Ag(NO3)∙H2O + water

Stirred for 30 min

Citric acid solution was added slowly separately

Solution was stirred at 80°C for 24 h

Gel

Dried gel for 15 h at 120°C

Calcined for 5 h at 600°C

Co-Ag/ZnO nanopowders

Figure 1: Flow chart for synthesis of Co-Ag/ZnO nanopowders by a sol-gel method.

measured by N2 adsorption-desorption technique using a rotaflow tube with magnetic stirring immersed in bath oil.
Micromeritics analyser P/N 05098-2.0 Rev A. The stretching The activity of the catalyst (Zn1−x−yAgxCoyO) was studied
vibration frequency of the catalyst was recorded by FT-IR varying the following parameters: doping percents of
spectroscopy in the range of 400–4000 cm−1 using a Bruker 0 ≤ x ≤ 0.05 and 0 ≤ y ≤ 0.05, H2O2/styrene molar ratios from
vertex 70 DTGS. Spectrometer XRD measurements were 1.1 to 3, reaction temperatures range (40°C–120°C), and the
performed on a XPERT-MPD Philips diffractometer using amount of the catalyst (0.005–0.02 g) in aprotic and protic
Cu-Kα radiation as the X-ray source in the 2θ range of solvents. Aliquots samples from the reaction mixture were
20°–80°. The size and morphology of the microstructures taken at regular intervals and were monitored by gas chro-
were carried out on VEGA3 TESCAN microscope equipped matography (GC) equipped with FID using Rtx-5 capillary
with an energy dispersive X-ray spectrometer (EDAX column. Dodecane was used as an internal standard for the
TEAM). quantitative analysis of the reaction products. The conversion
of styrene was based on the unreacted substrate.

2.3. Preparation of the Catalyst. Pure ZnO nanopowders were 3. Results and Discussion
prepared by a sol-gel method. Zn(CH3COO)2 2H2O (50 mL,
0.5 M in ethanol) and citric acid (50 mL, 0.5 M in ethanol) 3.1. Characterization of the Catalysts. Figure 2 shows XRD
were stirred separately for 30 min. Then, the citric acid so- patterns of pure ZnO and Zn1−x−yAgxCoyO nanopowders
lution was added slowly into the solution of zinc acetate. This calcined at 600°C. According to pure ZnO reference (00-036-
hydroalcoholic solution was heated at 80°C for 24 h, giving 1451), the sample corresponding to C3 is highly crystallized
an opaque white gel which was dried at 120°C overnight and all diffraction peaks are well indexed to the diffraction
and calcined at 600°C for 5 hours under air to offer pure ZnO. pattern of hexagonal ZnO with the P63mc space group.
The same procedure was used to prepare nanopowders of However, the ZnO doped with 1% mol of Ag (C2) revealed
Zn1−x−yAgxCoyO by adding the needed amount of Co new peaks with weak intensities at 38.20° and 44.62°, as it
(NO3)2·6H2O (0.5 M) and Ag(NO3) (0.5M) (Figure 1). Six was reported by Zeferino et al. [13]. The doping concen-
samples were prepared: C1 (pure ZnO); C2 (1% mol Ag-doped tration of 2% to 10% mole of Co-Ag (C5 and C6) can lead
ZnO); C3 (1% mol Co-doped ZnO); C4 (1% mol Co-1% mol to the formation of Co3O4 with a corresponding trace at
Ag codoped ZnO); C5 (2.5% mol Co-2.5% mol Ag codoped 64.66° [14].
ZnO), and C6 (5% mol Co-5% mol Ag codoped ZnO). Table 1 summarizes the position and the width at
midheight (FWHM) of the main peaks, along with the lattice
parameter values calculated from the XRD patterns of the
2.4. Catalytic Activity. The oxidation of styrene with hy- pure and codoped ZnO nanopowders. The incorporation of
drogen peroxide as the oxidant was carried out in a 50 mL Co-Ag on ZnO results in the decrease of the FWHM,
Advances in Materials Science and Engineering 3

C6
∗ ∗ +
C5
∗

Intensity (a. u.)

C4
∗
C3
∗
C2

002
101

110
C1

100

103

112
102

201
200
10 15 20 25 30 35 40 45 50 55 60 65 70 75 80
2θ (°)
∗ Ag
+ Co3O4

Figure 2: XRD patterns of Zn1−x−yAgxCoyO.

Table 1: Position, FWHM, and the lattice parameters of Zn1−x−yAgxCoyO nanopowders.

Lattice parameters (Å)
Nominal Ag-Co concentration Position of the (101) peak FWHM (degree)
a c
0% mol 36.2583 0.2134 3.2498 5.2066
1% mol Ag 36.3177 0.082 3.24509 5.18829
1% mol Co 36.1927 0.325 3.25037 5.19644
1% mol Ag-1% mol Co 38.279 0.200 3.28825 5.23984
2.5% mol Ag-2.5% mol Co 36.4427 0.078 3.24454 5.19797
5% mol Ag-5% mol Co 36.3177 0.075 3.24016 5.21778

indicating an increase in crystallinity. A shift position of the 910–1537 cm−1 may be attributed to the residual NO3– ions
diffraction peak (002) could be attributed to the incor- [18]. A weak band at 2375 cm−1 is attributed to the CO2
poration of Ag+ and Co2+ ions in the ZnO lattice sites. As it present in air. The bands at 3400 cm−1 and 1630 cm−1
was shown earlier, Ag+ ions in the ZnO lattice sites, probably correspond to the stretching of hydroxyl groups due to the
substitute Zn2+ ions [13]. adsorption of water on the particles’ surface [19].
On the other hand, the peaks associated with the cobalt The scanning electron microscopy (SEM) of the undo-
oxide or cobalt hydroxide phases such as CoO or Co(OH)2 ped and the Ag-Co codoped ZnO nanopowders are shown in
were not detected as shown in the XRD patterns (Figure 2). Figure 3. Ag and Co do not bring significant change in the
According to Wojnarowicz et al. [15], some precipitation of morphology. The EDX results confirmed that the products
Co3O4 was observed in the XRD investigation for the 10% consist of zinc, cobalt, and silver elements in ZnO nano-
mol Co-Ag sample in synthetic air. powders, which are in good agreement with XRD patterns.
TG/DTG curves of the prepared materials (supple-
mentary data 2) reveal one thermal event at 162°C attributed
3.2. Catalytic Experiments. The oxidation reaction of styrene
to the loss of crystal water from the catalyst (2.42 wt.%).
is influenced by several parameters. In an attempt to find out
To investigate the specific areas and the porous nature of
the suitable reaction conditions providing an optimum of
the C4 nanopowders, Brunauer–Emmett–Teller (BET) gas
conversion and yield, effects of different reaction conditions
sorption measurements were performed. The nitrogen
have been carried out.
adsorption-desorption isotherm and the pore size distri-
bution plots of the C4 sample are shown in supplementary
data 3. The sample corresponds to type IV and V isotherm 3.2.1. Effect of Catalyst Loading. As shown in Table 2, when
and type H3 hysteresis loop appearing which is attributed to the loading amount of Co and Ag was increased from 2 to
the predominance of mesopores [16]. The determined surface 10% mol, there was an obvious increase in styrene con-
area of the C4 sample was 5.90 m2/g, and the calculated BJH version from 61 to 80% (entries 5–7), but the selectivity of
pores size was 5.42 nm. benzaldehyde decreases for more than 2% mol (entries 6-7).
FT-IR spectrum (supplementary data 4) of C4 nano- However, with 1% mol, either with Co or Ag, a similar result
powder shows a strange band at 600 cm−1 and a relatively was obtained (entries 3-4). In the presence of pure ZnO or in
weak band at 500 cm−1 which could be assigned to the the absence of the catalyst, no significant conversion was
stretching modes of Zn–O [17]. The bands in the range observed.
4 Advances in Materials Science and Engineering

16.0
Zn
14.4
12.8
Zn
11.2
9.6

Counts (K)
8.0
6.4
4.8
3.2 O
Zn
10 μm 1.6 Zn
0.0
0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00
Energy (kev)
(a)
Zn
8.19
7.28
Zn
6.37
5.46
Counts (K)

4.55
3.64
2.73
O Zn
10 μm 1.82
Co Ag
0.91
Ag Co Ag Co Co Zn
0.00
0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00
Energy (kev)
(b)
3.80
Zn
3.42
3.04
2.66 Zn
Counts (K)

2.28
1.90
1.52
1.14 O Zn
50 μm 0.76 Co Ag
0.38 Ag Co Ag Co Co Zn
0.00
0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00
Energy (kev)
(c)

Figure 3: SEM images and EDX spectra of (a) C1, (b) C4 before used, and (c) C4 after the 4th cycles.

3.2.2. Effect of Catalyst Amount. To investigate the catalyst was formed as the major product. This compound reached
amount effect on the oxidation reaction, different amounts a maximum after 24 hours with 61% in conversion and 95%
of the C4 catalyst have been studied. As shown in Table 2, the in selectivity.
optimal catalyst amount was found to be 0.02g with high
selectivity of benzaldehyde (95%).
3.2.4. Effect of Molar Ratio H2O2/Styrene. The catalytic
oxidation of styrene using the C4 catalyst was performed by
3.2.3. Effect of the Reaction Time. In order to shed more varying the molar ratio of the H2O2/styrene. The increase in
light on this point, a kinetic study was carried out with molar ratio from 1 : 1 to 1 : 2.5 resulted in a significant in-
0.02 g of C4 catalyst using GC to determine the conversion crease in the conversion. The yield of benzaldehyde in-
and product distribution (Figure 4). As depicted, the creased from 57% to 72% mol. However, the selectivity of
evolution of styrene versus time shows that benzaldehyde benzaldehyde slightly decreases (Table 3).
Advances in Materials Science and Engineering 5

Table 2: Effect of the catalyst’s amount and loading.

Yielda (% mol)
Entry Catalyst Amount of catalyst (g) Styrene conversion
Benzaldehyde Acetophenone
1 Without — 1 1 0
2 C1 0.02 5 5 0
3 C2 0.02 30 30 0
4 C3 0.02 25 25 0
5 C4 0.02 61 58 3
6 C5 0.02 75 45 33
7 C6 0.02 80 48 16
8 C4 0.005 30 30 0
9 C4 0.01 50 50 0
10 C4 0.015 53 53 0
Reaction conditions: H2O2/styrene, 1; temperature, 80°C; solvent, acetonitrile; reaction time, 24 h; ayields determined by GC using dodecane as an internal
standard.

70
60
50
40
(%)

30
20
10
0
2 4 6 8 12 24
Time (h)
Conversion (%)
Yield of benzaldehyde
Yield of acetophenone
Figure 4: Effect of reaction time on the oxidation of styrene. Reaction conditions: H2O2/styrene, 1; temperature, 80°C; solvent, acetonitrile.
Yields are determined by GC using dodecane as an internal standard.

Table 3: Effect of styrene, H2O2 molar ratio, temperature, and solvent.

Yielda (% mol)
Entry H2O2/Styrene Solvant Temperature (°C) Styrene conversion
Benzaldehyde Acetophenone
1 1.1 Acetonitrile 80 61 57 3
2 1.5 Acetonitrile 80 66 62 3
3 2 Acetonitrile 80 70 67 3
4 2.5 Acetonitrile 80 81 72 3.5
5 3 Acetonitrile 80 95 73 5
6 2.5 Acetonitrile 40 10 10 0
7 2.5 Acetonitrile 70 50 50 0
8 2.5 Acetonitrile 100 94 60 4
9 2.5 Acetonitrile 120 98 50 9
10 2.5 Acetone 80 90 77 12
11 2.5 Water 80 12 12 0
12 2.5 Methanol 80 75 59 6
13 2.5 Ethanol 80 50 31 7
Reaction conditions: C4 catalyst (0.02 g); reaction time, 24 h; ayields determined by GC using dodecane as an internal standard.

3.2.5. Effect of Reaction Temperature. Table 3 depicts the temperature, the benzaldehyde selectivity decreases in
influence of reaction temperature on the oxidation of styrene competition with the formation of acetophenone and other
catalyzed by the C4 catalyst. The increase of the temperature products. This confirms that the cleavage of C � C bond is
from 40°C to 120°C results in the increased conversion from greater at lower temperatures and epoxidation participates
10 to 98, indicating that the styrene conversion has a strong more favorably against C � C cleavage to high temperatures
dependency on the reaction temperature. Hence, at high [20, 21].
6 Advances in Materials Science and Engineering

100
90
80
70
60

(%)
50
40
30
20
10
0
1 2 3 4
Cycles
Conversion
Benzaldehyde
Acetophenone
Figure 5: Reusability of the catalyst in oxidation of styrene. Reaction conditions: C4 catalyst (0.02 g); H2O2/styrene, 2.5, temperature, 80°C;
solvent, acetone; reaction time, 24 h. Yields are determined by GC using dodecane as an internal standard.

3.2.6. Effect of the Solvent. An examination of the effects of

Table 4: EDX analysis of C4 before using and at the 1st, 2nd, 3rd,
a variety of protic and aprotic solvents on the model reaction and 4th cycles.
using C4 as the catalyst has been carried out (Table 3).
According to Kumar [22], aprotic solvents are more fa- Elements Wt.% Atomic %
vorable for the styrene oxidation than protic ones. The se- OK 14.73 41.58
lectivity towards benzaldehyde with respect to percentage AgL 1.88 0.76
As-prepared catalyst
yield is in the following order: CH3CN > CH3COCH3 > CoK 0.42 0.32
CH3OH > C2H5OH > H2O. The styrene conversion in acetone, ZnK 82.96 57.31
methanol, ethanol, and water is, respectively, equal to OK 18.05 47.58
90% mol, 75% mol, 50% mol, and 12% mol, with 77% mol, AgL 1.97 0.76
1st cycle
59% mol, 31% mol, and 12% mol yield of benzaldehyde, CoK 0.45 0.32
ZnK 79.54 51.31
respectively. Among the solvents, acetonitrile appears to be
the best one (entry 4). OK 20.80 52.01
AgL 2.08 0.77
2nd cycle
CoK 0.44 0.30
3.2.7. Recycling of Catalyst. To investigate the reusability of ZnK 76.68 46.92
C4, the catalytic activity of this catalyst was evaluated in four OK 25.54 58.63
consecutive cycles (Figure 5). Before reusing the catalyst, it AgL 2.26 0.77
3rd cycle
was separated from the reaction mixture by filtration, CoK 0.43 0.27
washed with water, and finally dried at 200°C for 2 hours. As ZnK 71.77 40.32
shown in Figure 5, the catalyst still exhibits a good catalytic OK 31.36 65.43
activity in the first three reuse cycles. However, a noticeable AgL 2.49 0.77
4th cycle
CoK 0.36 0.20
drop in styrene conversion was observed after the fourth
ZnK 65.73 33.59
consecutive run due to agglomerated particles.
SEM image of C4 before and after four cycles of oxi-
dation has been studied (Table 4). Before the catalytic test, oxidation of styrene. Among all the catalysts examined, the
SEM image of the Ag-Co codoped ZnO shows relatively C4 catalyst exhibited the best activity and provided 76% yield
dispersed nanoparticles (Figure 3(b)). However, SEM mor- of benzaldehyde in the presence of H2O2 as an oxidant after
phology of the catalyst after four cycles of oxidation showed 24 hours. The optimum reaction conditions was acetonitrile,
agglomerated particles with the presence of smaller single temperature reaction 80°C, H2O2/styrene molar ratio equal
particles (Figure 3(c)). Even by SEM, the physical change of to 2.5, catalyst loading of 1% mol Ag-1% mol Co, and the
the matrix is well visible due to probable decomposition catalyst amount of 0.02 g. Under the optimized conditions,
during the reaction. In fact, EDX on various regions of the the Co-Ag codoped ZnO shows a high degree of efficiency
catalyst after 4 cycles confirmed the presence of Co and Ag and selectivity towards the oxidation reactions.
elements without any significant variation. The analysis in-
dicates a predominance of oxygen species, which comes Conflicts of Interest
mainly from the oxidation of Co and Ag species, leading to the
deactivation of the catalyst. The authors declare that they have no conflicts of interest.

4. Conclusion Supplementary Materials

In this study, the C4 catalyst was prepared by a sol-gel General scheme, SEM images, EDX, FT-IR spectra, and
method, and its catalytic activity was investigated in the other analytical data are available free of charge via the
Advances in Materials Science and Engineering 7

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