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Journal of the Taiwan Institute of Chemical Engineers

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Catalytic oxidation of ethyl acetate over CuO/ZSM-5 catalysts: Effect of

preparation method
Yue Zhou, Huiping Zhang, Ying Yan∗
School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, PR China

a r t i c l e i n f o a b s t r a c t

Article history: A series of CuO/ZSM-5 catalysts with different copper loadings were prepared by impregnation (IM)
Received 2 September 2017 and chemical vapor deposition (CVD) methods, respectively. Their physicochemical properties were
Revised 13 January 2018
investigated by N2 adsorption/desorption, X-ray diffraction (XRD), transmission electron microscopy
Accepted 14 January 2018
(TEM), X-ray photoelectronic spectra (XPS), temperature-programmed reduction by hydrogen (H2 -TPR)
Available online xxx
and temperature-programmed desorption of NH3 (NH3 -TPD). The XRD and TEM results demonstrated
Keywords: that the crystallite size of the CuO prepared by CVD method was smaller than that by IM, and the XPS
Catalytic oxidation results illustrated that the copper specie was mostly in Cu2+ state and Cu+ co-existed. The performance
Ethyl acetate of catalytic oxidation of ethyl acetate was conducted in the fixed-bed reactor based on CuO/ZSM-5
CuO/ZSM-5 catalysts catalysts. The experimental results showed that the preparation method affected the catalytic activity of
Chemical vapor deposition CuO/ZSM-5; the CVD catalysts exhibited a higher catalytic activity for ethyl acetate oxidation compared
with the IM catalysts at the same copper loadings. Ethanol and acetaldehyde are observed to be the
intermediate products in the combustion of ethyl acetate over the synthesized catalysts. The relative
amounts of acetaldehyde and ethanol are determined by the selectivity of the catalyst toward acetalde-
hyde production from ethanol. Particularly, the 3 wt% CVD catalyst showed the best catalytic activity
for ethyl acetate oxidation with 90% conversion of ethyl acetate at 235 °C, which was much lower than
that of the 3 wt% IM catalyst (278 °C), meanwhile, the intermediate products of the 3 wt% CVD for ethyl
acetate oxidation were completely oxidized into CO2 and H2 O at temperature as low as 288 °C.
© 2018 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction
Volatile organic compounds (VOCs) are a group of major envi-
ronmental pollutants emitted from human activities, petrochemi-
cal industry, pharmaceutical industry, surface corrosion, paint dec-
oration industry and printing industry [1,2]. These volatile organic
compounds, which are responsible for the stratospheric depletion,
tropospheric ozone formation, smog information, climate change
and carcinogenic effects in humans, are a class of compounds with
various types, complex ingredients and wide range of sources [3,4].
As most of the countries have enacted a strict legal system to limit
VOCs emissions, there are many researchers seeking highly effi-
cient, low energy consumption technologies to meet the standards
[5].
Catalytic oxidation based on low operation temperature, wide
range of applications, high purification efficiency and environmen-
tal benefits is the most widely used techniques for handling VOCs
compared with the traditional methods [6]. The active components
∗
Corresponding author.
E-mail address: yingyan@scut.edu.cn (Y. Yan).
of the catalyst can be broadly classified into two categories: noble
metal catalysts [7–9] and transition metal oxide catalysts [10–13].
Noble metals exhibit excellent efficiency and activity in the purifi-
cation of VOCs at low temperatures, but the high manufacturing
cost and low thermal stability limit their commercial application
[5,14]. As for transition metal oxides, which present low activity
but have the advantages of excellent stability, masking tolerance,
long lifetime and low cost compared with noble oxides [15,16].
Among the transition metal oxide catalysts, copper oxide is con-
sidered to be one of the catalysts with the highest catalytic activity
for the total oxidation of VOCs [5,11].
Moreover, the physicochemical properties of the support mate-
rials play a critical role in the catalytic performance of the cata-
lysts, which can improve the dispersion of the active component
on the support surface or determine the oxidation state and thus
enhancing the activity of the catalysts. Among the available sup-
port materials, zeolites have been employed as promising support
in various catalysts for the combustion of VOCs due to their pore
structures, corrosion resistance, ion exchange properties and acidic
properties [17,18]. Commonly used zeolites can be roughly divided
into mesoporous [16,19] (MCM-41, SBA-15) and microporous zeo-
lites [6,18,20,21] (ZSM-5) according to the size of pore channels.

https://doi.org/10.1016/j.jtice.2018.01.016
1876-1070/© 2018 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Please cite this article as: Y. Zhou et al., Catalytic oxidation of ethyl acetate over CuO/ZSM-5 catalysts: Effect of preparation method,
Journal of the Taiwan Institute of Chemical Engineers (2018), https://doi.org/10.1016/j.jtice.2018.01.016
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ZSM-5 zeolite possesses a high specific surface area, uniform pore
structure, high acidity, and good chemical stability, which is ben-
eficial to the removal of volatile organic compounds [20]. Ou et
al. [22] found that the microwave-assisted secondary growth syn-
thesis can effectively prepare ZSM-5 coating on SiC foam with
the uniform coating thickness. Li et al. [20] reported the ZSM-5
zeolite was used as structured support for volatile organic com-
pounds oxidation and the catalysts obtained presented outstanding
catalytic activity and superior stability in ethyl acetate complete
oxidation.
The preparation method also affects the morphology of the cat-
alysts, thus altering the pore structure and affecting the catalytic
activities [6]. Various preparation methods can be applied in sci-
entific research including co-precipitation [23], ion exchange [24],
impregnation [25] and chemical vapor deposition method [26–28].
As a result of the advantages of simple operation, low cost, high
utilization rate and suitable for most zeolites, impregnation is the
most widely used way of supporting the active component of the
catalyst as a traditional method. However, the disadvantage is that
the active components are mainly distributed on surface of the
support and the migration of active components leads to uneven
distribution thus affecting the catalytic activity [29]. Chemical
vapor deposition (CVD) has proven to be a cost-effective and
single-step gas-phase preparation technique. According to the
literatures [29–32], the enhanced activity was attributed to the
fact that the gas-phase process enables the highly dispersed ability
of the active ingredient, independent of the nature of the sup-
port material and stronger interaction with the support material.
Therefore, the CVD method is a promising technique for prepar-
ing catalysts via depositing active phases from gaseous metal
precursors into porous materials. Assebban et al. [27] utilized
pulsed spray evaporation chemical vapor deposition to prepare
cobalt oxide catalyst with clay as the support for the treatment
of unsaturated hydrocarbons. The results revealed that cobalt
oxide crystals are uniformly supported on the surface of the clay
and the catalyst has excellent catalytic activity, which is due
to a synergistic interaction between the cobalt oxide films and
the clay. Bahlawane et al. [32] investigated the catalytic activity
of Co3 O4 catalysts prepared by CVD for methane combustion,
the results showed that monolithic cordierites with low specific
surface area were uniformly coated with cobalt oxide thin films on
controlled thickness using the CVD process and these films exhibit
a remarkably high efficiency.
Ethyl acetate is one of the typical ester compounds and gaseous
pollutant that predominantly existed in various industrial pro-
cesses and emitted into the atmosphere without prior further
purification. In the present study, little attention has been fo-
cused on the research of CuO/ZSM-5 catalysts prepared by the CVD
method as the potential catalysts for ethyl acetate combustion.
Therefore, CuO/ZSM-5 catalysts were synthesized for ethyl acetate
combustion to investigate the catalytic efficiency of these differ-
ent catalysts. The main purposes of this study were to (1) compare
the physicochemical properties of CuO/ZSM-5 catalysts prepared by
the IM and CVD method; (2) investigate the effect of preparation
method on the performance of ethyl acetate over these catalysts,
including analyzing the conversion of ethyl acetate into intermedi-
ate products.
2. Experimental
2.1. Materials
Columnar ZSM-5 with an atomic Si/Al ratio of 50 was pur-
chased from The Catalyst Plant of Nankai University (Tianjin,
China). Copper acetylacetonate (Cu(acac)2 ) was obtained from
Aladdin Industrial Corporation (Shanghai, China). Copper ni-
Please cite this article as: Y. Zhou et al., Catalytic oxidation of ethyl acetate over CuO/ZSM-5 catalysts: Effect of preparation method,
Journal of the Taiwan Institute of Chemical Engineers (2018), https://doi.org/10.1016/j.jtice.2018.01.016
[m5G;February 7, 2018;1:0]
trate (Cu(NO3 )2 •3H2 O, >99.0%) was purchased from Guangzhou
Chemical Regent Factory (Guangzhou, China). Ethyl acetate
(C4 H8 O2 , ≥ 99.5%) and ethanol (C2 H5 OH, >99.7%) were supplied by
Guangdong Guanghua Technology Co., Ltd (Guangzhou, China).
2.2. Catalyst preparation
The metal oxides modified ZSM-5 catalysts with the corre-
sponding copper loadings of 1, 3, 5, 10 wt% were prepared by
impregnation (IM) and chemical vapor deposition (CVD) methods,
respectively. The IM catalysts were prepared as follows: known
amounts of copper nitrate was added to deionized water and
mixed with 4 g of ZSM-5 granular at room temperature, and
the excess moisture was removed in an oven at 100 °C until
dryness and stirred several times in the process. Finally, the
samples were dried at 100 °C for 12 h. The CVD catalysts were
synthesized as follows: copper supported on ZSM-5 zeolite was
synthesized by chemical vapor deposition using copper acety-
lacetonate (Cu(acac)2 ) and ZSM-5 as copper source precursor
and target substrate, respectively. A known amount of Cu(acac)2
was sublimed at 180 °C and deposited at 350 °C under a static
nitrogen atmosphere in a sintering furnace (Hefei Kejing Material
Technology co., LTD). By varying the amounts of copper of 1, 3,
5 and 10 wt%, four samples with different copper loadings were
prepared. All catalysts were calcined at 550 °C for 4 h under static
air in a muffle furnace. In order to evaluate the catalytic activity,
the cylindrical catalyst was previously pelletized and sieved to
40–60 meshes (300–450 μm).
2.3. Catalyst characterization
X-ray diffraction patterns (XRD) of samples recorded on a D8
Advance (Bruker Co.) diffractometer with a X-ray diffractometer
using Cu Kα radiation operated at 40 kV and 40 mA in the 2θ range
of 5–80° with a 2θ step size of 1° and a step time of 10 s. In
addition, the average crystallite sizes of CuO in CuO/ZSM-5 cat-
alysts are calculated from CuO diffraction peak by the Scherrer
equation [27,33]:
Kλ
D= (1)
β cosθ
where K is a Scherrer constant related to crystallite shape, nor-
mally considered as 0.89, λ is X-ray wavelength (λ = 0.154056 nm),
β is the peak width of the diffraction peak profile at half maxi-
mum height, θ is the diffraction angle.
The transmission electron microscopy (TEM) images of sam-
ples were obtained on a JEM 2100 electron microscope operated
at 200 kV. The actual loading of the catalyst was measured us-
ing atomic absorption spectrophotometry (AA240FS, Varian Co.,
USA). Samples of about 0.1 g were dissolved in acidic solution (42%
HNO3 ) overnight, and diluted at a certain concentration and then
detected by atomic absorption spectrophotometry.
The nitrogen adsorption and desorption isotherms were mea-
sured on a 3H-20 0 0PS1 instrument in static measurement mode.
The samples were degassed at 200 °C for 2 h before measurement.
The BET specific area of the samples were calculated according
to Brunauer–Emmett–Teller (BET) method and the total pore vol-
ume was calculated by the analysis of N2 adsorption–desorption
isotherms, the micropore volume was calculated by HK (Horvath–
Kawazoe) method whereas the adsorption average pore diameter
was determined by the BJH (Barrett–Joyner–Halenda) method.
The X-ray photoelectron spectroscopy (XPS) experiments were
recorded on a Kratos Axis Ultra (DLD) spectrometer using an Al Kα
(1486.6 eV) radiation source operated at 15 kV and 10 mA. The car-
bonaceous C1s line (284.6 eV) was used as a reference to calibrate
the binding energy (BE).
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Fig. 1. A schematic diagram of the catalytic oxidation test setup.
Hydrogen temperature-programmed reduction (H2 -TPR) of
the samples was carried out on a Quantachrome Automated
Chemisorption Analyzer equipped with a thermal conductivity
detector (TCD). For the analysis, each sample(∼100 mg) was loaded
into the reactor and purged with helium (30 ml/min) at 300 °C for
1 h to eliminate contaminants, and then cooled down to room tem-
perature. H2 -TPR measurements were recorded in H2 (10 vol%)/Ar
flow (30 ml/min) at a heating rate of 10 °C/min from room temper-
ature to 700 °C.
Temperature-programmed desorption of NH3 (NH3 -TPD) was
performed on a TP-5080 instrument with a thermal conductivity
detector (TCD). After pretreatment at 500 °C under flowing helium
for 60 min, each sample (∼200 mg) was cooled to 50 °C at a rate
of 10 °C/min. The adsorption step was investigated by admitting
NH3 (5 vol%)/Ar flow (30 ml/min) at 100 °C to saturation. Ammo-
nia physically adsorbed on the catalyst was removed by flushing
the sample with helium (30 ml/min) for 60 min at 100 °C. Finally,
thermal desorption was carried out from 100 °C to 800 °C at a rate
of 10 °C/min.
specific concentration before entering the fixed bed. The gas flow
in the experimental operation was regulated by the mass flow con-
troller, and the reaction temperature of the fixed bed was con-
trolled by the programmed temperature heating furnace, which
can be adjusted by the control panel of the computer program.
The reactants and products in the experiment were analyzed by
gas chromatograph (Agilent 7890A, Palo Alto, CA) equipped with a
FID detector.
In each test, the CuO/ZSM-5 catalysts were filled in the reactor
with a bed height of 1 cm and the total flow rate was 200 ml/min,
which corresponds to a space velocity of 15,0 0 0 h−1 , the concen-
tration of ethyl acetate in the air feed was 1500 ppm. The reaction
temperature of the fixed bed, namely catalytic combustion tem-
perature, was regulated from 100 to 320 °C with the heating rate
of 5 °C/min. The reaction temperature was increased every 20 °C
and the tests were obtained after a stabilization for 20 min at the
desired temperature. The measured results took at least three sam-
ples at the same temperature and took the average of the results.
The catalyst activity was determined by the conversion of ethyl
acetate. The conversion of ethyl acetate was obtained by the fol-
lowing formula:
CVOCs(in) − CVOCs(out)
Con. (% )= ×100% (2)
CVOCs(in)
where CVOCs(in) (mg/L) and CVOCs(out) (mg/L) are the concentration
of ethyl acetate in the inlet and outlet, respectively.
The conversion of ethyl acetate to intermediate products
(ethanol and acetaldehyde) was obtained by the following formula
[34]:
Ci(out)
X (% )= ×100% (3)
2CVOCs(in)
where Ci(out) (mg/L) is the outlet concentration of intermediate
products.

2.4. Catalytic testing 3. Results and discussion

The catalytic performance tests of CuO/ZSM-5 for ethyl acetate
oxidation were measured in a fixed bed reactor with a stainless
steel tube (10 mm in diameter, 450 mm in length) at atmospheric
pressure. As shown in Fig. 1, the whole device is mainly composed
of three parts, which are gas supplying system, fixed bed catalytic
reaction system and detection system. Gaseous ethyl acetate was
produced by bubbling air through the VOCs saturator. The stream
containing ethyl acetate was diluted with another air stream to a
3.1. Structural properties of the catalysts
The X-ray diffraction patterns of CuO/ZSM-5 catalysts prepared
with various copper loadings, together with pure ZSM-5 are shown
in Fig. 2. As can be seen in Fig. 2, all of the XRD patterns presented
the strong diffraction peaks in the ranges of 2θ = 7.9°, 8.8°, 23°,
23.9°, 24.4°, matching well with the standard pattern of ZSM-5
zeolite, meanwhile, showing that the catalysts still retain the

♦ ♦ ZSM-5 A ♦ ♦ ZSM-5 B
♦ • CuO ♦ • CuO
♦ ♦ ♦ ♦
♦ ♦ •• ♦ ♦ •
• ♦
♦ 10 wt% CVD 10 wt% IM

•• 5 wt% IM
•• 5 wt% CVD
Intensity(a.u)

Intensity(a.u)

3 wt% IM
3 wt% CVD

1 wt% CVD 1 wt% IM

ZSM-5
ZSM-5
10 20 30 40 50 60 70 80 90 10 20 30 40 50 60 70 80 90
2 theta (degree) 2 theta (degree)
Fig. 2. XRD patterns of CuO/ZSM-5 catalysts prepared with various copper loadings: (A) CVD catalysts (B) IM catalysts.

Please cite this article as: Y. Zhou et al., Catalytic oxidation of ethyl acetate over CuO/ZSM-5 catalysts: Effect of preparation method,
Journal of the Taiwan Institute of Chemical Engineers (2018), https://doi.org/10.1016/j.jtice.2018.01.016
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Table 1
Pore structure characteristics of ZSM-5, IM catalysts and CVD catalysts.

Samples BET surface Micropore Total Micropore Adsorption Actual copper Average
area SBET area (m2 /g) volume volume average pore loadingsa /wt% crystallite sizeb
(m2 /g) (cm3 /g) (cm3 /g) diameter (nm) (nm)

ZSM-5 299 165 0.26 0.08 3.52 0 —

1 wt % CVD 297 147 0.27 0.07 3.66 0.54 —
3 wt % CVD 273 138 0.25 0.07 3.67 2.35 —
5 wt % CVD 276 143 0.25 0.07 3.57 4.69 21
10 wt % CVD 246 125 0.23 0.06 3.72 8.48 23
1 wt % IM 270 149 0.26 0.08 3.65 0.89 —
3 wt % IM 264 140 0.24 0.07 3.69 2.73 —
5 wt % IM 255 136 0.24 0.07 3.70 4.34 25
10 wt % IM 244 125 0.23 0.06 3.73 9.16 32
a
calculated from the AAS results.
b
calculated from the XRD results.

original microporous structure after the addition of copper. When

the Cu loading was less than 5 wt%, the samples show no diffrac-
tion peaks attributed to crystalline copper oxide, indicating that
the copper oxide species might be present in a highly dispersed
amorphous state on the surface of ZSM-5 support [20,35,36]. The
high surface area of the ZSM-5 support might be beneficial to
improve the dispersion of the active ingredients at low loading.
However, we cannot exclude the possibility that the copper oxide
crystallites may be present as small size, which are too small to
be detected by XRD [35,36]. With an increase of copper content,
two weak diffraction peaks of crystalline monoclinic tenorite
phase of copper oxide phase were discovered at 2θ values at 35.5°
and 38.7 °corresponding to the (1, 1, −1), (1, 1, 1) crystal faces,
which represents the low crystallinity of CuO. The results are in
accordance with the diffraction patterns of crystalline cubic CuO
(JCPDS 45-0937) [33]. The crystallite sizes of CuO in CuO/ZSM-5
catalysts are calculated from the CuO (1, 1, −1) diffraction peak
by the Scherrer equation and shown in Table 1. It can be seen
that the crystallite size of the CVD catalysts was smaller than
that of the IM catalysts at the same copper loadings. For the IM Fig. 3. TEM images of (A1–A2) CVD, (B1-–B2) IM catalysts.
catalysts, because of a relative weak interaction between metallic
species and the ZSM-5 support in the process of impregnating,
copper species may be redistributed during calcination, leading and the ZSM-5 support [37]. At the beginning of the N2 adsorp-
to an aggregation of copper oxide on the ZSM-5 support [6]. tion and desorption isotherms, the volume adsorbed increased sig-
However, for the CVD catalysts, the strong interaction between nificantly as the relative pressure increased, which was caused by
metal precursor and the ZSM-5 support, the active component the volume filling of the micropores. As the relative pressure keeps
evenly distributed on the ZSM-5 support surface during the metal increasing, the volume adsorbed increases as well, which should
deposition process, resulting in a small crystallite size of CuO [33]. be attributed to the multilayer adsorption [38]. It can be observed
The transmission electron microscopy (TEM) images of samples that the N2 adsorption–desorption isotherms of all samples were
in Fig. 3 show that the particle sizes of CuO/ZSM-5 are influenced similar with those of ZSM-5, indicating that the catalysts still re-
by the different preparation method. Histograms of the size distri- tain the original microporous structure after the addition of copper.
bution of CVD and IM catalysts are shown in Fig. 4 (after counting In particular, the preparation method with various copper loadings
100 particles). The CVD catalysts (Fig. 3 A1, A2) present a relatively had effect on the BET surface area, the BET surface area of the pure
uniform spherical nanoparticle of 50–100 nm. For the IM catalysts ZSM-5 support was found to be 299 m2 /g. As shown in the Table 1,
(Fig. 3 B1, B2), the samples show large polygons and rod-like parti- the BET surface area and other pore structure characteristics of the
cles of ∼300 nm and may be an aggregate of crystallites of copper CuO/ZSM-5 catalysts decreased with the copper loadings increased,
oxide. It can be seen in Figs 3 and 4 that the particle size of the which could be attributed to crystallites of CuO cover the external
CVD catalysts is smaller than that of the IM catalysts, which is con- surface of the ZSM-5 support and block the zeolite pore channel
sistent with the XRD results. [20]. These results match well with the explanation of the X-ray
diffraction.
3.2. Surface area and porosity N2 adsorption and desorption The different preparation method has effect on the BET surface
area. The IM catalysts have the lower the BET surface area and
The N2 adsorption–desorption isotherms of the ZSM-5 support total volume than the CVD catalysts at the same copper loadings,
and CuO/ZSM-5 catalysts with various copper loadings were inves- the possible reason is that metallic species can be easily migrated
tigated, as shown in Fig. 5. The BET surface area and pore struc- and accumulated during the heat treatment of the wet impreg-
ture characteristics of CuO/ZSM-5 catalysts prepared by different nated sample whereas the CVD method with good thermal stability
methods are shown in Table 1. As can be seen in Fig. 5, all the could distribute the active component more uniformly on the sur-
CuO/ZSM-5 samples present typical Ⅱ shape isotherms with a hys- face of the ZSM-5 support [6]. However, it cannot be ruled out that
teresis loop at a high relative pressure, which could be ascribed to the actual copper loadings may affect the specific surface area of
the existence of mesopores between the particles of copper oxide the catalyst. The actual loading of the catalyst was measured using

Please cite this article as: Y. Zhou et al., Catalytic oxidation of ethyl acetate over CuO/ZSM-5 catalysts: Effect of preparation method,
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35 35
A B
30 30

25 25
Distribtuion (%)

Distribtuion (%)
20 20

15 15

10 10

5 5

0 0
50 75 100 125 150 175 200 200 225 250 275 300 325 350
Particle size (nm) Particle size (nm)

Fig. 4. Histograms of the size distribution of CVD (A) and IM (B) catalysts (after counting 100 particles).

A
ZSM-5(adsorption) ZSM-5(adsorption)
ZSM-5(desorption) ZSM-5(desorption) B
1 wt% Cu/ZSM-5 CVD(adsorption) 1 wt% Cu/ZSM-5 IM(adsorption)
1 wt% Cu/ZSM-5 CVD(desorption) (a) 1 wt% Cu/ZSM-5 IMdesorption)
(a)
3 wt% Cu/ZSM-5 CVD(adsorption) 3 wt% Cu/ZSM-5 IMadsorption)
3 wt% Cu/ZSM-5 CVD(desorption) (b) 3 wt% Cu/ZSM-5 IM(desorption) (f)
Volume adsorbed/(cm3/g)

5 wt% Cu/ZSM-5 CVD(adsorption) Volume adsorbed/(cm3/g) 5 wt% Cu/ZSM-5 IM(adsorption)

5 wt% Cu/ZSM-5 CVD(desorption) (c) 5 wt% Cu/ZSM-5 IM(desorption)
(g)
10 wt% Cu/ZSM-5 CVD(adsorption) 10 wt% Cu/ZSM-5 IM(adsorption)
10 wt% Cu/ZSM-5 CVD(desorption)
(d) 10 wt% Cu/ZSM-5 IM(desorption)
(h)
(e) (i)

0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Relative Pressure(P/P )O Relative Pressure(P/P ) O

Fig. 5. N2 adsorption–desorption isotherms of the ZSM-5 support, CVD catalysts (A) and IM catalysts (B) at 77K: (a) ZSM-5, (b) 1 wt% CVD, (c) 3 wt% CVD, (d) 5 wt% CVD,
(e) 10 wt% CVD, (f) 1 wt% IM, (g) 3 wt% IM, (h) 5 wt% IM, (i) 10 wt% IM.

Table 2
Surface element composition of ZSM-5, IM catalysts and CVD catalysts.

Samples 1 wt% 3 wt% 5 wt% 10 wt% 1 wt% 3 wt% 5 wt% 10 wt%

CVD CVD CVD CVD IM IM IM IM

Cu2+ /Cu+ a 2.54 2.86 2.70 3.26 3.26 2.57 1.38 2.03
Oadsorbed /Olattice a 4.35 2.60 5.70 5.54 3.24 2.35 1.25 2.62
a
calculated from the XPS results.

atomic absorption spectrophotometry. It can also be seen that the peaks at a binding energy of 944 eV are typical characteristics of
actual copper loadings of the CVD catalyst was lower than that of Cu2+ species, whereas the lower binging energy (932.5 eV) and the
the IM catalyst at the same theoretical loading. absence of shake-up peaks are indicative of Cu+ . Similarly, the ex-
perimental results present that the Cu 2p1 / 2 binding energy can be
3.3. X-ray photoelectron spectroscopy (XPS) deconvoluted into two peaks of 954.5 and 952.5 eV, correspond-
ing to the chemical states Cu2+ and Cu+ , respectively. It can be
The CuO/ZSM-5 catalysts were analyzed by X-ray photoelec- observed that the copper species was present as Cu2+ in all sam-
tronic spectra to detect the influence of the preparation method ples as indicated by the shake-up peaks, meanwhile, the copper
with various copper loadings on the surface composition and the species was exhibited as the further reduced copper species (Cu+ )
element chemical states. The XPS spectra of Cu 2p and O 1s of in all catalysts. The absence of shakeup peaks in Fig. 6 at low Cu
CuO/ZSM-5 catalysts are shown in Figs. 6 and 7, respectively. The loadings (1 wt % and 3 wt %) might be ascribed to the appearance
surface element composition data are summarized in Table 2. All of CuO in a highly dispersed amorphous state, which was in agree-
spectrums exhibit two wide and asymmetric main peaks of Cu ment with the previous XRD results. In addition, the peak inten-
2p1/2 and Cu 2p3/2 at around 950–960 eV and 930–938 eV, to- sity of the Cu 2p spectra increased with the copper loadings in-
gether with the shake-up satellite peaks centered at 937–947 eV. creased as shown from XRD results. According to the results in
According to the literatures [20,21,36], the binding energy of the Table 2, it can be observed that the preparation method slightly
Cu 2p3/2 peaks at 934.7 eV, along with the presence of shake-up influences the relative surface content ratio of Cu2+ /Cu+ , the ratio

Please cite this article as: Y. Zhou et al., Catalytic oxidation of ethyl acetate over CuO/ZSM-5 catalysts: Effect of preparation method,
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Cu 2p1/2 Satellite Cu 2p3/2 A Cu 2p1/2 Satellite Cu 2p3/2 B

Cu2+ + Cu2+ +
Cu Cu
10 wt% IM

Relative Intensity (a.u.)

Relative Intensity (a.u.)

10 wt% CVD

5 wt% CVD 5 wt% IM

3 wt% IM
3 wt% CVD

1 wt% IM
1 wt% CVD

960 950 940 930 920 960 950 940 930 920
Binding energy (eV) Binding energy (eV)
Fig. 6. XPS spectra of Cu 2p of CuO/ZSM-5 catalysts prepared with various copper loadings: (A) CVD catalysts (B) IM catalysts.

O 1s Adsorbed O Lattice O A O 1s Adsorbed O Lattice O B

10 wt% IM
10 wt% CVD
Relative Intensity (a.u.)

Relative Intensity (a.u.)

5 wt% CVD 5 wt% IM

3 wt% CVD 3 wt% IM

1 wt% CVD 1 wt% IM

540 535 530 525 540 535 530 525

Binding Energy (eV) Binding Energy (eV)
Fig. 7. XPS spectra of O 1s of CuO/ZSM-5 catalysts prepared with various copper loadings: (A) CVD catalysts (B) IM catalysts.

of Cu2+ /Cu+ for the CVD catalysts are higher than that of the IM results are shown in Fig. 8. All the CuO/ZSM-5 catalysts exhibit two
catalysts at the same copper loadings (3, 5, 10 wt% catalysts). The reduction peaks, which are denoted as α and β . It was reported
higher Cu2+ /Cu+ ratio is, the more copper oxides exist in the CVD that the surface copper oxide species on the support is more eas-
catalyst, which may enhance the catalytic activity for ethyl acetate ily reduced than the big aggregates of CuO also known as bulk CuO
oxidation. crystallites [35]. Thus, the α peak is attributed to the reduction of
The XPS spectra of O 1s of CuO/ZSM-5 catalysts are shown in the well dispersed surface copper oxide species on the ZSM-5 sup-
Fig. 7, symmetric curves can be observed for all samples. The XPS port, whereas the β peak is ascribed to the reduction of the bulk
spectrum was deconvoluted into two different oxygen species, the copper oxides [36]. That is to say: highly dispersed copper (II) ox-
higher binding energy at 531.55 eV was ascribed to the adsorbed ide and bulk copper (II) oxides were reduced to metallic copper
oxygen (Oadsorbed ), whereas the lower binding energy at 530.3 eV (CuO→Cu), giving peaks α and β [39]. The results show that the
was assigned to the lattice oxygen (Olattice ) [37]. It could be ob- copper oxide species prepared by the two methods increase with
served that the oxygen species was present in all samples as lat- the increase of copper loadings, demonstrating that both methods
tice/adsorbed oxygen and the peak intensity of all samples was tend to generate the surface copper oxide instead of generating
similar, indicating that different methods with various copper load- the amount of bulk CuO crystallites under the low copper load-
ings had no effect on the oxygen species. However, the ratio of ings (1wt% and 3wt%). Furthermore, under the high copper load-
Oadsorbed /Olattice for the CVD catalysts is higher than that of the IM ings (5wt% and 10wt%), the β peak (namely the bulk CuO crystal-
catalysts at the same copper loadings, the probable reason could lites) of the IM catalysts is significantly larger than that of the CVD
be the CVD catalysts with perfect storage enhancement of oxy- catalysts, revealing that the CVD catalysts are more dispersible and
gen. It has been reported that the appearance of oxygen vacancies have less bulk CuO crystallites. These results match well with the
was significant for the physicochemical properties of materials and explanations of the X-ray diffraction and N2 adsorption–desorption
their catalytic performances [37]. isotherms. And the results present that the preparation method ap-
parently affects the reduction temperature; the IM catalysts have
the lower reduction temperature than the CVD catalysts. In partic-
3.4. Temperature-programmed reduction by hydrogen
ular, the two main reduction peaks are generally shifted to lower
temperatures with increasing copper loadings. It is possible that
The reduction behavior of ZSM-5 support and CuO/ZSM-5 cat-
the reduction at low copper loadings demands that hydrogen dif-
alysts with various copper loadings was investigated, and the

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Fig. 8. H2 -TPR profile of CuO/ZSM-5 catalysts prepared with various copper loadings: (A) CVD catalysts (B) IM catalysts.

fusion into lattice oxygen and lattice oxygen diffuses to the catalyst
surface, meanwhile, the interaction of copper oxide with the sup-
port decreases as the copper loadings increase [36]. However, the
results show that α peak in the 10 wt% CVD is shifted to higher
temperature (harder to reduce species). This is because the 10 wt%
CVD catalyst has more copper oxide species on the surface than
other CVD catalysts [40].
3.5. Temperature-programmed desorption of ammonia
The acid properties of the catalysts were explored via the
TPD of ammonia. The NH3 -TPD profile of the ZSM-5 support and
CuO/ZSM-5 catalysts are shown in Fig. 9. As shown in Fig. 8, the
NH3 -TPD profile of ZSM-5 zeolite displayed two desorption peaks.
The low temperature desorption peak around 230 °C is associated
with weakly bound NH3 , which causes NH3 physisorbed on Si–OH
or from non-zeolitic impurities. The high temperature desorption
peak around 460 °C around is assigned to the NH3 bound to strong
acid sites of Si–OH–Al [41]. Upon introduction of copper by dif-
ferent methods into ZSM-5, the weakly bound NH3 uptake of all
catalysts remain unchanged, indicating that the copper is able to
bind a significant amount of physisorbed NH3 ; however, the up-
take of strongly bound NH3 decreases considerably and then in-
creases with the increase of copper loadings. The desorption peak
of strong acid sites shifts to the low temperature with the incorpo-
ration of copper for the CuO/ZSM-5 catalysts, thus suggesting that
a low temperature is easy to strip the adsorbate after the addi-
tion of metal oxides [21]. Although the addition of copper results
in a decrease in strongly bound NH3 sites, new strongly bound
NH3 sites are created at 460–600 °C for the 5 wt% and 10 wt%
catalysts. According to the results from XRD and XPS that copper
are enriched on the surface of ZSM-5 support, it is reasonable to
conclude that the strong acid sites in the temperature range of
460–600 °C mainly arise from metal oxide nanoclusters [41]. Par-
ticularly, comparison of NH3 desorption profiles of the CVD cata-
lysts and the IM catalysts presented that the NH3 storage capacity,
namely the total acidity (area under the curve) of the CVD catalysts
is higher than IM catalysts.
3.6. Catalytic performances for ethyl acetate
The catalytic performance tests of CuO/ZSM-5 catalysts for ethyl
acetate oxidation were measured in a fixed-bed reactor, and the
results are shown in Fig. 10. The temperature required for 50%
and 90% conversion of ethyl acetate donated as T50 and T90 can
be used to evaluate the catalytic activity of catalysts [37], respec-
tively. Temperatures of 50% and 90% of ethyl acetate conversion
over CuO/ZSM-5 catalysts prepared by different methods with var-
ious copper loadings are summarized in Table 3. It can be seen in
Table 3 that the catalytic activity of the prepared catalysts is in
the following order: ZSM-5 (330 °C) < 5 wt% IM (282 °C) < 5 wt%
CVD (281 °C) < 3 wt% IM (278 °C) < 10 wt% IM (275 °C) < 10
wt% CVD (267 °C) < 1 wt% CVD (250 °C) < 1 wt% IM (240 °C) < 3
wt% CVD (235 °C). The order of catalytic activity is the same at the
relatively low conversion (T10 , T50 ) of ethyl acetate. Besides, ZSM-
5 support without active component presents the worst catalytic
behavior. It can be observed that the 3 wt% CVD catalyst demon-
strates a much higher catalytic activity (T50 = 188 °C, T90 = 235 °C)
than the 1 wt% CVD. When further increasing the copper loadings
(5 wt% CVD, 10 wt% CVD), the catalysts demonstrate a much lower
catalytic activity than the 3 wt% CVD catalyst. The results indicate
that appropriate copper loadings of prepared catalysts correspond
to a higher catalytic activity, the possible reason is that the cata-
lyst with lower copper loadings limits active sites of ethyl acetate
oxidation, which show a relatively lower catalytic activity. How-
ever, the BET data shows that the higher copper loadings corre-
spond to the lower specific surface area of ethyl acetate oxidation,
and the relatively higher metal loading may influence the disper-
sion of the copper oxides on the surface of the ZSM-5 support and
blocking the zeolite pore channel, all resulting in a decrease of cat-
alytic activity [42]. In particular, the results above indicate that the
CVD catalysts exhibit a higher catalytic activity for ethyl acetate
oxidation than that of the IM catalysts at the same copper load-
ings, such as the temperature (T90 ) of the 3 wt% CVD catalyst is
as low as 235 °C, which is lower by 43 °C compared with the 3
wt% IM catalyst that have a T90 of 278 °C. The possible reason is
that the IM method can easily lead to the migration and accumu-
lation of the active component as the CVD method can distribute
the active ingredient more evenly on the surface of the ZSM-5 sup-
port, and the CVD catalyst can provide the relatively higher ratio of
Cu2+ /Cu+ [6].
Ethyl acetate can be completely oxidized to CO2 and H2 O un-
der certain conditions, while a small amount of ethyl acetate can
be converted into intermediate products such as ethanol, acetalde-
hyde and acetic acid at relatively low temperatures. Probably in a
first stage ethyl acetate initially hydrolyzes to ethanol and acetic
acid, and this last one finally oxidizes through acetaldehyde to CO2
and H2 O [43]. On the one hand, acetic acid would be unstable and
it was easily decomposed. On the other hand, acetic acid was pref-
erentially oxidized with respect to ethanol due to the strong ad-
sorption on the ZSM-5 support surface, which all results in only a

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Fig. 9. NH3 -TPD profile of CuO/ZSM-5 catalysts prepared with various copper loadings: (A) CVD catalysts (B) IM catalysts.

Table 3
Temperatures of 50% and 90% of ethyl acetate conversion over CuO/ZSM-5 catalysts prepared by different methods with various copper loadings.

Samples 1 wt% CVD 3 wt% CVD 5 wt% CVD 10 wt% CVD 1 wt% IM 3 wt% IM 5 wt% IM 10 wt% IM ZSM-5

T50 (°C)a 200 188 232 209 193 219 245 222 264
T90 (°C)a 250 235 281 267 240 278 282 275 330
a
temperature at which the conversion of isopropanol reaches 50% (T50 ), 90% (T90 ).

trace amount of acetic acid in the reaction byproduct [34]. There-

fore, the main intermediate products are ethanol and acetaldehyde.
In general the scheme of these reactions can be represented as
follows [43]:

The scheme of ethyl acetate reaction pathway via ethanol is:

hydrolysis
CH3 COOCH2 CH3 + H2 O → CH3 COOH + CH3 CH3 OH (4)

CH3 CH2 OH + 0.5O2 → CH3 CHO + H2 O (5)

The conversion of ethyl acetate to ethanol and acetaldehyde

over CuO/ZSM-5 catalyst is shown in Fig. 11, and Fig. 12 presents
the conversion into intermediate product at the T50 and T90 tem-
peratures of the CuO/ZSM-5 catalysts. It can be noticed in Fig.
11 that the curves of the conversion of ethyl acetate into ethanol
and acetaldehyde reveal the same trend, which initially increased
slowly with increase of temperature, and then reached the max-
imum before the relatively rapid decrease and finally until the
byproducts vanish, and the intermediate products of ethyl acetate
oxidation were completely oxidized into CO2 and H2 O at about
320 °C. It was also observed that the maximum conversion to
ethanol did not exceed 15% at 180 °C, while the maximum con-
version to acetaldehyde reached about 30% at 240 °C. The Tmax (the
temperature corresponding to the maximum conversion to byprod-
uct) of ethanol (Tmax = 180 °C) was about the onset temperature of
acetaldehyde, and the conversion to acetaldehyde increased as the
conversion to ethanol decreased when the temperature was above
180 °C. This phenomenon may be attributed to the discovery that
the intermediate product of ethanol oxidation was found to be ac-
etaldehyde via the reaction (5) and ethanol was more susceptible
to catalytic oxidation than acetaldehyde [20,34]. Particularly, when
the temperature was below 200 °C, we have observed ethanol as a
Fig. 10. Catalytic oxidation performances for ethyl acetate over CuO/ZSM-5 catalysts
prepared by different methods with various copper loadings.
major and acetaldehyde as a minor intermediate product during
ethyl acetate oxidation according to the relative amounts of ac-
etaldehyde and ethanol. Whereas the main intermediate product
was acetaldehyde when the temperature exceeds 200 °C, and the
final products were CO2 and H2 O when the temperature was above
320 °C. It can be inferred that the relative amounts of acetaldehyde
and ethanol are determined by the selectivity of the catalyst to-
ward acetaldehyde production from ethanol [34]. The results of the
experimental are similar to what has been found in ref. [34] con-
cerning ethyl acetate oxidation over CuO catalyst, however, there
are differences in the relative amounts of ethanol and acetaldehyde
produced over CuO catalyst.
As can be seen from Fig 11, the ethanol selectivity over various
catalysts is generally similar. ZSM-5 support without active compo-
nent corresponds to the maximum conversion into acetaldehyde.
In addition to the ZSM-5 sample, a maximum in acetaldehyde

Please cite this article as: Y. Zhou et al., Catalytic oxidation of ethyl acetate over CuO/ZSM-5 catalysts: Effect of preparation method,
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Fig. 11. Intermediate products of ethyl acetate oxidation over CuO/ZSM-5 catalysts. (A) Conversion into ethanol; (B) Conversion into acetaldehyde.

Fig. 12. Intermediate products of ethyl acetate oxidation over CuO/ZSM-5 catalysts at Temperature of T50 and T90 ; (A) Conversion into ethanol; (B) Conversion into
acetaldehyde.

selectivity is observed over the 1 wt% catalyst, while further
increase of catalyst copper loading generally results in progres-
sive increase of the amount of produced acetaldehyde. It can be
observed in Fig. 11 that the acetaldehyde selectivity of the IM
catalysts is lower than that of the CVD catalysts at the same cop-
per loadings. However, the CVD catalysts show a higher catalytic
activity for ethyl acetate oxidation than that of the IM catalysts
at the same copper loadings. The possible reason is that the
CVD catalyst is more conducive to acetaldehyde production from
ethanol. The removal of ethanol further accelerates the oxidation
of ethyl acetate over the CVD catalyst, confirming the higher
catalytic activity of the CVD catalyst. This may be attributed to the
relatively small particle size and good dispersion of CVD catalyst
actives. In addition, it can be seen in the Fig 11(B) and Fig. 12(B)
that 1 wt% catalysts based on relatively high consumption of
ethyl acetate produce highest relative amount of acetaldehyde
(excluding the ZSM-5 sample), the possible reason is that the
lower copper loadings lack sufficient active component of copper
oxide to catalyze the oxidation of acetaldehyde into CO2 and H2 O.
And the 5 wt% IM and 10 wt% IM catalysts based on relatively
low consumption of ethyl acetate produce the lowest relative
amount of acetaldehyde, the possible reason is that high loading
of the catalyst prepared by the impregnation process resulting in
the aggregation of copper oxide on the ZSM-5 support, thus the
catalysts exhibit low catalytic activity [6]. In general, for the 3
wt% CVD catalyst with the highest catalytic activity, the Tmax of
ethanol was as low as 160 °C, which was low by 20 °C compared
with other catalysts; and the Tmax of acetaldehyde was around
230 °C, which was lower 30 °C than those of the other catalysts.
It can be seen that higher catalytic activity results in the lower
Tmax . It can be seen in the Fig. 11(A) that the 3 wt% CVD catalyst
corresponds to the maximum ethanol selectivity. However, the
3 wt% CVD catalyst based on the highest consumption of ethyl
acetate corresponds to a relatively low acetaldehyde selectivity,
which shows its highest catalytic activity. Moreover, the interme-
diate products of ethyl acetate oxidation over 3 wt% CVD catalyst
were completely oxidized into carbon dioxide and water at about
288 °C, which was lower by 30 °C than those of other catalysts,
further indicating that it has the highest catalytic activity (Fig. 12).

Please cite this article as: Y. Zhou et al., Catalytic oxidation of ethyl acetate over CuO/ZSM-5 catalysts: Effect of preparation method,
Journal of the Taiwan Institute of Chemical Engineers (2018), https://doi.org/10.1016/j.jtice.2018.01.016
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10 Y. Zhou et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2018) 1–11
4. Conclusions
In summary, the CuO/ZSM-5 catalysts have exhibited good cat-
alytic activity for ethyl acetate catalytic combustion, ethyl acetate
was completely converted to CO2 and H2 O under 320 °C. The char-
acteristics of the CuO/ZSM-5 catalysts were investigated by using
N2 adsorption/desorption, XRD, TEM, XPS, H2 -TPR, as well as NH3 -
TPD method. The analysis results show that the catalysts still retain
the original microporous structure after the addition of copper, the
copper was mainly in Cu2+ state and Cu+ co-existed based on the
results of XPS. The experimental results indicate that the 3 wt%
CVD exhibited the best catalytic activity for ethyl acetate oxidation
with 90% conversion of ethyl acetate at 235 °C, meanwhile, the
intermediate products were completely oxidized into CO2 and H2 O
as low as 288 °C. In addition, the preparation methods affected
the catalytic activity of CuO/ZSM-5, and the CuO/ZSM-5 catalysts
prepared by CVD exhibited higher catalytic activity than the IM
catalysts in catalytic combustion of ethyl acetate at the same
copper loadings, which may be attributed to the relatively small
particle size and well dispersion of the CVD catalyst actives. There-
fore, the CVD catalysts are a promising catalyst for ethyl acetate
oxidation.
Acknowledgments
The authors gratefully acknowledge the financial support from
the National Natural Science Foundation of China (Grant No.
21776106), and Pearl River S&T Nova Program of Guangzhou (Grant
No. 201610010171) for this work.
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Please cite this article as: Y. Zhou et al., Catalytic oxidation of ethyl acetate over CuO/ZSM-5 catalysts: Effect of preparation method,
Journal of the Taiwan Institute of Chemical Engineers (2018), https://doi.org/10.1016/j.jtice.2018.01.016