Applied Catalysis A: General 500 (2015) 1222

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Applied Catalysis A: General

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

Ni/CeO2 Al2 O3 catalysts for the dry reforming of methane: The effect
of CeAlO3 content and nickel crystallite size on catalytic activity and
coke resistance
Igor Luisetto a, , Simonetta Tuti a,b , Chiara Battocchio a,b , Sergio Lo Mastro a , Armida Sodo a
a
b

Department of Sciences, University of Rome Roma Tre, Via della Vasca Navale 79, 00146 Rome, Italy
C.I.S.Di.C Center, University of Rome Roma Tre, Via della Vasca Navale 79, 00146 Rome, Italy

a r t i c l e

i n f o

a b s t r a c t

Article history:
Received 29 January 2015
Received in revised form 22 April 2015
Accepted 1 May 2015
Available online 11 May 2015

The catalytic performances of Ni/CeO2 Al2 O3 catalysts for the dry reforming of CH4 (DRM) were investigated. Catalysts with different Ni dispersion and different amount of CeAlO3 species were prepared by
different methods and characterized by BET, XRD, XPS, Raman, TPR and TPO techniques. Catalytic activity
was studied during time on stream in the range 8731073 K with a mixture of CH4 :CO2 :Ar = 40:40:20 vol.%
and GHSV 90,000 cm3 g1 h1 . The intrinsic catalytic activity increased with the increasing of Ni crystallite
size. Carbon was deposited as nano-bres and graphite when catalysts worked at lower temperature, and
the largest amount was found on the catalyst with the largest Ni crystallite size. The formation of graphitic
deposits is limited by the presence of CeAlO3 species formed during catalyst activation. CA preparation
method results particularly attractive because it allows to obtain catalysts with small Ni crystallite size
and high content of CeAlO3 species, which both have a role in suppressing the carbon deposition and
therefore in obtaining stable catalytic performances.
2015 Elsevier B.V. All rights reserved.

Keywords:
Ni/CeO2 Al2 O3
Dry reforming
Nickel particle size
CeAlO3
Carbon deposition

1. Introduction
The CO2 reforming of CH4 (Eq. (1)), also called dry reforming
(DRM), has been recently recognized as an efcient way for the
CH4 and CO2 valorization [14]. In fact, the produced syn-gas has
an H2 /CO ratio equal to one suitable for the synthesis of oxygenated
hydrocarbons and synthetic fuels. The feedstock that can be used
for the DRM, ranges from CO2 -rich natural gas reserves to renewable biogas produced by anaerobic fermentation of waste sludge
(mainly composed by CH4 and CO2 ), offering thus the possibility to
enlarge their utilization and to avoid the release of the CO2 in the
atmosphere.
CH4 + CO2 2H2 + 2CO

0
H298
K

= 247 kJ mol

(1)

The DRM plays also an important role on determine the electrochemical performances and the long-term stability of solid oxide
fuel cells (SOFCs) fed by CH4 or biogas. In particular, the DRM occurs
internally to the cell stack producing H2 used to feed the anode and
it helpfully limits the carbon deposition [57].

Corresponding author. Tel.: +39 0657333370; fax: +39 0657333390.

E-mail address: igor.luisetto@uniroma3.it (I. Luisetto).
http://dx.doi.org/10.1016/j.apcata.2015.05.004
0926-860X/ 2015 Elsevier B.V. All rights reserved.

Due to its high endothermicity the DRM has also been proposed
for the energy storage and the energy transfer, for example in the
conversion of the solar energy to chemical energy, which is referred
to as solar reforming [810].
Regarding the application of the DRM for syn-gas production, to
date its industrial implementation is impeded mainly by the following issues: (i) the co-occurrence of the reverse water gas shift
reaction (RWGS) (Eq. (2)) that, consuming H2 , lowers the H2 /CO
ratio;
H2 + CO2 CO + H2 O

0
H298

= 41 kJ mol1

(2)

(ii) the catalyst deactivation and/or the reactor plugging due to

carbon deposits formed by the methane cracking (Eq. (3)) and the
Boudouard reaction (Eq. (4)).
CH4 C + 2H2

0
H298

= 75 kJ mol1

(3)

2CO C + CO2

0
H298

= 172 kJ mol1

(4)

The DRM is operated at high temperatures (generally above

923 K) to achieve suitable CH4 and CO2 conversions. In that condition, the Boudouard reaction is thermodynamically unfavoured,
the RWGS is suppressed by the low CO2 concentration, whereas, on
the contrary, the methane cracking is favoured [11].

I. Luisetto et al. / Applied Catalysis A: General 500 (2015) 1222

Therefore, the development of catalysts, selective for the DRM,

with high resistance towards carbon deposition and proper thermal stability, is pivotal for the DRM implementation and is still a
challenge. Catalysts containing noble metal such as Pt, Ru and Rh
show high activity and selectivity for the DRM reaction in addition
to good stability towards the coke deposition [1214]. However
their high cost and low availability make them not economically
competitive in comparison with other transition metal based materials. Among non-precious transition metals, Ni-based catalysts are
so far the most active, but also highly prone to carbon formation,
because, together with the ability to activate the C H bond, Ni has
a high afnity to carbon.
In the search of active and stable Ni-based catalysts, several
approaches have been explored in order to suppress the carbon
deposition. The addition of a second metal, such as Co, Cu and
Sn, results in the formation of less C-sensitive alloys [1517]. The
Ni particle size has a strong effect on the carbon tolerance of the
catalyst, and generally, particles smaller than 5 nm have low catalytic activity towards the C H cracking [11,18,19]. Therefore, the
stabilization of small Ni nanoparticles at high temperatures is a
promising way for the lifetime increase [20,21]. However, together
with the properties of the active metal sites, the support choosing is of great importance in designing high-performance catalysts.
Supports with basic character, such as MgO [22], and those containing lanthanum [23], showed limited carbon deposition during
DRM because of their small number of Lewis acid sites, which
are involved in carbon formation, and because the presence of
La2 O2 CO3 that helps the gasication of carbonaceous deposits.
Among different supports, those containing cerium seem to be
the most promising in limiting the deactivation by coking and
therefore they are extensively investigated. CeO2 is known for its
oxygen storing capacity due to the redox couple Ce4+ /Ce3+ . Owing
to this property, during dry reforming the oxygen vacancies over
the CeO2 -surface may adsorb the oxygen formed by the dissociation
of CO2 on Ni sites, improving the reforming activity and the gasication of coke [24]. However, the positive effect of CeO2 support
on carbon removal has been reported to be particularly dependent
on the catalyst preparation method which may affect Ni dispersion and metal support interaction [24,25]. The addition of ZrO2 to
CeO2 yields solid solution with high oxygen mobility and thermal
stability [26], therefore the Ce(1x) Zr(x) O2 family has been applied
as support for robust DRM catalysts. Several authors have investigated the effect of the Ce/Zr ratio on carbon resistance. However,
the results are not conclusive [27,28]. Moreover, as for the pure
CeO2 support, the catalytic performance of the transition metals
supported on Ce(1x) Zr(x) O2 are strictly dependant on the preparation methods [29].
CeO2 is used also as promoter of -Al2 O3 based catalysts because
of the combination of the large surface area and stability of -Al2 O3
with the oxygen storage and release capability of CeO2 [30,31]. The
promotion of the catalytic performances by CeO2 addition is also
related with the ability to increase the Ni dispersion [32,33]. Moreover, in reducing atmosphere at high temperature, CeO2 supported
on -Al2 O3 reacts to form CeAlO3 -like species [34]. As reported by
several authors these species play a key role in the removal of carbon residues [35]. A possible reaction mechanism has been recently
proposed by Chen et al. [36]: the CeAlO3 formed during catalyst
activation or in reaction condition, could react with CO2 to form CO
and CeO2 (Eq. (5)). CeO2 oxidizes the CHx species located at the Nisupport boundary, precursors of carbonaceous residues, restoring
the CeAlO3 sites (Eq. (6)).
2CeAlO3 + CO2 Al2 O3 + 2CeO2 + CO

(5)

Al2 O3 + 2CeO2 + CHx CO + 2CeAlO3 + (x/2)H2

(6)

13

Despite recent advances, the role of CeO2 Al2 O3 interaction and

Ni particle size in determining the catalyst performance and stability remains open.
Therefore, in the present work we studied Ni/CeO2 Al2 O3 catalysts with different Ni crystallite size and Ce3+ /Ce4+ ratio, with
the aim to better understand their interplay with regard to carbon
formation and catalytic activity. Catalysts were prepared by coprecipitation, wet impregnation, solgel and citric acid methods,
and characterized by several techniques. The effect of the preparation method on the solid-state reaction between CeO2 and -Al2 O3
to form CeAlO3 was studied by XRD, XPS and H2 -TPR. Catalytic
activity was studied in the range 8731073 K with high ow rate
and during time on stream. Carbonaceous deposits were characterized by XRD, Raman spectroscopy and O2 -TPO.
2. Experimental
2.1. Catalyst synthesis
Catalysts with nominal composition of 10 wt.% Ni supported on
20 wt.% CeO2 promoted -Al2 O3 have been prepared according to
the following procedures.
2.1.1. Co-precipitation method (CP)
Stoichiometric amounts of nitrate salts (Ni(NO3 )2 6H2 O;
Ce(NO3 )3 6H2 O Al(NO3 )3 9H2 O) and ionic surfactant
cetyl trimethyl ammonium bromide (CTAB) with molar ratio
CTAB/(Ni2+ + Ce3+ + Al3+ ) = 0.4 were dissolved in water. The temperature was raised to 383 K and triethylamine (TEA) was rapidly
added until pH 10. The precipitation of hydroxide instantaneously
occurred and the obtained mixture was aged for 20 h. The precipitated solid was ltered and washed with water and ethanol, dried
at 393 K overnight and calcined at 873 K for 5 h.
2.1.2. Solution excess wet impregnation method (WI)
Aqueous solution of Ni(NO3 )2 6H2 O and Ce(NO3 )3 6H2 O was
added to a commercial mesoporous alumina powder (Alfa Aesar)
to form a slurry. The solvent was evaporated at 353 K under vigorous stirring. The impregnated alumina was further dried at 393 K
overnight and calcined at 873 K for 5 h.
2.1.3. Sol gel method (SG)
Stoichiometric amounts of Ni(NO3 )2 6H2 O, Ce(NO3 )3 6H2 O
and aluminium-tri-sec butoxide were added to ethanol acidied
with a small amount of HNO3 (65 wt.%). The solution was mixed
under vigorous stirring at ambient temperature for 5 h, than the
solvent was evaporated at 333 K during 48 h. The dried gel was
calcined at 873 K for 5 h.
2.1.4. Citric acid method (CA)
Stoichiometric amounts of nitrate salts (Ni(NO3 )2 6H2 O,
Ce(NO3 )3 6H2 O and Al(NO3 )3 9H2 O) and citric acid monohydrate (CA) with molar ratio CA/(Ni2+ + Ce3+ + Al3+ ) = 1.5 were
dissolved in water. Then NH4 OH solution (28 wt.%) was added until
pH 8. The solvent was evaporated at 393 K yielding a gel, and then
the temperature was increased up to about 523 K to ignite the autocombustion. The obtained dark powder was calcined at 873 K for
5 h.
The chemical composition of samples was conrmed by energy
dispersive X-ray analysis (EDAX) using a SEM FEI XL30. Sample
powder was pressed in pellets at about 280 MPa. Several spots with
size of about 10 m were performed and the results are reported
as average values in Table 1.

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I. Luisetto et al. / Applied Catalysis A: General 500 (2015) 1222

Table 1
Chemical composition, textural properties (surface area, pore volume, main pore size) and Ni crystallite size of catalysts.
Catalyst

CP
WI
SG
CA
a
b

Composition (wt.%)
Ni

CeO2

9.4
10.0
9.3
10.7

19.1
20.2
22.7
21.4

Surface area (m2 g1 )

Pore volume (cm3 g1 )

Pore size (nm)

DNi (nm)b

285 (147)a
200 (167)
71 (47)
135 (130)

1.143 (0.832)a
0.720 (0.678)
0.159 (0.120)
0.136 (0.128)

17.0 (17.0)a
9.8 (10.8)
4.1, 6.9, 11.8 (4.9, 13.5)
4.0 (3.3)

22.6
11.1
9.5
5.8

In parenthesis are reported the BET, pore volume and pore size values of the reduced catalysts.
Calculated from XRD by Scherrers equation of the Ni (2 0 0) reection.

2.2. Catalyst characterization

2.2.1. BET
N2 adsorptiondesorption isotherms were obtained at 77 K
using a Micromeritics Gemini V apparatus. The surface area was
calculated by the BrunauerEmmettTeller (BET) method in the
equilibrium pressure interval 0.05 < P/P < 0.5. The pore size distribution was obtained from the desorption branch of the isotherm
using the BarrettJoynerHalenda (BJH) method and the total pore
volume was calculated from the maximum adsorption point at
P/P = 0.99. Prior to the N2 adsorption, the sample was treated at
623 K in owing He in order to remove adsorbed molecules.
2.2.2. XRD
Powder X-ray diffraction patterns were collected using a Scintag
source and
X1 diffractometer equipped with a Cu K ( = 1.5418 A)
the Brag-Brentano  conguration in the 1070 2 range, with
0.05 step size and 3 s acquisition time. The Ni0 and CeO2 crystallite
size were estimated by Scherrers equation from the Ni (2 0 0) and
CeO2 (1 1 1) reection, respectively.
2.2.3. H2 -TPR
Temperature programmed reduction (TPR) experiments were
performed by a Thermo Scientic TPDRO1100 ow apparatus.
Sample (0.050 g) was pre-treated in a ow 5% O2 /He mixture
(20 cm3 min1 ) at 573 K for 30 min. The TPR was conducted owing
a 5% H2 /Ar mixture (10 cm3 min1 ) starting at 313 K and heating up
to 1273 or 1073 K, with a rate of 10 K min1 . The H2 consumption
was measured by a TCD detector, calibrated by the reduction of a
known amount of CuO (99.99% purity from Sigma Aldrich). Before
owing into the TCD detector, the H2 O generated in the reduction
was removed by a trap.
2.2.4. O2 -TPO
Temperature programmed oxidation (TPO) of the used catalysts were performed in the same apparatus used for the TPR
experiments. Prior to TPO analysis, the used catalyst was carefully homogenized in an agate mortar. About 0.010 g was ramped
from 313 up to 1073 K, with a rate of 10 K min1 owing 5% O2 /He
mixture (50 cm3 min1 ). Before owing into the TCD detector, the
H2 O and CO2 generated by the oxidation were removed by a trap.
In identical experimental condition, CO was not observed by GC
analysis of the exhaust stream gas.
2.2.5. XPS
XPS analysis was performed in an instrument of our own design
and construction, consisting of a preparation and an analysis UHV
chamber, equipped with a 150 mm mean radius hemispherical
electron analyser with a four-elements lens system with a 16channel detector giving a total instrumental resolution of 1,0 eV as
measured at the Ag 3d5/2 core level. Al K non-monochromatised
X-ray radiation (h = 1486.6 eV) was used for acquiring core level
spectra of all samples (C1s, Ce3d, Ni2p, Al2p and O1s). The spectra were energy referenced to the C1s signal of aliphatic C atoms

having a binding energy BE = 285.00 eV, due to surface contamination, as expected for XPS measurements performed on solid
samples exposed to air. Atomic ratios were calculated from peak
intensities by using Scoelds cross-section values and calculated
 factors [37]. Curve-tting analysis of the C1s, Ce3d, Ni2p, Al2p
and O1s spectra was performed using Gaussian proles as tting
functions, after subtraction of a Shirley-type background [38].
2.2.6. Raman
Raman measurements were performed by using a Labram
Micro-Raman spectrometer by Horiba, equipped with a HeNe
laser sources at 632.8 nm (nominal output power 18 mW). The
illumination and collecting optics of the system consists in a microscope in confocal conguration. The system achieves the high
contrast required for the rejection of the elastically scattered component by an edge lter. The backscattered light is dispersed by a
1800 line/mm grating and the Raman signal is detected by a Peltier
cooled (203 K) 1024 256 pixel CCD detector. Nominal spectral resolution was about 1 cm1 . Spectral acquisitions (3 accumulations,
30 s each, in the range 10002800 cm1 ) were performed with a
long distance 20 objective (N.A. = 0.35).
2.3. Catalytic activity
The catalytic activity was measured in a xed-bed quartz reactor
at atmospheric pressure connected to a ow apparatus equipped
with mass ow controllers. The reactor was specially designed to
remove the inner part containing the catalyst bed. Sample (0.050 g)
was reduced in situ with 50% H2 /Ar ow (30 cm3 min1 ) increasing the reactor temperature from RT up to 1073 K with a ramp
of 10 K min1 and isothermally kept at this temperature for 1 h.
The dry reforming of methane was studied with a mixture of
CH4 :CO2 :Ar = 40:40:20 vol.% and ow rate of 75 cm3 min1 (GHSV
90,000 cm3 g1 h1 ). After reduction of the catalyst at 1073 K, the
reactor was cooled to 873 K and purged with Ar ow (15 cm3 min1 )
for 15 min, then the gas ow was switched to the reactant mixture.
The catalytic run was performed in the temperature range from
873 to 1073 K with 50 K temperature increments. Each temperature
step was maintained for 5 h. Reaction stream was analyzed on line,
at regular times, by a Agilent 7820 gas chromatograph equipped
with a Molecular Sieve X13 (for the H2 , Ar, CO, CH4 separation) a
Hayesep Q (for CO2 separation) columns and a TCD detector. After
each catalytic run at specied temperature, the catalyst was cooled
to RT in Ar ow (15 cm3 min1 ) and the catalyst bed was weighted
in order to verify the formation of massive carbon. Then, the catalyst was warmed up to the following temperature step in Ar ow
(15 cm3 min1 ) thus preventing the oxidation of catalyst surface
due to the exposure to ambient atmosphere. CH4 and CO2 percent
conversions (Xi %) were calculated according to Eq. (7) using Ar as
internal standard.


Xi (%) = 100

0
Ci CAr

Ci0 CAr


(7)

I. Luisetto et al. / Applied Catalysis A: General 500 (2015) 1222

15

0 are the inlet concentrations of the reactants

where Ci0 and CAr
(i = CH4 or CO2 ) and Ar respectively and Ci and CAr are the corresponding outlet concentrations.
The site time yield (STY) of hydrogen was calculated according
to Eq. (8)

STYH2 = 2

0
F 0 CCH
XCH4
4

22.414 NNi

(8)

0
is the inlet
where F0 is the inlet ow of reactants (in L s1 ), CCH
4
concentration of methane in the reactants mixture, XCH4 is the initial CH4 conversion at 1073 K, 22.414 is the volume of one mole of
gas at standard condition (L mol1 ) and NNi is the number of moles
of the Ni active sites.
The number of moles of the Ni active sites NNi was calculated
according to Eq. (9)

NNi =

g WNi
DNi
MNi

(9)

where g is the mass of catalyst, WNi is the weight fraction of Ni in

the sample as determined by EDAX, MNi is the molar mass of Ni
(58.71 g mol1 ), DNi is the Ni0 dispersion.
The nickel dispersion DNi was estimated by the Vannice method
[39,40] (Eq. (10)):
DM = 6 107

VM
1

AM d(nm)

(10)

where DM is the metal dispersion, VM is the bulk atomic volume

of the metal (cm3 ), AM is the atomic area (cm2 ), and d is the metal
crystallite size (nm) from XRD.
The rate of carbon formation rc (h1 ) was calculated according
the Eq. (11):
rC (h1 ) =

m
gcat. h

(11)

where m represents the difference between the mass of the catalyst bed at the start and at the end of the time on stream test at a
specied temperature, gcat is the mass of the freshly charged catalyst (0.050 g) and h is the time in hours of the catalytic step run
(5 h).
3. Results and discussions
3.1. Structural and textural characterization
The XRD patterns of samples calcined at 873 K are reported
in Fig. 1A. The CA sample showed a broad and weak XRD peak
at about 2 = 33 indicative of the amorphous phase. The other
samples showed peaks of uorite CeO2 (JCPDS 81-0792) with different crystallinity, beside those of -Al2 O3 . In particular the largest
CeO2 crystallite size of 7.0 nm was observed in WI sample, while in
the other samples, CeO2 was intimately dispersed in the -Al2 O3
skeleton as smaller and less crystalline particles. Indeed the CeO2
crystallite size was 3.5 nm for SG and 4.8 nm for CP samples; moreover the peaks of CeO2 of the SG sample were much less intense
suggesting that CeO2 was partially amorphous. Peaks corresponding to NiO cubic phase (JCPDS 78-0643) were observed only in SG
sample. The NiO absence in the other specimens was likely due to
the low size of particles or to the formation of NiAl2 O4 spinel. The
latter species is hard to distinguish from the -Al2 O3 phase since
most of their diffraction lines overlap.
The XRD patterns of samples reduced at 1073 K are reported in
Fig. 1B. All samples showed peaks at about 44.8 and 51.8 assigned
to the (1 0 0) and (2 0 0) reections of cubic Ni0 (JCPDS 87-0712)
originated from the reduction of NiO and Ni2+ -species. The crystallite size of Ni0 , calculated by Scherrers equation, ranges between

Fig. 1. XRD patterns of the catalysts calcined at 873 K (A) and reduced at 1073 K (B):
CA (a); SG (b); WI (c); CP (d).

5.8 nm and 22.6, increasing in the sample order CA < SG WI < CP

(Table 1). In CA sample no other peaks were observed, indicating
that the oxide lattice remained amorphous even after reduction. In
the other samples -Al2 O3 , CeO2 and CeAlO3 phases were detected.
In particular, peaks of cubic CeO2 (at 28.5 ; 33.0 ; 47.5 ) were
clearly observed on WI and SG samples and barely detected on CP
sample, moreover peaks of CeAlO3 (at 23.6 ; 33.5 ; 41.5 ; 60.0 )
were observed only on SG sample. The Ce2 O3 , formed by H2 reduction of CeO2 (Eq. (12)), was not observed due to the rapid oxidation
of Ce3+ to Ce4+ upon exposure to ambient atmosphere.
The disappearance of CeO2 in CP sample and the presence
of CeAlO3 peaks in SG sample were due to the solid-state reaction between Ce2 O3 and -Al2 O3 (Eq. (13)), generally observed
above 873 K under reducing condition. However on WI sample the
absence of modications of CeO2 phase suggested that the large
and well crystallized CeO2 particles were only partially reduced to
Ce2 O3 in H2 at 1073 K, and that a very small fraction of Ce3+ has been

16

I. Luisetto et al. / Applied Catalysis A: General 500 (2015) 1222

incorporated into alumina as CeAlO3 species. These results agree

with the literature data. In fact Shyu et al. [34] reported that highly
dispersed CeO2 nanoparticles supported on Al2 O3 have become
CeAlO3 above 873 K and agglomerated CeO2 particles have been
reduced only at temperature higher than 1073 K.
2CeO2 + H2 Ce2 O3 + H2 O

(12)

Ce2 O3 + Al2 O3 2CeAlO3

(13)

The textural properties (BET surface area, pore volume and main
pore size) of calcined and reduced catalysts are summarized in
Table 1. According to the IUPAC classication [41], calcined CP, WI
and CA catalysts belonged to IV type isotherms, characteristic of
mesoporous materials, whereas the calcined SG sample showed
a composite isotherm between type IV and type II, indicating the
presence of mesoporous and macroporous structures (Fig. S1A in
the Supporting information). The hysteresis loop of SG samples was
H3-type, characteristic of aggregate particles with no uniform size
and shape, whereas on the other samples was H1-type, indicating the presence of cylindrical mesopores. The PSD curve analysis
(Fig. S1B in the Supporting information) showed that CA sample
had the most uniform pore texture with small primary pore width
of 4.0 nm. The SG sample showed a broad pore size distribution
mainly in the mesoporous region (<50 nm) with a primary pore
width of 4.1 nm, with shoulders at 6.9 and 11.8 nm, and a broad
and weak peak centred at 50 nm, suggesting the presence of some
macropore. The WI and CP samples showed a broad pore size distribution with large mesopore of 9.8 and 17.0 nm, respectively. The
BET surface area ranges from 71 to 285 m2 g1 depending on the
preparation method. The large surface area of CP sample was due
to the use of surfactant in the synthesis whereas the low surface
area of SG sample was attributed to the rapid hydrolysis and condensation of the alkoxide precursor. The N2 adsorptiondesorption
isotherms of reduced catalysts showed the same IUPAC classication of calcined catalysts, suggesting that the mesoporous structure
was mostly retained after the thermal treatment at 1073 K. PSD
analysis of CA sample showed the shrinkage of pore size; on the
contrary a slight increase of pore size was observed for WI and SG
samples. The latter showed a bimodal distribution in the mesoporous region conrming its heterogeneity. The CP sample did not
change the primary pore size, however its pore distribution become
narrow.
Supplementary material related to this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.apcata.2015.05.
004.
3.2. XPS
To get a deeper insight on the electronic and chemical properties at the surface of the samples, XPS studies have been performed.
With this aim, the C1s, Al2p, Ni2p and Ce3d core level spectra
have been collected and analyzed. The core level binding energy
(BE) and the full width at half-maxima (FWHM) were analyzed
with particular attention to the Ni2p and Ce3d signals components,
which are of major interest for rationalizing the observed catalytic
activity. The BE, FWHM and atomic percent values observed for
calcined and reduced catalysts are collected in Table 1S in the Supporting Information. Al2p core level spectra were also investigated.
In agreement with the literature, the individual BE positions for the
Al2p signal contribution strongly depend on the preparation condition of the samples, thus Al O associated peaks are found in quite
wide BE ranges. Al2p3/2 BE is observed between 71.8 and 74.2 eV
(Table 1S). As an example, Al2p spectrum of CA is reported in Fig. 2c.
Supplementary material related to this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.apcata.2015.05.
004

Ni2p spectra are made complicated by the presence of high BE

satellites adjacent to the main peaks; as an example, CA Ni2p spectrum is reported in Fig. 2a. However, by following a peak tting
procedure, a single pair of spinorbit components was individuated for all calcined samples. The spinorbit component of higher
intensity 2p3/2 was taken as reference, and with the exception of SG
sample, was found at about 856 eV, typical of oxidized nickel. This
value was slightly higher than that reported for bulk NiO, characterized by a BE of about 854 eV, and was ascribed to the presence of
Ni2+ in strong interaction with the support [42]. SG sample showed
an intermediate situation with a BE value of 855 eV suggesting the
presence of Ni2+ in weak interaction with the support. The above
assignments were supported by the XRD analysis detecting bulk
NiO only on SG sample. For reduced samples, a second contribution
was observed at lower BE values (Ni2p3/2 = 853.0853.5 eV), indicative of metallic Ni [25]. However, the spectral contribution arising
by Ni(OH)2 on Ni particle surface [43] was still intense (about 50% of
total Ni2p signal), due to the sample exposure to the atmosphere
during preparation and prior the introduction into the UHV XPS
measurement chamber.
Ce3d core level spectra were widely and deeply investigated
because Ce3+ ions in CeAlO3 species, formed under reaction condition, are involved in the CO2 dissociative adsorption (Eq. (5)). This
step has been proposed to enhance the conversion of CHx intermediates at the metal support interface, avoiding their accumulation
as carbon (Eq. (6)). Therefore it is expected that samples with higher
Ce3+ amount are the most efcient. Ce3d spectra of all samples are
reported in Fig. 2b. Ce3d spectra were extremely complicated, due
to the different components arising by Ce3+ and Ce4+ ions and by
Ni2p1/2 satellites superimposed to the rst peaks. By following a
peak-tting procedure, ve spin orbit pairs related to Ce3d were
individuated, and the resulting components were associated to different ions by comparison with literature data [34,44]. The small
peak observed at higher BE values (nearly 916 eV BE), that is not
observed in pure CeAlO3 reference samples [34], is the 3d3/2 spin
orbit component associated to the higher BE 3d5/2 peak (in purple in Fig. 2b) and can be associated to the presence of Ce4+ ions
[44]. By estimating the intensity percent of this peak, it was possible to compare Ce4+ amounts in the calcined and reduced samples.
The obtained values, indicative for oxidized Ce4+ cerium amount
trend, are collected in Table 2. On calcined samples, the intensity
of the Ce4+ 3d3/2 peak was very similar to that of pure CeO2 for CP,
WI and SG, whereas it was particularly less intense for CA. After
reduction at 1073 K the intensity of the peak lowered, indicating
that CeO2 was partially reduced to CeAlO3 -like species, which are
stable in the atmosphere during preparation and prior the introduction into the UHV XPS measurement chamber. The reduction
extent depended by the preparation method. More in detail it is
possible to distinguish the reduced samples in two types: WI and
SG with high Ce4+ content, namely less reducible, and CA and CP
with low Ce4+ content, namely more reducible.
3.3. Reducibility
From the literature it is known that CeO2 supported on Al2 O3 is reduced in three main temperature regions. Peaks at low
temperature (773873 K) correspond to the reduction of surface
Ce4+ of small ceria crystallites. Peaks at intermediate temperature (9001100 K) correspond to the reduction of large and bulk
ceria crystallites. Peaks at high temperature (>1100 K) correspond
to the reduction Ce4+ Ce3+ of bulk related to the CeAlO3 formation. The position of these peaks is strongly dependent from
the CeO2 loading, the interaction with -Al2 O3 and the particle size [32,34,45,46]. Regarding Ni2+ supported on -Al2 O3 , four
species with increasing reduction temperatures have been recognized in the literature: bulk NiO, scarcely interacting with -Al2 O3

I. Luisetto et al. / Applied Catalysis A: General 500 (2015) 1222

17

Fig. 2. XPS core level spectra of (a) Ni2p (sample CA); (b) Ce3d (from top to bottom: sample CP, WI, SG, CA. The spectral component associated with Ce3d5/2 signal of Ce4+ is
in purple); (c) Al2p (sample CA). (For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)

(Ni- species), reduced in the temperature range of pure NiO

(573753 K); NiO interacting with the support (Ni-1 species), like
bi-dimensional NiOAlOx monolayer, reduced at mild temperature
(773873 K); non-stoichiometric spinel in strong interaction with
the surface (Ni-2 species) and bulk NiAl2 O4 (Ni- species), both
reduced at high temperatures (8731153 K) [4749].
The H2 -TPR proles of samples reduced up to 1273 K are
reported in Fig. 3. Several overlapped peaks corresponding to
reduction processes described above were observed. All samples
showed two weak peaks below 750 K ascribed to the reduction of
Ni- and of Ce4+ located at the surface of CeO2 nanoparticles [50].

In agreement with XRD and XPS analysis, SG sample showed Ni peak with the highest intensity. CP sample showed a large and
asymmetric peak with maximum at 1090 K attributed to the reduction of Ni-2 and Ni- species, and a very weak peak at 811 K due to
the reduction of Ni-1 . WI sample showed a main and broad peak
at 1090 K ascribed to the reduction of Ni-2 and Ni-, a shoulder at
846 K assigned to the reduction of Ni-1 , and a sharp peak at 1187 K
due to the reduction Ce4+ Ce3+ with formation of CeAlO3 . SG catalyst showed a similar TPR prole with broad and overlapped peaks
at 864, 930 and 1043 K assigned to the reduction of Ni-1 , Ni-2 ,
Ni- species, respectively, and a sharp peak at 1168 K indicative of

Table 2
XPS Ce4+ diagnostic component percent (depth: 14 nm max); hydrogen consumption in TPR experiments and Ce3+ percentage in calcined catalysts.
Catalyst

CP
WI
SG
CA

XPS analysis

TPR analysis

Ce4+ diagnostic peak %

H2 consumption (mmol g1 )
a

% Ce3+ d
b

Calcined

Reduced at 1073 K

Theoretical

TPR 1273 K

TPR 1073 K

19.0
26.7
23.0
9.3

2.5
10.0
14.9
1.6

2.17
2.29
2.24
2.45

2.04
2.19
2.17
2.13

1.94
1.70
1.65
2.12

5.85
4.27
2.65
12.9

a
Theoretical H2 consumption for the reduction of Ni and Ce assuming as reduction reactions Ni2+ + H2 Ni0 + 2H+ and 2Ce4+ + H2 2Ce3+ + 2H+ . Ni and Ce content by EDAX
analysis used in calculation.
b
Hydrogen consumption in TPR experiment up to 1273 K.
c
Hydrogen consumption in TPR experiment up to 1073 K.
d
Percentage of Ce3+ calculated according to Eq. (14) (see text) using the hydrogen consumption in TPR experiment up to 1273 K.

18

I. Luisetto et al. / Applied Catalysis A: General 500 (2015) 1222

analysis of the Ce3d core level. In fact, CA sample showed the lowest
intensity of the peak at 916 eV BE assigned to Ce4+ .
With the aim of studying the effect of the activation treatment used in the DRM reaction on the oxidation state of the
sample, H2 -TPR experiments were also conducted up to 1073 K
and then maintained in isothermal step. During the isothermal
step at 1073 K, the hydrogen consumption rapidly decreased to the
baseline (Fig. S2 in the supporting information). The hydrogen consumption (Table 2) of CA and CP samples was comparable to that
observed in the H2 -TPR up to 1273 K, conversely, that of WI and SG
samples was signicantly lower. Since the reduction temperature
of Ni- species (the most difcult to reduce) in WI and SG samples
was similar or lower than that observed in CP and CA (Fig. 3), and
taking into account the very similar hydrogen consumption in TPR
up to 1273 K and up to 1073 K of CP and CA samples, it is reasonable
to conclude that the Ni2+ species in all samples were completely
reduced. Therefore, the lower hydrogen consumption in reduction
up to 1073 K of WI and SG samples may be attributed to the lower
reducibility of Ce4+ species, in agreement with XRD and XPS analysis. Indeed XRD diffraction lines of CeO2 were still observed on WI
and SG samples after reduction up to 1073 K, whereas they almost
disappeared on CP catalyst (Fig. 1B). Moreover, XPS analysis of samples reduced at 1073 K, showed that the intensities of the Ce4+ peaks
of WI and SG samples were approximately six times higher than
those observed on the other specimens, indicating larger amount
of unreduced CeO2 (Table 2).
Supplementary material related to this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.apcata.2015.05.
004
3.4. Catalytic activity

Fig. 3. H2 -TPR proles of catalysts calcined at 873 K: CA (a); SG (b); WI (c); CP (d).

the CeAlO3 formation. CA sample showed a main reduction peak

at 930 K attributed to the reduction of Ni-1 and Ni-2 and a less
intense peak at 1123 K assigned to the reduction of Ni-. Among the
catalysts, CA has the highest intensity of Ni-1 and Ni-2 peaks. In
all samples the weak peak of bulk CeO2 reduction was not distinguished because superimposed to Ni reduction. Moreover in CP and
CA samples also the high temperature peak of CeAlO3 formation is
not observed. However, as reported in the literature, the CeAlO3
peak position may depends from many features like CeO2 loading,
particle size and support interaction. Furthermore, the quantitative
analysis of the hydrogen consumption (see below) suggests that the
reduction of both cerium species occurred. These considerations let
us to claim that also CeAlO3 peak in CP and CA catalysts was masked
by Ni reduction.
The hydrogen consumptions are reported in Table 2. The theoretical hydrogen consumption for the Ni2+ Ni0 and Ce4+ Ce3+
reduction is calculated from the chemical composition. The experimental hydrogen consumption was slightly lower than the
theoretical one for CP, WI and SG catalysts whereas it was significantly lower for CA sample. Assuming that the Ni2+ species were
completely reduced to Ni0 , the difference between the theoretical
and experimental hydrogen consumption ([H2 ]) suggested that
part of cerium was present as Ce3+ after synthesis and the corresponding amount, was calculated as percentage according to Eq.
(14), where Ce(EDAX) is the cerium content obtained by EDAX.
%Ce3+ = 100

[H2 ]
2 Ce(EDAX)

(14)

The CA sample showed the largest amount of Ce3+ followed

by CP, WI and SG samples. This nding was in line with the XPS

The methane and carbon dioxide conversions as a function of

temperature and time on stream are reported in Fig. 4a and b. Being
endothermic, the DRM reaction is thermodynamically and kinetically favoured at high temperatures, therefore, the conversions
increased with the increasing of temperature in the studied range
8731073 K. The CO2 conversions were higher than methane conversions at all temperatures, indicating the occurrence of the side
reverse water gas shift reaction (RWGS). Both methane and CO2
conversions slightly decreased during 5 h of time on stream. The
deactivation was mild at high temperatures, for example at 1073 K
only WI catalyst showed a 4% deactivation, whereas on CP and CA
catalysts the conversions remained almost constant and on SG catalyst they slightly increased. The catalytic activity strongly depended
on the preparation method. At 873 K the activity followed the sample order SG < WI < CA < CP whereas at 1073 K the order changed in
WI < SG  CA < CP. In particular, at 1073 K the highest methane conversion was obtained for CP and CA catalysts with similar values of
75% and 70%, respectively. The H2 /CO ratio as a function of temperature and time on stream is reported in Fig. 5. Consistently with
the RWGS occurrence, the H2 /CO ratio was lower than unity at all
temperatures. However, its values increased with the increasing
of temperature, suggesting a better selectivity towards the DRM
at high temperatures. The highest H2 /CO ratio value of 0.9 was
observed for the most active CP and CA catalysts at 1073 K.
The mechanism of DRM reaction has been widely investigated
[5155]: CH4 dissociates over Ni0 sites leaving reactive carbon atom
C*. This carbon atom may be converted to CO by reacting with oxygen deriving from CO2 activation on Ni0 or on support sites. The
dehydrogenation of CH4 on Ni0 sites has been recognized as the
rate determining step for the DRM reaction.
In order to compare the specic DRM activity of the catalysts, the STY of hydrogen at 1073 K was calculated (Table 3). In
the DRM the only reactant containing hydrogen is CH4 , however
the H2 produced by the DRM may further react with CO2 by the

I. Luisetto et al. / Applied Catalysis A: General 500 (2015) 1222

19

Table 3
Ni dispersion, active Ni site, STY and oxygen consumption of used catalysts.
Catalyst

DNi a

Ni sites (mol 106 )b

STY (s1 )

CP
WI
SG
CA

2.9
5.9
6.9
11.4

2.3
5.1
5.5
10.4

16.0
5.3
4.7
3.2

a
b

Oxygen consumption (mmol g1 )

C

74.33
9.60

8.73
46.45
27.67
7.48

Ni dispersion calculated by the Vannice method (Eq. (10)).

Active Ni sites calculated as DNi Ni mol.

Fig. 5. H2 /CO ratio as a function of time on stream under different reaction temperatures:  CA;  SG;  WI; CP. Reaction condition: catalyst loading 0.050 g, reactant
mixture composition CH4 :CO2 :Ar = 40:40:20 vol.%, GHSV 90,000 cm3 g1 h1 .

Fig. 4. Methane conversion (A) and carbon dioxide conversion (B), as a function
of time on stream under different reaction temperatures:  CA;  SG;  WI;
CP. Reaction condition: catalyst loading 0.050 g, reactant mixture composition
CH4 :CO2 :Ar = 40:40:20 vol.%, GHSV 90,000 cm3 g1 h1 .

RWGS. Therefore, in order to exclude the H2 consumption by RWGS

reaction, the H2 produced was calculated from the methane consumption. The STY increased with the increasing of Ni crystallite
size. This behaviour is consistent with the observations of several
authors [18,56] that reported the increase of TOF with Ni particle
size. Moreover it is known that the rate of methane dehydrogenation depends on Ni particle size [57]. Thus, the trend of specic DRM
activity observed in the present study, was primarily due to the different ability of Ni nanoparticles to activate the C-H bond, which

is mainly related to the particle size. On the other hand, small Ni

crystallite size provides a high number of active sites; therefore the
sample CA, despite having the lowest STY, showed nearly the same
activity of the CP sample having the highest STY value.
Differences in H2 /CO ratio for the catalysts reected the differences in the catalytic activity and the lower reactants conversion
yields a lower H2 /CO ratio. In fact the RWGS, which is responsible for the low H2 /CO ratio, is reported to be near equilibrium in
the 700850 K temperature range [4,58]. At high temperature the
DRM is favoured and the CH4 and CO2 reactants are converted efciently. Therefore the less amount of CO2 available for the RWGS
gives H2 /CO ratio closer to unity as expected when only the DRM
reaction occurs.
Coke may be formed during DRM reaction by the conversion of
accumulated C* atoms to less reactive carbon species, which may
encapsulate the surface of Ni0 or may dissolve in the nickel crystallite. The dissolved carbon diffuses through the nickel to nucleate
at the metal-support interface forming carbon laments [59]. The
carbon formation rate (rc ) and the amount of accumulated carbon
during 5 h of time of stream at different temperatures are reported
in Fig. 6a and b. On all catalysts the highest rc was observed at 873 K.
The rc abruptly decreased with the increasing of temperature up
to 973 K and it decreased less or do not vary at higher temperature. The high rc observed on our catalysts at low temperature is
attributed to a low rate of the C* intermediates oxidation and to
the occurrence of the CO disproportionation reaction. Moreover,
CP catalyst showed a slight increase of rc above 973 K, suggesting that on this catalyst the C* was gasied slower in comparison
with the other catalysts. The rc increased in the following sample
order CA  SG < WI  CP, namely it increased with Ni0 crystallite

20

I. Luisetto et al. / Applied Catalysis A: General 500 (2015) 1222

Fig. 7. XRD patterns of the used catalysts: CA (a); SG (b); WI (c); CP (d).

carbon (JCPDS 41-1487) in addition to phases observed on the

freshly reduced catalysts. The peak intensity was in agreement with
the carbon amount weighted at the end of the catalytic test, being
the highest for CP and the lowest for CA. Furthermore, the Ni0 crystallite size on used samples was nearly the same than on reduced
samples indicating that during the catalytic cycle, the metal sintering was minimal.
Raman spectroscopy was used to investigate the order of the
deposited carbon on the used Ni catalysts (Fig. 8). For each sample,
at least three Raman spectra were collected in different areas to
assess the homogeneity of the investigated material. All the spectra collected on the same sample showed exactly the same features
thus conrming the homogeneity of the carbon deposits. Raman
spectra of CP, SG and WI samples display two main bands at 1325 (D
band) and at 1576 cm1 (G band), a shoulder at 1590 cm1 (D band)
and a less intense band at 2642 cm1 (G band). Raman spectra of
CA sample shows two large bands at 1320 (D band) and 1593 cm1

Fig. 6. Carbon formation rate at different temperatures (A), and the corresponding cumulative carbon deposition (B), each temperature lasted for 5 h: CA (red), SG
(blue), WI (black), CP (green) catalysts. (For interpretation of the references to colour
in this gure legend, the reader is referred to the web version of this article.).

size, conrming the structure-sensitive nature of methane decomposition reported by other authors [19].
The mass of carbon deposited on the surface, increased with the
increasing of temperature reaching a plateau (Fig. 6b). On all samples the much greater amount of carbon was accumulated at 873 K;
at higher temperature the carbon increased by a small amount, suggesting a better oxidation of C* carbon. The amount of deposited
carbon strongly depends on catalyst preparation method being
nearly negligible on CA and about 13 times greater on CP catalyst.
In order to shed light on the possible reasons of the stability
of catalysts having different amount of coke, the deposited carbon
was investigated by XRD, Raman and TPO analysis.
3.5. Characterizations of used catalysts
The XRD patterns of the catalysts after catalytic tests (Fig. 7)
showed a broad peak at about 2 = 26.1 corresponding to graphitic

Fig. 8. Raman spectra of the used catalysts: CA (a); SG (b); WI (c); CP (d).

I. Luisetto et al. / Applied Catalysis A: General 500 (2015) 1222

21

quantity of C compared to samples CP and CA, with high Ce3+ content. Despite this positive effect, coke deposition is mainly driven
by the nickel crystallite size, in fact CP catalyst, having the largest
Ni crystallite, showed the greater carbon amount.
It is worth to note that CP catalyst showed high activity and stability despite of the greater carbon content. This behaviour may be
explained considering the nature of the carbon deposits. In fact, the
lamentous carbon C does not result in fast deactivation because
does not encapsulate Ni0 sites that remain accessible to the reactants.
4. Conclusions

Fig. 9. O2 -TPO proles of the used catalysts: CA (a); SG (b); WI (c); CP (d).

(D band). The G and G bands are related to the stretching vibration

in the aromatic layers of graphite (in-plane displacement of carbon
atoms in the hexagonal sheet) and they are the only bands present
in perfect crystalline graphite [6062]. The D and D bands are
defect bands that appear when disorder is introduced into graphite
structure and they have been assigned to the non-zone centred
phonons associated to the disorder-induced vibration of C C bond
[6365]. The relative intensity ratio of D and G bands (ID /IG ) can be
used to investigate the graphitization of carbon and the degree of
disorder in the structure [66]. An ID /IG ratio near zero indicates high
order whereas a ratio around 1 reveals high disorder due to abundant defects in the graphite structure. In our case, ID /IG it is 1.4 for
CP and WI samples and 1.3 for SG sample, indicating that graphitic
carbon deposits have a high degree of disorder. The absence of G
and G bands on CA sample indicate that the small amount of carbon
deposit, revealed by XRD, has a much higher degree of disorder.
O2 -TPO experiments were carried out with the aim to study the
reactivity of coke with the oxygen. TPO proles are reported in Fig. 9
and the corresponding oxygen consumption in Table 3.
TPO proles showed two peaks of oxygen consumption with
maximum at about 813 and 945 K, assigned to the oxidation of the
C and C carbon species, respectively. In agreement with literature
data [20], the C species, corresponding to lamentous graphitic
carbon, were oxidized at lower temperature in comparison with
the C species, which are more stable moss like graphitic carbon
deposits. The C species were the main on CP sample, whereas they
were found in low amount on WI and were not observed on the
other samples. On the other hand, the C species were the main on
sample WI and the only carbon species on SG and CA.
TPO analysis showed that the reactivity of carbon deposits
depended by their morphology more then their disorder degree.
In fact, despite the similar ID /IG ratio observed on CP, WI and SG,
they present different distribution of C and C species.
The amounts of deposited carbon estimated from the consumption of oxygen in TPO experiment were in good agreement with
the increase of the weight of samples at the end of the catalytic
test, and with the intensity of XRD peak assigned to graphite. It is
interesting to note that on samples CP and CA the content of the
C carbon species were similar, suggesting that the nature of carbonaceous residues is also inuenced by the presence of CeAlO3 .
Indeed samples WI and SG, with low Ce3+ content, have a greater

The dry reforming of methane was studied on catalysts with

10 wt.% Ni and 20 wt.% CeO2 supported on -Al2 O3 having different
Ni crystallite size, Ce3+ /Ce4+ ratio and textural properties.
The textural properties and thermal stability of catalysts depend
on the preparation method. The highest stability of surface area and
pore size, is showed by the sample prepared using the citric acid
method that, allowing the mixing of cations at atomic level, yields
a Ni Ce Al Ox mixed oxide with amorphous phase. By using the
co-precipitation and citric acid methods, Al O Ce bonds are
formed and CeO2x results well dispersed within -Al2 O3 lattice.
CeO2x , strongly interacting with -Al2 O3 , presents greater amount
of Ce3+ in comparison with segregated CeO2 .
The specic catalytic activity for DRM increased with the
increasing of Ni crystallite size, regardless of the textural properties
and of the Ce3+ /Ce4+ amount.
Carbon deposition is limited by operating at temperature higher
than 1023 K on catalysts having Ni crystallites smaller than 10 nm.
The amount of less reactive carbonaceous deposits, graphitic moss
carbon, is lower on catalysts containing great amount of Ce3+ stabilized as CeAlO3 like species.
The citric acid method results particularly attractive because
allows to obtain catalysts with very small Ni crystallite size (5.8 nm)
and high content of CeAlO3 , that have a benecial role in increasing
the rate of carbon gasication.
The most active catalysts CA and CP are stable during time on
stream: because CA catalyst accumulates a low amount of coke,
whereas CP accumulates mainly lamentous carbon which does
not encapsulate Ni0 active sites, causing only a slightly decrease
of the catalytic activity. However excessive carbon accumulation
may results in the reactor plugging and in the pressure increase,
therefore the catalyst prepared by citric acid method, showing comparable performances with minor carbon deposition, results the
most suitable catalyst for long term operation.
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