Microporous and Mesoporous Materials 279 (2019) 165–177

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Microporous and Mesoporous Materials

journal homepage: www.elsevier.com/locate/micromeso

Plasma-enhanced dispersion of Cr2O3 over ceria-doped MCM-41 T

nanostructured catalyst used in CO2 oxidative dehydrogenation of ethane to
ethylene
Saeed Asgharia,b, Mohammad Haghighia,b,∗, Parisa Taghavinezhada,b
a
Chemical Engineering Faculty, Sahand University of Technology, P.O.Box 51335-1996, Sahand New Town, Tabriz, Iran
b
Reactor and Catalysis Research Center (RCRC), Sahand University of Technology, P.O.Box 51335-1996, Sahand New Town, Tabriz, Iran

A R T I C LE I N FO A B S T R A C T

Keywords: A series of chromium oxide catalysts supported on the mesoporous Ce-MCM-41 molecular sieves with different
Hydrothermal (Si/Ce) molar ratios have been synthesized by hydrothermal/impregnation method and compared with the
Impregnation catalysts treated by plasma energy. The effect of Si/Ce molar ratio on the catalytic activity of Cr/MCM-41
Cr2O3/Ce-MCM-41 nanocatalysts in dehydrogenation of ethane with CO2 was examined. The nanocatalysts were characterized by
Dehydrogenation
XRD, FESEM, EDX, TEM, BET and FTIR analysis. According to the results obtained by XRD analysis, by in-
Ethane
Ethylene
creasing the amounts of ceria in the support the content of α-Cr2O3 phase decreased. Also, the results of FESEM
analysis indicates that particle size decreased by increasing ceria content and more uniform morphology
achieved. Actually, the better characteristic properties and catalytic activity obtained when the molar ratio of Si/
Ce was considered 25. On the other hand utilization of plasma energy in catalyst treatment developed a catalyst
with better dispersion of chromium oxide and more uniform morphology and smaller particle size compared to
the untreated catalyst. This nanocatalyst remains stable after 300 min time on stream reaction and 62.3% of
ethylene yield achieved on it at 700 °C.

1. Introduction dispersion, redox properties and the oxidation state of chromium oxide
species affected the catalytic performance. The Cr6+, Cr5+ or Cr3+
Ethylene is a substantial feedstock for petrochemical, polymer and should be appear on the chromium supported nanocatalysts. According
chemical industries [1–3]. Light olefins such as ethylene are produced to the literature data Cr6+, dispersed uniformly on the support being
through dehydrogenation process which operates at the higher tem- raised as the most active and selective agent among the oxidation states
perature. The drawbacks such as high energy input and fast catalyst of chromium oxide [20–22]. The inappropriate dispersion of chromium
deactivation limit the operation of dehydrogenation of alkanes [4–6]. oxide creates polymeric species, which are less active and selective in
Nowadays oxidative dehydrogenation (ODH) of alkanes which operates ethane ODH. In order to attain highly dispersed chromium supported
at a milder condition and overcomes the equilibrium limitation asso- nanocatalyst, below monolayer coverage of active phase on the support
ciated to dehydrogenation process is taken into consideration [7–9]. is needed. Actually, utilization of support with high surface area could
Due to restrictions such as scant catalytic activity and low selectivity to be satisfy with this specification. The mesoporous materials provide
the desired product related to the ODH process, the researchers have high surface area required to the uniform dispersion of Chromium oxide
focused on the materials that activated only C-H bond of light alkanes [17,23]. The MCM-41 is the most studied kind of mesoporous material
[10–12]. In order to find selective and active catalyst for producing with hexagonal array and one dimensional pore. The pore size of MCM-
ethylene, various catalytic systems have been investigated, among them 41 altered from 2 to 10 nm according to the structure directing agent
the supported vanadium oxide [13,14], chromium oxide [15–17] and used [24–26]. The MCM-41 has a natural structure and is not sufficient
molybdenum oxide [18,19] exhibited higher ethylene yield. In the for the process that acidic or basic properties are required. By in-
presence of CO2, the chromium oxide supported materials are the most troduction of the other metal atom on the MCM-41 framework, the
promising catalyst for ODH of ethane. The features like chromium oxide acidic properties could be changed. On the other hand, the introduction

∗
Corresponding author. Reactor and Catalysis Research Center, Sahand University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz, Iran
E-mail address: haghighi@sut.ac.ir (M. Haghighi).
URL: http://rcrc.sut.ac.ir (M. Haghighi).

https://doi.org/10.1016/j.micromeso.2018.12.025
Received 5 January 2018; Received in revised form 7 December 2018; Accepted 17 December 2018
Available online 19 December 2018
1387-1811/ © 2018 Elsevier Inc. All rights reserved.
S. Asghari et al. Microporous and Mesoporous Materials 279 (2019) 165–177

Fig. 1. Hydrothermal synthesis of Ce-MCM-41 with various Si/Ce molar ratios and impregnation dispersion of Cr2O3 over support.

of the other atom on the MCM-41 array changed the hydrothermal and by improving the interaction between support and active phase
stability and redox properties of support [27–29]. CeO2 is a reducible modifies the active phase dispersion and impresses the activity and
metal oxide and its utilization in the ODH of ethane could be effective stability of the catalyst.
[30,31]. On the other hand the higher oxygen storage capacity of ceria However, significant attentions have been allocated to verification
makes it as a suitable candidate for reverse water-gas shift (WGS) re- of effect of micro- and mesoporous support morphology on the ODH of
action which is involved in the ethane ODH process [32]. However, the propane and butane (for example MCM-41 [1–8], SBA-15 [9–13] and
lower thermal stability and high cost of ceria precursor limit its appli- silicalite [14]) but only few paper deals with ODH of ethane over MCM-
cation singly, as catalyst support. According to the literature data, the 41, SBA-15 and other silica-based materials [17,40,41]. Al-Awadi et al.
combination of CeO2 with the other metal oxide displays higher cata- investigated the effect of sequence of precursors adding. Results showed
lytic activity [33–35]. Laha and co-workers synthesised Ce-MCM-41 that the pore and surface characteristics of the developed catalysts
and compared its performance when Ce+4 incorporated on the MCM-41 strongly depend on the employed sequence [42]. For this reason in the
framework and concluded that the second ones showed better catalytic current study at first, Cr supported MCM-41 was used in the ODH of
activity toward cyclohexene dehydrogenation [32]. ethane. The superior performance of Cr/MCM-41 catalyst toward
Apart from the increased catalytic activity, the active phase dis- ethane ODH levitated from the small sizes of silica nanoparticles that
persion is an important factor because the increase in the dispersion leads to the high degree of dispersion for CrOx species into pores and
and stability of the catalyst leads to a reduction in the utilization of surface of MCM-41 but it suffers from the activity loss during the on
chemicals and precursors. In this study in order to reach high dispersion stream reaction. The main objective of this study is improving the
of chromium oxide on the surface of support glow discharge plasma is catalytic activity and stability of Cr/MCM-41 toward oxidative dehy-
used. The application of this kind of plasma is simple and the input drogenation of ethane. With respect to that incorporation of the other
energy required is low [36,37]. For the catalyst treatment by glow metal oxide produced new acidic and basic sites, Ce was introduced in
discharge plasma approximately, "1 Wh/g-catalyst" energy is needed the MCM-41 framework with a different molar ratio of Si/Ce. At the
[38,39]. On the other hand, the utilization of glow discharge plasma final step, the Cr/Ce-MCM-41(Si/Ce = 25) as the best catalytic system
modifies the crystallinity and surface properties of supported catalyst was treated by glow discharge plasma in order to increase the

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Fig. 2. Experimental setup for plasma treatment of synthesized Cr2O3/Ce-MCM-41 nanocatalysts.

dispersion of chromium oxide species on the support. The experimental setup for plasma treatment of synthesized Cr/Ce-
MCM-41 nanocatalysts has been shown in Fig. 2.
2. Materials and methods Fig. 3 schematically shows the methodology of Cr/CeO2 catalyst
preparation. CeO2 support was prepared by hydrothermal method. The
2.1. Materials appropriate amount of cerium nitrate hexahydrate was dissolved in de-
ionized water and stirred and then pH value was adjusted to 11 with
In order to synthesize Cr/Ce-MCM-41catalysts with different Si/Ce sodium hydroxide 1 N. The gel was transferred into an autoclave and
molar ratio, sodium metasilicate (Na2O3Si, Aldrich, 99.9%), cerium hold in an oven for 12 h at 140 °C. After that, the solid sample was
nitrate hexahydrate (Ce(NO3)3·6H2O, Merck) and cetyltrimethyl-am- filtered and washed with de-ionized water and dried at 110 °C for 6 h.
monium bromide (C19H42BrN, Merck, extra pure) were used as the Then calcined at 550 °C for 6 h to form the CeO2 support. The CeO2
sources of the silica, ceria and template respectively. Chromium nitrate support was impregnated with a proper amount of chromium nitrate
(Aldrich, 96%) was used as active phase source. NaOH and de-ionized aqueous solution for 1 h at 50 °C then dried at 120 °C for 24 h and cal-
water were used as precipitant and ion exchange media. cined at 700 °C in air ambient for 4 h. Finally, as-synthesized Cr/CeO2
catalyst was formed.
2.2. Nanocatalysts preparation and procedures
2.3. Nanocatalysts characterization
Fig. 1 shows schematically the methodology of the formation of Cr/
MCM-41 and Cr/Ce-MCM-41 catalysts. The MCM-41 and Ce containing Powder X-ray diffraction (XRD) analysis was performed on a
(Ce-MCM-41) supports were prepared by hydrothermal method. A re- D5000 S with Cu Kα radiation (λ = 0.154056 nm) and operated at
quired amount of cerium nitrate was added to the mixture of cetyl- 40 kV and 40 mA in order to identify the crystal structure and crystal-
trimethyl-ammonium bromide and sodium metasilicate and stirred. It is linity. The morphology of the synthesized catalysts was studied by field
worth noting, the amounts of cerium nitrate and sodium metasilicate emission scanning electron microscope (FESEM) on (HITACHI S-4160).
have been chosen in a way that the molar ratio of Si/Ce in the prepared The elemental analysis and determination of components dispersion on
support fixed at 25 and 50. The pH value was adjusted to 11 by drop the surface was conducted by energy dispersive X-ray (EDX).
wisely addition of sodium hydroxide. The white formed gel was Transmission electron microscopy (TEM) images were captured on a
transferred into an autoclave and kept an oven for 12 h set at 140 °C. JEOL, JEM-2100 electron microscope operated at 200 kV. Sample was
After cooling, the solid sample was filtered and washed with de-ionized ultrasonically dispersed in ethanol and then, the suspension was de-
water and dried at 110 °C for 6 h, then calcined at 550 °C for 6 h to posited on a thin carbon film-coated on Cu grid. For addressing surface
remove the surfactant and formation of Ce-MCM-41(Si/Ce = 25), Ce- functional groups, The FT-IR spectra was gained with a Unicam 4000
MCM-41(Si/Ce = 50) and MCM-41 supports. MCM-41 and Ce-MCM-41 FTIR spectrometer using KBr plate in the range of 400–4000 cm−1 wave
supports with various Si/Ce molar ratio were impregnated with a number. The Brunauer–Emmett–Teller (BET), specific surface area of
proper amount of chromium nitrate aqueous solution, for 1 h at 50 °C the samples studied by a Quantachrome ChemBET 3000 instrument.
then dried at 120 °C for 24 h. A part of Cr/Ce-MCM-41(Si/Ce = 25) Samples were pre-treated at 200 °C for 30 min and were examined using
support modified by plasma energy for 45 min before calcination and nitrogen adsorption at 77 K.
finally, all of the samples calcined at 700 °C in air ambient for 4 h to
remove the surfactant. As could be seen from the Fig. 1 the Cr/Ce-MCM- 2.4. Nanocatalysts performance test
41(Si/Ce = 25)-p (“p” referred to plasma) was prepared by plasma rout
and the other samples were prepared through conventional method. Experimental setup for testing of catalytic performance of

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Fig. 3. Hydrothermal synthesis of CeO2 and impregnation dispersion of Cr2O3 over support.

synthesized nanocatalysts used in CO2 oxidative dehydrogenation of FC2 H4

SC2H4 (%) = 100 ×
ethane to ethylene has been shown in Fig. 4. The oxidative dehy- (FC2 H4 + FCH4) (2)
drogenation of ethane was measured in a fixed-bed quartz reactor
(6 mm i.d.) with 500 mg catalyst loading under atmospheric pressure at FC2 H4
YC2H4 (%) = 100 ×
temperatures ranging from 600 to 700 °C. The reaction feed gases (FC2 H6)in (3)
contained 10% ethane, 50% carbon dioxide and 40% nitrogen reported
into the U-shape quartz reactor at a flow rate of 75 ml/min. The re- Where, Fi is the molar flow rate of each component.
actant and reaction products were analyzed on-line by a gas chroma-
tograph (GC Chrom, Teif Gostar Faraz, Iran) equipped with FID detector 3. Results and discussions
and a Carboxen™ 1000 column, under ambient pressure at a gas hourly
space velocity (GHSV) of 6000 h−1. 3.1. Nanocatalysts characterization
Conversion of ethane (X), selectivity to ethylene (S) and yield of
ethylene (Y) were calculated as described below: 3.1.1. XRD analysis
Fig. 5 shows the X-ray diffraction patterns of prepared MCM-41
(FC2H6)in − (FC2H6)out (JCPDS 00-049-1712) support in the range of 1-10°. The characteristic
X C2H6 (%) = 100 ×
(FC2H6)in (1) peaks at 2.1, 3.7, 4.2 and 5.6° are related to the (1 0 0), (1 1 0) and (2 0
0) plans of MCM-41. The existence of these diffraction peaks certifies

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Fig. 4. Experimental setup for testing of catalytic performance of synthesized nanocatalysts used in CO2 oxidative dehydrogenation of ethane to ethylene.

Fig. 5. XRD patterns of synthesized MCM-41.

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this result showed that introduction of Ce to the MCM-41 structure did

not change the MCM-41 framework greatly. The overall look at the
images suggests that particles of all samples are in nanometer-scale. A
detailed examination of micrographs revealed that by utilization higher
amount of ceria in the support, the particles aggregation and formation
of the hunk on the catalyst surface reduced and it could be due to
improved distribution of chrome oxide species. This observation has
been confirmed earlier by the XRD analysis. On the other hand, in the
Cr/Ce-MCM-41(Si/Ce = 50) the particles distribution is inappropriate
and heterogeneous but by adding more ceria to the sample in the Cr/Ce-
MCM-41(Si/Ce = 25) catalyst the particles distribution become more
uniform and homogeneous. On the other hand, comparison of the
morphology of Cr/Ce-MCM-41(Si/Ce = 25) and Cr/Ce-MCM-41(Si/
Ce = 25)-p indicated that plasma treatment enhances the uniformity of
catalysts particles due to improved distribution of catalyst particles
[43]. Surface particles size histogram of Cr/Ce-MCM-41(Si/Ce = 25)-p
nanocatalyst is elucidated in Fig. 8. By applying ImageJ software and
FESEM image the particle size distribution and average particles size of
Cr/Ce-MCM-41(Si/Ce = 25)-p obtained. All particles distributed in the
narrow range of 7.4–22 nm. The average particle size calculated about
13.1 nm. According to what mentioned above it is expected that Cr/Ce-
MCM-41(Si/Ce = 25)-p with the best surficial features displays better
catalytic performance in ODH of ethane in the presence of CO2.

3.1.3. TEM analysis

The morphological features of the Cr/Ce-MCM-41(Si/Ce = 25)-p
were studied by TEM technique and results are shown in Fig. 9. How-
ever, the FESEM analysis, proved the formation of hexagonal array of
MCM-41 in the Cr/Ce-MCM-41(S/Ce = 25)-p sample the order of the
framework, channels and pore system became slightly disturbed. This
result indicates that the maximum content of ceria introduced to the
MCM-41 array is restricted by structure destruction. Some black spots
Fig. 6. XRD patterns of synthesized Cr2O3/Ce-MCM-41 nanocatalysts with are observed on the surface of disordered hexagonal Ce-MCM-41(S/
various Si/Ce molar ratios: (a) Cr/MCM-41, (b) Cr/Ce-MCM-41(Si/Ce = 50), Ce = 25)-p, attributed to particles of chromium oxide deposited on the
(c) Cr/Ce-MCM-41(Si/Ce = 25), (d) Cr/Ce-MCM-41(Si/Ce = 25)eP and (e) Cr/
surface of the support. As could be seen from Fig. 9 the nanosized
CeO2.
particles of Cr distributed in the limited range of 9.3–14.3 nm which,
illustrated homogenous distribution of active phase. On the other hand,
formation of hexagonal mesostructure of MCM-41. The X-ray diffrac- the synergistic effect of ceria presence and plasma treatment reinforced
tion patterns of the Cr/Ce-MCM-41 catalysts with a variety of Si/Ce the interaction between MCM-41 and chromium oxide species and
molar ratio are shown in Fig. 6 in the 2θ range of 20–70°. The dif- impede the migrations of active phase particles. Therefore, the size of
fraction peaks observed at 2θ = 28.8, 33.2, 47.7, 56.6, 59.4, 69.8, 77.1, Chromium oxide hocks decreased and the uniform dispersion of active
79.5, 88.9° are indexed to the (111), (200), (220) and (311) diffraction phase achieved.
lines of CeO2 (JCPDS01-075-0076). With an overview on XRD patterns,
it is clear that by increasing the amount of reinforcing Ce content in the
support the intensity of the CeO2 diffraction peaks increases. This result 3.1.4. EDX analysis
showed that Ce entered correctly in the structure. Moreover the dif- Fig. 10 shows the EDX analysis and surface composition of the as
fraction peaks observed at 2θ = 24.5, 33.6, 36.2, 41.5, 50.2, 54.9, 63.3 synthesized Cr/Ce-MCM-41 nanocatalysts with 7% Cr2O3 loading. All
and 65.1° are related to Cr2O3 (JCPDS 00-006-0504). The comparison elements used in the synthesised catalyst could be seen in the spectrum
of XRD patterns of all synthesized samples revealed that by introduction that indicating the presence of all the elements used in the catalyst
of Ce in the catalyst support the intensity of the peaks assigned to Cr2O3 structure. In addition, it is not observed any pollution of the catalyst to
decrease. This result is in line with the idea that presence of Ce together other elements of precursors used in the catalysts synthesising. Fur-
with MCM-41 enhances Cr species dispersion. In addition the utilization thermore, in all samples, surface chemical compositions are in agree-
of non-thermal plasma in the synthesizing of Cr/Ce-MCM-41(Si/ ment with the expected values. The comparison of the images illu-
Ce = 25)-p, leads to drop the crystallinity of Cr2O3 phase. On the hand strated that reinforcement of support by ceria utilization affected the
reduces the size of active phase particles and enhances the interaction distribution of chrome particles and obviously better chromium oxide
between active phase and support. The stronger interaction between dispersion was found for the ceria-containing catalysts, which are
support and active phase prevent the migration of Cr species and con- consistent with XRD analysis. The utilization of plasma in catalysts
trol the size of Cr ensembles. treating results more homogeneous distribution of chrome oxide species
and disrupted the ensembles formed on the corner side of the catalysts.
In the case of Cr/CeO2 catalyst, the low surface area of support leads to
3.1.2. FESEM analysis the formation of accumulation of Cr apiece. On the other hand, the
The morphology of the Cr/Ce-MCM-41 samples with various (Si/Ce) better dispersion and absence of hunk on the surface of Ce-containing
molar ratios was examined by FESEM analysis and captured images are catalysts improve the interaction between support and active phase and
shown in Fig. 7. The hexagonal or spherical edges morphology could be enhances the catalytic performance. From what mentioned above it is
observed for the Cr/MCM-41, Cr/Ce-MCM-41(Si/Ce = 25), Cr/Ce- expected that Cr/Ce-MCM-41(Si/Ce = 25)- p exhibited better catalytic
MCM-41(Si/Ce = 50) and Cr/Ce-MCM-41(Si/Ce = 25)-p catalysts and activity.

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Fig. 7. FESEM images of synthesized Cr2O3/Ce-MCM-41 nanocatalysts with various Si/Ce molar ratios: (a) Cr/MCM-41, (b) Cr/Ce-MCM-41(Si/Ce = 50), (c) Cr/Ce-
MCM-41(Si/Ce = 25), (d) Cr/Ce-MCM-41(Si/Ce = 25)eP and (e) Cr/CeO2.

3.1.5. BET analysis morphology obtained. All of these features lead to the higher surface
The specific surface area of the Cr loaded support was measured and area of Cr/Ce-MCM-41(Si/Ce = 25)-p.
was given in Fig. 11. Based on the results, Cr/MCM-41 provides the
comparable surface area with the literature [44–46]. This surface area
is appropriate in order to prevent from the formation of agglomerates 3.1.6. FTIR analysis
and establishes suitable interaction between support and active phase. The FTIR spectrum of synthesised Cr/Ce-MCM-41 catalysts with
The surface area of Cr/CeO2 is much lower than the other catalyst. various Si/Ce molar ratios is captured in the range of 400-4000 cm−1
Actually, the high surface area provided required active sites for the and is shown in Fig. 12. In the case of Cr/Ce-MCM-41, Cr/Ce-MCM-
ODH of ethane. High specific surface area creates active sites for ad- 41(Si/Ce = 25) and Cr/Ce-MCM-41(Si/Ce = 25)-p catalysts the peaks
sorption of reactants and facilitates the C-H bond and oxidant activa- observed at 480, 810 and 1075 cm−1 are assigned to symmetric
tion. The application of ceria in the support decreased the surface area stretching vibration of Si-O-Si bond [47,48] and confirmed the suc-
of catalyst. The specific surface area reduction may be due to pore cessfully synthesizing of the MCM-41 substrate. The presence of peak at
blockage of MCM-41 by ceria species. The application of plasma 1650 cm−1 is related to the physically adsorbed water [49–51]. On the
somewhat compensate for this reduction. This result is in accordance other hand, the peaks appeared at 3450 cm−1 referring to the chemi-
with FESEM and EDX analysis. By the application of glow discharge cally adsorbed water [52–54]. The intensity of this peak indicated the
energy, the small particles are formed and particles distributed in strength of catalysis in coke removing [55], which is more intense in
narrow ranges and in comparison with the other catalyst, more uniform the Cr/CeO2 catalyst and confirm the idea that higher oxygen capacity
of CeO2 is useful for ethane ODH. The peaks observed at 620 cm−1 is

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Fig. 8. Surface particle size distribution histogram of synthesized Cr2O3/Ce-MCM-41 nanocatalyst: Cr/Ce-MCM-41(Si/Ce = 25)-P.

Fig. 9. TEM of synthesized Cr2O3/Ce-MCM-41 nanocatalyst: Cr/Ce-MCM-41(Si/Ce = 25)-P.

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Fig. 10. EDX analysis of synthesized Cr2O3/Ce-MCM-41 nanocatalysts with various Si/Ce molar ratios: (a) Cr/MCM-41, (b) Cr/Ce-MCM-41(Si/Ce = 50), (c) Cr/Ce-
MCM-41(Si/Ce = 25), (d) Cr/Ce-MCM-41(Si/Ce = 25)eP and (e) Cr/CeO2.

assigned to the α-Cr2O3 [56] and confirmed the presence of Cr oxide 3.2. Catalytic performance toward ethane to ethylene
species in all investigated samples and is in accordance with XRD
analysis. The peaks appeared at 480, 560 and 1075 cm−1 could be re- 3.2.1. C2H6 conversion
lated to the stretching bond of Cr-O and Cr-OH stretching bond re- Dehydrogenation of C2H6 with CO2 at different temperatures is
spectively [56]. depicted in Fig. 13 for Cr/Ce-MCM-41 nanocatalysts with different Si/
Ce molar ratio. As could be seen, the ethane conversion has sig-
nificantly increased with temperature enhancement due to the en-
dothermic nature of reaction. On the other hand, the ethane conversion
depends on the ceria content at the support. The comparison of all

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Fig. 11. BET specific surface area analysis of synthesized Cr2O3/Ce-MCM-41 nanocatalysts with various Si/Ce molar ratios.

nanocatalyst conversion revealed that simultaneous utilization of Ceria

and MCM-41 as support improved the initial catalytic activity this ob-
servation could be explained by the better dispersion of Cr species and
smaller surface particle size which are proved by XRD, EDX dot map-
ping and FESEM analysis. Furthermore, the redox behavior associated
with the CeO2 activated CO2 and enhances the concentration of active
oxygen required to the ODH reaction so the conversion of Ce containing
nanocatalysts is higher than Cr/MCM-41 [57]. Utilization of plasma
energy in treatment of Cr/Ce-MCM-41(Si/Ce = 25) enhances the
ethane conversion at all temperature which is related to the better
dispersion of Cr species, uniform morphology and higher surface area of
treated nanocatalyst. These features were confirmed previously by
XRD, FESEM, EDX and BET analysis.

3.2.2. C2H4 yield

Fig. 14 illustrates the ethylene yield for synthesized Cr/Ce-MCM-41
nanocatalysts with different Si/Ce molar ratio at temperature range of
600–700 °C. According to Fig. 14 the ethylene yield increased by tem-
perature increasing too. The proximity of the amounts of ethane con-
version and ethylene yield in all synthesised nanocatalysts, pointed to
the high selectivity, even at higher temperature because of the milder
nature of oxidizer used and also the proper acidic properties of sup-
ports. As could be seen the ethylene yield over Cr/Ce-MCM-41(Si/
Ce = 25) is higher than the other catalysts prepared by conventional
route, suggesting that the molar ratio of Si/Ce = 25 generates more
active, selective and accessible active site for ethylene production. On
the other hand, the better morphological properties associated with the
Cr/Ce-MCM-41(Si/Ce = 25), leads to better dispersion of chrome oxide
species and prevents from the formation of active phase agglomeration.
In comparison with Cr/Ce-MCM-41(Si/Ce = 25) the Cr/Ce-MCM-
41(Si/Ce = 25)-p has higher ethylene yield due to better interaction
between MCM-41 as a support and reinforcing ceria and uniform dis-
persion of particles in the Cr/Ce-MCM-41(Si/Ce)-p catalyst. The ethy-
lene yield reached 62% at 700 °C over Cr/Ce-MCM-41(Si/Ce = 25)-p.

3.3. Time on stream performance

Fig. 12. FTIR spectra of synthesized Cr2O3/Ce-MCM-41 nanocatalysts with The catalyst stability is introduced as one of the important factors in
various Si/Ce molar ratios: (a) Cr/MCM-41, (b) Cr/Ce-MCM-41(Si/Ce = 25),
choosing an appropriate catalyst. The catalytic performance of Cr/Ce-
(c) Cr/Ce-MCM-41(Si/Ce = 25)eP and (d) Cr/CeO2.
MCM-41(Si/Ce = 25)-p nanocatalyst as the best catalytic system

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evaluated at 700 °C for 5 h time on stream and results are shown in

Fig. 15. The results indicate that catalyst approximately remains stable
after 5 h reaction. The coke formation and diminishing redox chromium
species caused catalyst deactivation. Actually one of the reasons that
Cr/Ce-MCM-41(Si/Ce = 25)-p remains active and selective toward
ethylene production is the unique properties of ceria amplifier that
prevents the reduction of catalytic activity. The slight deactivation has
been observed in the literature for Cr/MCM-41 catalyst due to coke
formation and diminishing redox Cr species [17]. On other hand, the
presence of ceria in the catalyst improved the acid base properties,
redox behavior and chromium dispersion. The presence of Ce+3 and
Ce+4 redox couple act as CO2 oxidation agent and re-oxidized the re-
duced Cr species and relief the deactivation rate caused by declining
active sites. In addition, according to what mentioned above, the
treatment of catalyst by plasma energy generates many active sites in
this sample because of a uniform distribution of fine particles of chro-
mium. It is well known that more active sites provided more stable
catalyst.
Fig. 13. C2H6 conversion over synthesized Cr2O3/Ce-MCM-41 nanocatalysts
with various Si/Ce molar ratios at various temperatures.
3.4. Comparison of catalytic performance to the literature

Catalytic activity and stability of Cr/Ce-MCM-41(Si/Ce = 25)-p

catalyst was compared with those studied by other researchers and
results are exhibited in Table 1. Nevertheless, direct comparison of data
from various studies is very complicated due to different conditions
applied to the catalytic tests by various research groups. It seems that
activity comparison of different catalysis according to the ethylene
yield and activity loss during the on stream reaction is justifiable. Ac-
cording to Table 1, silica-based catalysis presented acceptable ethylene
yield. Especially Cr/MSU could effectively dehydrogenate ethane to
ethylene with yield of 55.6%. However, its activity decreased to 42%
after 3 h exhibited lower stability of this catalyst. Moreover, the oper-
ating condition, which applied in our study, is milder than those ap-
plied in this study. The results obtained from Ref. [60] revealed that
SiO2 is the activist support among the studied metal oxide. The com-
pression 5 Cr/SBA-15 and 5Cr–5Ce/SBA-15 at the same operating
condition is interesting and shows the beneficial effect of ceria addition
on the enhancing catalytic activity of 5 Cr/SBA-15 catalyst. Moreover
the life time of catalyst increased by ceria addition. According what
Fig. 14. C2H4 yield over synthesized Cr2O3/Ce-MCM-41 nanocatalysts with
mentioned above designing of Ce modified silica based catalyst could
various Si/Ce molar ratios at various temperatures.
be useful for ethane ODH. Cr/Ce-MCM-41(Si/Ce = 25)-p with the 62%
ethylene yield and negligible activity loss considered as the best cata-
lytic system among the studied catalyst.

3.5. Reaction mechanism of ethane to ethylene

The reactions involved in the ethane ODH over chromium oxide

supported catalysts followed the Mars-van Krevelen mechanism
[69,70]. According to Mars-van Krevelen mechanism at the first step,
the reduction of chromium oxide occurred through the reaction of ad-
sorbed ethane and lattice oxygen. At the next step the reduced active
site, re-oxidized by the oxidant. According to what mentioned above
the type of oxidizer has an important impact on the ODH of ethane. The
CO2 is a mild oxidant and its activation is harder than the activation of
O2 and affects the ethane conversion and ethylene selectivity. A reac-
tion mechanism has been shown in Fig. 16 for ODH of ethane on Cr/Ce-
MCM-41 nanocatalyst and suggested according to the literature data
and experimental results. According to Fig. 16 at first, the cleavage of
first C-H bond of ethane occurred; ethyl radical and hydroxyl atom
Fig. 15. Time on stream behaviour of synthesized Cr2O3/Ce-MCM-41 nanoca- separately were adsorbed on the surface of catalyst. At this part, the
talysts with various Si/Ce molar ratios toward CO2-oxidative dehydrogenation chromium oxide species reduced. This step is known as rate limiting
of ethane to ethylene. step and the lattice oxygen existed on the chromium oxide play an es-
sential role at this part. The distribution of final products depends on
the path that reaction goes through. The β hydrogen abstraction of
ethoxide generates ethylene while the α hydrogen abstraction leads to
formation of non-stable aldehyde and goes further reaction and formed

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S. Asghari et al. Microporous and Mesoporous Materials 279 (2019) 165–177

Table 1
Catalytic performance of various catalysts evaluated for ethane ODH.
Catalyst T(°C) GHSV (ml/gcat.h) Wcat (g) Feed Composition XC2H6 YC2H4 TOS (h) Activity Loss (%) Ref

5 Cr/ZrO2 650 4500 0.2 CO2/C2H6/Ar = 3/1/1 77.4 35.9 6 20 [58]

8 Cr/MCM41TEOS-Cr 700 9000 0.3 CO2/C2H6/N2 = 5/1/4 44 40 – – [42]
8 Cr/MCM41-I 700 9000 03 CO2/C2H6/N2 = 5/1/4 41 37 – –
5Cr2O3 HZSM-5-ZrO2 (10) 700 6000 0.5 CO2/C2H6/N2 = 5/1/4 64.6 56.4 5 Neg. [16]
5Cr/SAPO-34(0.2) 700 6000 0.5 CO2/C2H6/N2 = 5/1/4 52 50 5 Neg. [22]
Cr/Clinoptilolit (I) 700 6000 0.5 CO2/C2H6/N2 = 5/1/4 30 29 5 5 [9]
Cr/Clinoptilolit–ZrO2 (U) 600 55 48 5 25
Cr (8%)/MCM-41 700 9000 0.5 CO2/C2H6/N2 = 5/1/4 40.9 30.8 10 22 [59]
5Cr2O3/TiO2 − ZrO2 (3-1) 41.4 39.3 10 17
5Cr2O3/TiO2 700 9000 0.5 CO2/C2H6/N2 = 5/1/4 28 26 – – [15]
5Cr2O3/ZrO2 32 28 – –
Cr-MCM-41 700 3600 0.5 CO2/C2H6/He = 1/2/17 51.2 48.3 24 Neg. [60]
Cr/MSU 700 3600 0.2 CO2/C2H6 = 3/1 68.1 55.6 3 24 [23]
Cr-MSu 700 3600 0.2 CO2/C2H6 = 3/1 58 53.4 3 25
Cr2O3/Al2O3 − ZrO2 650 3600 1 CO2/C2H6/He = 1/1/2 36 20.3 – – [61]
3Cr/NaZSm-5-160 0.2 CO2/C2H6 = 7/1 64.9 49.4 6 5
3Cr/NaZSm-5-160 0.2 CO2/C2H6 = 5/1 65.5 49.4 – –
3Cr/NaZSm-5-160 650 3600 0.2 CO2/C2H6 = 3/1 60.5 49.1 – – [62]
3Cr/NaZSm-5-160 0.2 CO2/C2H6 = 1/1 55.2 46.5 – –
Cr/Al2O3 19.2 18.5
Cr/TiO2 650 3600 1 CO2/C2H6/N2 = 5/1/4 5.9 5.8
Cr/ZrO2 57.3 34.3 [63]
Cr/SiO2 56.1 52.1
5.0Cr/SBA-15 700 3600 0.2 CO2/C2H6 = 3/1 46.3 43.8 5 49 [64]
5.0Cr–5Ce/SBA-15 48.4 46.7 5 18
2.5Cr/SBA-15/Al/FeCrAl 41.6 37.9 – –
5Cr/SBA-15/Al/FeCrAl 750 4500 – CO2/C2H6 = 2/1 47.4 41.2 12 Neg. [65]
7.5Cr/SBA-15/Al/FeCrAl 46.1 37.9 – –
VOx/Mg-Zr-MCM-41 700 6000 0.5 CO2/C2H6/N2 = 5/1/4 43 10 11.45 [66]
VOx/SBA-15 600 3600 0.2 CO2/C2H6 = 0.25/0.75 21 13 – – [67]
Mo/SBA-16 650 3600 0.3 CO2/C2H6 = 1/3 60 31.3 12 4 [68]
Cr/Ce-MCM-41(Si/Ce = 25)-p 700 9000 0.5 CO2/C2H6/N2 = 5/1/4 64 62 5 Neg. This study

CO and CO2 and CH4. Obviously, the product distribution depends on

the amount of acidic or basic sites. The existence of Bronsted acid site
leads to overtaking of β hydrogen abstraction and production more
ethylene. The substitution of Ce atom in the MCM-41 altered its neutral
nature and created Bronsted acid sites. In order to complete the ODH
cycle, the reduced active sites should be re-oxidized. In the ODH of
ethane with CO2, the re-oxidation of reduced sites was done by active
oxygen generated from dissociative adsorption of CO2 on the catalyst
surface.

4. Conclusions

Important differences were observed between Ce containing catalyst

and parent Cr/MCM-41. The results of characterization showed that Ce
introducing to the support could improve the chromium dispersion,
particle size and particle size distribution. However, there was a lim-
itation on the amount of ceria adding to the MCM-41, the active phase
dispersion and uniformity of catalyst particles enhances by ceria in-
creasing. In the case of Cr/CeO2 catalysts the existence of ensembles
and non-uniform morphology were observed due to low surface area of
CeO2. Among the catalysts prepared by conventional route the Cr/Ce-
MCM-41(Si/Ce = 25) showed the better catalytic activity. With the aim
of enhancing C2H6 conversion and C2H4 yield, glow discharge plasma
was used to treat the catalyst. The utilization of glow discharge plasma
increases the interaction between support and active phase and prevent
the formation of chromium oxide ensembles. The Cr/Ce-MCM-41(Si/
Ce = 25)-p dehydrogenated ethane to ethylene effectively and the
ethylene yield of 62% and ethane conversion of 63.76% was obtained at
Fig. 16. Reaction mechanism of CO2-enhanced dehydrogenation of ethane to 700 °C over Cr/Ce-MCM-41(Si/Ce = 25)-p.
ethylene over synthesized Cr2O3/Ce-MCM-41 nanocatalyst.

Acknowledgements

The authors gratefully acknowledge Sahand University of

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Technology for the financial support of the project as well as Iran 247–257.
Nanotechnology Initiative Council for complementary financial sup- [37] M. Ojeda, M.L. Granados, S. Rojas, P. Terreros, F.J. Garcı́a-Garcı́a, J.L.G. Fierro,
Appl. Catal. Gen. 261 (2004) 47–55.
port. [38] J.-g. Wang, C.-j. Liu, Y.-p. Zhang, K.-l. Yu, X.-l. Zhu, F. He, Catal. Today 89 (2004)
183–191.
References [39] D.-g. Cheng, X. Zhu, Y. Ben, F. He, L. Cui, C.-j. Liu, Catal. Today 115 (2006)
205–210.
[40] Y.-L. Bi, V.C. Corberán, H. Zhuang, K.-J. Zhen, Oxidehydrogenation of Ethane with
[1] Z. Geng, Y. Li, Y. Han, Q. Zhu, Energy 142 (2018) 400–410. CO2 over transition metal doped MCM-41 mesoporous catalysts, in: J.-S.C. Sang-
[2] Q. Chen, M. Lv, D. Wang, Z. Tang, W. Wei, Y. Sun, J. Clean. Prod. 142 (Part 4) Eon Park, L. Kyu-Wan (Eds.), Studies in Surface Science and Catalysis, Elsevier,
(2017) 3109–3116. 2004, pp. 343–346.
[3] I. Rossetti, M. Compagnoni, E. Finocchio, G. Ramis, A. Di Michele, Y. Millot, [41] X. Wang, G. Zhou, Z. Chen, W. Jiang, H. Zhou, Microporous Mesoporous Mater. 223
S. Dzwigaj, Appl. Catal. B Environ. 210 (2017) 407–420. (2016) 261–267.
[4] Y. Cheng, H. Gong, C. Miao, W. Hua, Y. Yue, Z. Gao, Catal. Commun. 71 (2015) [42] A.S. Al-Awadi, A.M. El-Toni, M. Alhoshan, A. Khan, J.P. Labis, A. Al-Fatesh,
42–45. A.E. Abasaeed, S.M. Al-Zahrani, Ceram. Int. 45 (2019) 1125–1134.
[5] Y. Cheng, C. Miao, W. Hua, Y. Yue, Z. Gao, Appl. Catal. Gen. 532 (2017) 111–119. [43] S.B. Bagherzadeh, M. Haghighi, Energy Convers. Manag. 142 (2017) 452–465.
[6] Y. Cheng, L. Zhou, J. Xu, C. Miao, W. Hua, Y. Yue, Z. Gao, Microporous Mesoporous [44] V. Elías, E. Sabre, K. Sapag, S. Casuscelli, G. Eimer, Appl. Catal. Gen. 413–414
Mater. 234 (2016) 370–376. (2012) 280–291.
[7] A. Klisińska, K. Samson, I. Gressel, B. Grzybowska, Appl. Catal. Gen. 309 (2006) [45] V.R. Elías, E.V. Sabre, E.L. Winkler, L. Andrini, F.G. Requejo, S.G. Casuscelli,
10–16. G.A. Eimer, J. Solid State Chem. 213 (2014) 229–234.
[8] D. Mukherjee, S.-E. Park, B.M. Reddy, J. CO2 Util. 16 (2016) 301–312. [46] K.-T. Li, W.-T. Weng, J. Taiwan Inst. Chem. Eng. 40 (2009) 48–54.
[9] F. Rahmani, M. Haghighi, S. Mahboob, Ultrason. Sonochem. 33 (2016) 150–163. [47] S. Allahyari, M. Haghighi, A. Ebadi, S. Hosseinzadeh, Energy Convers. Manag. 83
[10] M.A. Atanga, F. Rezaei, A. Jawad, M. Fitch, A.A. Rownaghi, Appl. Catal. B Environ. (2014) 212–222.
220 (2018) 429–445. [48] M. Abdollahifar, M. Haghighi, A.A. Babaluo, J. Ind. Eng. Chem. 20 (2014)
[11] O.O. James, S. Mandal, N. Alele, B. Chowdhury, S. Maity, Fuel Process. Technol. 1845–1851.
149 (2016) 239–255. [49] S.R. Yahyavi, M. Haghighi, S. Shafiei, M. Abdollahifar, F. Rahmani, Energy Convers.
[12] E.S. Rudakov, J. Mol. Catal. Chem. 426 (Part B) (2017) 465–473. Manag. 97 (2015) 273–281.
[13] A.H. Elbadawi, M.S. Ba-Shammakh, S. Al-Ghamdi, S.A. Razzak, M.M. Hossain, [50] E. Aghaei, M. Haghighi, Microporous Mesoporous Mater. 196 (2014) 179–190.
Chem. Eng. J. 284 (2016) 448–457. [51] F. Rahmani, M. Haghighi, P. Estifaee, Microporous Mesoporous Mater. 185 (2014)
[14] M.V. Martínez-Huerta, X. Gao, H. Tian, I.E. Wachs, J.L.G. Fierro, M.A. Bañares, 213–223.
Catal. Today 118 (2006) 279–287. [52] E. Aghaei, M. Haghighi, Powder Technol. 269 (2015) 358–370.
[15] A. Talati, M. Haghighi, F. Rahmani, Adv. Powder Technol. 27 (2016) 1195–1206. [53] S. Aghamohammadi, M. Haghighi, Chem. Eng. J. 264 (2015) 359–375.
[16] F. Rahmani, M. Haghighi, B. Mohammadkhani, Microporous Mesoporous Mater. [54] P. Sadeghpour, M. Haghighi, Particuology 19 (2015) 69–81.
242 (2017) 34–49. [55] F. Rahmani, M. Haghighi, M. Amini, J. Ind. Eng. Chem. 31 (2015) 142–155.
[17] E. Asghari, M. Haghighi, F. Rahmani, J. Mol. Catal. Chem. 418–419 (2016) [56] H.R. Mahmoud, J. Mol. Catal. Chem. 392 (2014) 216–222.
115–124. [57] G. Raju, B.M. Reddy, S.-E. Park, J. CO2 Util. 5 (2014) 41–46.
[18] J. Li, J. Liu, L. Ren, Q. Liu, Z. Zhao, Y. Chen, P. Zhu, Y. Wei, A. Duan, G. Jiang, J. [58] S. Deng, H. Li, S. Li, Y. Zhang, J. Mol. Catal. Chem. 268 (2007) 169–175.
Energy Chem. 23 (2014) 609–616. [59] E. Asghari, M. Haghighi, F. Rahmani, J. Mol. Catal. Chem. 418–419 (2016)
[19] N. Haddad, E. Bordes-Richard, A. Barama, Catal. Today 142 (2009) 215–219. 115–124.
[20] T.V.M. Rao, E.M. Zahidi, A. Sayari, J. Mol. Catal. Chem. 301 (2009) 159–165. [60] Y.-L. Bi, V.C. Corberán, H. Zhuang, K.-J. Zhen, Oxidehydrogenation of Ethane with
[21] P.T. bai, V. Manokaran, P.S. Saiprasad, S. Srinath, Procedia Eng. 127 (2015) CO2 over transition metal doped MCM-41 mesoporous catalysts, in: S.-E. Park, J.-
1338–1345. S. Chang, K.-W. Lee (Eds.), Studies in Surface Science and Catalysis, Elsevier, 2004,
[22] F. Rahmani, M. Haghighi, J. Nat. Gas Sci. Eng. 27 (Part 3) (2015) 1684–1701. pp. 343–346.
[23] L. Liu, H. Li, Y. Zhang, Catal. Today 115 (2006) 235–241. [61] H. Bathula, Y. Ramesh, P.T. Bai, L. Nakka, S. Kamaraju, P.S. Sai Prasad, Oxidative
[24] K.C. Chanapattharapol, S. Krachuamram, S. Youngme, Microporous Mesoporous Dehydrogenation of Ethane to Ethylene on Cr2O3/Al2O3-zro2 Catalysts: the
Mater. 245 (2017) 8–15. Influence of Oxidizing Agent on Ethylene Selectivity, (2015).
[25] S. Karnjanakom, T. Suriya-umporn, A. Bayu, S. Kongparakul, C. Samart, C. Fushimi, [62] Y. Cheng, F. Zhang, Y. Zhang, C. Miao, W. Hua, Y. Yue, Z. Gao, Chin. J. Catal. 36
A. Abudula, G. Guan, Energy Convers. Manag. 142 (2017) 272–285. (2015) 1242–1248.
[26] Z. Shariatinia, Z. Zahraee, J. Colloid Interface Sci. 501 (2017) 60–76. [63] S. Wang, K. Murata, T. Hayakawa, S. Hamakawa, K. Suzuki, Appl. Catal. Gen. 196
[27] A. Vinu, K. Ariga, S. Saravanamurugan, M. Hartmann, V. Murugesan, Microporous (2000) 1–8.
Mesoporous Mater. 76 (2004) 91–98. [64] X. Shi, S. Ji, K. Wang, Catal. Lett. 125 (2008) 331–339.
[28] V. Umamaheswari, M. Palanichamy, V. Murugesan, J. Catal. 210 (2002) 367–374. [65] X. Shi, S. Ji, K. Wang, C. Li, Energy Fuels 22 (2008) 3631–3638.
[29] V. Parvulescu, B.L. Su, Catal. Today 69 (2001) 315–322. [66] P. Taghavinezhad, M. Haghighi, R. Alizadeh, Microporous Mesoporous Mater. 261
[30] B. Chu, H. An, T.A. Nijhuis, J.C. Schouten, Y. Cheng, J. Catal. 329 (2015) 471–478. (2018) 63–78.
[31] Y. Peng, C. Wang, J. Li, Appl. Catal. B Environ. 144 (2014) 538–546. [67] L. Čapek, J. Adam, T. Grygar, R. Bulánek, L. Vradman, G. Košová-Kučerová,
[32] S.C. Laha, P. Mukherjee, S.R. Sainkar, R. Kumar, J. Catal. 207 (2002) 213–223. P. Čičmanec, P. Knotek, Appl. Catal. Gen. 342 (2008) 99–106.
[33] A. Setiabudi, J. Chen, G. Mul, M. Makkee, J.A. Moulijn, Appl. Catal. B Environ. 51 [68] L. Kong, J. Li, Z. Zhao, Q. Liu, Q. Sun, J. Liu, Y. Wei, Appl. Catal. Gen. 510 (2016)
(2004) 9–19. 84–97.
[34] A.M. Venezia, G. Pantaleo, A. Longo, G. Di Carlo, M.P. Casaletto, F.L. Liotta, [69] Z. Skoufa, E. Heracleous, A.A. Lemonidou, J. Catal. 322 (2015) 118–129.
G. Deganello, J. Phys. Chem. B 109 (2005) 2821–2827. [70] A. Tribalis, G. Tsilomelekis, S. Boghosian, Compt. Rendus Chem. 19 (2016)
[35] A. Martínez-Arias, A.B. Hungría, M. Fernández-García, J.C. Conesa, G. Munuera, J. 1226–1236.
Phys. Chem. B 108 (2004) 17983–17991.
[36] S.A. Hedrick, S.S.C. Chuang, A. Pant, A.G. Dastidar, Catal. Today 55 (2000)

177