Peyman I 2016

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e1 0
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Preparation of highly active and stable

nanostructured Ni/CeO2 catalysts for syngas
production by partial oxidation of methane
Mohammad Peymani a, Seyed Mehdi Alavi b, Mehran Rezaei a,c,*

a
Catalyst and Advanced Materials Research Laboratory, Chemical Engineering Department, Faculty of Engineering,
University of Kashan, P.O. Box 8731751117, Kashan, Iran
b
Chemical Engineering Department, Iran University of Science and Technology, Tehran, Iran
c
Institute of Nanoscience and Nanotechnology, University of Kashan, P.O. Box 8731751117, Kashan, Iran
article info abstract
Article history: Nickel catalysts supported on nanocrystalline CeO2 were prepared with impregnation
Received 4 December 2015 method and employed in methane partial oxidation. The prepared catalysts were char-
Received in revised form acterized by BET, XRD, TPR, SEM and TPO techniques. The effect of Ni loading on the
10 February 2016 catalytic performance of the catalysts was investigated and the results showed that 10%
Accepted 6 March 2016 Ni/CeO2 catalyst possessed the highest catalytic activity. This catalyst showed high sta-
Available online xxx bility exposed to the reaction conditions for 48 h without any decrease in activity and
selectivity. The results also showed that increasing in O2/CH4 molar ratio from 0.25 to 0.75
Keywords: decreased the amount of deposited carbon and increased methane conversion. Also, with
Catalytic partial oxidation increasing the reaction temperature, amount of deposited carbon slightly increased. The
Coke formation results indicated that methane conversion decreased with increasing the catalyst calci-
Activity nation temperature due to sintering and decreasing in surface area.
Stability Copyright 2016, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
Nickel catalyst reserved.
save energy. (ii) The H2/CO molar ratio is close to 2, which is

Introduction suitable for Fischer-Tropsch process and methanol synthesis.
(iii) POM can be performed under very high gas hourly space
Synthesis gas (syngas), the mixture of hydrogen and carbon velocity (GHSV), which can reduce the investment cost and
monoxide, is an important raw material for the chemical in- the reactor size compared to the other methods [3,4].
dustry [1,2]. There are three common processes for producing Supported group VIII metal catalysts (Fe, Co, Ni, Ru, Rh, Pd,
syngas from methane: the steam reforming (SMR), the dry Ir and Pt) were investigated in POM reaction. Both Ni and Rh-
reforming (DRM) and the partial oxidation of methane (POM). based catalysts have been reported to be the most promising
POM possesses advantages as follows: (i) POM reaction is a POM catalysts. However, noble metals are highly active and
mild exothermic, while SMR and DRM are highly endothermic show better performances, but they are much more expen-
reactions. Thus, the industrial process based upon POM can sive. Nickel is inexpensive compared to noble metals, but it
* Corresponding author. Catalyst and Advanced Materials Research Laboratory, Chemical Engineering Department, Faculty of Engi-
neering, University of Kashan, P.O. Box 8731751117, Kashan, Iran. Fax: 98 31 55559930.
E-mail address: Rezaei@kashanu.ac.ir (M. Rezaei).
http://dx.doi.org/10.1016/j.ijhydene.2016.03.033
0360-3199/Copyright 2016, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
Please cite this article in press as: Peymani M, et al., Preparation of highly active and stable nanostructured Ni/CeO2 catalysts for syngas
production by partial oxidation of methane, International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/
j.ijhydene.2016.03.033
2 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e1 0
shows a tendency to sintering and coke formation [5,6].

Table 1 e Structural properties of the prepared supports
Therefore researchers have attempted to develop the catalyst
and catalysts.
with high stability, activity, and resistance to carbon
Sample BET surface Pore Pore Crystallite
formation.
area (m2/g) volume diameter size (nm)
Different materials such as Al2O3, TiO2, ZrO2, MgAl2O4,
(cm3/g) (nm)
La2O3, MgO and SiO2 are employed as catalyst support for
CeO2 137.7 0.45 16.3 10.8
nickel catalyst in catalytic partial oxidation (CPO) reaction
2.5Ni/ 112.7 0.39 14.6 e
[7,8]. CeO2 because of its special properties such as different CeO2
oxidation states and stable fluorite like structure may be 5Ni/ 107.3 0.37 14.3 e
proposed as a promising alternative to the standard supports CeO2
[9]. Recently, nickel ceria catalysts were prepared by 7.5Ni/ 101.1 0.36 13.8 9.4
surfactant-assisted coprecipitation method and employed in CeO2
10Ni/ 98.8 0.35 14.2 10.9
reaction of CO methanation [10,11]. CeO2 as a promoter is
CeO2
added to the reforming catalysts in order to improve the
12.5Ni/ 88.3 0.32 15.2 15.5
dispersion of active metal, carbon elimination and minimize CeO2
the sintering of metallic species [12]. The effect of CeO2 addi- 15Ni/ 82.0 0.33 14.8 33.4
tion on the catalytic activity of Ni and Pd catalysts supported CeO2
on alumina was investigated and the results showed
improvement in CH4 conversion, CO and H2 selectivity and
resistance to deactivation [13]. and Ce precursors and cationic surfactant, respectively. So-
In this work, Ni catalysts supported on nanocrystalline dium hydroxide solution was used as precipitation agent. All
cerium oxide with high surface area were prepared and chemical materials were used as received without any further
employed in the partial oxidation of CH4 for production of purification.
synthesis gas. The effects of Ni loading, reaction temperature,
GHSV and feed ratio on the activity and selectivity of different
catalysts were investigated. Also, the effect of reaction tem-
perature and feed ratio on deposited carbon was investigated. Cerium oxide preparation
Finally, the effect of calcination temperature on the catalytic
and structural properties was studied. In a typical preparation, NaOH as precipitation agent was
added dropwise to an aqueous solution of cerium precursor
(Ce (NO3)3$6H2O) and CTAB at room temperature under rapid
stirring with careful control of pH at 11. The molar ratio of
Experimental CTAB/CeO2 was chosen 0.6. After precipitation, the slurry was
refluxed at 80 C under continuous stirring for 20 h. The
Materials mixture was then filtered and washed with plenty de-ionized
water for effective removal of surfactant and Na cation. The
The starting materials were nickel nitrate hexahydrate (Loba cake was then dried at 80 C for 20 h and calcined at 600 C or
chemie, 99%), cerium nitrate hexahydrate (Merck, 99%) and 800 C for 3 h in air atmosphere.
cetyltrimethyl ammonium bromide (CTAB) (Merck, 99%) as Ni
Fig. 2 e XRD patterns of 10% Ni/CeO2 at different calcination

Fig. 1 e XRD patterns of the prepared samples. temperatures.
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e1 0 3
Table 2 e Structural properties of 10% Ni/CeO2 at different calcination temperatures.

Calcination temperature ( C) BET surface area (m2/g) Pore volume (cm3/g) Pore diameter (nm) Crystallite size (nm)
500 102.15 0.34 13.38 9.8
600 98.8 0.35 14.22 10.9
700 82.5 0.32 15.58 21.25
800 43.9 0.21 19.10 23.6
Catalyst preparation Catalyst performance
The catalysts with different nickel contents were prepared by The catalytic performance test was performed in a quartz
a wetness impregnation technique. For this purpose the tubular fixed bed reactor (70 cm length, 8 mm internal diam-
calcined CeO2 at 600 C was first dried at 200 C to remove the eter) under atmospheric pressure. For detecting the bed tem-
adsorbed moisture. After that the aqueous solution of Ni perature, a thermocouple was inserted in bottom of the
(NO3)2$6H2O with appropriate concentration was added to catalyst bed. For each reaction, 100 mg catalyst (30e60 mesh)
dehydrated catalyst support and the suspension was stirred was used. Prior to reaction, the catalysts were reduced in situ
for 3 h at room temperature. The suspension was then dried in H2 (30 mL/min) stream at 600 C for 3 h. The reactant gas
overnight at 80 C and calcined at 600 C for 3 h. stream consisted of CH4 and O2 with desired molar ratio and
the activity tests were carried out at various temperatures
Fig. 4 e (a) N2 adsorptionedesorption isotherms and (b)

Fig. 3 e (a) N2 adsorptionedesorption isotherms and (b) Pore size distributions of 10% Ni/CeO2 calcined at different
Pore size distributions of the prepared samples. temperatures.
ranging from 500 C to 700 C in steps of 50 C. Oxygen was high dispersion of NiO crystals on these catalysts. By
totally consumed at all temperature range. The exhaust gas increasing of nickel content, a series of peaks were observed at
mixture was cooled to separate water and then analyzed using positions of 37.44, 43.47, 63.21, 75.37 and 79.87, corresponding
an online gas chromatograph (Young Lin 6500) equipped with to (111), (200), (220), (311) and (222) plans of NiO cubic crystal
a HID detector. Helium was chosen as the carrier gas and the structure. It was indicated that increasing in nickel loading
gas separation was performed using a Carboxen 1010 column. leads to intensify of characteristic peaks of NiO due to in-
The values of CH4 conversion, CO and H2 selectivities were crease in NiO crystallite size.
obtained using the following equations: The crystallite sizes of ceria and nickel oxide were calcu-
lated by using Scherrer's method and the results are presented
FCH4 ;in FCH4 ;out
XCH4 100 (1) in Table 1. It is seen that the prepared ceria exhibited a nano
FCH4 ;in
structure (10.9 nm) and increasing in nickel content increased
the NiO crystallite size from 9.4 to 33.4 nm.
FCO;out
SCO 100 (2) Fig. 2 shows the XRD patterns of the prepared 10% Ni/CeO2
FCH4 ;out FCH4 ;in
at different calcination temperatures. It can be shown that
increasing in calcination temperature intensified the diffrac-
FH2 ;out
SH2 100 (3) tion peaks related to both CeO2 and NiO phases, which in-
2 FCH4 ;out FCH4 ;in
dicates the increase in NiO and CeO2 crystallite size, Table 2.
where Fin and Fout are the molar flow rate of component in the The structural properties of NiO/CeO2 catalysts with
feed and effluent gas, respectively. different Ni loadings are summarized in Table 1. It is seen that,
increasing in Ni loading decreased the pore volume and SBET.
Characterization
The crystal phases of the support and catalyst were deter-

mined by X-ray powder diffraction (XRD) method with a
PANalytical X'Pert-Pro X-ray diffractometer using a Cu-Ka
monochromatized radiation source and a Ni filter. XRD data
were collected between 2 10e80 . The BET (Bru-
nauereEmmetteTeller) surface areas were measured by a
programmed gas adsorption analyzer (Tristar 3020, Micro-
meritics). The BarretteJoynereHalenda (BJH) method was
employed for determining the pore size distribution. Surface
morphology of the samples was studied by a scanning elec-
tron microscope (SEM, Vega@Tescan). Temperature-
programmed reduction (H2-TPR) was carried out using an
automatic apparatus (Chemisorb 2750, Micromeritics) equip-
ped with a TCD detector. Prior to the TPR experiment, the
fresh sample was degassed under N2 atmosphere at 250 C for
1.5 h, and then subjected to a reduction treatment in a
reducing gas flow (20 mL/min) containing a mixture of 5 vol. %
H2 in Ar with a heating rate of 10 C/min. Temperature-
programmed oxidation (TPO) analyses of the spent catalysts
were performed in a similar apparatus as mentioned for TPR
analysis by introducing a gas flow (20 mL/min) containing a
mixture of O2:He (5:95). In this analysis, the temperature was
increased up to 1000 C at a heating rate of 10 C/min.
Results and discussion
Structural properties of the catalysts
Fig. 1 displays the XRD patterns of the prepared CeO2 powder

and catalysts. The catalysts show the mixed diffraction peaks
of cerium oxide (CeO2, JCPDS 02-8709) and nickel oxide (NiO,
JCPDS 01-1239). The diffraction peaks at 28.67, 33.22, 47.69,
56.6, 59.36, 69.75, 77.08 and 79.47 are related to plans of (111),
(200), (220), (311), (222), (400), (311) and (420) according to CeO2
cubic structure. For 2.5 and 5% Ni/CeO2 samples, the NiO Fig. 5 e eH2-TPR profiles of (a) support and catalysts and (b)
diffraction peaks were not observed due to low content and 10% Ni/CeO2 calcined at different temperatures. .
Fig. 6 e (a) CH4 conversion, (b) H2/CO ratio, (c) H2 selectivity and (d) CO selectivity of catalysts as a function of temperature,
O2/CH4 0.5, GHSV 90,000 (ml/hgcat).
The decrease in pore volume and BET surface area is due to interaction. According to IUPAC classification, The H2 shaped
the blocking of catalyst pores with loaded nickel. In addition, hysteresis loop generally is characteristic of solids consisting
the BET analysis shows a high specific surface area for the of particles crossed by nearly cylindrical channels consoli-
catalyst support. Fig. 3a displays the nitrogen adsorption/ dated by aggregates or agglomerates. Hysteresis is usually
desorption isotherms of these catalysts. All the prepared ascribed to different size of pore mouth and pore body (this is
catalysts showed IV type isotherm with H2 shaped hysteresis the case of ink-bottle shaped pores) [10,14]. Furthermore, the
loop, representing the mesoporous structures with strong pore size distributions of the samples are presented in Fig. 3b.
Fig. 7 e Effect of gas hourly space velocity on the activity Fig. 8 e Effect of feed ratio on the activity and selectivity of
and selectivity of 10% Ni/CeO2, O2/CH4 0.5, T 600 C. 10% Ni/CeO2, GHSV 90,000 mL/(gcat.h), T 600 C.
It is seen that all prepared catalysts presented a mesoporous reduction temperature (from 470 C to 508 C for 5Ni/CeO2 and
structure with a pore size located in the range of 5e20 nm. As 15Ni/CeO2 catalyst, respectively). Furthermore, with
can be seen, increasing in nickel loading shifted the pore size increasing in nickel loading, the area of all peaks increased,
distribution to smaller size. which was related to reduce of more nickels.
Table 2 presented the structural properties of 10% NiO/ TPR analysis of pure CeO2 calcined at 600 C and 800 C
CeO2 catalyst calcined at different temperatures. It is seen that shows two reduction peaks. The first peak is related to the
the SBET and pore volume decreased with increasing in calci- surface oxygen and the reduction peak observed at higher
nation temperature due to sintering of particles at high tem- temperatures is assigned to the reduction of bulk Ce4 to Ce3.
perature. Fig. 4a displays the nitrogen adsorption/desorption It is seen that both peaks were shifted to higher reduction
isotherms of these catalysts at different calcination temper- temperatures when CeO2 calcination temperature increased.
atures. It is seen that all the samples showed IV type isotherm As can be seen, due to peak overlapping, the reduction peaks
with H2 type hysteresis loop. The formation point of hyster- of ceria are not observed in the TPR profile of the nickel based
esis loop was observed at higher relative pressure by catalysts.
increasing in calcination temperature, confirming the exis- Fig. 5b shows the TPR profiles of the 10% Ni/CeO2 catalyst
tence of bigger pores on the samples calcined at higher tem- calcined at different temperatures. Increasing in calcination
peratures. The pore size distributions of the catalyst calcined temperature shifted the Tmax of reduction peaks to higher
at different temperatures revealed that increasing in calcina- temperatures. For the catalyst calcined at 500 C, the b peak
tion temperature shifted the pore size distribution to larger was merged to g peak. It is seen that with increasing in
sizes, Fig. 4b. calcination temperature; the b peak disappeared due to
decreasing of the weak interacted NiO with support. Also,
Temperature-programmed reduction
TPR profiles of the catalysts with different Ni loadings are

shown in Fig. 5a. It is seen that the reduction of all catalysts
occurred in the temperature range 200e700 C. As can be seen,
three kinds of reduction peaks (assigned by a, b and g symbols)
are observed in these patterns. The a peak located at
200e360 C can be attributed to the oxygen species reduction
in oxygen vacancies. Therefore, the adsorbed oxygen species
in oxygen vacancies of CeO2 could be reduced by hydrogen at
low temperatures. The peak at 400 C (b) can be ascribed to the
reduction of free NiO and weak interacted NiO with CeO2 as
support in the catalysts. In addition, the peak may contain the
reduction of surface CeO2 to Ce2O3. The g peak observed
around 500 C is due to the reduction of NiO, which is strongly
interacted with CeO2 support [15,16]. The stronger interaction
between NiO with CeO2 leads to shifting the g peak to higher
Fig. 10 e (a) CH4 conversion versus calcination

Fig. 9 e Stability of CH4 conversion, H2 and CO selectivities temperatures and (b) H2/CO ratio of 10% Ni/CeO2 catalysts
of 10% Ni/CeO2, GHSV 90,000 mL/(gcat.h),T 600 C,O2/ as a function of reaction temperature, O2/CH4 0.5,
CH4 0.5. GHSV 90,000 (ml/hgcat).
with increasing in calcination temperature; the g peak was the catalysts. This is due to the fact that with increasing
shifted to higher temperature. It is clear that with increasing amount of oxygen the complete oxidation occurs instead of
calcination temperature the interaction between NiO and partial oxidation. So, with increasing O2/CH4 ratio, combus-
CeO2 increased and the g peak shifted to higher reduction tion reaction is more favorable than partial oxidation and CO2
temperature. The high temperature peak (d) can be attributed and H2O content increased and consequently both the CO and
to the reduction of bulk CeO2. It is seen that increasing in H2 selectivities decreased.
calcination temperature intensified the reduction peak of
CeO2, which is in agreement with the results obtained in Long time stability tests
Fig. 5a. Fig. 9 shows the stability of CH4 conversion, CO and H2 se-
lectivities for 10% Ni/CeO2 catalyst during 48 h time on stream
Catalytic performance at 600 C. It is seen that the catalyst exhibited a high stability
during the reaction without any decrease in methane con-
Effect of temperature and Ni loading version and product selectivities.
The effects of Ni loading and temperature on the catalytic ac-
tivity of Ni/CeO2 catalyst were studied. CH4 conversions of the Effect of calcination temperature
prepared catalysts are shown in Fig. 6a. As can be seen, the CH4 The effect of calcination temperatures on the activity of 10%
conversions increased in the temperature range of 550e700 C Ni/CeO2 catalyst was investigated. CH4 conversions of the
due to enhance the rate of POM reaction. It was found that the catalysts are shown in Fig. 10a. As expected, the methane
conversion of CH4 increased with the increase of Ni loading conversion increased with increasing the reaction
from 2.5 to 10 wt% due to providing more active sites as Ni
loading increased. Further increase in nickel loading slightly
decreased the CH4 conversion, due to increase in nickel crys-
tallite size and decrease in nickel dispersion. The 10% Ni/CeO2
catalyst exhibited the highest activity among the prepared
catalysts. In addition, increasing in reaction temperature
decreased the H2/CO ratio from 2.5 to 1.8 for all catalysts,
shown in Fig. 6b. At higher temperatures the H2 was consumed,
which is due to endothermic nature of reverse water gas shift
reaction (RWGS) [3]. H2 and CO selectivities of the catalysts at
different reaction temperatures are shown in Figs. 6c and 7d,
respectively. The results showed that the H2 and CO selectiv-
ities increased with increasing reaction temperature. Mecha-
nism of POM reaction could be explained as follow. At the first
step of reaction, H2O and CO2 were produced via combustion
reaction of CH4 and O2, then because of reforming (steam and
dry) of these two components, H2 and CO were formed. Since
the reforming reaction is endothermic, increasing in reaction
temperature improved both the H2 and CO selectivities.
Effect of GHSV
The effect of gas hourly space velocity (GHSV) on the catalytic
performance of 10% Ni/CeO2 catalyst was studied by keeping
the reaction temperature and feed ratio constant in the sys-
tem (T 600 C, CH4:O2 2:1). Fig. 7 demonstrates that with
the increase of GHSV from 22,500 to 175,500 mL/(gcat$h), the
CH4 conversion increased from 60.95 to 76.73. The reason for
this might be driven from the increase in heat release from the
catalyst bed by increasing the space velocity. Although the
temperature of the catalyst bed was controlled, the increase of
inner surface temperature of the catalyst granules was inev-
itable. It is obvious that enhancing of the space velocity indi-
rectly increased the temperature [17].
Effect of feed ratio

The CH4/O2 ratio can affect the catalytic activity of the cata-
lysts. The effect of feed ratio on the catalytic activity and
selectivity of the catalysts is shown in Fig. 8. An increase in Fig. 11 e (a) TPO profiles of 10% Ni/CeO2 evaluated under
oxygen content in the feed stream resulted in increasing CH4 different feed ratios (T 600 C, GHSV 90,000 mL/(gcath))
conversion because the occurrence of both partial and com- and (b) Effect of reaction temperature on the TPO profile of
plete oxidation. Also, CO and H2 selectivities decreased for all 10% Ni/CeO2 (O2/CH4 0.25, GHSV 90,000 mL/(gcath)).
Fig. 12 e SEM images of 10% Ni/CeO2 catalyst at (a) O2/CH4 0.5, (b) O2/CH4 0.3 and (c) O2/CH4 0.2.
temperature. It is seen that increasing in calcination temper- observed over the spent catalyst evaluated under O2/
ature up to 700 C did not have a significant effect on the CH4 0.2. It is known that the thermodynamic risk of carbon
methane conversion. However, the CH4 conversion decreased formation in the CPO could only be avoided by using an inlet
with further increase in calcination temperature, due to stream with high contents of oxygen [18].
decrease in surface area and increase in nickel crystallite size. The effect of reaction temperature on the carbon formation
In addition, as seen in Fig. 10b, increasing in calcination over the 10% Ni/CeO2 at constant feed ratio (O2/CH4 0.25)
temperature from 500 C to 700 C slightly increased the H2/CO was studied and the TPO results are shown in Fig. 11b. It is
ratio for all reaction temperatures and further increase led to shown that with increasing reaction temperature, the area
sudden decrease of H2/CO ratio. and the intensity of the peak in the TPO profile are increased,
which is related to higher amounts of deposited carbon at
Temperature-programmed oxidation higher temperature. This is related to endothermic nature of
methane decomposition. The methane decomposition is
TPO profiles of the spent 10% Ni/CeO2 catalysts with different favored at higher reaction temperature and consequently in-
feed ratios are shown in Fig. 11a. It is seen that decreasing the creases the rate of carbon formation [19,20]. As seen in
O2/CH4 ratio increased the amount of carbon deposition. As Fig. 11b, two oxidation peaks are detected for catalysts
can be seen, no carbon deposition was observed for the spent maintained at 500 C and 600 C. It indicates that two kinds of
catalyst under stoichiometric feed ratio. The low content of carbonaceous species were formed on the catalysts. Consid-
deposited carbon could be due to high oxygen mobility of ering these results, the first peak is related to filamentous
ceria, which may accelerate the surface oxidation reactions of carbon species (Cb) and the latter peak is assigned to graphitic
carbon and also high concentration of oxygen in the feed gas. carbon species (Cg). It is seen that with increasing the reaction
It is seen that the highest amount of deposited carbon was temperature, the amount of filamentous carbon increased.
Fig. 13 e SEM images of 10% Ni/CeO2 catalyst at (a) T 500 C, (b) T 600 C and (c) T 700 C.
SEM analysis different Ni loadings (2.5e15 wt %) were prepared by impreg-

nation method and employed in partial oxidation of methane.
SEM results of 10% Ni/CeO2 catalysts with different O2/CH4 The results showed that 10% Ni/CeO2 have the highest cata-
ratios are presented in Fig. 12. It is obvious that the amount of lytic activity. This catalyst showed high stability exposed to
filamentous carbon formed over the catalyst increased with reaction conditions for 48 h without any decrease in catalyst
decreasing O2/CH4 ratio. It is seen that no carbon deposition activity. Increasing in calcination temperature from 500 C to
was observed on the catalyst in O2/CH4 0.5. This is in 800 C led to decrease the surface area and pore volume but up
agreement with TPO results, which showed higher amount of to 700 C did not have a significant effect on the methane
deposited carbon over the catalysts with lower O2/CH4 ratio. conversion. Increasing the reaction temperature and
Fig. 13 shows the SEM analysis of the 10% Ni/CeO2 evaluated at decreasing the feed ratio increased the amount of deposited
different reaction temperatures. As can be seen the amount of carbon over the catalyst surface. SEM images show filamen-
filamentous carbon increased with increasing reaction tous carbon formed over the catalyst and TPO analysis indi-
temperature. cate two types of carbonaceous species formed on the
catalysts.
Conclusions
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Peyman I 2016

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i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e1 0

Available online at www.sciencedirect.com

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

Preparation of highly active and stable

Mohammad Peymani a, Seyed Mehdi Alavi b, Mehran Rezaei a,c,*

article info abstract

save energy. (ii) The H2/CO molar ratio is close to 2, which is

shows a tendency to sintering and coke formation [5,6].

Fig. 2 e XRD patterns of 10% Ni/CeO2 at different calcination

Table 2 e Structural properties of 10% Ni/CeO2 at different calcination temperatures.

Catalyst preparation Catalyst performance

Fig. 4 e (a) N2 adsorptionedesorption isotherms and (b)

The crystal phases of the support and catalyst were deter-

Results and discussion

Structural properties of the catalysts

Fig. 1 displays the XRD patterns of the prepared CeO2 powder

TPR profiles of the catalysts with different Ni loadings are

Fig. 10 e (a) CH4 conversion versus calcination

Effect of feed ratio

SEM analysis different Ni loadings (2.5e15 wt %) were prepared by impreg-

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