Applied Catalysis B: Environmental 93 (2010) 346–353

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Applied Catalysis B: Environmental

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Synthesis and characterization of a LaNiO3 perovskite as precursor for methane

reforming reactions catalysts
Rosa Pereñı́guez, Vı́ctor M. González-DelaCruz, Juan P. Holgado, Alfonso Caballero *
Instituto de Ciencia de Materiales de Sevilla and Dep. Quimica Inorganica (CSIC-Universidad de Sevilla), Avenida Américo Vespucio, 49, 41092 Sevilla, Spain

A R T I C L E I N F O A B S T R A C T

Article history: The objective of the present work has been the study of the physicochemical and catalytic properties of a
Received 14 July 2009 Ni/La2O3 catalyst obtained by reduction of a lanthanum nickelite, LaNiO3, with perovskite structure. The
Received in revised form 23 September 2009 perovskite, obtained by means of a spray pyrolysis method, provides a Ni/La2O3 system active in
Accepted 30 September 2009
different methane reforming reactions. The catalyst was characterized by scanning electron microscopy
Available online 4 November 2009
(SEM), X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), X-Ray photoemission spectroscopy
(XPS), temperature-programmed reduction and oxidation (TPR, TPO) and catalytic activity tests.
Keywords:
Although not evidenced by XRD data, XAS and TPR measurements show the presence of an amorphous
Methane reforming
LaNiO3 catalysts
NiO phase in the original sample, together with the crystalline LaNiO3 phase. Upon reoxidation
In situ XAS treatment of the reduced Ni/La2O3 catalyst, the LaNiO3 structure is partly recovered which provides a
Nickel perovskite convenient way to regenerate a waste catalyst (reoxidation and new reduction in hydrogen). The catalyst
Partial oxidation of methane is active in several reactions of methane with oxygen, water and CO2, showing a remarkable stability
specially under dry reforming of methane (DRM) reaction conditions. This quite great catalytic
performance has been explained by the high resistance of the nickel particles to be oxidized, as detected
by in situ XAS. In the presence of water, as in steam reforming of methane (SRM) reaction conditions,
these metallic particles are gradually oxidized, which explains the linear decreasing of the catalytic
performance observed for the SRM reaction.
ß 2009 Elsevier B.V. All rights reserved.

1. Introduction reactive mixture, giving a global reaction of CO2 +2CH4 + -

Systems for energy production based on fuel cells are nowadays
considered as the most efficient and the lowest pollutant emission
energy sources. Therefore, production of hydrogen from fuels, such
as gasoline, natural gas or alcohols, has become a scientific topic
with a great activity, since we are probably on the verge of a jump
from a ‘‘hydrocarbon economy’’ to a ‘‘hydrogen economy’’ [1,2]. In
such a way, steam reforming of methane (SRM) is nowadays,
together with water electrolysis, the more economic and used
method to obtain this energetic vector (H2) [3–6]. Besides this SRM
process, some other alternatives have been proposed, such as
autothermic reforming, where oxygen addition to reaction mixture
provides the energy necessary to compensate the endothermic
term of the SRM reaction, and also the more recent dry reforming
with CO2, which has been specially studied in last few years [7–9],
due to the fact that both CH4 and CO2 are considered as greenhouse
effect gases and, therefore, responsible of global warming.
Nevertheless, the use of CO2 increases the formation of coke,
and for practical applications it is necessary to add H2O to the
* Corresponding author.
E-mail address: caballero@us.es (A. Caballero).
H2O $ 3CO + 5H2 [10,11].
Although for industrial use Ni catalysts are especially attractive,
due to the high activity and low cost, these tend to deactivate with
coke formation, specially, as mentioned before, in the case of CO2
dry reforming [12]. This process of coke deposition has been
related by different authors with the morphology and distribution
of Ni particles onto oxide support [13,14] since the first step in the
catalytic reaction of SRM is the dehydrogenation of CH4 over Ni
particles [15] and the coke deposition occurs through a reaction
‘‘sensitive to structure’’ [16–18]. In this sense, several authors have
proposed the preparation of a highly dispersed Ni system based on
so called method ‘‘solid phase crystallization’’, where Ni is
‘‘extracted’’ from solids with well defined structures after
treatment under reducing conditions [7,19–21]. Using this
method, catalysts have been prepared from several solids contain-
ing Ni, such as perovskites or hydrotalcites of Ni and Mg
[7,16,17,22]. In order to obtain such solids containing Ni, we have
prepared a perovskite of Ni and La (LaNiO3) by means of a spray
pyrolysis method, a well known and useful method to obtain
ceramic materials [23,24]. In fact, this method presents advan-
tages, such as its simplicity, high purity, excellent stoichiometric
control on multicomponent systems, and a good control on
particles shape and size. All this features, jointly with its

0926-3373/$ – see front matter ß 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcatb.2009.09.040
 R. Pereñı´guez et al. / Applied Catalysis B: Environmental 93 (2010) 346–353
continuous production capacity, make this method a perfect
candidate for industrial production [25].
This work reports on the characterization of a LaNiO3 solid
prepared by spray pyrolysis, its reduction in H2 at high temperature,
to obtain a dispersed Ni/La2O3 catalytic system, and its reactivity in
some of the reforming reactions previously mentioned. We also
discuss the changes observed on the reduced catalyst after a
reoxidation treatment. This is relevant because a way to recover the
poisoned catalysts is their treatment under oxidizing conditions,
burning out the carbon deposited on the catalyst and also changing
the state of the metallic phase. The aim of this study is, therefore, to
verify the changes in the physicochemical properties of the catalysts
and the influence of these treatments on the reactivity of the
samples during methane reforming reactions.
2. Experimental
2.1. Catalyst preparation
LaNiO3 was prepared by spray pyrolysis using the experimental
set-up described elsewhere [26]; it consists in a quartz tube divided
into two independent temperature zones. In our case, these zones
were controlled at 250 8C (drying) and 600 8C (decomposition),
respectively. LaNiO3 perovskite was prepared from a solution
containing La(NO3)3 and Ni(NO3)2 with a concentration of 0.05 M
each. The solution is introduced in the reactor as a spray by means of
an ultrasonic transductor. Once the aerosol is obtained, it is
transported through the reactor (in an air atmosphere), forced by
a suction pump located at the end of the system. Particles of
synthesized material are collected in a funnel with a porous frit,
heated at ca. 100 8C to avoid its physical blocking. Finally, the solid is
dried in an oven at ca. 150 8C and calcined in air at a temperature
equal or above to that of decomposition furnace.
2.2. Scanning electron microscopy (SEM) and X-ray diffraction (XRD)
SEM images were obtained in a Hitachi S-5200 microscope,
with a field emission filament, using an accelerating voltage of 4–
5 kV, and an extraction current of 10 mA.
X-ray diffractograms were recorded in a Siemens D-500
equipment, with a Bragg–Brentano configuration, using Cu Ka
(l = 1.5418 Å). Spectra were collected in the range 2u = 20–808,
with a step of 0.058 and an acquisition time of 1 s for each point.
2.3. X-ray absorption spectroscopy
X-Ray absorption spectra (XAS) were recorded at the BM25
beam line (SPLINE) of the ESRF synchrotron (Grenoble, France). The
spectra were acquired in transmission mode using a modified
commercial infrared cell (Specac) according to the procedure
described elsewhere [27]. The sample is resistively heated on a
stainless steel holder directly in contact with the gas mixture
atmosphere. This sample holder allows mounting of self-
supported wafers pressed in a standard 13-mm die. In all cases
the pellets were prepared using the optimum weight to maximise
the signal-to-noise ratio in the ionisation chambers (log I0/I1  1).
For energy calibration, a standard Ni foil was introduced after the
ionisation chamber (I1) and measured simultaneously. Typical
EXAFS spectra of Ni K-edge were recorded from 8230 to 9190 eV,
with a variable step energy value, with a minimum 0.5 eV step
across the XANES region (8315–8375 eV). EXAFS spectra were
analysed using the analysis package ATHENA [28], using the
theoretical amplitude and phase shift functions proposed by Rehr
et al. (version 7.02 [29]). Reference spectra for Ni and NiO were
recorded using standard reference samples. For the LaNiO3, a
reference spectrum was taken from the literature [30].
347
Original sample was recorded in the cell after purging it with inert
gas at room temperature. The sample was treated in situ at 1073 K for
every treatment (reduction, oxidation and steam and dry reforming),
using a heating ramp of 10 K min1 and the spectra were collected
after cooling down to RT. The compositions of the gas mixtures were
similar to that used in the TPR/TPO experiment, for the reduction and
oxidation treatment, and in catalytic test, for the reforming reaction
experiments (DRM and SRM) using mass flow controllers for dosing
the gases to the cell and a total flow of 100 ml/min.
2.4. X-Ray photoemission spectroscopy (XPS)
XPS Spectra were recorded in an LHS-10 Leybold Heraus
Spectrometer, with a base pressure of 3  1010 Torr, and working
in constant pass energy mode (40 eV). Mg Ka (hy = 1253.6 eV) was
used as excitation radiation. Calibration of spectra was done on
spurious C1 s peak, fixing it at a value of 284.5 eV. The thermal
treatments of the sample were performed in a prechamber
attached to the main chamber of the spectrometer. The transfer
between them was done avoiding the contact with air or other
gases before data acquisition.
2.5. Temperature-programmed reduction and oxidation (TPR, TPO)
Temperature-programmed experiments were done according
to the experimental conditions described elsewhere [31], using
12 mg of LaNiO3. A H2/Ar mixture (5% H2, 50 ml/min flow) was
used as the reducing atmosphere and for TPOs the gas mixture was
an O2/He (3% O2, 25 ml/min flow), both from room temperature up
to 1073 K, with a heating rate of 10 K/min. A thermal conductivity
detector (TCD), previously calibrated using CuO, and a mass
spectrometer in line with the TCD, calibrated with reference
mixtures, were used to detect variations of H2 concentration, and
monitor possible sub-products formation. After the first reduction
process (TPR-a), the sample was cooled down to RT in H2/Ar, and
then purged with He. After this treatment, a temperature-
programmed oxidation (TPO-a) run in O2/He (3% vol. O2) was
recorded. Successive TPR and TPO runs were recorded using the
same methodology (TPR-b, TPO-b, TPR-c and TPO-c).
2.6. Catalytic activity tests
Reaction was carried out in a tubular reactor (‘‘U’’ shaped),
using 20 mg of catalysts between two pompons of quartz wool.
Mixtures of gases consisted of CH4 (5–14% vol.) diluted in He, and
molar equivalent of O2 (1:1, 2:1), H2O (1:1) and CO2 (1:1). In the
case of CH4 + H2O reaction, a Fresenius ‘‘Orchestra’’ perfursor was
used for injecting the water onto the CH4 + He mixture with all the
pipes from this point up to chromatograph heated at 65˚ C. Samples
of LaNiO3 in contact with the reaction mixture were heated from
room temperature up to 1073 K at 1 K/min rate, holding the
samples at 1073 K during 12 h, and cooled down to room
temperature in the same reaction mixture.
Reactives and products, with the exception of water, were
analysed using a gas chromatograph (Varian, GC-3800) equipped
with a thermal conductivity detector (TCD), and two columns with
an ‘‘in line’’ configuration (Molecular Sieve 5 Å, Porapak1-N).
3. Results and discussion
3.1. Catalysts characterization
3.1.1. SEM microscopy
SEM images of original LaNiO3 sample and after the treatments
of reduction at 1073 K and subsequent oxidation at 1073 K are
presented in Fig. 1.
348 R. Pereñı´guez et al. / Applied Catalysis B: Environmental 93 (2010) 346–353
Fig. 1. SEM images of the LaNiO3 sample after calcination at 800 8C (a), reduction at
800 8C (b) and reoxidation at 800 8C (c).
It can be seen that the fresh LaNiO3 particles are in the form of
pseudo-spherical particles, with a variable size of 150–500 nm,
constituted by aggregates of smaller nanoparticles. Some of the
aggregates show a slight sinterization among them. After the
reduction, morphology of aggregates changes, presenting a
rougher surface, and the spheres generally destroyed. By reoxida-
tion at 1073 K, the aggregates again become less rough in surface,
and as in the case of reduced sample, the spherical geometry has
practically disappeared.
3.1.2. X-ray diffraction
Fig. 2 presents the XRD diffractograms of the LaNiO3 sample,
together with those of the samples after the treatments of
reduction at 1073 K (on the right) and subsequent oxidation at
1073 K. It also includes the diffractograms for references of
metallic Ni, La2O3 (right) LaNiO3 and NiO (left).
In spite of the width peaks obtained in the diffractogram of the
original calcined sample, comparison with LaNiO3 phases in ICDD
2000 database [32] allows us to assign the peaks at 47.38, 23.28 and
338 (the last corresponding to a no resolved doublet) to a
Rhombohedral (R-3m) structure as the main phase in our sample.
Fig. 2. XRD diagrams of the LaNiO3 sample after calcination, reoxidation (left) and
reduction (right). Appropriate references are also included.
By applying the Scherrer equation at peak 47.38 (2 0 2), the LaNiO3
crystallite size results in 31 nm, which corresponds to the size of
the aggregates of nanoparticles previously observed by SEM.
The shape of this diagram obtained after reoxidation is similar
to that of the original sample, and mainly depicts peaks
corresponding to the presence of a LaNiO3 rhombohedral phase.
The presence of weak peaks at ca. 378 and 448, not present in the
original sample, can also be detected that can be ascribed to the
cubic phase of NiO. So, it is possible to recuperate the LaNiO3 phase
after reduction/oxidation cycles, worthy for catalysts regeneration
by oxidation after the reforming reaction, that can provide an
adequate method for redispersion of nickel in the La2O3 support
after successive reduction and reoxidation treatments.
The profile obtained after the reduction treatment (Fig. 2 right)
shows the presence of two main phases: one corresponding with a
hexagonal (P-3m1) La2O3, with its most intense peak at ca 308, and
a second corresponding to a cubic Ni metallic phase, determined
mainly by the presence of peaks at 44.58 and 52.58. The analysis of
Ni crystallite size by Scherrer equation (peak at 44.58, 111) gives a
value of 38 nm, which is no distinguishable by SEM. No other nickel
phases are detected in these conditions, showing that no notice-
able oxidation of Ni has occurred during the manipulation of the
sample.
3.2. EXAFS characterization of calcined, reduced and
reoxidized samples
Fig. 3 shows the Fourier transforms (FTs) of the EXAFS
oscillations of LaNiO3 after in situ reduction and oxidation
treatments. The FTs of a metallic Ni foil, NiO and a well
characterized LaNiO3 sample [30] are also included as references.
FT of LaNiO3 sample presents three mayor peaks, centered at ca.
1.9, 2.9 and 3.3 Å (the last one with a shoulder at 3.8 Å). A simple
comparison with the references clearly reveals that the peaks at 1.9
and 3.3 Å (with the 3.8 Å shoulder) could be assigned to a
perovskite phase, while the peak at 2.9 Å, not corresponding to any
LaNiO3 peak, is in the same position as the Ni–Ni second
coordination shell in the NiO, thus reflecting the presence of an
amorphous NiO phase not detected previously by XRD (Fig. 2).
After the reduction treatment, the FT shape changes drama-
tically, and only one peak at ca. 2.5 Å can be detected, at the same
position of that corresponding to Ni–Ni first coordination sphere in
the metallic Ni used as a reference, showing a complete reduction
to metallic Ni. A coordination number of 12 at 2.5 Å has been
obtained for the Ni–Ni sphere, which is in agreement with the
relatively large particle size detected by XRD. It is worth to note
that during the reduction process no other nickel phases were
detected, suggesting that the perovskite reduction proceeds just in
one step.
 R. Pereñı´guez et al. / Applied Catalysis B: Environmental 93 (2010) 346–353
Fig. 3. FTs of the in situ Ni K-edge EXAFS spectra obtained for the LaNiO3 sample.
LaNiO3, NiO and Ni references are also included. All the spectra have been collected
in situ at room temperature after the indicated treatments.
Finally, the FT of the reoxidized sample is quite similar to that of
the original sample, presenting again peaks associated with the
LaNiO3 phase (at ca. 1.9, 3.3 and 3.8 Å), and the NiO amorphous
phase (2.9 Å), with some differences in the relative intensity. So,
Fig. 4. XPS spectra of La 3d (left) and Ni2p (right) of the LaNiO3 sample after calcination at 800 8C (a), reduction at 800 8C (b) and reoxidation at 800 8C (c).
349
data obtained from EXAFS have unambiguously shown the
presence of an amorphous NiO phase, hardly detected by XRD,
also confirming the almost complete regeneration of the original
LaNiO3 phase after a redox cycle.
3.3. X-Ray photoelectron spectroscopy (XPS)
XPS spectra of the original, reduced and reoxidized LaNiO3
samples, corresponding to the zones of La 3d (left) and Ni2p (right)
regions are presented in Fig. 4. The reduced sample shows a profile
characteristic of a La2O3 phase, with a doublet at 833.2 (3d5/2) and
850.0 eV (3d3/2), corresponding to the splitting caused by the spin–
orbit coupling. Each of these peaks also present a pair of maxima
(833.2 eV and 836.8 eV for 3d5/2 peak) as a consequence of two
different final states in the photon emission, and as result of
hybridization of 4f orbitals of La atoms with surrounding atoms
(3d94f1 and 3d94f0 final states, for higher and lower binding energy
peaks, respectively) [33].
The spectra of the original (calcined) and reoxidized samples
are very similar, with the same doublet structure as those
previously described for the reduced sample [33,34], although
the peaks are slightly shifted and the satellites present a different
intensity ratio. The larger width of these peaks must be due to the
simultaneous presence of a lanthanum perovskite phase and some
La2O3, compensating the presence of the NiO phase detected
previously by XAS. Nevertheless, some of the lanthanum species
must be as hydroxides and/or carbonates at the surface of the
catalyst which can also explain the wider peaks.
The Ni 2p region shows important changes when samples are
submitted to the indicated treatments. The spectrum of the
original sample shows a maximum at ca. 871.5 eV, that can be
attributed to Ni3+ species, even though some contribution of Ni2+
species cannot be discarded [35]. XPS cannot be used as an
unequivocal proof of the existence of LaNiO3, because Ni2+ and Ni3+
are difficult to distinguish, specially taking into account the low
signal detected and the overlapping of La 3d peaks with Ni 2p3/2
peaks. Nevertheless, the position of the Ni 2p1/2 and La 3d doublet
(in particular, the intensity ratio observed between the La 3d5/2 and
350 R. Pereñı´guez et al. / Applied Catalysis B: Environmental 93 (2010) 346–353

its satellite) are, according to the literature, consistent with the

presence of a LaNiO3 phase [35].
Surprisingly, after the reduction treatment at 1073 K, no Ni 2p
signal can be detected, while the subsequent reoxidation of this
sample at 1073 K gives a Ni2p signal similar to that obtained for
the original sample. The main difference comes from the better
resolution of the doublet characteristic of the NiO, which is in
agreement with the more crystallized NiO phase detected by
XRD in the reoxidized sample (Fig. 2). Taking these two effects
into account, we may suggest that the loss of Ni 2p signal after
the reduction treatment could be related with the formation of
small Ni metallic particles and its burial into La2O3. This
homogeneous and massive distribution of the Ni in the La2O3
support can justify the fact of recuperation of the LaNiO3 phase
after reoxidation of the Ni/La2O3 coming from the reduction of
the LaNiO3. Obviously, this is not surprising considering the
‘‘solid phase crystallization’’ process occurring during the
reduction of the LaNiO3. Although the La2O3 support is not a
reducible oxide, this burial process resembles to that named
‘‘Strong Metal Support Interaction’’ (SMSI), a well described
phenomenon in many Metal/oxide systems [36,37], consisting of
the ‘‘decoration’’ of metallic particles with ‘‘moieties’’ of the
oxide acting as support (La2O3) or even its complete burial in the
bulk of it. Nevertheless, it should be remarked that this partial/
Fig. 5. Temperature-programmed reduction (TPR) profiles of the LaNiO3 after
total covering of metallic particles due to SMSI effect not always calcination at 600 8C. (a) 1st cycle; (b) 2nd cycle; (c) 3rd cycle.
decreases the activity of the active phase, but in many cases it
produces a significant improvement on it. Other explanation to
this effect such as the formation of great amounts of carbonates relatively high dispersion of the metallic nickel on the support, as
and/or hydroxides on the surfaces covering the metal particles smaller particles are easier to reduce.
can be neglected because, as indicated before, after the reduction The values of H2 and O2 consumption determined from these
treatment the sample is conducted to the analysis chamber of the profiles, expressed as total micromoles of hydrogen for the 12 mg
XPS without further contact with air or other gases. Even more, of sample, and the equivalent change in oxidation state of the
no remarkable changes are detectable in the C 1s and O 1s signal reducible phase (Nin+/Ni0), are presented on Table 1. Even
(not included). considering a margin of error of about 10%, these values can be
used to assess the phases present in the sample. As can be
3.4. Temperature-programmed reduction and oxidation (TPR, TPO) observed, the H2 consumption in the first TPR is very close to that
expected considering the reduction from Ni3+ (in LaNiO3) to Ni0.
The reactivity of the calcined LaNiO3 sample in successive The Dn+ value (change in oxidation state) of 2.9 is compatible with
reducing and oxidizing cycles has been tested, and the results are the presence of about 10% of nickel in the form of an amorphous
collected in Figs. 5 and 6, respectively. Profiles for NiO and Ni
references are also included in the figure.
The as-calcined solid presents a first TPR profile of LaNiO3
(Fig. 5, line a) showing a broad peak, with its maximum centered at
768 K and a shoulder at ca. 698 K. After reoxidation, the second TPR
(Fig. 5b) shows a different shape, depicting two clearly separated
peaks. The first of these two peaks shows a sharp shape, and its
maximum centered at ca. 715 K, mostly resembles that of NiO
profile, while the second peak, broader, shows a maximum at
higher temperature (818 K). This profile, unchanged after a further
oxidation step (Fig. 5c) is similar to those reported previously in
the literature [38–40], and has been previously interpreted as the
reduction of LaNiO3 to La2NiO4 (first peak) and to metallic nickel
(second peak). In our case, taking into account the presence of the
NiO phase detected by EXAFS, we assign the first peak at low
temperatures to the reduction of the NiO phase to Ni0 and the
second peak, at higher temperatures, to the reduction of the LaNiO3
phase.
Regarding the oxidation processes (TPO, Fig. 6), the first profile
corresponding to the oxidation of a previously reduced sample,
outlines a broad peak with a maximum at ca. 685 K, and a shoulder
at around 785 K, coincident with one of the peaks observed in the
oxidation profile of Ni reference. The second and third oxidation
profiles are quite similar to the first one, and only a slight shift to
lower temperatures (ca. 665 K) could be observed on the maxima
of the oxidation process of these oxidation processes. The lower Fig. 6. Temperature-programmed oxidation (TPO) profiles of the LaNiO3 after
temperature of the main oxidation peak could be related with the reduction at 800 8C. (a) 1st cycle; (b) 2nd cycle; (c) 3rd cycle.
 R. Pereñı´guez et al. / Applied Catalysis B: Environmental 93 (2010) 346–353 351

Table 1 ago. These authors indicate that the low temperature peak
Consumption of H2 or O2 for the different redox cycles of the LaNiO3 sample and
observed by us and most of reported TPRs of LaNiO3 [38–40]
calculated changes in the mean oxidation state (12 mg of sample).
should not be ascribed to the reduction of LaNiO3 to La2NiO4, but to
Redox cycles H2/O2 consumed (mmol) Dn+ reduction of the amorphous NiO phase, a suggestion that is also
TPR-a 73 2.9 supported by the coincidence in shape and temperature with the
TPO-a 31 2.4 reduction profile of NiO and is supported by our results.
TPR-b 59 2.4
TPO-b 27 2.2
3.5. Study under reaction conditions: catalytic performances and in
TPR-c 54 2.2
TPO-c 32 2.5 situ XAS in dry and steam reforming

The catalytic performances of this LaNiO3 system have been

NiO phase. The Dn+ value of just 2.4 obtained for the oxidation of
the reduced sample (TPO-a) could be attributed to a bigger
contribution of Ni2+ (ca. 50% NiO). The increase in the NiO
percentage explains the change in the TPR profile after the first
cycle, which remains constant after the second reduction.
It should be remarked that the presence of this NiO amorphous
phase has almost not been detected in any previous paper of
LaNiO3, especially in the field of methane reforming. Although it
can be related with the preparation method used by us, it was
previously suggested by Ruckenstein et al. [41] more than a decade
tested on different methane conversion reactions: partial oxida-
tion (under two different CH4:O2 stoichiometries), steam reform-
ing and dry reforming of methane, looking at the transformation of
this hydrocarbon under progressively harder reduction conditions.
Fig. 7 shows the results of CH4 and O2 conversion (left) and the
micromoles of CO2 (right) as a function of temperature for the
partial oxidation reaction using a reactive gas mixture of CH4:O2
equal to 1:1 (5% CH4 + 5% O2, He balance). As only CO2 and water
are detected as products in the whole range of temperature, the
nickel phase must remains oxidized under these reaction

Fig. 7. Conversion of CH4 and O2 and amount of products for LaNiO3 in the partial oxidation of methane. Catalyst: 0.02 g, GHSV = 3  105 L/kg h, reactants = CH4 + O2 1:1.

Fig. 8. Conversion of CH4 and O2 and amount of products for LaNiO3 in the partial oxidation of methane. Catalyst: 0.02 g, GHSV = 3  105 L/kg h, reactants = CH4 + O2 2:1.
352 R. Pereñı´guez et al. / Applied Catalysis B: Environmental 93 (2010) 346–353

conditions. According to the stoichiometry of the reaction:
(CH4 + 2O2 ! CO2 + 2H2O), the oxygen in this mixture is a
defective reactive, which explain the complete consumption of
this reactive at 1073 K, but only a 50% of conversion of CH4. After an
initial deactivation process, the activity remains stable at about
45% (methane combustion).
When the LaNiO3 sample is exposed to a CH4:O2 mixture with a
2:1 ratio (14% CH4, 7% O2, He balance), the behaviour of the catalyst
is drastically modified (Fig. 8). At temperature lower than 1073 K,
the activity is similar to that previously obtained with the 1:1
composition and only CO2 and water were detected as products of
the reaction. Accordingly, the total consumption of the oxygen is
reached with 25% CH4 conversion. However, after some minutes at
1073 K, there is a dramatic change in the reactivity, and a sudden
increase in the conversion of CH4 is detected, reaching values close
to 90%. At the same time, there is a change on the product
distribution, the presence of CO2 and water is now negligible, and
CO and H2 are the major products, in a relation closer to 1:2, a
product distribution that corresponds to the partial oxidation
reaction of methane: CH4 + 1/2O2 ! CO + 2H2. As this reaction is
catalyzed by metallic nickel, this result shows that the transition in
the catalytic performance at 1073 K occurs when the LaNiO3 phase
is completely reduced to metallic nickel, even in the presence of a
certain amount of oxygen in the reaction mixture.
The catalytic performance in the reforming of methane has also
been tested in steam and dry conditions. The data obtained from
steam reforming of methane (SRM) (Fig. 9) show that the
conversion of methane starts abruptly at ca. 1000 K, coinciding
with the reduction of LaNiO3 to metallic nickel by the reaction
mixture, reaching a maximum conversion of 75% at 1050 K. The
main products are H2 and CO, with a ratio close to that of the
reforming reaction CH4 + H2O ! CO + 3H2. A more careful exam-
ination of data shows the presence of small amounts of CO2 and a
H2/CO ratio slightly bigger than expected (3:1). This effect seems to
indicate that the reduced LaNiO3 system is also active in the WGSR,
which implies that part of CO produced in the methane reforming
reaction is later transformed according to the process:
CO þ H2 O ! CO2 þ H2
As shown in the figure, the catalyst is strongly deactivated at
1073 K with an almost linear decrease in its activity after 1500 min

Fig. 9. Conversion of CH4 and amount of products for LaNiO3 in the steam reforming of methane. Catalyst: 0.02 g, GHSV = 3  105 L/kg h, reactants = CH4 + H2O 1:1.

Fig. 10. Conversion of CH4 and CO2 and amount of products for LaNiO3 in the dry reforming of methane. Catalyst: 0.02 g, GHSV = 3  105 L/kg h, reactants = CH4 + CO2 1:1.
 R. Pereñı´guez et al. / Applied Catalysis B: Environmental 93 (2010) 346–353 353

important to point out that upon reoxidation treatments most of

the LaNiO3 phase is recovered from the reduced Ni/La2O3 catalyst,
which could provide a convenient way to regenerate a waste
catalyst. The remarkable stability shown by this catalyst under
DRM reaction has been explained by its high resistance of the
nickel particles to be oxidized, while in the presence of water, these
metallic particles are gradually oxidized, decreasing linearly the
catalytic performance in the SRM reaction.

Acknowledgements

Authors want to express their gratitude to Spanish Ministry of

Fig. 11. In situ Ni K-edge XANES spectra of LaNiO3. All spectra have been collected in
situ at room temperature after the indicated treatments.
Science and Education and Junta de Andalucia for approval and
funding of research projects (ENE2004-01660, ENE2007-67926-
C02-01 and P07-FQM-02520), and the PhD grants of R. Pereñiguez
and V.G. de la Cruz. We also thank the staff of the ESRF BM25
beamline and ESRF facility for funding and helping with the XAS
experiments.

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