Applied Catalysis A: General 392 (2011) 36–44

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Applied Catalysis A: General

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

Effect of Ce/Zr composition and noble metal promotion on nickel based

Cex Zr1−x O2 catalysts for carbon dioxide methanation
Fabien Ocampo a , Benoit Louis a,∗ , Lioubov Kiwi-Minsker b , Anne-Cécile Roger a,∗
a
Laboratoire des Matériaux, Surfaces et Procédés pour la Catalyse LMSPC, UMR 7515 du CNRS, Université de Strasbourg, 25 rue Becquerel, 67087 Strasbourg Cedex 2, France
b
Group of Catalytic Reaction Engineering (GGRC-ISIC), Station 6, Ecole Polytechnique Fédérale de Lausanne (EPFL), Switzerland

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

Article history: Carbon dioxide methanation was carried out over a series of Ni–Cex Zr1−x O2 catalysts prepared by a pseudo
Received 8 July 2010 sol–gel method. The influence of CeO2 /ZrO2 mass ratio and noble metal addition was investigated. The
Received in revised form 4 October 2010 catalysts were subsequently characterized by means of XRD, TPR, BET, H2 -TPD and SEM-EDX. The modifi-
Accepted 20 October 2010
cation of structural and redox properties of these materials was evaluated in relation with their catalytic
Available online 30 October 2010
performances. All catalysts gave impressive CO2 conversion and extremely high selectivity to methane
(superior to 98%). Ni2+ incorporation into the CZ structure was proved to enhance catalysts specific activ-
Keywords:
ity. The global performance of the studied systems depended not only on the surface of available metallic
Methanation
Carbon dioxide
nickel but also on the composition of the support and on its modification by Ni2+ doping. As a result
Mixed oxides of these two phenomena, the Ni-based mixed oxide having a CeO2 /ZrO2 = 60/40 exhibited the highest
Ceria–zirconia catalytic activity, owing to an optimal Ni2+ /Ni0 ratio. Noble metal addition led to higher Ni dispersion,
Synthetic fuels resulting in a raise of both activity and catalyst life-time. It did not modify the support intrinsic activity.
The deactivation was shown not to be due to carbon deposits but rather to nickel particles sintering. The
investigated parameters thus allowed an improvement of the previously studied 5 wt% Ni–Ce0.72 Zr0.28 O2
system.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction magnitude higher than chemicals’ one, CO2 has to be mainly con-
verted into energy carriers such as methane [8–10,16], methanol
Human activities have resulted in an impressive raise in car- or dimethylether [11–13].
bon dioxide emissions in the atmosphere, estimated to reach 30 Gt CO2 methanation remains the most advantageous reaction with
worldwide in 2008 [1]. Because of its impact on the environ- respect to thermodynamics when compared to other hydrocar-
ment through the greenhouse effect [2], its fixation has gained a bons or alcohols production [17]. This reaction has been mainly
lot of interest in recent years and has become a world challenge investigated using Ni-based catalysts on various oxide supports
and priority. Among the viable solutions to mitigate CO2 emis- [8–10,18–21]. In our previous work [16], Ni based catalyst on
sions, many studies focused on two strategies: its capture and Ce0.72 Zr0.28 O2 mixed oxides (80% of CeO2 in weight), i.e., Ni(80–20),
storage [3–5] and its chemical recycling [6–13]. Indeed, raising were investigated for the first time in CO2 methanation reaction.
attempts are made by industries to consider CO2 as a valuable They turned out to be greatly efficient in terms of activity and
resource rather than a waste [13–15]. Hence, a compound without stability. Their astonishing performances were attributed to their
any value (or even negative value when considering carbon taxes) high oxygen storage capacity [22,23] and to their ability to highly
is converted into commercial chemicals or fuels. Furthermore, disperse nickel [24]. Ni2+ cations insertion into the Ce–Zr (CZ)
such companies involved in environmental issues now benefici- structure improved the redox properties [25] of the material and
ate from this growing positive image, thus leading to a further restricted the metal sintering, leading thus to a further improve-
increase in their benefits. It is noteworthy to add that increas- ment in their catalytic performance. 5Ni(80–20) (5% Ni in weight)
ing amounts of low-cost and concentrated CO2 will be available presented the highest specific activity, however it also exhibited
from carbon sequestration and storage units in a nearly future. the smallest degree of CO2 conversion and the lowest stability on
Taking into account that the consumption of fuels is two orders of stream during 150 h while 10Ni(80–20) was the most efficient. In
this study, we focused on 5 wt% Ni loaded material with the aim of
enhancing both its catalytic activity and stability.
∗ Corresponding author. Tel.: +33 3 6885 27 60; fax: +33 3 6885 27 61.
It is well admitted that the use of bimetallic systems [26] or
E-mail addresses: [email protected], [email protected] (B. Louis),
noble metals as rhodium and ruthenium generally has the specific
[email protected] (A.-C. Roger). ability to achieve this goal. According to the literature, they pro-

0926-860X/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2010.10.025
 F. Ocampo et al. / Applied Catalysis A: General 392 (2011) 36–44 37

mote oxide-based catalysts such as LaCoO3 [27] or Ni/MgO [28–29] flow of 50 mL min−1 . TPR profiles were presented as a function of
in hydrocarbon reforming reactions. Our group has observed the temperature herein, but H2 consumptions were calculated using
same effects on Co or Ni based Cex Zr1−x O2 (CZ) systems for ethanol the profiles expressed as a function of time for which the baseline
and methane reforming reactions respectively [30–31]. Therefore, returns to its initial value.
the H2 spillover from noble metals should restrict Ni oxidation in Scanning electron microscopy (SEM) micrographs were
the CO2 methanation reaction. It is known that Ce/Zr composition recorded on a JEOL FEG 6700F microscope working at 9 kV acceler-
is another factor that strongly influences the catalytic activity of CZ ating voltage. EDX spectra were acquired at an accelerating voltage
like systems in all types of reactions such as NO reduction in three- of 15 kV.
way catalysts [32], methane partial oxidation [33] or ethanol and The surface of metallic Ni (m2 ) was calculated from the
methane reforming [31,34]. amount of chemisorbed hydrogen, measured by H2 temperature-
In this work, noble metal and Ni based CZ catalysts were pre- programmed desorption (H2 -TPD) on a Micromeritics AutoChem II
pared in a powder form by a sol–gel like method [35]. Ni–CZ with (performed at GGRC-ISIC-EPFL-Switzerland). Prior to H2 -TPD, the
several CeO2 /ZrO2 (C/Z) mass ratios was prepared to determine the catalyst (200 mg) was pre-reduced at 400 ◦ C at a heating rate of
influence of structural modifications on catalytic activity and selec- 2 ◦ C min−1 and held for 1 h under a 10% H2 /Ar flow and another
tivity. In order to evaluate the impact of noble metal addition, Rh 90 min in pure Ar flow to desorb any H2 that might have been spilled
and Ru were loaded on 0 and 5Ni(80–20) systems. All catalysts were over the support. The catalyst was then cooled down to room tem-
tested in a fixed-bed down-flow reactor under the optimal reac- perature and H2 chemisorption pulses were performed. The sample
tion conditions settled down in our previous study [16]. Long-term was then purged with pure Ar to remove the reversibly adsorbed
experiments were performed during 150 h at 350 ◦ C to investigate H2 . The TPD analysis was carried out from room temperature to
the deactivation of the catalysts. 800 ◦ C at a heating rate of 15 ◦ C min−1 under pure Ar flow. The cal-
ibration of the system was based on mass 44 (corresponding to
CO2 ).
2. Experimental
Carbon deposits formed during long test runs were carried
out by means of temperature-programmed oxidation (TPO) on
2.1. Preparation of the catalysts
a Micromeritics Autochem II equipped with a mass spectrom-
eter (at GGRC-ISIC-EPFL-Switzerland). Prior to TPO, a TPD was
The fluorite oxides Ni–CZ, Ni–Rh–CZ and Ni–Ru–CZ were
performed up to 600 ◦ C under pure He, with a heating ramp of
synthesized by a pseudo sol–gel method, based on the ther-
15 ◦ C min−1 , using 50 mg of catalyst having reacted for 150 h in the
mal decomposition of propionate precursors. Ni loading was
CO2 methanation reaction in order to clean up the catalyst sur-
5 wt% (coded 5Ni) and noble metal loading was 0.5 wt%. In
face. Temperature was then cooled down to room temperature.
addition, several C/Z mass ratios were prepared: 4, 1.5 and
The TPO analysis was carried out up to 900 ◦ C, at a heating ramp of
0.25 referenced (80–20), (60–40) and (20–80) and referring to
15 ◦ C min−1 under a 2% O2 /He flow.
Ce0.72 Zr0.28 O2 , Ce0.5 Zr0.5 O2 and Ce0.14 Zr0.86 O2 in terms of molar
composition respectively. The starting materials were cerium(III)
acetate sesquihydrate, zirconium(IV) acetylacetonate, nickel(II) 2.3. Catalytic activity
acetate tetrahydrate, rhodium(II) acetate, ruthenium(III) acetylace-
tonate. These starting salts were individually dissolved in boiling The catalysts were reduced in situ before reaction in a 80% H2 /N2
propionic acid in a concentration of 0.12 mol L−1 in cation, at 100 ◦ C stream for 6 h with a total gas flow of 45 mL min−1 at 400 ◦ C with a
for 1 h, leading exclusively to propionate precursors. The boiling heating ramp of 2 ◦ C min−1 .
solutions were mixed during 2 h under reflux and then the sol- Carbon dioxide methanation was conducted at atmospheric
vent was evaporated until a resin was obtained. Finally, the resin pressure in a fixed-bed down-flow reactor within the temperature
was calcined under air at 500 ◦ C for 6 h, with a heating ramp of range from 150 to 400 ◦ C. Five injections were performed within
2 ◦ C min−1 . 25 min and an average value was calculated each 50 ◦ C. A thermo-
couple was inserted in the furnace to measure the pretreatment and
reaction temperatures in situ. The reactor was heated in a tubular
2.2. Characterization of the catalysts furnace monitored by a temperature controller.
The flow of reactants was regulated by calibrated mass flow
The obtained metal contents in CZ mixed oxides were deter- controllers (Brooks). H2 and CO2 were mixed at a H2 :CO2 ratio of
mined by Inductively Coupled Plasma (ICP) for elemental analysis 4:1 and N2 was added as an internal standard. They were intro-
(Service Central d’Analyse de Vernaison, CNRS, France). duced into the reactor at a molar ratio of H2 :CO2 :N2 = 36:9:10 and
Specific surface areas (SSA) of the different catalysts were deter- the total flow rate was set to 55 mL min−1 . 150 mg of catalyst was
mined by N2 adsorption–desorption measurements at 77 K by loaded into the reactor. The gas hourly space velocity was kept
employing the Brunauer–Emmet–Teller (BET) method (Micromet- fixed at 43,000 h−1 . The feed and products were analyzed on-line
rics sorptometer Tri Star 3000). Prior to N2 adsorption, the sample by a micro gas chromatograph (Hewlett Packard, Quad Series Micro
was outgassed at 200 ◦ C overnight to desorb moisture adsorbed on GC) equipped with TCD: alumina, poraplot and molecular sieve
the surface and inside the porous network. 5 Å columns. CO2 conversion and CH4 selectivity were defined as
X-ray diffraction patterns (XRD) were recorded on a Bruker D8 follows:
Advance diffractometer with a VANTEC detector side and Ni filtered  CO2

Cu K␣ radiation (1.5418 Å) over a 2 range of 10–90◦ and a position XCO2 (%) = 1− × 100 (carbon balance)
sensitive detector using a step size of 0.05◦ and a step time of 1 s. The CO2 +CH4 +CO+2C2 H6
crystallite size of the samples was evaluated from X-ray broadening or
by using the well-known Debye–Scherrer equation [36].  CO2 × (N2 )in

Temperature-programmed reduction (TPR) was conducted on a XCO2 (%) = 1− × 100 (internal standard)
N2 × (CO2 )in
Micromeritics AutoChem II to study the reducibility of the catalysts.
TPR measurements were carried out on 100 mg of catalyst, loaded  H2 × (N2 )in

in a quartz U-tube and heated from room temperature to 900 ◦ C XH2 (%) = 1− × 100
at a heating rate of 15 ◦ C min−1 under 10% H2 /Ar with a total gas N2 × (H2 )in
38 F. Ocampo et al. / Applied Catalysis A: General 392 (2011) 36–44

Table 1
Elemental analysis obtained by ICP and SSA values obtained by BET.

Catalyst Metal contents (wt%) and C/Z ratio: experimental value–theoretical value SSA (m2 g−1 )
a
Ni C/Z ratio Noble metal

5Ni(80–20) 4.71–5.00 4.25–4.00 / 70

5Ni(60–40) 4.80–5.00 1.59–1.50 / 62
5Ni(20–80) 4.91–5.00 0.26–0.25 / 78
5Ni–0.5Rh(80–20) 4.77–5.00 4.24–4.00 0.50–0.50 86
5Ni–0.5Ru(80–20) 4.75–5.00 4.25–4.00 0.51–0.50 82
a
C/Z ratio refers to CeO2 /ZrO2 weight ratio.

CH4
SCH4 (%) = × 100
CO + 2C2 H6 + CH4

where X is the conversion, S the selectivity, P and (P)in the reac-

tant/product molar quantities at the exit and at the entrance of the
reactor respectively.
The temperature at which half of carbon dioxide was converted,
T50 value, was used to compare catalytic activities. T50 was deter-
mined under quasi steady state conditions.

3. Results and discussion

Fig. 2. XRD patterns of (a) 5Ni(80–20), (b) 5Ni–0.5Rh(80–20) and (c)
3.1. Physical properties of the catalysts 5Ni–0.5Ru(80–20).

Table 1 summarizes the Ni and noble metal contents analyzed in Fig. 2 presents the XRD patterns of 5Ni(80–20) catalysts loaded
the mixed oxides, as well as the C/Z mass ratio which is compared to with noble metal after calcination at 500 ◦ C for 6 h. Again, these
the theoretical ones. Ni loadings were always slightly lower than patterns perfectly matched the face-centered cubic Ce0.75 Zr0.25 O2
expected, and Ce was in excess with respect to Zr, probably due fluorite structure and no segregation phase was observed. Bulk NiO
to the hygroscopicity of the starting salts. Nevertheless, all values was also detected on these samples.
remained consistent, close to the theoretical ones. Table 2 gives CZ and NiO crystallite sizes, as well as the lat-
Fig. 1 shows the XRD patterns of 5Ni–CZ systems after calcina- tice parameters of the fluorite structures considered as cubic and
tion at 500 ◦ C for 6 h. The diffractograms of 5Ni(80–20), 5Ni(60–40) calculated by using the four most intense reflections.
and 5Ni(20–80) respectively matched the patterns of the face- Fig. 3 displays CZ experimental cubic lattice parameters versus
centered cubic Ce0.75 Zr0.25 O2 , the tetragonals Ce0.5 Zr0.5 O2 and Ce wt% for Ni-free and for 5Ni loaded catalysts synthesized under
Ce0.16 Zr0.84 O2 fluorite structures (JCPDS No. 28-0271, 38-1436 and the same preparation and calcination conditions. The calculated
38-1437 respectively). The determination of solid solution crys- value of the pseudo-cubic lattice parameter was 5.35, 5.29 and
talline phases remains a rather difficult task, and requires further 5.20 Å respectively for the following supports: (80–20), (60–40)
characterization techniques than XRD [37]. To further investigate and (20–80). The pseudo-cubic lattice parameter of the CZ mixed
the modification of CZ lattices, we have therefore calculated a oxides linearly increased with Ce content. Indeed, Ce4+ ionic radius
pseudo-cubic lattice parameter for all catalysts, without assum- value in cubic coordination is higher than the one of Zr4+ (0.97
ing that it is the real crystalline phase. In addition, no segregation versus 0.84 Å). Although previously mentioned trend was still valid,
phases such as CeO2 or ZrO2 were detected, thus indicating the the pseudo-cubic lattice parameter was lower for all Ni-containing
formation of a homogeneous solid solution. The patterns also exhib- oxides than for corresponding Ni-free samples. It clearly appears
ited small reflections attributed to NiO, meaning that nickel is at from Fig. 3 that the deviation observed between Ni–CZ and CZ sys-
least partially present as NiO species outside the fluorite structure. tems was enhanced for low Ce content with values of 5.34, 5.27 and
The intensity of NiO diffraction peaks differed and declined with 5.15 A for 5Ni(80-20), 5Ni(60-40) and 5Ni(20-80), respectively.
a decrease in Zr content due to the competition between Zr4+ and
Ni2+ cations to enter the CZ structure.

Fig. 3. Experimental CZ lattice parameters versus Ce wt% (a) Ni-free systems and
Fig. 1. XRD patterns of (a) 5Ni(80–20), (b) 5Ni(60–40) and (c) 5Ni(20–80). (b) 5Ni-loaded systems.
 F. Ocampo et al. / Applied Catalysis A: General 392 (2011) 36–44 39

Table 2
Crystallite sizes (D) and CZ lattice parameter (a), obtained by XRD calculations, before and after reaction.

Catalyst D CeZrO2 (nm) D NiO (nm) CZ ap-cubic (Å) D Ni (nm) ara CZ ap-cubic (Å) ara

5Ni(80–20) 6.3 26.3 5.34 37.2 5.35

5Ni(60–40) 6.0 20.8 5.27 39.0 5.28
5Ni(20–80) 6.4 14.4 5.15 35.0 5.16
5Ni–0.5Rh(80–20) 6.3 16.1 5.34 31.0 5.35
5Ni–0.5Ru(80–20) 6.4 18.7 5.34
a
ar, after reaction.

According to the literature, other cations having a lower oxi- by EDX analysis. It detected 4.45 wt% Ni and gave a C/Z mass ratio
dation of state (Fe3+ , Co2+ , Ni2+ , Ca2+ ) can be incorporated in pure of 4.38. These results are in agreement with XRD calculations and
ceria or CZ mixed oxides structure [16,38–40]. The solubility of such elemental analyses summarized in Tables 1 and 2.
cations into the CZ structure strongly depends on their charge, and
their coordination in the lattice. When substituted, cations present 3.2. Catalysts reducibility
in octahedral coordination lead to local perturbations of the Ce4+
environment, thus rendering difficult the phase determination by In our previous study [16], Ni(80–20) catalysts were char-
XRD [37]. For Ce–Ca oxides, a pyrochlore structure was reported acterized by TPR. It resulted that Ni loading greatly increased
[40]. It is well admitted the reduction of fluorites tend to form surface CeO2 reducibility, shifting the hydrogen consumption peak
pyrochloric-like structures [41–42], generating oxygen vacancies assigned to this species from 570 to around 320 ◦ C. Two other peaks
and thus favouring the oxygen mobility in the material [43]. For were observed around 360 and 450 ◦ C respectively ascribed to bulk
the same reasons, doping a CZ sample with transition metals is NiO present at the surface of the catalyst and to Ni2+ cations incor-
also known to enhance the redox properties of the material [39]. In porated into the fluorite structure. These conclusions were drawn
our case, the decrease in the lattice parameter by Ni doping would
be consistent with octahedral Ni2+ (ionic radius of 0.69 Å) incorpo-
ration into the CZ lattice. Higher deformation at low Ce content is
in agreement with results published by Ambroise et al. for Co–CZ
oxides [39]. Indeed, it was demonstrated that octahedral Co2+ sub-
stitution rate into the CZ lattice was strongly dependent on the CZ
composition, and favoured at low Ce content.
Besides, the size of NiO crystallites decreased when reducing the
Ce content in the mixed oxide composition (Table 2), decreasing
from 26.3 to 14.4 nm when going from 5Ni(80–20) to 5Ni(20–80).
Indeed, the more nickel was incorporated into the CZ structure, the
less was present as bulk NiO at the surface of the catalyst. A decrease
in NiO quantity led to a lower extend of sintering of its particles and
thus to a better dispersion on the surface of the material.
Structural modifications were observed when a noble metal
was loaded on 5Ni(80–20). The lattice parameter of 5Ni(80–20)
remained unchanged at 5.34 Å after noble metal addition. However
bulk NiO crystallite size largely decreased, from 26.3 nm to 16.1 and
18.7 nm for 5Ni–0.5Rh(80–20) and 5Ni–0.5Ru(80–20) respectively.
These observations suggest that Rh or Ru enabled a better disper-
sion of NiO, which was mostly rejected out of the CZ structure.
Table 2 also displays XRD results after reaction. One can observe
that both Ni crystallite size and CZ lattice parameter were raised
after reaction for all catalytic systems. These results will be dis-
cussed in Section 3.5.
The specific surface areas of the studied mixed oxides are dis-
played in Table 1. All SSA values varied from 62 to 78 m2 g−1 within
the Ni–CZ series, which is in agreement with values given in the
literature for Ni–CZ catalysts also prepared by a pseudo sol–gel
method [44,45], 5Ni(60–40) exhibited the lowest one (62 m2 g−1 ).
This result can be explained by the existence of two antagonistic
phenomena. On the one hand, the SSA of the supports decreased
when raising Zr content in the CZ composition (95, 64 and 39 m2 g−1
were respectively obtained for (80–20), (60–40) and (20–80) mate-
rials). In contrast, as previously observed by XRD, NiO particle size
diminished when Zr content was increased, meaning that the SSA
increased when raising Zr content.
Fig. 4 shows SEM micrographs of 5Ni(80–20) fresh catalyst. NiO
particles were found to be more or less regular at the surface of the
sample, with an average in particle diameter of 30 nm as seen in
Fig. 4a. At higher magnification, CZ particles were observed with
extremely homogeneous size exhibiting a diameter of 6 nm as seen Fig. 4. SEM images of 5Ni(80–20): (a) Ni particles and (b) CeZr particles and EDX
in Fig. 4b. The elemental composition of the material was obtained analysis.
40 F. Ocampo et al. / Applied Catalysis A: General 392 (2011) 36–44

Table 3
Hydrogen consumption and ceria reducibility obtained by TPR and Ni0 surface cal-
culated from H2 -TPD.

Catalyst H2 con- Ce3+ /Cetot after Ni0 surface

sumption TPR (m2 gcat −1 )
(mmol/gcat )

5Ni(80–20) 2.96 0.64 3.8

5Ni(60–40) 2.76 0.75 3.1
5Ni(20–80) 1.70 0.88 1.6
5Ni–0.5Rh(80–20) 3.45 0.76
5Ni–0.5Ru(80–20) 3.06 0.66 4.8

it is also noteworthy that no contribution from incorporated Ni2+

was observed at higher temperatures on the TPR profile. In agree-
Fig. 5. TPR of (a) 5Ni(80–20), (b) 5Ni(60–40) and (c) 5Ni(20–80).
ment with XRD results, it thus appears that Ni2+ cations were not
incorporated into the CZ structure in this case.
according to several TPR studies undertaken for this type of mate- Table 3 shows H2 consumption results obtained by TPR. Assum-
rials [37,46–49]. ing that the different metals were completely reduced after TPR
Fig. 5 shows the TPR profiles of 5Ni–CZ systems. For 5Ni(80–20), and taking into account the mass contents given by ICP results, the
the peak corresponding to incorporated Ni2+ was barely observed, reducibility of CeO2 was evaluated for the different catalysts. H2
meaning that Ni was mostly present at the surface of the support consumption was strongly related to C/Z mass ratio, in agreement
as NiO phase. For 5Ni(60–40), the peak located at 450 ◦ C was much with several studies in the literature [51,52] which concluded that
more important and at the opposite, the peak at 375 ◦ C and ascribed the addition of zirconia to ceria increases the oxygen mobility in
to surface NiO is smaller. This suggests that more Ni2+ cations were the ceria lattice and improves the process of vacancy formation,
able to substitute themselves for Zr4+ , thus decreasing the quan- rendering the material more reducible. Calculations gave the fol-
tity of NiO at the surface when compared to 5Ni(80–20). Likewise, lowing results: 64, 78 and 88% of CeO2 reduced for 5Ni(80–20),
the same observation was further amplified for 5Ni(20–80) system. 5Ni(60–40) and 5Ni(20–80) respectively. CeO2 reducibility was also
Indeed, the major peak was centered at 650 ◦ C and no typical peak clearly improved by the presence of a noble metal and particularly
for surface NiO was observed at the top of the small one at 400 ◦ C Rh, as this value was 2.96 mmol/gcat for 5Ni(80–20) against 3.06 and
ascribed to surface CeO2 . This suggests that nickel was mostly incor- 3.45 mmol/gcat when the system was respectively promoted by Ru
porated into the CZ structure as Ni2+ cations. These observations are and Rh. Indeed, the respective proportions of CeO2 reduced/total
in agreement with the lattice parameter calculations given by XRD. CeO2 were calculated to be 64, 66 and 76%.
Fig. 6 displays the TPR profiles of noble metal-promoted cat- Fig. 7 displays the H2 -TPD profiles from the reduced support
alytic systems. Rh and Ru addition shifted the H2 consumption (0Ni(80–20)) and 5Ni loaded systems with various C/Z mass ratios.
peaks to much lower temperatures when compared to both pure One cannot completely rule out several phenomena that render H2 -
CeZrO2 mixed oxide and Ni-loaded catalysts, in accordance with TPD results on metal–CZ systems complex to analyze: H2 spillover
the literature. This suggests that noble metal promoted the reduc- effect, electronic deactivation due to the presence of Ce3+ or decora-
tion of this support as previously reported [32,50]. Indeed, pure tion and alloys formation [53,54]. However, our aim was to evaluate
CZ (80–20) exhibited two peaks at 540 and 720 ◦ C corresponding the role of the support for catalysts belonging to the same series
respectively to surface and bulk CeO2 reduction. In comparison, (Ni–CZ materials) and to determine a general trend using relative
these peaks were observed at 185 and 345 ◦ C over 0.5Rh(80–20). values. The amount of hydrogen chemisorbed on 0Ni(80–20) was
It is noteworthy that all noble metal-promoted samples exhibited very low when compared to 5Ni(80–20) (46 versus 1050 ␮L/gcat ).
the same type of profile, with one peak between 140 and 190 ◦ C It was thus considered for Ni containing samples, that all H2 was
and another around 330 ◦ C. The first peak was attributed to surface chemisorbed on metallic nickel (support contribution could be
Ce and noble metal oxides reduction. As noble metals were loaded neglected). On the basis of these conclusions, the surface of metal-
in small amounts (0.5 wt%), these peaks can be mainly ascribed to lic nickel (m2 ) was calculated and listed in Table 3. This surface
the reduction of CeO2 in strong interaction with Rh or Ru. It can be was 3.8, 3.1 and 1.6 m2 gcat −1 for C/Z mass ratios of 80/20, 60/40
noted that the lowest reduction temperature was achieved by Ru and 20/80 respectively. Even though NiO crystallite size decreased
promotion. The second peak was attributed to bulk CeO2 and sur- when lowering C/Z mass ratio (Table 2), Ni0 surface decreased at
face NiO reduction, and was observed at lower temperatures than the same time. This observation is consistent with Ni2+ insertion
for noble metal-free catalysts (around 345 versus 370 ◦ C) suggest-
ing a strong interaction between Ni and the noble metal. Finally,

Fig. 7. H2 -TPD profiles of pre-treated (a) 0Ni(80–20), (b) 5Ni(20–80), (c) 5Ni(60–40)
Fig. 6. TPR of (a) 0.5Rh(80–20), (b) 5Ni–0.5Rh(80–20) and (c) 5Ni–0.5Ru(80–20). and (d) 5Ni(80–20), and (e) 5Ni–0.5Rh(80–20) catalysts.
 F. Ocampo et al. / Applied Catalysis A: General 392 (2011) 36–44 41

Fig. 8. CO2 conversion versus temperature over 5Ni–CZ catalytic systems. Fig. 9. CO2 conversion versus time at 350 ◦ C over 5Ni–CZ catalytic systems.

3.3.2. Catalytic activity versus time on stream

proportions. Metallic nickel surface is thus inversely proportional
Fig. 9 shows the catalytic activity during 150 h on stream at
to the amount of Ni2+ inserted into the CZ structure.
350 ◦ C for these materials. The main results are also summarized
in Table 4. As previously mentioned, selectivity towards methane
3.3. Effect of C/Z mass ratio on catalytic performance appeared to be directly proportional to CO2 conversion and was
extremely high during the whole run, remaining above 94.7% for
3.3.1. Catalytic activity versus temperature 5Ni(80–20) and above 97.8% for the others. The other products were
Selectivity towards CH4 was always proportional to CO2 con- CO and C2 H6 . The order in performance observed in short run tests
version on Ni–CZ systems for all temperatures. The catalytic was confirmed, and remained the same for catalyst stability.
performances were therefore evaluated in terms of CO2 conversion The initial degrees of conversion for 5Ni(80–20), 5Ni(60–40)
(%) for short test runs. and 5Ni(20–80) were 71.5, 79.7 and 73.0% respectively. 5Ni(80–20)
The catalytic activity of 5Ni–CZ catalysts with C/Z mass ratios never stabilized and slowly deactivated with a constant slope end-
from 4 to 0.25 was studied at temperatures varying from 150 ing up with 41.1% CO2 conversion. Although 5Ni(20–80) showed a
to 400 ◦ C and a GHSV of 43,000 h−1 . Fig. 8 shows CO2 conver- similar starting activity to 5Ni(80–20), its deactivation curve was
sion versus temperature. The same global observations were made less steep with 54.3% CO2 conversion after 100 h versus 46.2% for
when compared to 5–15Ni(80–20) systems [16]. Indeed, no activ- the former. Its last stage was extremely stable with only 1.9% CO2
ity was detected at 150 ◦ C and very little CO2 conversion was conversion loss between 100 and 150 h on stream. In contrast,
achieved at 200 ◦ C (below 0.6%). A further raise in temperature 5Ni(60–40) outperformed the two other systems during the whole
led to an increase in CO2 conversions. T50 value, corresponding to course of the run, and with respect to all catalytic properties: a
the temperature at which half of carbon dioxide was converted, better CO2 conversion thus a higher specific activity together with
was used to compare catalytic activities. This value was 320, 287 higher CH4 selectivity, and also an improved stability. The initial
and 311 ◦ C for 5Ni(80–20), 5Ni(60–40) and 5Ni(20–80) respec- degree of conversion was nearly 80%, then slightly decreased to
tively. It clearly established an order in the catalyst performances 70.6% after 50 h and to 65.9% after 150 h. This suggests that the opti-
as follows: 5Ni(80–20) < 5Ni(20–80) < 5Ni(60–40). These catalytic mal proportion of incorporated Ni2+ towards surface Ni0 obtained
systems respectively reached 69.0, 71.9 and 80.5% at 350 ◦ C versus for 60/40 as C/Z mass ratio optimized not only the catalytic conver-
89.8% given by thermodynamic calculations. It is noteworthy that sion but also its stability towards deactivation.
owing to thermodynamic limits, no significant improvement could
be observed at 400 ◦ C with a maximal CO2 conversion of 81.8% over 3.4. Effect of noble metal promotion on catalytic performance
5Ni(60–40).
Owing to XRD and TPR results, one can argue that more nickel 3.4.1. Catalytic activity versus temperature
was inserted in the 5Ni(60–40) when compared to 5Ni(80–20), Noble metal-promoted Ni(80–20) systems were evaluated via
explaining its higher efficiency. In contrast, this trend is no longer the same manner. Fig. 10 presents CO2 conversion versus temper-
valid when passing from 5Ni(60–40) to 5Ni(20–80) as the latter ature. About 4.75 wt% Ni was detected for these catalysts and they
exhibited lower catalytic activity, even though Ni2+ insertion was displayed a lattice parameter of 5.34 Å (Tables 1 and 2), thus indi-
rendered easier. Indeed, metallic Ni0 appears to be the active phase cating that nearly all Ni was rejected out of the CZ structure. These
and its availability at the surface of the support was hindered, as observations suggest that an equivalent quantity of Ni was present
the major part of Ni species was incorporated into the CZ struc- on their surface, rendering their comparison easier.
ture for 5Ni(20–80). Therefore, a compromise between the two Ni Both Rh and Ru enhanced the catalytic activity and presented
species has to be found in order to optimize the catalyst activity. the same behaviour till 300 ◦ C. At 350 ◦ C they respectively exhib-
According to Bahr’s mechanism proposition for CO2 methanation ited 77.0 and 74.3% CO2 conversion versus 69.0% for the noble
[55], CO2 must be activated into CO prior to methanation. As men- metal-free sample. T50 value for the latter system was 320 ◦ C versus
tioned, the cations inserted in the CZ structure improved the redox 294 ◦ C for the two others. The order in performance was thus as
properties of the mixed oxide [25], by oxygen vacancies genera- follows: 5Ni–0.5Rh(80–20) > 5Ni–0.5Ru(80–20) > 5Ni(80–20). The
tion. Incorporated Ni2+ are thus believed to favour the first step improvement in activity gained by the promotion of noble metals
of the reaction. In contrast, metallic Ni is commonly considered to can be assigned to two properties of these materials. First, a higher
be the active phase in the methanation reaction [19], dissociating dispersion of the Ni active phase on the surface of the support.
hydrogen which then reduces the activated CO into CH4 . Indeed, before reduction, NiO average particle size was 26.3 nm
42 F. Ocampo et al. / Applied Catalysis A: General 392 (2011) 36–44

Table 4
−1
Effect of C/Z mass ratio and noble metal promotion on catalyst activity measured in terms of specific activity in molCO2 transf gNi s−1 for CO2 conversion and on selectivities.
And also, C deposit evaluated by means of TPO.

Catalyst Time on stream (h) Specific activity X (%) S (%) %Ca

−1
(molCO2 conv gNi s−1 )–(mmolCO2 conv m−2 s−1 )

CO2 H2 CH4 CO C2 H6

5Ni(80–20) Initial 2.20–26.99 71.5 69.3 98.5 0.9 0.6 1.8 × 10−4
50 1.66 54.0 52.1 97.2 2.2 0.6
150 1.27 41.1 38.4 94.7 4.6 0.7
5Ni(60–40) 0 2.41–37.95 79.7 76.1 99.3 0.6 0.1
50 2.14 70.6 68.2 98.6 1.2 0.2
150 2.00 65.9 64.7 98.2 1.6 0.2
5Ni(20–80) Initial 2.16–67.13 73.0 70.9 99.0 0.9 0.1 1.3 × 10−4
50 1.83 61.8 60.2 98.5 1.3 0.2
150 1.55 52.4 50.1 97.8 2.0 0.2
5Ni–0.5Rh (80–20) Initial 2.37–23.57 77.8 76.3 99.2 0.8 0 2.7 × 10−4
50 2.03 66.5 62.9 98.2 1.7 0.1
150 1.86 61.2 57.5 97.5 2.3 0.2
a
Moles of Cdeposited by moles of CO2transformed determined by TPO.

over 5Ni(80–20) versus 16.1 and 18.7 nm with 0.5 wt% Rh and Ru dation in methane steam reforming [56,57] via H2 spillover from
promotion respectively (Table 2). Thus, noble metal enhanced the noble metal. Although the atmosphere is rather reductive in car-
surface/volume ratio of the Ni0 active phase after reduction improv- bon dioxide methanation, metallic Ni could be gradually reoxidized
ing the catalyst activity. Secondly, TPR analyses showed that Ni by CO2 or by water produced, deactivating the catalyst. Moreover,
loading on CZ mixed oxides enhanced CeO2 reducibility. Noble Rh was found to be more effective for restricting Ni oxidation [47]
metal addition resulted in a further raise in its reducibility ren- which could explain the higher stability towards deactivation of Rh
dering CeO2 reduction easier but also increasing the proportion of promoted system in comparison to Ru promoted one.
ceria reduced. This means an improvement in the redox properties 0.5Rh(80–20) was investigated to evaluate the catalytic activity
of the material favouring oxygen transfer which would be required of a Ni-free CZ system containing Rh. It started with a relatively low
for CO2 activation. 28.5% CO2 conversion and quickly dropped to stabilize at around 5%.
5Ni–0.5Rh(80–20) system exhibited higher catalytic activity when
3.4.2. Catalytic activity versus time on stream compared to a simple addition of 5Ni(80–20) and 0.5Rh(80–20).
Fig. 11 displays the catalytic activity of noble metal-promoted Although this effect was barely noted at the beginning of the test,
systems versus time on stream. Both Rh and Ru helped to increase it increased with time on stream. For instance, 5Ni–0.5Rh(80–20)
catalytic conversion. 5Ni–0.5Rh(80–20) and 5Ni–0.5Ru(80–20) showed 65.7% CO2 conversion after 60 h on stream, while only
started to convert CO2 at 78% versus 71.5% over 5Ni(80–20). These 56.7% was obtained when adding together the activity of the two
observations are in agreement with the short term runs. It can be other catalysts. From these observations, one can argue a synergetic
added that noble metal addition enabled a large raise in stabil- effect between Ni and Rh.
ity. After 150 h on stream, Rh and Ru promoted materials ended Table 4 presents the specific activity values for CO2 conversion
up with 61.1 and 55.9% CO2 conversion respectively, whereas only defined as the number of CO2 molecules converted per gram of
41.1% was achieved for the noble metal-free sample. This cannot be nickel and per second over several catalysts evaluated in this work.
explained by a higher stabilization of the Ni0 phase on the support As all mentioned systems contained about 5 wt% Ni, this value was
surface as the three previously mentioned catalysts exhibited the directly proportional to the catalytic activity observed. 5Ni(60–40)
same Ni particle size after reaction (around 30 nm based on XRD and 5Ni–0.5Rh(80–20) allowed major improvements compared to
calculations). However, Nurunnabi et al. demonstrated that noble 5Ni(80–20), with specific activity values after 150 h on stream just
metal promotion over NiO–MgO was effective for inhibiting Ni oxi- below the starting value encountered over 5Ni(80–20) catalyst
(2.00 and 1.86 versus 2.20 molCO2 converted gNi−1 s−1 respectively).

Fig. 10. CO2 conversion versus temperature over 5Ni(80–20) and noble metal- Fig. 11. CO2 conversion versus time at 350 ◦ C over Rh–CZ, Ni–CZ, Ni–Rh–CZ and
promoted catalysts. Ni–Ru–CZ catalytic systems with a C/Z mass ratio of 80–20.
 F. Ocampo et al. / Applied Catalysis A: General 392 (2011) 36–44 43

It was proven that C/Z mass ratio influenced catalytic activ- parameter could also result from the partial reduction of Ce4+ into
ity, and an order in performance was established as follows: Ce3+ , as the ionic radius from the latter is larger.
60/40 > 20/80 > 80/20. On the other hand, metallic nickel surface Moreover, the redox properties of the support are believed to
was directly proportional to Ce content (80/20 > 60/40 > 20/80). One favour CO2 molecules activation during the reaction first step. In the
can therefore argue that the catalytic performance is related to a case of highly basic catalysts, it could thus be considered that CO2
combination of different phenomena. With the aim of better under- molecule is strongly chemisorbed via the C-atom onto the support
standing the catalyst behaviour, the specific activity was expressed active site, thus causing catalyst deactivation. Further studies are
in mmol of CO2 converted per square meter of metallic nickel and under progress to investigate the deactivation(s) mode(s) by means
per second (Table 4). Based on H2 -TPD results, it was only calculated of additional characterization techniques.
at the beginning of the reaction as fresh catalysts were used for H2 -
TPD experiments and as nickel sintering was observed during this
4. Conclusions
reaction [16]. 5Ni(80–20), 5Ni(60–40) and 5Ni(20–80) respectively
exhibited values of 26.99, 37.95 and 67.13 mmolCO2 conv m−2 s−1 .
In this study, 5 wt% Ni based Cex Zr1−x O2 with C/Z mass ratios
The aforementioned specific activity was clearly proportional to
ranging from 4 to 0.25 and Ru or Rh promoted Ce0.72 Zr0.28 O2 cat-
Zr content in the CZ composition, emphasizing the effect of the
alysts were synthesized. The influence of C/Z composition and
support in catalyst performance in CO2 methanation reaction. The
noble metal addition on the physical properties and on the cat-
efficiency of Ni0 thus appears to highly depend on the amount
alytic behaviour of the materials in carbon dioxide methanation
of Ni2+ cations incorporated into the CZ structure. Studies are in
was investigated.
progress in order to determine whether this insertion boosts the
The catalytic activity and stability of these systems were found
catalytic results by improving the material redox properties or by
to highly depend on one major parameter: the C/Z composition of
restricting the sintering effect.
the mixed oxide determining the proportion between Ni2+ cations
5Ni(60–40) thus appeared to present an optimal intermediate
incorporated into the CZ fluorite structure and surface Ni0 . Ni2+
between the C/Z mass ratios studied, exhibiting a sufficient metallic
inserted were proved to enhance catalysts specific activity. The
nickel surface (higher than 5Ni(20–80) one) promoted by a bene-
global performance of the studied systems depended not only on
ficial effect of the support (more important than 5Ni(80–20) one).
the available metallic nickel surface but also on the composition
These results reinforced previous observations showing the need
of the support and on its modification by Ni2+ doping. As a result,
of finding a compromise between Ni2+ and Ni0 species in order to
it was found that a compromise between these two nickel species
optimize the catalytic system.
had to be done in order to optimize the catalytic system. Accord-
Concerning noble metal addition, it can be noticed that
ing to this observation, a C/Z mass ratio of 60/40 led to the best
5Ni–0.5Rh(80–20) exhibited a similar specific activity when com-
Ni2+ /Ni0 ratio, resulting in the best catalytic activity. Likewise, a
pared to 5Ni(80–20) (26.99 and respectively). One can therefore
higher stability towards deactivation was achieved.
argue that noble metal addition did not lead to a modification of the
Concerning noble metal addition, a synergy was observed
support and that it only affected nickel dispersion on the catalyst
between Rh or Ru and Ni over 5Ni(80–20), enabling an improve-
surface.
ment in both activity and catalyst life-time. These improvements
were ascribed to a better nickel dispersion induced by noble metal
promotion, enhancing Ni0 surface/volume ratio.
3.5. Catalyst deactivation
Catalytic deactivation due to carbonaceous deposits could be
excluded, and appeared to be induced by nickel particles sinter-
The deactivation of the studied Ni–Rh/Ru–CZ catalytic systems
ing during the reaction. However, support modifications as Ni2+
in the CO2 methanation reaction could result from metal deactiva-
rejection out of the CZ structure could also play a role in this pro-
tion.
cess. Further studies are under progress to better understand the
In Table 4, carbon deposit was evaluated in relation
deactivation process.
to the amount of CO2 transformed and is expressed as
molCdep /molCO2 trasnf . The values obtained were extremely low
(below 3 × 10−4 %), meaning that a very small amount of carbon Acknowledgments
was deposited on the surface of the catalysts. One can therefore
consider that carbon deposit was not the cause of the catalytic This work was financially supported by the French Government
deactivation. in the frame of a Ministerial Grant and by the EU commission within
Noble metals are known to be efficient in restricting the sin- IDECAT network of excellence. The authors are grateful to Yvan
tering effect. In addition, Rh or Ru addition to Ni–CZ systems Zimmermann for his technical assistance.
enabled an increase in NiO dispersion (Table 2) and catalytic sta-
bility (Fig. 11), which could mean that catalytic deactivation was References
due to this peculiar phenomenon. This idea was further reinforced
by XRD measurements after reaction. Indeed, in Table 2, one can [1] International Energy Agency (IEA), World Energy Outlook, 2008.
[2] C. Creutz, E. Fujita, Carbon Dioxide as a Feedstock, Carbon Management, The
observe that Ni crystallite size increased after reaction for all cata- National Academic Press, 2001.
lysts, thus proving the sintering of the particles. [3] Y. Wu, C.W. Chan, Expert Syst. Appl. 36 (2009) 9949–9960.
However, it was proved that the CZ support played an important [4] K. van Alphen, J. van Rujiven, S. Kasa, M. Hekkert, W. Turkenburg, Energy Policy
37 (2009) 43–55.
role in the system activity owing to its structural properties. Thus,
[5] S. Walspurger, L. Boels, P.D. Cobden, G.D. Eizinga, W.G. Haije, R.W. van den
deactivation could also result from support modification during the Brink, ChemSusChem 1 (2008) 643–650.
run. [6] C. Song, Catal. Today 115 (2006) 2–32.
[7] I. Omae, Catal. Today 115 (2006) 33–52.
It was noticed that CZ lattice parameter slightly increased for all
[8] G.D. Weatherbee, C.H. Bartholomew, J. Catal. 68 (1981) 67–76.
catalysts after reaction (Table 2). This could be due to Ni2+ rejec- [9] D.E. Peebles, J.M. Goodman, J.M. White, J. Phys. Chem. 87 (1983) 4378–4387.
tion out of the fluorite structure during the reaction. As previously [10] M. Yamasaki, H. Habazaki, K. Asami, K. Izumiya, K. Hashimoto, Catal. Commun.
discussed, incorporated Ni2+ cations improved catalytic activity. 7 (2006) 24–28.
[11] M. Kilo, J. Weigel, A. Wokaun, R.A. Koeppel, A. Stoeckli, A. Baiker, J. Mol. Catal.
Any rejection out of the structure could therefore lead to a loss A 126 (1997) 169–184.
of catalytic performance. Nevertheless, the decrease in CZ lattice [12] I. Melián-Cabrera, M. López Granados, J.L.G. Fierro, J. Catal. 210 (2002) 273–284.
44 F. Ocampo et al. / Applied Catalysis A: General 392 (2011) 36–44

[13] G.A. Olah, A. Goeppert, G.K.S. Prakash, Beyond Oil and Gas: The Methanol Econ- [36] H.P. Kulg, L.E. Alexander, X-ray Diffraction Procedures, John Wiley and Sons,
omy, Wiley-VCH, Verlag GmbH and Co. KGaA, Weinheim, Germany, 2006. New York, 1954.
[14] G. Centi, S. Perathoner, Catal. Today 148 (2009) 191–205. [37] T. Montini, A. Speghini, L. De Rogatis, B. Lorenzut, M. Bettinelli, M. Graziani, P.
[15] S.K. Ritter, Chem. Eng. News 85 (2007) 11–17. Fornasiero, J. Am. Chem. Soc. 131 (2009) 13155–13160.
[16] F. Ocampo, A.C. Roger, B. Louis, Appl. Catal. A 369 (2009) 90–96. [38] R. Nedyalkova, D. Niznansky, A.C. Roger, Catal. Commun. 10 (2009) 1875–1880.
[17] T. Inui, T. Takeguchi, Catal. Today 10 (1991) 95–106. [39] E. Ambroise, C. Courson, A. Kiennemann, A.C. Roger, O. Pajot, E. Samson, G.
[18] F.W. Chang, M.S. Kuo, M.T. Tsay, M.C. Hsieh, Appl. Catal. A 247 (2003) 309–320. Blanchard, Topic Catal. 52 (2009) 2101–2107.
[19] G. Du, S. Lim, Y. Yang, C. Wang, L. Pfefferle, G.L. Haller, J. Catal. 249 (2007) [40] L. Stronek, J. Majimel, Y. Kihn, Y. Montardi, A. Tressaud, M. Feist, C. Legein, J.-Y.
370–379. Buzaré, M. Body, A. Demourgues, Chem. Mater. 19 (2007) 5110–5121.
[20] M. Yamasaki, M. Komori, E. Akiyama, H. Habazaki, A. Kawashima, K. Asami, K. [41] T. Montini, N. Hickey, P. Fornasiero, M. Graziani, M.A. Banares, M.V. Martinez-
Hashimoto, Mater. Sci. Eng. A 267 (1999) 220–226. Huerta, I. Alessandri, L.E. Depero, Chem. Mater. 17 (2005) 1157–1166.
[21] A.E. Aksoylu, Z. Misirli, Z.I. Önsan, Appl. Catal. A 168 (1998) 385–397. [42] P.R. Shah, T. Kim, G. Zhou, P. Fornasiero, R.J. Gorte, Chem. Mater. 18 (2006)
[22] N. Laosiripojana, S. Assabumrungrat, Appl. Catal. A 290 (2005) 200–211. 5363–5369.
[23] R. Monte, P. Fornasiero, J. Kaspar, P. Rumori, G. Gubitosa, M. Graziani, Appl. [43] S. Bernal, G. Blanco, J.J. Calvino, J.C. Hernandez, J.A. Perez-Omil, J.M. Pintado,
Catal. B 24 (2000) 157–167. M.P. Yeste, J. Alloys Compd. 451 (2008) 521–525.
[24] A. Trovarelli, Catalysis by Ceria and Related Materials, vol. 2, Imperial College [44] M.H. Youn, J.G. Seo, K.M. Cho, S. Park, D.R. Park, J.C. Jung, K. Song, Int. J. Hydrogen
Press, Universita di Udine, 2002. Energy 33 (2008) 5052–5059.
[25] R. Strobel, F. Krumeich, S.E. Pratsinis, A. Baiker, J. Catal. 243 (2006) 229–238. [45] P. Kumar, Y. Sun, R.O. Idem, Energy Fuels 21 (2007) 3113–3123.
[26] L. de Rogatis, T. Montini, B. Lorenzut, P. Fornasiero, Energy Environ. Sci. 1 (2008) [46] A. Trovarelli, Catal. Rev. Sci. Eng. 38 (1996) 439–520.
201–509. [47] A.M. Diskin, R.H. Cunningham, R.M. Ormerod, Catal. Today 46 (1998) 147–154.
[27] R.M. Navarro, M.C. Alvarez-Galvan, J.A. Villoria, I.D. Gonzalez-Jimenez, R. Rosa, [48] R. Gomez-Reynoso, J. Ramirez, R. Nares, R. Luna, F. Murrieta, Catal. Today 107
J.L.G. Fierro, Appl. Catal. B 73 (2007) 247–258. (2005) 926–932.
[28] Y. Chen, K. Tomishige, K. Yokoyama, K. Fujimoto, Appl. Catal. A 165 (1997) [49] S. Xu, X. Yan, X. Wang, Fuel 85 (2006) 2243–2247.
335–347. [50] G. Ranga Rao, P. Fornasiero, R. Di Monte, J. Kasper, G. Vlaic, G. Balducci, S.
[29] T. Miyata, M. Shiraga, D. Li, I. Atake, T. Shishido, Y. Oumi, T. Sano, K. Takehira, Meriani, G. Gubitosa, A. Cremona, M. Graziani, J. Catal. 162 (1996) 1–9.
Catal. Commun. 8 (2007) 447–451. [51] P. Fornasiero, R. Di Monti, G. Ranga Rao, J. Kaspar, S. Meriani, A. Trovarelli, M.
[30] M. Virginie, M. Araque, A.C. Roger, J.C. Vargas, A. Liennemann, Catal. Today 138 Graziani, J. Catal. 151 (1995) 168.
(2008) 21–27. [52] K. Otsuka, Y. Wang, E. Sunada, I. Yamanaka, J. Catal. 175 (1998) 152.
[31] B. Koubaissy, A. Pietraszek, A.C. Roger, A. Kiennemann, Catal. Today 157 (2010) [53] S. Bernal, J.J. Calvino, M.A. Cauqui, J.M. Gatica, C. Larese, J.A. Perez Omil, J.M.
436–439. Pintado, Catal. Today 50 (1999) 175–206.
[32] M. Haneda, K. Shinoda, A. Nagane, O. Houshito, H. Takagi, Y. Nakahara, K. Hiroe, [54] J.M. Gatica, R.T. Baker, P. Fornasiero, S. Bernal, J. Kaspar, J. Phys. Chem. B 105
T. Fujitani, H. Hamada, J. Catal. 259 (2008) 223–231. (2001) 1191–1199.
[33] P.P. Silva, F.A. Silva, L.S. Portela, L.V. Mattos, F.B. Noronha, C.E. Hori, Catal. Today [55] H.A. Bahr, Gesammelte Abh. Kennt. Kohle 8 (1929) 219.
107–108 (2005) 734–740. [56] M. Nurunnabi, B. Li, K. Kunimori, K. Suzuki, K. Fujimoto, K. Tomishige, Appl.
[34] M.H. Youn, J.G. Seo, K.M. Cho, S. Park, D.R. Park, J.C. Jung, I.K. Song, Int. J. Hydro- Catal. A 292 (2005) 272.
gen Energy 33 (2008) 5052–5059. [57] M. Nurunnabi, K. Fujimoto, K. Suzuki, B. Li, S. Kado, K. Kunimori, K. Tomishige,
[35] J.C. Vargas, S. Libs, A.C. Roger, A. Kiennemann, Catal. Today 107 (2005) 417–425. Catal. Commun. 7 (2006) 73–78.