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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].
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)
0
H298
= 75 kJ mol1
(3)
2CO C + CO2
0
H298
= 172 kJ mol1
(4)
(5)
(6)
13
14
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
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.
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)
15
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)
VM
1
AM d(nm)
(10)
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).
16
(12)
(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
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.)
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
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
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).
[H2 ]
2 Ce(EDAX)
(14)
19
Table 3
Ni dispersion, active Ni site, STY and oxygen consumption of used catalysts.
Catalyst
DNi a
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
74.33
9.60
8.73
46.45
27.67
7.48
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 .
20
Fig. 7. XRD patterns of the used catalysts: CA (a); SG (b); WI (c); CP (d).
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).
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).
22
[43] A.V. Naumkin, A. Kraunt-Vass, S.W. Gaarenstroom, C.J. Powell, NIST X-ray
Photoelectron Spectroscopy Database, NIST X-ray Photoelectron Spectroscopy
Database, Version 4. 1, National Institute of Standards and Technology, 2012,
http://srdata.nist.gov/xps/.