Nano Research

DOI 10.1007/s12274-016-1296-2

Thermally stable Ir/Ce0.9La0.1O2 catalyst for high

temperature methane dry reforming reaction
Fagen Wang1,2 (), Leilei Xu3, Weidong Shi2, Jian Zhang4, Kai Wu5, Yu Zhao6, Hui Li6, He Xing Li6,
Guo Qin Xu1,4 (), and Wei Chen1,4,7 ()

1
Laboratory of Energy and Environment Interface Engineering, National University of Singapore Suzhou Research Institute, Suzhou
215123, China
2
School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, China
3
School of Environmental Science and Engineering, Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution
Control, Collaborative Innovation Center of the Atmospheric Environment and Equipment Technology, Nanjing University of Information
Science & Technology, Nanjing 210044, China
4
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore
5
College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China
6
Department of Chemistry, Shanghai Normal University, Shanghai 200234, China
7
Singapore-Peking University Research Center for a Sustainable Low-Carbon Future, 1 CREATE Way, #15-01, CREATE Tower, Singapore
138602, Singapore

Received: 20 July 2016 ABSTRACT

Revised: 12 September 2016
Accepted: 23 September 2016
© Tsinghua University Press
and Springer-Verlag Berlin
Heidelberg 2016
KEYWORDS
thermally stable catalyst,
Ir/Ce0.9La0.1O2,
metal–support interaction,
methane dry reforming
In this study, the use of a thermally stable Ir/Ce0.9La0.1O2 catalyst was investigated
for the dry reforming of methane. The doping of La2O3 into the CeO2 lattice
enhanced the chemical and physical properties of the Ir/Ce0.9La0.1O2 catalyst,
such as redox properties, Ir dispersion, oxygen storage capacity, and thermal
stability, with respect to the Ir/CeO2 catalyst. Hence, the Ir/Ce0.9La0.1O2 catalyst
exhibits higher activity and stabler performance for the dry reforming of methane
than the Ir/CeO2 catalyst. This observation can be mainly attributed to the
stronger interaction between the metal and support in the Ir/Ce0.9La0.1O2 catalyst
stabilizing the catalyst structure and improving the oxygen storage capacity,
leading to negligible aggregation of Ir nanoparticles and the Ce0.9La0.1O2 support
at high temperatures, as well as the rapid removal of carbon deposits at the
boundaries between the Ir metal and the Ce0.9La0.1O2 support.

1 Introduction decomposition of organic wastes, lead to continuous

increase in the concentrations of greenhouse gases in
Considerable emissions of CO2, NOx, and CH4, the atmosphere. The greenhouse gas effect results
attributed to the combustion of fossil fuels and the in the adverse consequence of climate change, which

Address correspondence to Fagen Wang, fagen.wang@gmail.com; Guoqin Xu, chmxugq@nus.edu.sg; Wei Chen, chmcw@nus.edu.sg
2 Nano Res.
in turn endangers humans. For sustainable human
development, it is imperative to reduce the emissions
of or utilize these greenhouse gases [1].
CO2 is the one of the main components contributing
to the greenhouse gas effect; hence, CO2 reduction has
attracted considerable attention. In recent years, several
carbon capture and sequestration (CCS) technologies
and catalytic transformations have been developed
for CO2 reduction [2–4]. Among catalytic processes,
the dry reforming of methane is crucial, as CH4 and
CO2 produce syngas, which can be further used for
synthesizing energy chemicals, such as hydrocarbons
or olefins [5, 6]; this process not only decreases green-
house gas emissions but also provides important raw
feedstock for chemical industries, which are beneficial
from aspects of environment and energy.
Among the catalysts investigated for the high-
temperature dry reforming of methane, Ni catalysts
exhibit the best performance, attributed to their high
activity for C–H bond cleavage [7, 8]. Unfortunately,
methane rapidly decomposes on Ni nanoparticles,
and the Ostwald ripening of the catalyst results
in considerable amounts of deposited carbon and
aggregates of Ni nanoparticles, leading to catalyst
deactivation [9]. Hence, a majority of studies have
been focused on the synthesis of small Ni nanoparticles
located in a confined space for decreasing carbon
deposits and limiting Ni particle sintering, such as the
immobilization of Ni nanoparticles into mesoporous
materials or yolk–shell frameworks [5, 10–13] and the
addition of other elements, such as Fe and Pt, for
enhancing the resistance of carbon in Ni catalysts
[14, 15]. Noble metals catalysts, such as those of Rh, Pt,
and Ir, also exhibit high activity for the dry reforming
of methane [16–18]. Although negligible carbon
deposits are observed, the sintering of noble metal
nanoparticles is inevitable, owing to the difficulty
in the stabilization of small metal nanoparticles at
high temperatures. Furthermore, depending on the
interaction between the noble metal and support
material, these small noble metal nanoparticles tend
to either aggregate into large clusters or react with the
support, resulting in decreased active sites, and hence
reduced catalytic performance [19].
These detrimental issues of catalyst sintering and
carbon deposition at high temperatures have prevented
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the large-scale industrialization of the dry reforming
of methane. For commercialization, it is imperative
to develop a rational design of catalysts exhibiting
characteristics of no sintering and no carbon deposition.
To avoid sintering, a possible way is to isolate the
nanoparticles in a confined space (similar to core–shell
catalysts) to avoid aggregation [20]. Another potential
way is to strengthen the interaction between the
metal and support in supported catalysts to prevent
enlargement [21]. As compared to the sophisticated
methods required for synthesizing confined catalysts,
the strengthening of the interaction between the metal
and support in supported catalysts is more suitable,
attributed to simple preparation methods that can
facilitate easy scale-up. To maximize the interaction
between the metal and support in supported catalysts,
the size and shape of the active metal and support
need to be finely tuned to obtain a stable catalyst
structure [19, 21–24]. To avoid carbon deposition, the
gasification rate of the carbon precursors at the
boundary between the metal and support should be
more rapid as compared to the formation rate of the
precursor at the metal sites, which can be achieved by
using oxides exhibiting oxygen storage capacity (OSC)
[25]. OSC aids in the removal of carbon deposits by
exploiting high oxygen mobility, related to the surface
oxygen and partial bulk oxygen species [26]. In addition,
OSC can lead to the significant enhancement of the
metal–support interaction, affording enhanced ability
for removing carbon [27].
From the above discussion, catalysts exhibiting
properties of strong metal–support interaction and
high OSC, such as ceria-based catalysts, are suggested
as excellent candidates for the high-temperature dry
reforming of methane [28, 29]. However, catalyst per-
formance gradually decreases because of the thermal
instability of pure ceria at high temperature, leading to
the decreased Brunauer–Emmett–Teller surface areas
and enlarged ceria nanoparticles [30, 31]. The sintering
of the active metal and formation of carbon deposits
are observed because of the weakened metal–support
interaction and unstable catalyst structure [32, 33].
For enhancing thermal stability, doped ceria, such as
Ce–Zr–O, Ce– Pr–O, Ce–Gd–O, and Ce–La–O, has been
synthesized to improve the metal–support interaction
with the aim of limiting sintering of the active metal
Nano Res.
and reducing the deposition of carbon [21, 34–36].
Previously, our group has reported that the doping
of ceria results in the significant enhancement of
the metal–support interaction in catalysts, leading to
increased catalytic performance and stability for the
dry reforming of methane [21, 37]. However, although
the sintering of the active metal is limited and deposition
of carbon is reduced, the sintering of the support is
still observed. Hence, for further limiting the sintering
of doped ceria, La2O3-doped ceria is synthesized as
the support for the dry reforming of methane in this
study. Results revealed that doping with La2O3 leads
to the enhancement of the interaction between the
metal and support in the Ir/Ce0.9La0.1O2 catalyst, and
significant improvement in the performance and
stability of the Ir/Ce0.9La0.1O2 catalyst, as compared
to the Ir/CeO2 catalyst, for the dry reforming of
methane is observed. Furthermore, the sintering of
the Ir nanoparticles and Ce0.9La0.1O2 support was not
observed at a high temperature of 1,073 K for 1,000 h,
and negligible carbon deposits were observed on the
used Ir/Ce0.9La0.1O2 catalyst, demonstrating immense
potential for the Ir/Ce0.9La0.1O2 catalyst as a candidate
for facilitating the industrialization of the dry reforming
of methane.
2 Experimental
2.1 Catalyst preparation
The Ir/Ce0.9La0.1O2 catalyst was prepared by deposition–
precipitation. First, a homogeneous mixture of
CO(NH2)2, Ce(NO3)3, and La(NO3)3 in a molar ratio of
20:9:1 was heated to 363 K under stirring for 3 h. Next,
the mixture was filtered and washed with hot water,
and the obtained slurry was dried at 373 K for 12 h,
followed by calcination at 673 K for 4 h at a heating
rate of 1 K/min, affording the Ce0.9La0.1O2 support. The
Ce0.9La0.1O2 support and H2IrCl6 solution (nominal Ir
loading of 2 wt.%) were then homogeneously mixed
in water at 338 K, followed by the slow addition of
Na2CO3(aq) with stirring until the pH of the mixture
changed to pH 8–9. After the suspension was aged
for 2 h, it was filtered and thoroughly washed several
times using hot water. Finally, the powder was dried
overnight at 373 K, followed by calcination at 1,023 K
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3
for 4 h at a heating rate of 1 K/min. For comparison, an
Ir/CeO2 catalyst was prepared by the same procedure,
but without La(NO3)3.
2.2 Catalyst characterization
Power X-ray diffraction (XRD) patterns were recorded
on a PANalytical Empyren DY708 diffractometer
operated at 40 kV and 30 mA using Ni-filtered Cu Kα
(0.15418 nm) radiation. Transmission electron micros-
copy (TEM) images were recorded on a JEOL 2010
instrument operated at 200 kV. Specimens were
prepared by the ultrasonic dispersion of samples in
ethanol. Droplets of the suspension were deposited
on a thin carbon film supported on a standard copper
grid. X-ray photoelectron spectroscopy (XPS) mea-
surements were carried out on an AMICUS spectrometer
using Mg Kα radiation. The charging effect was
corrected by adjusting the binding energy of C 1s
to 284.6 eV. Temperature-programmed desorption of
oxygen (O2-TPD) from supports was performed in a
U-shaped reactor connected to a mass spectrometer
(PrismaPlus). First, the supports were pretreated by
20% O2/He at 673 K for 30 min, the samples were then
purged with He, and the temperature was cooled to
room temperature. Next, the samples were heated
to 1,073 K at a rate of 5 K/min. The signal of oxygen
(m/e = 32) was detected by the mass spectrometer.
Temperature-programmed reduction of hydrogen
(H2-TPR) from fresh catalysts and supports were con-
ducted in a U-shaped reactor connected to the mass
spectrometer (PrismaPlus). Samples were loaded and
pretreated under He (50 mL/min) at 573 K for 1 h.
After cooling to room temperature, a mixture of 10%
H2/He (50 mL/min) was introduced over the samples
to attain a steady state. Then, the temperature was
increased to 1,023 K at a rate of 5 K/min and maintained
at that temperature for 30 min. The signal of H2 (m/e = 2)
was detected by the mass spectrometer. The OSCs for
the supports and catalysts were measured after the
samples were cooled to 573 K under He (50 mL/min).
A stream of O2/He (10 vol.%) was periodically injected
over the reduced sample until saturation. Temperature-
programmed desorption of CO 2 (CO 2-TPD) was
performed in the U-shaped reactor. First, the samples
were pretreated by He (20 mL/min) at 573 K for
30 min. Next, 5% CO2/He (50 mL/min) was passed
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4 Nano Res.
over the samples at room temperature for 30 min.
After purging with He (50 mL/min), the samples
were heated to 1,073 K at a rate of 5 K/min, and the
signal of CO2 (m/e = 44) was detected by the mass
spectrometer (PrismaPlus). Temperature-programmed
surface reaction desorption of CH4 (CH4-TPSR) was
performed in the U-shaped reactor. First, the samples
were reduced at 1,023 K for 30 min by 10% H2/He and
then cooled to room temperature. Next, 5% CH4/He
(50 mL/min) was introduced to attain a stable state.
Finally, the temperature was increased to 1,023 K at a
rate of 5 K/min and maintained at that temperature
for 30 min. The signals of CH4 (m/e = 16), CO2 (m/e =
44), CO (m/e = 18), H2O (m/e = 18), and H2 (m/e = 2) were
monitored by the mass spectrometer (PrismaPlus).
Temperature-programmed surface reaction desorption
of CO2+CH4 (CO2+CH4-TPSR) was performed in the
U-shaped reactor. First, the samples were reduced at
1,023 K for 30 min by 10% H2/He and then cooled to
room temperature, followed by adsorption with 25%
CO2/He (50 mL/min) for 30 min. Next, 5% CH4/He
(50 mL/min) was introduced to attain a stable state.
Finally, the temperature was increased to 1,023 K at a
rate of 5 K/min and maintained at that temperature
for 30 min. The signals of CH4 (m/e = 16), CO2 (m/e = 44),
CO (m/e = 18), H2O (m/e = 18), and H2 (m/e = 2) were
detected by the mass spectrometer (PrismaPlus).
Temperature-programmed oxidation (TPO) of the used
catalysts was conducted in the U-shaped reactor. First,
the used samples were heated to 573 K for 30 min
under He to eliminate possible contaminants. Then,
the samples were heated from room temperature
to 1,073 K under 5% O2/He (50 mL/min). The effluent
composition of CO2 (m/e = 44) was detected by the
mass spectrometer (PrismaPlus).
2.3 Catalytic activity tests and kinetic parameter
measurements
The dry reforming of methane was performed in
a continuous-flow fixed-bed tubular quartz reactor
(i.d. = 6 mm, L = 300 mm). The fresh catalyst powder
was reduced under 20% H2/N2 (30 mL/min) at 1,023 K
for 30 min. After purging the reactor with N2, a mixture
of undiluted CH4 and CO2 (molar ratio CH4/CO2 = 1)
was introduced into the reactor at a gas hourly space
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velocity (GHSV) of 18,000 mL/(g·h). Catalytic perfor-
mance was tested from 873 to 1,023 K at intervals
of 50 K. To attain a steady state, measurements were
performed for at least 1 h at each designated tem-
perature. Stability tests were conducted at a GHSV of
18,000 mL/(g·h) at 1,023 K for 200 h and at a GHSV of
36,000 mL/(g·h) at 1,073 K for 1,000 h. The effluent
from the reactor was mixed with an internal standard
gas (N2, 5 mL/min), followed by injection into an
on-line GC system (Aglient 7890A). The mixture was
separated on a packed column (TDX-01) and analyzed
by a thermal conductivity detector (TCD). Conversions
of CH4 and CO2 were calculated by the following
formula
FCH4 ,inlet  FCH4 ,outlet
X CH4   100%
FCH4 ,inlet
FCO2 ,inlet  FCO2 ,outlet
X CO2   100%
FCO2 ,inlet
The molar ratio of H2 to CO was calculated as
follows
nH2 FH2 ,outlet

nCO FCO,outlet
In all formulae, Fi represents the flow rate of the i
species.
Kinetic experiments were also conducted in the
same fixed-bed reactor at atmosphere pressure. In
each run, 50 mg of catalyst (80–100 mesh) mixed with
200 mg SiC was loaded for each experiment. The
height of the catalyst bed was approximately 12 mm.
Conversions of CH4 and CO2 were limited to less than
15% by adjusting the reaction temperature in the
range of 823 to 873 K. For confirming mass and heat
transfer limitations in kinetic experiments, the internal
diffusion, external mass diffusion, and heat diffusion
were calculated according to typical equations [38, 39].
3 Results and discussion
3.1 Physical and chemical properties of the fresh
catalysts and supports
Figure 1 shows the XRD patterns of the fresh Ir/CeO2
and Ir/Ce0.9La0.1O2 catalysts. All samples exhibited
Nano Res. 5

defects that positively affect the dispersion of Ir

species [23].
Figure 2 shows the high-resolution TEM (HRTEM)
images of the reduced Ir/CeO2 and Ir/Ce0.9La0.1O2
catalysts. For all samples, randomly oriented polyhedral
nanoparticles were observed. The sizes of CeO2 and
Ce0.9La0.1O2 ranged from 10 to 20 nm. Larger Ir nano-
particles of approximately 6.0 nm were observed on
CeO2 surfaces (Fig. 2(b)), while smaller Ir nanoparticles
of approximately 2.5 nm were observed on Ce0.9La0.1O2
surfaces (Fig. 2(d)). Next, Ir dispersion was appro-
ximately estimated by the reciprocal of the Ir particle
size. As shown in Table 1, the dispersion of Ir for the
Ir/CeO2 catalyst was approximately 16.6%, slightly
less than that observed for the Ir/Ce0.9La0.1O2 catalyst
Figure 1 XRD patterns of the fresh and used Ir catalysts. (a) Fresh (approximately 40.0%). The above observations are in
Ir/CeO2, (b) fresh Ir/Ce0.9La0.1O2, (c) used Ir/CeO2-200, (d) used good agreement with the XRD results obtained earlier;
Ir/Ce0.9La0.1O2-200, and (e) used Ir/Ce0.9La0.1O2-1000. these result also reflect the effect of ceria- based solid
solutions on the stabilization of the active metal
diffraction peaks of CeO2 without La2O3 signals,
dispersion [36].
indicating that La3+ is doped into the CeO2 lattice
Figure 3 shows the H2-TPR profiles of the supports
in the Ir/Ce0.9La0.1O2 catalyst. The lattice parameter of
and Ir catalysts. With respect to the reduction behavior
Ce0.9La0.1O (5.4257 Å) was slightly greater than that
of the supports, main broad reduction peaks were
of CeO2 (5.3940 Å), indicating that the CeO2 lattice
observed at 650–700 and 890–910 K, attributed to the
expands with the introduction of La3+, attributed to
reduction of surface lattice oxygen in CeO2 [40]. Also
the fact that the ionic radius of La3+ (106 pm) is greater
than that of Ce4+ (92 pm). The average crystallite sizes
of Ce0.9La0.1O2 and CeO2 were 10 and 13 nm, respec-
tively. The smaller size of Ce0.9La0.1O2 suggested that
nanoparticle aggregation in Ce0.9La0.1O2 is effectively
hindered, better than in CeO2, contributing to the
higher thermal stability of the crystallite structure. The
higher thermal stability is attributed to the doping of
La3+ into the ceria lattice, which decreases the lattice
parameter of the crystallite as well as the thermal
expansion of the ceria lattice. With respect to the Ir
species, diffraction peaks of IrO2 were observed in the
fresh Ir/CeO2 catalyst but not detected for the fresh
Ir/Ce0.9La0.1O2 catalyst. Furthermore, the size of IrO2
nanoparticles in the fresh Ir/CeO2 catalyst was appro-
ximately 6 nm, while that of IrO2 nanoparticles in the
fresh Ir/Ce0.9La0.1O2 catalyst could not be measured
because no signals were detected. This result is
indicative of higher dispersion for the Ir species in
the Ir/Ce0.9La0.1O2 catalyst, attributed to the stronger Figure 2 HRTEM images of reduced Ir/CeO2 ((a) and (b)) and
metal–support interaction as well as increased oxygen Ir/Ce0.9La0.1O2 ((c) and (d)) catalysts.

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6 Nano Res.

Table 1 O2 desorption, H2 consumption, Ir dispersion, and OSC of samples

Samples O2 desorption (molO/g) H2 consumption (mol/g) OSC (molO/g) Ir dispersiona (%)
CeO2 648 614 634 —
Ce0.9La0.1O2 806 821 796 —
Ir/CeO2 — 910 924 16.6
Ir/Ce0.9La0.1O2 — 1,176 1,065 40.0
a 1
Dispersion of Ir was approximately calculated by D   100% , where dIr is the diameter of Ir nanoparticles; it is determined from
d Ir
HRTEM images of the fresh samples (Fig. 2).

addition, corresponding minor reduction peaks were

Figure 3 H2-TPR profiles of the supports and Ir catalysts.
shown to the left of Fig. 3 is the magnified image
showing the minor reduction peaks observed at a
temperature of less than 600 K: Two larger reduction
peaks were observed at approximately 512 and 550 K
for Ce0.1La0.1O2, while significantly smaller peaks were
observed for CeO2, attributed to the surface-active
oxygen (superoxide species) of CeO2 [41, 42]. The
relatively higher amounts of superoxide species
implied that significantly more active oxygen species
are formed in Ce0.9La0.1O2 oxide, which in turn exhibits
enhanced chemical activity with hydrogen. Hydrogen
consumption values for CeO2 and Ce0.9La0.1O2 were
614 and 821 mol/g (Table 1), respectively. The higher
hydrogen consumption for Ce0.9La0.1O2 is attributed
to the structural modification of the ceria lattice,
attributed to the substitution of Ce4+ by La3+; this
substitution favors the diffusion of O2– to the Ce0.9La0.1O2
support surfaces. With respect to the reduction profiles
of the Ir catalysts, hydrogen was mainly consumed at
550–630 and 510 K for the Ir/CeO2 and Ir/Ce0.9La0.1O2
catalysts, respectively, attributed to the co-reduction
of IrO2 and the partial surface oxygen of CeO2 [37]. In
observed at 753 and 880 K, attributed to the further
removal of surface oxygen from the supports. The
above results indicated that the redox property and
hydrogen consumption (Table 1) for the Ir/Ce0.9La0.1O2
catalyst, as compared to the Ir/CeO2 catalyst, are
significantly improved because of the stronger metal–
support interaction, which facilitates the reduction of
Ir species and surface oxygen from the support [43].
The reduction of bulk oxygen from ceria always
requires a temperature of greater than 1,100 K [37];
thus, it is difficult to reduce bulk oxygen with the
current temperature employed.
To demonstrate the higher oxygen mobility and
higher oxygen vacancy formation in the Ir/Ce0.9La0.1O2
catalyst, as compared to the Ir/CeO2 catalyst, O2-TPD
from the support was carried out (Fig. 4), and the OSCs
of the catalysts were determined (Table 1). From the
O2-TPD profiles, O2 desorption was centered at 845 K
for CeO2, while it peaked at 880 K for Ce0.9La0.1O2.
The oxygen removal amount for Ce0.9La0.1O2 was
Figure 4 O2-TPD profiles of the CeO2 and Ce0.9La0.1O2 supports.

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Nano Res.
806 molO/gcat, slightly greater than that observed
for CeO2 (648 molO/gcat); this result is attributed to
the replacement of high-valance Ce4+ site in the ceria
lattice by low-valence La3+, which favors the movement
of bulk oxygen and leads to a higher oxygen mobility
for Ce0.9La0.1O2 [44]. The OSC for the Ir/Ce0.9La0.1O2
catalyst was 1,065 molO/gcat, slightly greater than
that observed for the Ir/CeO2 catalyst (924 molO/gcat).
This result indicated that higher amounts of oxygen
vacancies are filled by oxygen atoms in the Ir/Ce0.9La0.1O2
catalyst during oxygen treatment [36].
Figure 5 shows the XPS spectra of Ir 4f, O 2p, Ce 3d,
and La 3d in the reduced Ir/Ce0.9La0.1O2 and Ir/CeO2
catalysts. In the Ir 4f spectrum, peaks were observed
at binding energies of 60.8 and 63.6 eV, attributed to
Ir0 species; this result confirms the presence of Ir
on the surface of the support after pretreatment by
hydrogen reduction. In the O 1s spectrum, broad
peaks were observed at 531.8 and 528.9 eV, attributed
to the oxygen species corresponding to defect (Oβ) and
lattice oxygen (O), respectively. The O 1s spectra were
curve-fitted using a Gaussian–Lorentzian procedure
Figure 5 XPS spectra of (a) Ir 4f, (b) O 1s, (c) Ce 3d, and (d) La 3d of the Ir/Ce0.9La0.1O2 catalysts.
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7
after subtracting the background for tentatively
quantifying the relative percentage of Oβ, which is a
crucial parameter for measuring oxygen vacancy. The
relative concentrations of Oβ were approximately 54%
and 59% for the reduced Ir/CeO2 and Ir/Ce0.9La0.1O2
catalysts, respectively. The slightly higher concen-
trations of Oβ demonstrated the positive effect of
the doping of La3+ on the enhancement of oxygen
vacancies [45]. With respect to the Ce 3d spectrum,
eight peaks corresponding to four pairs of spin-orbit
splitting doublets were observed. The u’ and v’ peaks
were attributed to Ce3+ 3d3/2 and Ce3+ 3d5/2, respec-
tively, the u, u’’, and u’’’ peaks were attributed to
Ce4+ 3d3/2, and those of v, v’’, and v’’’ were attributed
to Ce4+ 3d5/2 [46]. The co-existence of Ce3+ and Ce4+
suggested the presence of oxygen defects in the sample,
which is in agreement with the detection of Oβ in the
O 1s profiles. The La 3d spectrum exhibited four peaks
at 833.3, 837.7, 850.4, and 854.8 eV, respectively. These
peaks are different as compared to those observed
for the binding energies of standard La2O3 (835.8
and 852.6 eV), attributed to the different coordination
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8 Nano Res.
conditions of La3+ and the La–O distance in Ce0.9La0.1O2
as compared with that in pure La2O3 [47].
3.2 Dynamic reaction analysis of the dry reforming
of methane over the supports and catalysts
3.2.1 Activation of CO2 on supports and catalysts
Figure 6 shows the CO2-TPD profiles of the supports
and Ir catalysts. For all supports, the desorption of
CO2 was observed at three temperatures. The first
peak at 474 K was attributed to the interaction of
monodentate carbonate with CeO2. The second peak
at 664 K was attributed to bidentate carbonate [48].
The third peak at 945 K was attributed to the internal
polydentate carbonates in the bulk of oxides [49].
After the loading of Ir, CO2 desorption was observed
at two temperature regions of 460–542 and 710–730 K,
attributed to monodentate and bidentate carbonates,
respectively. Polydentate carbonate was absent owing
to the decomposition of internal carbonates during
the high-temperature calcination, and because it could
not be formed in the CO2 treatment at room tem-
perature. Notably, the CO2 desorption temperatures
were slightly shifted to lower temperatures for the
doped oxides and catalysts, as compared to the
undoped oxides and catalysts, suggesting that the
doping of La3+ results in decreased basicity of the
samples. This decreased basicity possibly originates
from the lower oxidation state of La3+ as compared to
Figure 6 CO2-TPD profiles of the supports and the Ir catalysts.
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that of Ce4+, leading to a slightly weaker interaction
with CO2 [50]. However, CO2 desorption areas for
Ce0.9La0.1O2 and Ir/Ce0.9La0.1O2 were greater than those
observed for CeO2 and Ir/CeO2, indicating that more
CO2 can be adsorbed on the doped samples. Increased
adsorption should result in increased CO2 activation,
leading to enhanced catalytic performance for the dry
reforming of methane.
3.2.2 Interaction of CH4 with the supports and catalysts
(CH4-TPSR)
For investigating the interaction of CH4 with the
supports and catalysts, CH4-TPSR profiles were
obtained (Fig. 7). Traces of H2 were detected from
980 and 800 K for CeO2 and Ce0.9La0.1O2, respectively.
Negligible consumption of methane by the supports
was attributed to weak interaction between methane
and the supports (Fig. 7(a) and 7(b)). By contrast, the
significant enhancement of the interaction between
methane and the Ir catalysts was observed (Fig. 7(c)
and 7(d)). First, minor products CO2 and H2O were
observed at temperatures of less than 800 K, attributed
to the interaction between CHx intermediates and
the surface oxygen in ceria [21, 51]. Second, the main
products CO and H2 were formed at temperatures of
greater than 800 K, attributed to the surface reaction
between CHx intermediates and accessible bulk oxygen
in CeO2 [52]. The Ir/CeO2 catalyst exhibited loss of CO
and H2 at 600 and 700 K, respectively, slightly less
than that observed for the Ir/Ce0.9La0.1O2 catalyst (700
and 750 K, respectively). From the indirect dissociation
mechanism for the activation and transformation of
methane on noble catalysts, methane is proposed to
be activated on the active metal, affording adsorbed
H and CHx intermediates; these CHx intermediates
react with the bulk oxygen of oxide, generating CO
and H that are adsorbed on the metal site at the
boundary between the metal and support [3, 53, 54].
For the desorption of H2 and CO from the metal sites,
metal–H and metal–COad bonds should be broken.
As the energy required to break these bonds can
only be provided by the temperature in this case,
the slightly higher initial desorption temperature of
H2 and CO on the Ir/Ce0.9La0.1O2 catalyst indicated
stronger bond strength between CO and H2 and the
Ir sites as compared with those between CO and H2
Nano Res.
Figure 7 CH4-TPSR of the supports ((a) CeO2 and (b) Ce0.9La0.1O2) and catalysts ((c) Ir/CeO2 and (d) Ir/Ce0.9La0.1O2).
and the Ir/CeO2 catalyst. Methane consumption for
the Ir/Ce0.9La0.1O2 catalyst was observed at 920 K,
slightly less than that observed for the Ir/CeO2 catalysts
(940 K), indicative of the higher ability for methane
conversion on the Ir/Ce0.9La0.1O2 catalyst caused by
the smaller size of Ir nanoparticles and the easier
movement of partial bulk oxygen in the Ce0.9La0.1O2
support.
3.2.3 Temperature-programmed surface reaction of methane
on the supports and catalysts after CO2 adsorption (CO2+
CH4-TPSR)
Figure 8 gives the results of CO2+CH4-TPSR after CO2
adsorption on the supports and catalysts. Methane
consumption was clearly not detected, and only
traces of H2 were observed for CeO2 and Ce0.9La0.1O2
supports (Fig. 8(a) and 8(b)). In contrast, methane
consumption peaks were clearly observed at 964 and
940 K for Ir/CeO2 and Ir/Ce0.9La0.1O2 (Fig. 8(c) and 8(d)),
respectively. As compared with the result observed
from Fig. 7, the higher CH4 consumption temperatures
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9
can possibly be attributed to the different electronic
surroundings of Ir nanoparticles after CO2 adsorption.
Minor products H2 and CO2 were centered at 690 and
632–800 K, respectively, for the Ir/CeO2 catalyst, while
these products were observed at 710 and 655–810 K,
respectively, for the Ir/Ce0.9La0.1O2 catalyst. These
peaks are attributed to the reaction between CHx
intermediates and the surface oxygen of supports. At
temperatures of greater than 800 K, main products H2
and CO were observed for the catalysts, attributed
to the interaction of CHx intermediates with the
accessible bulk oxygen of supports. The above results
demonstrate that both the surface and bulk oxygen
of the support are involved in the transformation of
CHx intermediates, which can be considered as a route
for the elimination of carbon deposits during the dry
reforming of methane.
3.2.4 Kinetic parameters and turnover frequencies (TOFs)
for the dry reforming of methane over the catalysts
Before measuring the kinetic parameters and TOF, the
Research
10
Figure 8 CO2+CH4-TPSR of the supports ((a) CeO2 and (b) Ce0.9La0.1O2) and catalysts ((c) Ir/CeO2 and (d) Ir/Ce0.9La0.1O2).
criteria for external mass diffusion, internal diffusion,
and the combined interphase and intra-particle
heat and mass transport were calculated in Table 2.
The criterion values for methane and CO2 over the
Ir/CeO2 and Ir/Ce0.9La0.1O2 catalysts were less than 0.15,
indicative of no external mass-transport limitations.
Similarly, the internal criterion values of methane
and CO2 over the catalysts were below 1, indicative
of no internal mass diffusion limitations. The Mears
criterion for the combined interphase and intraparticle
heat and mass transport of methane and CO2 was
far less than 3, further indicative of no interphase
and intraparticle heat transfer or mass-transport
limitations. These values revealed that the mass- and
heat-transfer limitations can be neglected in kinetic
measurements.
The kinetic parameters and TOF values for the dry
reforming of methane (Table 3) were compared for
the catalysts. In the Arrhenius plots (Fig. 9), the Ea
values for CH4 were 60.7 and 70.1 kJ/mol, while those
for CO2 were 74.4 and 64.9 kJ/mol for the Ir/CeO2 and
Ir/Ce0.9La0.1O2 catalysts, respectively. The Ea values are
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Nano Res.
rather similar to previously reported values [55–57].
Although the Ea observed for CH4 over the Ir/Ce0.9La0.1O2
catalyst was slightly higher, the pre-exponential factor
was significantly enhanced, suggesting that the collision
frequency of CH4 is promoted at the catalyst surface,
caused by the higher dispersion of Ir. With respect
to the Ea values observed for CO2, the lower value
for the Ir/Ce0.9La0.1O2 catalyst indicated easier CO2
activation, attributed to the improved basicity caused
by doping with La3+ (Fig. 6). With respect to intrinsic
rate measurement, the TOF values for CH4 and
CO2 for the Ir/CeO2 catalyst were 0.09 and 0.12 s–1,
respectively, slightly less than the corresponding values
observed for the Ir/Ce0.9La0.1O2 catalyst (0.12 and
0.21 s–1). This result reflected the higher performance
for the Ir/Ce0.9La0.1O2 catalyst. As compared with the
previously reported TOF values, those observed for
CH4 and CO2 on the Ir/CeO2 and Ir/Ce0.9La0.1O2 catalysts
were similar to the values observed for the Ir/Al2O3
catalyst, albeit less than those observed for Ru/Al2O3,
Pd/Al2O3, and Rh/Al2O3 catalysts [57]. This result is
attributed to the different abilities for the activation
Nano Res. 11

Table 2 Rates of methane and CO2, and the criterion values for internal diffusion, external diffusion, and combined interphase and
a
intra-particle heat, and mass transport
Mears criterion for combined
CH4 rate CO2 rate Mears criterion for Weisz–Prater criterion
Catalyst interphase and intra-particle
(kmol/(kmolcat·s)) (kmol/(kmolcat·s)) external diffusion for internal diffusion
heat and mass transport
 rA  b Rn  c R 2
 rA(obs)  rA R 2
kcCAb DeCAs CAb De

CH4 CO2 CH4 CO2 CH4 CO2

Ir/CeO2 1.96E–05 3.08E–05 0.003 0.002 0.23 0.34 3.3E–05 4.7E–05
Ir/Ce0.9La0.1O2 2.28E–05 3.84E–05 0.005 0.004 0.33 0.56 4.6E–05 7.8E–05
<0.15 <1 <3
a
Catalyst particle size R = 180 m; bulk density of catalyst b = 707 kg/m ; solid catalyst density c = 7,132 kg/m ; reaction orders of
3 3

CH4 and CO2 are estimated 1 and 0.5, respectively [20]; bulk gas concentration CAb and gas concentration on the catalyst surface CAs are
both 0.0006 kmol/m3; mass-transfer coefficient kc = 1.02 m/s, the value of which was adopted from Ref. [39]; effective gas-phase diffusivity
De = 2.6 × 105 m2/s, the value of which was adopted from Ref. [39].

Table 3 Comparison of the kinetic parameters of MDR in this study with those reported previously
CH4 CO2 NIr b
Catalysts Refs.
Ea (kJ/mol) TOF (s–1) Ea (kJ/mol) TOFa (s–1) (mol/gcat)

2%Ir/CeO2 60.7 0.09 74.4 0.12 17 This work

2%Ir/Ce0.9La0.1O2 71.8 0.12 64.9 0.21 40 This work
c
1%Ir/Al2O3 111.7 0.07 131.0 0.18 —  [57]
1%Ru/Al2O3 92.5 0.53 131.0 1.36 —  [57]
1%Pd/Al2O3 87.1 0.36 90.4 0.64 —  [57]
1%Rh/Al2O3 66.1 0.22 52.7 0.32 —  [57]
1%Pt/ZrO2 77.0 0.77 62.8 — —  [17]
1%Pt/5%ZrO2/Al2O3 54.8 1.8 68.7 — — [17]
0.5%Rh/Al2O3 83.7 — — — — [3]
2%Rh/La2O3-ZrO2 143 — 113 — — [55]
0.6%Rh/La2O3-SiO2 61.5 — 49.4 — — [56]
a b
TOF: turnover frequencies of CH4 and CO2 over the Ir/Ce0.9La0.1O2 and Ir/CeO2 catalysts at 823 K. Surface Ir sites were calculated by
D
N Ir,surface   106 μmol/g cat , where ω is the weight faction of Ir, D is the dispersion of Ir, and MIr is the relative atomic weight of Ir;
M Ir
1
dispersion of Ir was approximately calculated by D   100% , where dIr is the diameter of Ir nanoparticles, which is determined
d Ir
from the HRTEM images of the fresh samples (Fig. 2); ratios of pre-exponential factors for CH4 and CO2 rates over the Ir/Ce0.9La0.1O2
and Ir/CeO2 catalysts are 145 and 0.15, respectively, calculated from the intercept of the Arrhenius plots shown in Fig. 9. cNot available.

or transformation of CH4 molecules on different metal
nanoparticles and CO2 molecules on the supports.
3.3 Performance and stability of the catalysts for
the dry reforming of methane
Figure 10 shows the performances of the Ir/CeO2 and
Ir/Ce 0.9La 0.1O2 catalysts for the dry reforming of
methane. CH4 and CO2 conversions progressively
increased with increasing temperature, attributed
to the endothermic characteristics associated with the
dry reforming of methane: High temperature promotes
high conversion of feedstock. At 823 K, methane and

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12
Figure 9 Arrhenius plots for CH4 and CO2 reaction rates over
the Ir/Ce0.9La0.1O2 and Ir/CeO2 catalysts.
Figure 10 Performances of Ir/CeO2 and Ir/Ce0.9La0.1O2 catalysts for
the dry reforming of methane (reaction conditions: mass of catalyst:
100 mg, molar ratio CH4/CO2 = 1, GHSV = 18,000 mL/(g·h)).
CO2 conversions for the Ir/CeO2 and Ir/Ce0.9La0.1O2
catalysts were less than 10%. Increasingly, CH4 and
CO2 conversions for the Ir/CeO2 catalyst improved to
55% and 71%, respectively; these conversions increased
to 74% and 85% over the Ir/Ce0.9La0.1O2 catalyst at a
temperature of 1,073 K. Considering the structural
properties of the catalysts, higher methane conversion
for the Ir/Ce0.9La0.1O2 catalyst was attributed to the
smaller size of Ir nanoparticles, which provides more
active sites for the activation and transformation of
methane. On the other hand, the higher CO2 conversion
for the Ir/Ce0.9La0.1O2 catalyst was attributed to the
modification of La2O3, which enhances the basicity of
supports (CO2-TPD) for the adsorption of CO2 and
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Nano Res.
the formation of oxygen vacancies for activating CO2.
Notably, the above conversion values were less than the
equilibrium conversion, indicating that dry reforming
is an equilibrium-limited reaction. In addition, the
conversion of CO2 was higher than that of CH4,
attributed to the occurrence of the reverse water-gas
shift reaction at high temperatures.
Figure 11 shows the effect of different GHSVs on
the performance of the Ir/Ce0.9La0.1O2 catalyst for the
dry reforming of methane. The results indicated that
both CH4 and CO2 conversions gradually decrease with
increasing GHSV. At the lowest GHSV of 6,000 mL/(g·h),
the CH4 and CO2 conversions for the Ir/CeO2 catalyst
were 70% and 80%, respectively, slightly less than
the corresponding conversions of 79% and 88% over
the Ir/Ce0.9La0.1O2 catalyst. In contrast, at the highest
GHSV of 36,000 mL/(g·h), CH4 and CO2 conversions
for the Ir/CeO2 catalyst decreased to 31% and 47%,
respectively, and the corresponding values for the
Ir/Ce0.9La0.1O2 catalyst decreased to 47% and 61%. The
decreased conversions observed at high GHSVs are
speculated to be caused by the shortened contact time
of reactants. With increasing GHSV, the flow rate of
reactants increased, and more reactant molecules were
introduced, reducing the contact time of reactants and
the more insufficient active sites, which inevitably
decreases catalytic conversion [58].
Figure 12 shows the results obtained from the stability
tests over the two catalysts. At 1,023 K and a GHSV
of 18,000 mL/(g·h), CH4 conversion decreased from
52% to 45% and CO2 conversion decreased from 71%
to 66% for the Ir/CeO2 catalyst after 200 h on stream.
By contrast, almost constant CH4 and CO2 conversions
of approximately 65% and 79%, respectively, were
observed for the Ir/Ce0.9La0.1O2 catalyst (Fig. 12(a)).
Even with the increase of GHSV to 36,000 mL/(g·h)
and temperature to 1,073 K, CH4 and CO2 conversions
were still retained at 60% and 70%, respectively, at
1,000 h for the Ir/Ce0.9La0.1O2 catalyst, further confirming
the high stability performance of the Ir/Ce0.9La0.1O2
catalyst. Results obtained from the stability tests were
strongly indicative of the higher thermal stability of
the Ir/Ce0.9La0.1O2 catalyst for the dry reforming of
methane, attributed to the enhanced interaction between
the metal and support for significantly limiting the
size enlargement of Ir and the support (as discussed
Nano Res. 13

Figure 11 Effect of space velocity on the performance of the Ir/CeO2 and Ir/Ce0.9La0.1O2 catalysts for dry reforming of methane.

Figure 12 (a) Stability test for the dry reforming of methane over the Ir/Ce0.9La0.1O2 and Ir/CeO2 catalysts at 1,023 K and GHSV =
18,000 mL/(g·h) for 200 h, and (b) stability performance over the Ir/Ce0.9La0.1O2 catalyst at 1,073 K and GHSV = 36,000 mL/(g·h) for 100,0 h.

below), as well as maintaining the sites for molecules
activation and the interfaces for intermediate tran-
sformation. Besides, the enhanced OSC attributed to
the doping of La3+ for the Ir/Ce0.9La0.1O2 catalyst also
contributes to the higher ability for the gasification of
carbon precursors, leading to significantly less carbon
deposits.
3.4 Characterization of the used catalysts
For determining the relationship between the catalytic
performance and catalyst structure, the used samples
were characterized by XRD, XPS, TEM, and TPO.
In the following measurements, used catalysts will
be referred to as used Ir/A-t, where A represents
Ce0.9La0.1O2 or CeO2, and t represents reaction time
(200 or 1,000 h).
From the XRD patterns of the used samples (Fig. 1),
the Ir diffraction peak was not observed for the used
Ir/Ce0.9La0.1O2-200 and Ir/Ce0.9La0.1O2-1000 catalysts,
indicating that the high dispersion of Ir is possibly
maintained in the used Ir/Ce0.9La0.1O2 catalysts. In
contrast, Ir diffraction was observed for the used
Ir/CeO2-200 catalyst, and the size of the Ir nano-
particles increased to 10 nm, indicative of the sintering
of Ir nanoparticles in the used Ir/CeO2 catalyst. With
respect to the supports, the size of the CeO2 nano-
particles clearly increased from 13 to 18 nm, while that
of the Ce0.9La0.1O2 nanoparticles slightly increased

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14 Nano Res.

from 10 to 13 nm only after 200 h on stream. Although

Ce0.9La0.1O2 reacted for 1,000 h at 1,073 K, its size was
only 15 nm for the used Ir/Ce0.9La0.1O2-1000 catalyst.
This size variation suggested that significantly limited
aggregation is observed for the Ce0.9La0.1O2 support
used in the Ir/Ce0.9La0.1O2 catalyst, indicating that its
structure is more stable than that of the Ir/CeO2
catalyst.
The XPS profiles of Ir 4f, O 1s, Ce 3d, and La 3d
of the used Ir/Ce0.9La0.1O2 catalysts shown in Fig. 5
also provide some insights into the stability of the
catalyst structure. Both the Ir 4f spectra on the used
Ir/Ce0.9La0.1O2-200 and used Ir/Ce0.9La0.1O2-1000 catalysts
exhibited two peaks at 60.8 and 63.6 eV, respectively,
attributed to metallic Ir0, indicating that Ir0 is retained
on the Ce0.9La0.1O2 support surface. O 1s profiles of the
used Ir/Ce0.9La0.1O2 catalysts demonstrated the presence
of oxygen defect and lattice oxygen species. The ratio
of the oxygen defects on the used Ir/Ce0.9La0.1O2-1000
catalyst surface was 9.5%, similar to a ratio of 11.0%
observed for the used Ir/Ce0.9La0.1O2-200 catalyst surface,
indicative of stable oxygen species in the catalyst. The
strength and shape of the Ce 3d and La 3d spectra for
the used catalysts were similar to those observed for
the fresh samples, indicative of the retained state of
Ce and La species in the used Ir/Ce0.9La0.1O2 catalysts. Figure 13 HRTEM images of used Ir/CeO2 ((a) and (b)) and
In the TEM images of the used Ir/CeO2-200 catalyst Ir/Ce0.9La0.1O2 ((c) and (d)) catalysts after 200 h on stream at
(Fig. 13(a) and 13(b)), approximately 9–10 nm Ir nano- 1,023 K and used Ir/Ce0.9La0.1O2 ((e) and (f)) catalysts after 1,000 h
particles observed on the ceria surface were covered on stream at 1,073 K.
by carbon deposits. In the former, the enlarged Ir
nanoparticles would decrease the boundaries between gasification of carbon precursors. Thus, significantly
the metal and support and weaken the metal–support more stable performance is observed for the Ir/
interaction. In the latter, the encapsulated Ir nano- Ce0.9La0.1O2 catalyst. In addition, although the size of
particles would block the activation of methane. Ir nanoparticles on the used Ir/Ce0.9La0.1O2-1000 catalyst
Both these effects led to decreased performance for slightly increased to 2–3 nm (Fig. 13(e) and 13(f)), the
the Ir/CeO2 catalyst in the stability test. In contrast, observed aggregation was too limited to affect catalyst
2–3 nm-sized Ir nanoparticles were still in intimate performance, attributed to the stronger metal–support
contact with the surface of the Ce0.9La0.1O2 support, interaction and the sufficient metal-support boundaries
and carbon deposits were not clearly observed for the to transform intermediates and gasify carbon pre-
used Ir/Ce0.9La0.1O2-200 catalyst (Fig. 13(c) and 13(d)). cursors at a high temperature of 1,073 K.
The constant size of the Ir nanoparticles was attributed For analyzing the carbon deposits observed on
to the stronger metal–support interaction of the Ir/ the used catalysts, TPO was performed, and Fig. 14
Ce0.9La0.1O2 catalyst in limiting the movement and shows the results obtained. CO2 was released at
aggregation of the Ir nanoparticles [23], which in turn 670 and 870–1,005 K, corresponding to amorphous
preserves the boundaries between the metal and carbon and graphitic carbon, respectively, for the
support for the transformation of intermediates and used Ir/CeO2-200 catalyst [59]. The ratio of the areas

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Nano Res.
Figure 14 TPO results of used Ir/CeO2 and Ir/Ce0.9La0.1O2
catalysts.
indicated that mainly graphitic carbon is formed.
Instead, almost amorphous carbon (620 K) with marginal
graphitic carbon (980 K) was observed for the used
Ir/Ce0.9La0.1O2-200 catalyst, and only graphitic carbon
(980 K) without amorphous carbon was observed for
the Ir/Ce0.9La0.1O2-1000 catalyst. This result indicated
that the nature of the carbon deposits is significantly
affected by catalysts and reaction conditions. Amorphous
carbon possibly undergoes the transformation to
graphitic carbon at higher temperatures. Although
carbon deposits were observed in the TPO profiles,
their weight estimated by thermogravimetry (TG) was
negligible (Fig. S1 in the Electronic Supplementary
Material). Only 0.45 wt.% of carbon was deposited
on the used Ir/Ce0.9La0.1O2-200 catalysts, which is less
than that observed on the used Ir/CeO2-200 catalysts
(0.70 wt.%). This result is attributed to the enhanced
interaction between Ir and the support, which in
turn leads to the improvement in the OSC of the
Ir/Ce0.9La0.1O2 catalyst and facilitates the gasification
of carbon precursors by the surface and accessible
bulk oxygen of support; hence, low amounts of
carbon deposits (0.6 wt.%) are observed on the used
Ir/Ce0.9La0.1O2-1000 catalyst.
4 Conclusions
In summary, Ir/Ce0.9La0.1O2 and Ir/CeO2 catalysts were
used for the dry reforming of methane. As compared
to the Ir/CeO2 catalyst, the Ir/Ce0.9La0.1O2 catalyst
formed by the doping of La2O3 resulted in significant
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15
improvement in the interaction between the metal
and support, leading to enhanced oxygen storage
capacity and redox behavior, improved Ir dispersion,
and a stable catalyst structure. The thermally stable
Ir/Ce0.9La0.1O2 catalyst afforded higher performance
and stability for the dry reforming of methane,
attributed to stronger metal-interaction in limiting the
size enlargement of Ir nanoparticles and the Ce0.9La0.1O2
support, as well as the improved oxygen storage
capacity for decreasing carbon deposition.
Acknowledgements
The authors acknowledge the financial supports from
National Natural Science Foundation of China (Nos.
21503142 and 21503113), Singapore National Research
Foundation CREATE-SPURc program (No. R-143-001-
205-592), Singapore MOE Tier II (No. R143-000-542-112),
and Academia-Industry Collaborative Innovation
Foundation from Jiangsu Science and Technology
Department (No. BY2014139).
Electronic Supplementary Material: Supplementary
material (TG analysis in the used samples) is available
in the online version of this article at http://dx.doi.org/
10.1007/s12274-016-1296-2.
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