Article

Journal of
Copyright © 2017 American Scientific Publishers
Nanoscience and Nanotechnology
All rights reserved Vol. 17, 3864–3872, 2017
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Influence of Thermal Treatments on the Reducibility and

Catalytic Properties of Pd Supported Over
Ce0
6Zr0
4Ox /SiO2 and Ce0
73Tb0
27Ox /SiO2 for
Methane Oxidation
Victor Ferrer1
∗ , Angeli Barroso1 , Jean Bracho1 , Dora Finol1 , Francisco Domínguez1,
Alexander Moronta1, Miguel Ramos2 , Fabrizio Puleo3 , and Leonarda F. Liotta3
∗
1
Instituto de Superficies y Catálisis, Facultad de Ingeniería, Universidad del Zulia, P.O. Box 15251, Maracaibo 4003A, Venezuela
2
Instituto Zuliano de Investigaciones Tecnológicas (INZIT), La Cañada de Urdaneta, Apartado 331, Maracaibo, Venezuela
3
Istituto per lo Studio dei Materiali Nanostrutturati (ISMN-CNR), via Ugo La Malfa 153, I-90146, Palermo, Italy

Pd/Ce0
6 Zr0
4 Ox /SiO2 and Pd/Ce0
73 Tb0
27 Ox /SiO2 catalysts were prepared by incipient wetness
impregnation method using aqueous solutions of Ce(NO3 3 · 6H2 O, ZrO(NO3 2 · nH2 O, Tb(NO3 3 ·
5H2 O and Pd(NO3 2 · nH2 O precursors. The catalysts were characterized by X-ray diffraction
(XRD), Temperature Programmed Reduction (TPR-H2 , CO Chemisorption, Oxygen Storage Capac-
ity (OSC) and Infrared spectroscopy of adsorbed CO (FTIR-CO). The catalytic activity was mea-
sured in the methane oxidation reaction. XRD patterns showed that after two activity cycles, the
solids crystallinity was not modified, while TPR results revealed that reduction maxima were shifted
to lower temperatures, indicating an improvement in sample reducibility. The CO/Pd ratio diminished
with increasing the reduction temperature, suggesting both, Pd inward diffusion/covering by Ce3+
ions (geometrical effects) and/or increase in Pd particles size. The IR spectrum of adsorbed CO
reported the presence of cationic palladium species interacting with CO regardless of reduction
temperature as well as carbonate species and weak interactions with ceria and silica. Zr and Tb
containing samples presented a high and stable OSC after undergoing various OSC cycles. The
catalytic activity was enhanced after two reaction cycles due to the formation of large PdO particles.
T50 values indicated that reduction treatments prior to methane reaction generated more active cat-
alytic species than those obtained by oxidation treatment; however, such active species were not
stable at high temperatures.
Keywords: Methane Oxidation, Mixed Oxides, OSC, Pd Catalysts, Thermal Treatments.

1. INTRODUCTION are considered as precursors of climate change.3 In big

Heterogeneous catalysis is focused to resolve one of the
most serious problems of anthropogenic origin: the atmo-
spheric pollution generated by vehicles.1 In a complete
combustion, the hydrocarbons are transformed into carbon
dioxide (CO2
and water (H2 O); however, due to ther-
modynamic reasons or mechanical flaw, the hydrocarbons
oxidation (e.g., gasoline or gasoil) is incomplete, gen-
erating carbon monoxide (CO), nitric oxides (NOx
and
non-burnt hydrocarbons (HC).2 The influence of these pol-
lutants over air quality has been widely studied, and they
∗
Authors to whom correspondence should be addressed.
cities, where vehicles concentration in low areas is high,
the accumulation of these pollutants in the lowest atmo-
sphere layer produces thermal inversion, generating photo-
chemical smog, acid rain, global warming and ozone layer
depletion.4
Three-way catalysts (TWC) are considered as the most
successful pollutants post-treatment for gasoline and diesel
motors.5 6 In heated TWC in stationary condition, con-
versions of 95% and higher are reached for CO, NOx
and HC. TWC can transform CO, NOx and HC into
CO2 , H2 O and molecular nitrogen.7 The TWC are con-
formed by noble metals such as Pd, Pt, Rh and a redox

3864 J. Nanosci. Nanotechnol. 2017, Vol. 17, No. 6 1533-4880/2017/17/3864/009 doi:10.1166/jnn.2017.14000

Ferrer et al. Influence of Thermal Treatments on the Reducibility and Catalytic Properties
promoter (typically cerium oxide) supported on a ceramic
monolith of high surface area and silicon content. It has
been reported that fluorite-structured solid solutions, based
on mixtures of CeO2 /La2 O3 /Pr2 O3 and CeO2 /Ln2 O3 /Pr2 O3
where Ln = Tb, Sm, Gd are effective catalysts for methane
combustion.8
Methane combustion has been of special interest since
natural gas, which consists mainly of methane, is a com-
mon fuel used worldwide. Since methane is the most
refractory hydrocarbon, it is often used as the model
hydrocarbon compound for activity tests.910 The use of
Pd has been known as the most active component for the
combustion of methane among noble metal catalysts.11
The use of CeO2 as an additive in the so-called three
way catalysts for automotive exhaust treatment have been
widely investigated because it has been found effective
in the promotion of various catalytic reactions including,
CO2 activation12 , CO oxidation13 and CO/NO removal.14
CeO2 has the capacity to shift between CeO2 under oxi-
dizing conditions and Ce2 O3 under reducing conditions,
respectively, and the ease of formation of labile oxygen
vacancies and, particularly, the relatively high mobility
of bulk oxygen species. However, the chemical proper-
ties of CeO2 can be affected when it is subjected to both
high temperature and reducing conditions,15 this can lower
OSC values and catalytic activity. Therefore, a great deal
of attention has been given to doping of CeO2 with iso-
valent/aliovalent cations to enhance the OSC properties,
especially to improve the bulk reducibility at lower tem-
peratures and to stabilize the structure against sintering.16
It has been reported that the addition of a dopant like Zr or
Tb to ceria, improves its textural stability,17 18 prevents Ce
sintering19 and enhances the mobility of lattice oxygen.15
The introduction of smaller isovalent non-reducible cations
like Zr4+ and Hf4+ into the ceria lattice enhances the OSC
by creating intrinsic oxygen vacancies thereby increasing
the oxygen mobility by facilitating the Ce3+ /Ce4+ redox
process.20 Tests carried out on CeO2 –ZrO2 mixed oxides
showed better thermal stability and OSC than that of pure
ceria6 21–24 and it has been established that the addition of
zirconium is important to stabilize performance after cal-
cination and to provide more reactive oxygen ions from
the surface and the bulk.25 Recently, the use of variable
valence dopants into the CeO2 lattice has attracted much
attention.2627 Among the reducible elements, terbium (Tb)
and praseodymium (Pr) are particularly suitable for mak-
ing solid solutions with ceria.28 Other mixed oxides such
as Ce08 Tb02 Ox have shown good redox behavior and cat-
alytic activity.29
For this reason, the studies related to the improve-
ment of chemical and catalytic properties of TWC are of
great relevance. Textural and redox properties of TWC
are closely related with operation conditions;23 however,
the effect of catalytic cycles as well as thermal treatments
over TWC properties is still under study. In this research,
the influence of thermal treatments over the reducibility
J. Nanosci. Nanotechnol. 17, 3864–3872, 2017
and catalytic activity of Ce06 Zr04 Ox and Ce073 Tb027 Ox
mixed oxides supported on SiO2 and impregnated with
Pd was studied. The use of silica as support was pre-
ferred to alumina in order to prevent the formation under
reducing conditions of the inactive CeAlO3 phase.30 The
samples were characterized by X-ray fluorescence (ED-
XRF), X-ray powder diffraction (XRD), Temperature pro-
grammed reduction (TPR), CO chemisorption, Oxygen
storage capacity (OSC) and Fourier transformed infrared
spectroscopy of adsorbed CO (FTIR-CO). The methane
oxidation reaction was studied under stoichiometric con-
ditions throughout two reaction cycles, and after reduction
treatments.
2. EXPERIMENTAL SECTION
2.1. Catalysts Preparation
SiO2 (Baker) was previously calcined at 400  C for 2 h in
order to remove any water, carbonate and any other volatile
impurities, then it was impregnated with aqueous solu-
tions of Ce(NO3
3 ·6H2 O, ZrO(NO3
2 ·nH2 O or Tb(NO3
3 ·
5H2 O. All these precursors have purity ≥99.0 and were
provided by Acros Organics. Cerium and zirconium or ter-
bium nitrates were mixed in appropriate amounts in order
to obtain a mass ratio of Ce/Tb = Ce/Zr = 2.3 (molar ratio
Ce/Tb = 2.70 and Ce/Zr = 1.5) and a mixed oxide compo-
sition of 17 wt.%. The so prepared samples were calcined
at 700  C for 4 h and labeled as Ce073 Tb027 Ox /SiO2 (CTS)
and Ce06 Zr04 Ox /SiO2 (CZS).
The corresponding Pd catalysts, Pd/CZS and Pd/CTS,
with a metal loading of 0.5 wt% were prepared by incip-
ient wetness impregnation method using Pd(NO3
2 · nH2 O
solution (Aldrich, 99.9%) in HCl 0.1 N. Finally, the cata-
lysts were calcined at 500  C for 2 h.
For comparison purposes, CeO2 /SiO2 (CS) and 0.5%Pd/
CeO2 /SiO2 (Pd/CS) samples were also prepared and used
for certain characterizations.
2.2. Techniques
The elemental concentrations of the samples were quanti-
fied by energy dispersive X-ray fluorescence spectroscopy
(ED-XRF) using a Shimadzu EDX-700HS spectrometer,
operating at 50 kV and 30 mA.
The X-ray powder diffraction (XRD) patterns were
acquired with a Bruker D8 Focus diffractometer operated
at 40 kV and 40 mA, with Cu K radiation ( = 15418 Å)
at a rate of 1.1 2 min−1 with 0.02 step size and time
per step of 0.5 s.
TPR measurements were carried out in a stainless steel
reaction line coupled to a thermal conductivity detec-
tor (TCD). 50 mg of calcined catalyst were loaded in a
quartz reactor and subjected to a cleaning/oxidation treat-
ment that consisted in heating the sample from room tem-
perature (RT) up to 550  C (10  C min−1
in a flow of
O2 (5%)/He (30 cm3 min−1 ) for 1 h, cool down to 150  C,
switching the gas flow to Ar (Praxair, 99.999%) and finally
3865
Influence of Thermal Treatments on the Reducibility and Catalytic Properties
cool down to room temperature. Pd containing samples
were cooled down at a flow rate of 30 cm3 min−1 of Ar
(Praxair, 99.995%) to −80  C in a cold trap. Then, the flow
rate was changed to 30 cm3 min−1 of H2 (5.22%)/Ar (Prax-
air) and the cold trap was removed, starting to compute
H2 consumption from −80  C to room temperature. After-
wards, the sample was heated up to 850  C using a heating
rate of 10  C min−1 . TPR experiments were also car-
ried out over exhausted samples subjected to two reaction
cycles (denoted as the corresponding notation followed by
−ex), previously dried at 120  C for 30 min in Ar to elim-
inate water formed during reaction.
CO chemisorption was carried out in the TPR line
described above. 50 mg of sample were submitted to the
oxidation treatment mentioned above (550  C, O2 /He). The
sample was cooled down until the reduction temperature
(300 or 500  C) and reduced in H2 (5%)/Ar flow for 1 h.
Afterwards, the sample was evacuated in He gas (Aga,
99.999%) for 30 min at the same reduction temperature.
When the treatment finished, the sample was cooled down
to room temperature. Finally, 1.47 mol of CO (Praxair,
99.5%) were injected repeatedly until no adsorption was
detected. The CO chemisorption was reported as mol CO
adsorbed per gram of sample.
For OSC measurements, the same TPR and CO
chemisorption line was used. First, the sample (50 mg) was
submitted to the oxidation treatment used in TPR tests.
Afterwards, the temperature was decreased up to reduction
temperature (300 or 500  C) in O2 (5%)/He flow. At this
temperature, the flow was switched to He (30 cm3 min−1 ,
Praxair, 99.999%) for 30 min. After evacuation, a flow
of H2 (5.22%)/Ar (60 cm3 min−1
was admitted into the
reactor for 1 min at the reduction temperature, and then
switched to He flow for 10 min at the same temperature.
Finally, successive O2 (5%)/He pulses of 40 L (STP) at
300  C were injected repeatedly until no changes in the
value of O2 peak area was detected. The result is reported
as Cycle 1. This procedure was repeated 2 or 3 times for
the same sample and the OSC values were reported as
cycles 2 and 3, respectively.
FTIR spectra of self-supported wafers (≈24 mg cm−2

were recorded by accumulation of 100 scans with a res-
olution of 2 cm−1 in a Shimadzu Prestige-21 equipment
provided with a MCT detector cooled with liquid N2 . The
wafers were loaded in a moveable glass sample holder,
equipped with an iron magnet, inserted in a conventional
pyrex-glass cell (NaCl window). The iron magnet allowed
the transfer of the catalyst sample from the heating region
to the infrared light beam. Prior to CO adsorption, the
wafer was dried at 120  C for 1 h in Ar (20 cm3 min−1 ,
Praxair, 99.995%). Then, the sample was submitted to a
reduction pre-treatment (H2 , 20 cm3 min−1 , Aga, 99.999%)
from 120  C until the reduction temperature (300 or
500  C) for 1 h at atmospheric pressure, followed by evac-
uation for 30 min in Ar flow at the same temperature.
After evacuation, the temperature was decreased to RT, and
3866
Ferrer et al.
the evacuation continued for 15 min. After finishing the
pre-treatment, the wafer was moved to the analysis region
and the spectrum was taken. Then, a continuous flow of
CO (Praxair, 99.5%) was admitted to a pyrex-glass cell
for 10 min at atmospheric pressure. The wafer was evac-
uated in a flow of Ar for 30 min and finally, the spectrum
was obtained. The spectrum of the pre-treated catalyst was
used as reference and subtracted from the spectra of the
catalyst exposed to CO.
2.3. Catalytic Activity
The methane oxidation reaction was performed from RT
up to 700  C, in a quartz reactor, using 50 mg of catalyst
in a fixed bed. Before reaction, catalyst was submitted to
the oxidation treatment described above. The reactor was
fed with a gas mixture (102.7 cm3 min−1
using a flow
of methane (2.7 cm3 min−1
, oxygen (5.4 cm3 min−1
and
helium as balance (94.6 cm3 min−1
in stoichiometric pro-
portion (CH4 /O2 = 05, space velocity = 14342 h−1
. The
methane composition was analyzed at the reactor exit with
a Perkin Elmer Clarus 500 gas chromatograph, equipped
with a FID and a molecular sieve 5A capillary column.
The exhausted samples (−ex) were obtained by a sec-
ond reaction cycle over the same catalyst. With the pur-
pose to study the effect of reduction treatments over the
catalytic activity, after the oxidation treatment, Pd/CZS
and Pd/CTS were submitted to a flow of a H2 (5%)/Ar
(60 cm3 min−1
at 300 or 500  C for 1 h before the
reaction. The methane oxidation reaction rate was cal-
culated at 300  C considering the reactor in differential
conditions.
3. RESULTS AND DISCUSSION
3.1. Catalysts Characterization
The chemical composition of prepared samples measured
by ED-XRF spectroscopy is reported in Table I. The ana-
lytic composition was close to the nominal one ±10%.
The ceria, CZ and CT nominal loading was chosen
equal to 17 wt% in order to form a monolayer over the
silica surface.31
The diffraction patterns are reported in Figures 1 and 2.
All samples showed diffraction peaks at 28.5, 33.1, 47.5
and 56.3. The first peak has been attributed to the crys-
tallographic plane (1 1 1) of fluorite structure of CeO2 ,5
and the others correspond to (2 0 0), (2 2 0) and (3 1 1)
CeO2 reflection planes, respectively.56 The slight devi-
ation of 28.5 signal to higher angles for CZS sample
(Fig. 1(b)) compared to CS sample (Fig. 1(a)) can be
associated to CeO2 –ZrO2 phases reflection with different
composition23 that could indicate the CeZr mixed oxide
formation.6 In contrast, a deviation of (1 1 1) CeO2 plane
for CTS (Fig. 1(d)) was not observed, suggesting that Tb
introduction into CeO2 lattice do not generate a noticeable
structural change in the CeO2 crystalline lattice that could
be detected by XRD.
J. Nanosci. Nanotechnol. 17, 3864–3872, 2017
Ferrer et al. Influence of Thermal Treatments on the Reducibility and Catalytic Properties

Table I. Chemical composition (wt.%) determined by ED-XRF spectroscopy, H2 consumption (cm3 H2 g−1 CeO2
and CO/Pd ratio for different
reduction treatments of prepared samples.

H2 consumption CO/Pd ratio

Sample Pd CeO2 ZrO2 Tb4 O7 SiO2 (cm3 H2 g−1 CeO2
(Reduction temperature 300  C or 500  C)

CS – 17.0 – – 83.0 65 –
CZS – 13.09 3.46 – 83.45 48 –
CTS – 11.25 – 9.22 79.53 60 –
Pd/CS 0.45 16.92 – – 82.63 39 0.378 [0.313]
Pd/CZS 0.46 13.03 3.44 – 83.07 37 0.695 [0.501]
Pd/CTS 0.45 11.20 – 9.18 79.17 49 0.646 [0.398]

Notes: Values in square brackets correspond to CO/Pd ratio after reduction at 500  C. No CO adsorption was detected for the supports.

Based on the methodology proposed by Kozlov et al.,32
considering the (1 1 1) peak position, the predominant
Ce–Zr phase for CZS sample could be Ce08 Zr02 O2 . This
result is similar to that obtained for this sample if it is
considered the complete incorporation of zirconium into
the CeO2 lattice (≈Ce073 Zr027 O2
. For CZS-ex sample
(Fig. 1(c)), the peak intensity corresponding to the (1 1 1)
CeO2 plane increased after two reaction cycles, which
can be related with a better crystallinity possibly due to
the catalyst sintering. However, for the CTS-ex sample
(Fig. 1(e)), no significant changes in the intensity of the
same peak was registered, indicating a good thermal sta-
bility. Accordingly, Hornés et al.27 reported that doping
ceria with Tb helps to stabilize to some extent the sys-
tems toward thermal sintering. No Pd peaks were detected
in the XRD patterns (Fig. 2), suggesting that PdO parti-
cles are finely dispersed,5 6 although we cannot exclude
that due to the low palladium content any PdO feature is
below the detection limit. The changes in the intensity of
the signal at 28.5 when Pd is incorporated suggest mod-
ifications in the cristallinity of the samples that could be
due to the redispersion of the ceria or mixed oxide when
this is impregnated with the Pd precursor solution and sub-
sequent calcination.
Figures 3 and 4 show the TPR profiles of calcined and
exhausted (ex) samples, ceria-based oxides and supported
Pd catalysts, respectively. The TPR profile of CS sample
(Fig. 3(a)) reported two signals with maxima at 542 and
837  C that correspond to the reduction of surface and bulk
Ce4+ ions.6 33 CZS (Fig. 3(b)) and CTS (Fig. 3(d)) samples
showed the typical CeO2 reduction signals but at lower
temperatures, suggesting the Zr and Tb incorporation into
the CeO2 lattice.6 29
The reduction signal observed at 489  C for CZS sam-
ple (Fig. 3(b)), previously assigned to reduction of surface
Ce4+ ions, becomes more intense than the correspond-
ing signal for CTS sample (Fig. 3(d)) sample registered
at 474  C, suggesting that Ce–Zr mixed oxide improves
the redox properties more than Ce–Tb mixed oxide. For
CeTb mixed oxides it has been reported that Tb ions
could be stabilized in two different oxidation states, i.e.,
3+ and 4+ ,26 34 so if part of Tb would be reduced, this
would affect also the cerium oxidation state and, therefore,
its reduction degree. On the other hand, by comparing the
reduction profile of CS and CTS samples (Figs. 3(a, d)),
a shift to lower temperatures can be observed, suggest-
ing that Tb incorporation improves the redox properties
of CeO2 .
33.1º
28.5º

47.5º
28.5º

56.3º
33.1º

47.5º

56.3º

(e) (e)
Intensity (a.u.)

(d)
Intensity (a.u)

(d)

(c)
(c)

(b)
(b)

(a)
(a)

25 30 35 40 45 50 55 60 65 70 25 30 35 40 45 50 55 60 65 70
2θ 2θ

Figure 1. X-ray diffraction patterns for (a) CS; (b) CZS; (c) CZS-ex; Figure 2. X-ray diffraction patterns for (a) Pd/CS; (b) Pd/CZS;
(d) CTS and (e) CTS-ex samples. (c) Pd/CZS-ex; (d) Pd/CTS and (e) Pd/CTS-ex samples.

J. Nanosci. Nanotechnol. 17, 3864–3872, 2017 3867

Influence of Thermal Treatments on the Reducibility and Catalytic Properties Ferrer et al.

790
along with reduction of surface Ce4+ ions.33 The signals
440 (e)
observed between 200 and 400  C (inset graphs) corre-
754 spond to reduction of PdOx species strongly interacting
474 with support.6 The negative reduction signals at 44 and
(d)
59  C (Figs. 4(c and e)) is attributed to -PdHx phase
TCD signal (a.u.)

478 decomposition and is related with the presence of large

489
542
×½
100 200 300 400 500
Temperature (ºC)
Figure 3. TPR profiles for (a) CS; (b) CZS; (c) CZS-ex; (d) CTS and
(e) CTS-ex samples.
The catalytic activity cycles modified the redox prop-
erties of CZS-ex (Fig. 3(c)) and CTS-ex (Fig. 3(e)), as
it is confirmed by the shift to lower temperature of the
reduction maxima for exhausted samples, excepted for the
signal registered at 790  C in CTS-ex sample that was
shifted to a higher temperature. The slight reduction sig-
nals registered for all mixed oxide between 500–700  C
could be related with the reduction of the mixed oxide in
different interaction with silica support. For TPR profiles
of Pd/CZS (Fig. 4(b)) and Pd/CTS (Fig. 4(d)) samples,
an important change over the reducibility was observed
with Pd incorporation. Even more, the presence of Tb or
Zr modified the reducibility when comparing TPR profiles
of Pd/CZS, Pd/CTS and Pd/CS (Fig. 4(a)) samples. The
reduction signals registered at T < 200  C can be assigned
to reduction of crystalline PdOx particles of different sizes5
81
383
44 94
TCD signal (a.u.)
803 PdOx particles that could be formed after the second reac-
(c) tion cycle.5 35
The overall hydrogen consumption registered for the
808
(b) so far discussed mixed oxides and Pd supported catalysts
(Table I) is well comparable with our previous investi-
837 gation on ceria-zirconia mixed oxides, ranging between
(a)
37–65 cm3 H2 g−1 CeO2 .23
CO chemisorption results are shown in Table I. No CO
adsorption was detected for supports, so the adsorbed CO
600 700 800 900 is referred to Pd. For Pd/CZS sample reduced at 300  C,
a CO/Pd ratio of 0.695 was reported while an increase
in reduction temperature to 500  C decreases this ratio
(0.501). The same trend was registered for Pd/CTS and
Pd/CS samples. Bernal et al.36 attributed similar behavior
to strong metal support interaction effect (SMSI) to explain
the suppress of CO chemisorption with the increase of
reduction temperature due to high electronic mobility of
reduced cerium particles (Ce3+ ) that could produce a
migration of these particles towards Pd metallic phase,
forming a thin layer that cover the Pd surface. Therefore,
it is possible to consider the results of adsorbed CO to
the strong interaction of Pd with the redox promoter gen-
erated by the reduction treatment at 500  C, causing the
partial blockage of Pd sites for CO chemisorption.37 How-
ever, when comparing the CO/Pd ratio of Pd/CS, Pd/CTS
and Pd/CZS samples, it is evident that the presence of the
mixed oxide can avoid the loss of chemisorption capac-
ity at both reduction temperatures. Another hypothesis that
could explain the decrease in CO/Pd ratio can be the sin-
tering of Pd particles produced by the increase of reduction
temperature.
OSC values of prepared samples are reported in Table II.
821 CTS and CZS supports registered low OSC values for the
(e)
first cycle compared to samples that contain Pd, which
showed an increase in OSC values with repetitive cycles.
758 For CTS sample, the OSC values were similar at both

(d) reduction temperatures, indicating that an increase in the

298
826
reduction temperature up to 500  C did not increase the
76 (c)
343 Table II. Oxygen storage capacity (mol O2 g−1
for different cycles
59 and after reduction at 300 or at 500  C.
82
817
(b) Sample Cycle 1a Cycle 2b Cycle 3c
58 268 760
CTS 4.1 (4.2) –d –d
(a) CZS 1.3 (10.8) 0.4 (27.1) 0.2 (25.4)
Pd/CTS 23.3 (20.9) 24.8 (32.2) 26.6 (34.1)
Pd/CZS 32.5 (30.6) 37.6 (39.6) 40.0 (42.7)
–100 0 100 200 300 400 500 600 700 800 900
Temperature (ºC) Notes: Values in round brackets correspond to OSC value for samples reduced
at 500  C. a Sample submitted to OSC procedure; b Sample resulting of Cycle 1
Figure 4. TPR profiles for (a) Pd/CS; (b) Pd/CZS; (c) Pd/CZS-ex; subjected to a new OSC procedure; c Sample resulting of Cycle 2 subjected to a
(d) Pd/CTS and (e) Pd/CTS-ex samples. new OSC procedure; d Test not carried out.

3868 J. Nanosci. Nanotechnol. 17, 3864–3872, 2017

Ferrer et al.
oxygen vacancies for this sample. The reduction treat-
ment at 300  C for CZS sample did not promote the
oxygen vacancies formation that could explain the low
quantity of oxygen chemisorbed, and, hence, after 3 repet-
itive cycles, the support redox capacity is almost null.
When the reduction temperature was increased to 500  C,
higher OSC values were obtained, that can be related with
a higher reduction grade of mixed oxide and formation
of more oxygen vacancies.33 Pd/CZS sample showed the
highest OSC for all cycles and both reduction tempera-
tures (42.7 mol O2 g−1 for cycle 3). Considering the
possibility of O2 spillover intrinsic to Pd,23 the presence
of Zr could be facilitating the O2 mobility into the CeO2
lattice in a higher proportion than Tb. It can be observed
the slight improvement in OSC values with the number
of cycles, especially for Pd/CZS sample at both reduction
temperatures, and for CZS and Pd/CTS samples reduced at
500  C. This behavior could be due to an organization of
the solid solution (cubic and tetragonal phases) after suc-
cessive redox treatments and the formation of bulk Ce3+
cations involving a thorough reorganization of the mixed
oxide network.21
FTIR spectra of adsorbed CO in samples reduced at 300
or 500  C are reported in Figure 5. Infrared spectra for
CZS sample are shown in Figure 5(A). Two absorption
Figure 5. IR spectra of CO adsorbed at 25  C for (A) CZS; (B) CTS; (C) Pd/CZS and (D) Pd/CTS samples, reduced at 300  C (1) or 500  C (2).
J. Nanosci. Nanotechnol. 17, 3864–3872, 2017
Influence of Thermal Treatments on the Reducibility and Catalytic Properties
bands were registered for the support reduced at 300  C:
the first one at 1867 cm−1 with a shoulder at 1994 cm−1
and the second one at 1625 cm−1 , while for the support
reduced at 500  C a low intensity band at 2003 cm−1 was
obtained. The band observed at 1625 cm−1 for the sup-
port reduced at 300  C is attributed to the presence of
carbonates.38 Thomas et al.39 carried out FTIR-CO tests
over Ce068 Zr032 O2 mixed oxide, reporting bands at 2167
and 1575 cm−1 correlated to the weak interaction of CO
with cerium surface sites and carbonate formation, respec-
tively. This result could indicate that the bands at 2003,
1994 and 1867 cm−1 corresponds to the weak CO interac-
tion with ceria. Similar bands (2003 cm−1 with a shoulder
at 2025 cm−1
were reported for CTS sample reduced at
500  C (Fig. 5(B)-2). When CTS support was reduced at
300  C (Fig. 5(B)-1), it is worth noting the low intensity
of the CO absorption bands. This behavior was opposite
to that registered for CZS support, which reported well-
defined absorbance signals in both reduction temperatures.
This result could be suggesting that Tb incorporation gen-
erates surface species of different nature to those obtained
for CZS sample.
FTIR-CO spectra for Pd/CZS sample previously
reduced at 300 or 500  C are shown in Figure 5(C).
The absorbance band observed at 2157 cm−1 corresponds
3869
Influence of Thermal Treatments on the Reducibility and Catalytic Properties Ferrer et al.

to CO adsorbed on cationic Pd species (Pd2+ –CO), the Table III. Methane reaction rate at 300  C (mol CH4 s−1 g−1
and
band at 2085 cm−1 can be assigned to CO species singly T50 of calcined and exhausted catalysts after reduction at 300 (R300) or
at 500  C (R500).
bonded to Pd0 atoms and the bands at 1975 and 1936 cm−1
correspond to bridged CO species bonded to zero-valent rCH4
Pd atoms (Pd02 CO).40 41 In this sample, the increase in Sample T50 ( C) T50 R300 ( C) T50 R500 ( C) (mol CH4 s−1 g−1 )
reduction temperature did not modify the spectra, indicat- CS nr nm nm 55
ing that the surface species have good thermal stability. CTS nr nm nm 110
FTIR-CO spectra for Pd/CTS sample reduced at 300 or CZS nr nm nm 221
500  C (Fig. 5(D)) present absorbance bands at 2083 and Pd/CTS 519 [457] 466 501 74 (258)
2087 cm−1 that correspond to linear CO adsorbed over Pd/CZS 440 [355] 395 498 294 (331)
Pd0 surface atoms. The low spectrum resolution did not Notes: Values in square brackets correspond to T50 of exhausted samples. Values
allow assigning other bands, but some contribution in the in round brackets corresponds to the reaction rate for exhausted samples. nr: Not
reached; nm: Not measured.
range of 2000–1850 cm−1 could be related to bridge CO
between two Pd atoms.42 The surface species present in
Pd/CTS sample have a good thermal stability. sense, large PdOx particles present in exhausted samples
can dissociate methane more readily.35 The methane oxida-
tion reaction rate (rCH4
at 300  C is reported in Table III.
3.2. Catalytic Activity
At this temperature, conversions were lower than 10%,
The curves of methane conversion (%) versus temperature
allowing to compute the reaction rate, because the reactor
for supports, Pd/CTS and Pd/CZS calcined and exhausted
is operating in differential conditions. The rCH4 increased
(ex) catalysts are reported in Figure 6. The supports
when Pd catalysts were exposed to two reaction cycles.
showed relatively low catalytic performance being not able
This trend was more evident in Pd/CTS catalyst, which
to reach 50% of conversion, although at low tempera-
rCH4 enlarged from 74 to 258 mol CH4 s−1 g−1 . For
ture (around 300–350  C) some CH4 conversion (<10%)
Pd/CZS catalyst, the increment in rCH4 was around 12%
was registered. T50 (Temperature corresponding to 50%
(from 294 to 331 mol CH4 s−1 g−1
. These results could
of methane conversion) values of exhausted samples were
indicate the presence of PdOx species of different nature;
lower than those of calcined counterparts (Table III). This
these findings are supported by the changes observed in the
behavior could be related to the formation of large PdOx TPR profiles of calcined and exhausted catalysts (Fig. 4).
particles,5 generated by the decomposition of -PdHx
In addition, the interaction between Pd and Ce would pro-
phase observed in TPR profiles of exhausted samples mote the presence of catalytic species of higher activity.
(Figs. 4(c, e)). Colussi et al.43 conducted tests of methane
Infrared tests showed the existence of this interaction due
combustion in Pd catalysts supported on alumina doped to the presence of absorbance bands above 2100 cm−1 ,
with various rare earths (Ce, La, Pr, Tb) and concluded that
related to the formation of Pd cationic species.
the high activity observed corresponds to the PdO phase, Even though, it has been reported that PdOx species are
which was identified by thermogravimetric analysis (TGA) highly active for methane combustion, the values found for
and temperature programmed oxidation (TPO). In this CZS and CTS supports (221 and 110 mol CH4 s−1 g−1 ,
respectively) indicates an important contribution in the
reaction rate of the corresponding Pd catalyst. Compar-
100 CZS ing the T50 of calcined and exhausted catalysts, it is evi-
CTS
Pd/CZS dent that Pd/CZS catalyst shows better performance than
80 Pd/CTS Pd/CTS catalyst, highlighting the effect of Zr incorpora-
Pd/CZS-ex
CH4 Conversion (%)

Pd/CTS-ex tion into the ceria lattice that generates a high oxygen stor-
15 age capacity, reported for Zr containing samples (Table II).
60
It has been reported that CeZr and CeTb mixed oxides
10
improve catalytic, thermal and redox properties compared
40 5 to pure CeO2 because these mixed oxides present a high
capacity to release oxygen at low temperatures.42 44 In
0
250 350 350 this regard, it is clear the improvement in the methane
20
oxidation reaction rate at 300  C for CeZr and CeTb
mixed oxides compared to CS catalyst (rCH4 = 55 mol
0 CH4 s−1 g−1
.
0 100 200 300 400 500 600 700 The curves of methane conversion (%) versus temper-
Temperature (ºC) ature for catalysts previously reduced before reaction are
Figure 6. Conversion versus temperature curves for methane oxida- reported in Figure 7. None of catalysts previously reduced
tion after oxidation treatment for (
) CZS; (•) CTS; () Pd/CZS; () at 300 or at 500  C reached 100% conversion. This find-
Pd/CTS; () Pd/CZS-ex and (♦) Pd/CTS-ex catalysts. ing disagrees with the high activity reported for the same

3870 J. Nanosci. Nanotechnol. 17, 3864–3872, 2017

Ferrer et al.
80
A
60
CH4 conversion (%)
40
20
0 Pd particles, generating species that catalyze the methane
0 100 200 300
Temperature (ºC)
80
B Pd/CTS
60
CH4 conversion (%)
40
20
0
0 100 200 300
Temperature (ºC)
Figure 7. Conversion versus temperature curves for methane oxidation
for (A) Pd/CZS and (B) Pd/CTS reduced at 300  C (
) or at 500  C (•).
samples subjected only to oxidation treatment (Fig. 6).
In particular, catalysts reduced at 300  C reported higher
conversion than those reduced at 500  C. This tendency
could indicate that the reduction treatment at 500  C would
produce a migration of Ce3+ ions to Pd particles.33 45
Pd/CZS catalyst reduced at 300  C shows the lowest T50
(395  C) while for reduction at 500  C a T50 of 498  C
was observed (Table III). Meyer et al.46 have suggested
that reduction treatments over a Pd/CeO2 sample before
methane oxidation reaction modify the nature of Pd parti-
cles. They proposed that before exposure the catalyst to the
reaction mixture, the sample was submitted to an oxida-
tion and reduction treatments, that is, at the beginning the
Pd oxidized was reduced and finally reoxidized when the
catalyst was in contact with the reaction mixture. These
oxidation-reduction-oxidation cycles can change the nature
of PdOx towards a more active phase that can generate
high conversion.
Considering that the PdOx phase has been reported as
the most active for methane oxidation,47 a possible expla-
nation for the decrease in the catalytic activity with the
J. Nanosci. Nanotechnol. 17, 3864–3872, 2017
Influence of Thermal Treatments on the Reducibility and Catalytic Properties
Pd/CZS
increase of reduction temperature could be related with the
occurrence of two steps:
(i) The transformation of PdOx to Pd0 , existing a mini-
mum PdOx fraction which particle size depends of reduc-
tion temperature,
(ii) Afterwards, the high reaction temperature favors a
growing of PdOx fraction in the Pd0 /PdOx phase, which
can occur due to the availability of oxygen in the reaction
mixture.
Therefore, it is suggested that a similar behavior in Pd/CZS
catalyst can happen, where the reduction treatment and
subsequent exposure to reaction mixture could reoxidize
400 500 600 700
combustion. It was not possible to reach 100% conver-
sion for any catalysts under the reduction temperatures
employed, while complete conversions were obtained over
the same samples only subjected to oxidation treatment
(Fig. 6). For Pd/CZS and Pd/CTS catalysts previously
reduced at 300  C (Table III), the T50 results were substan-
tially lower than those reported for Pd/CZS and Pd/CTS,
indicating that the catalytic species generated by the previ-
ous reduction treatment are active but no thermally stable
because complete conversions at 700  C were not obtained.
4. CONCLUSIONS
XRD results showed that successive oxidation/activity
cycles did not greatly modify the samples crystallinity.
The shift of reduction maxima to lower temperatures in
400 500 600 700 the mixed oxides and the presence of large PdOx parti-
cles indicated that previous reduction treatment generates
species more easy to reduce with high activity. CO/Pd ratio
of the samples decreased with the increase in reduction
temperature, suggesting a Pd encapsulation by ceria and/or
an increase in Pd particles. FTIR-CO results of supports
reported the presence of carbonates species, while Pd/CZS
sample registered bands up to 2100 cm−1 related to CO
adsorbed on Pdn+ species attributed to Pd–CeO2 interac-
tions which could be responsible for the improvement in
catalytic activity. Pd/CZS sample showed the highest OSC
and catalytic activity due to the formation of Ce–Zr mixed
oxide that promotes the high oxygen mobility into the
CeO2 lattice. The catalytic activity was enhanced after two
reaction cycles due to the formation of large PdO parti-
cles. T50 values indicated that reduction treatments carried
out before catalytic tests, generated species catalytically
more actives than those obtained by the oxidation treat-
ment, however, these active species were not stables at
high temperatures.
Acknowledgments: This research was partially sup-
ported by the Consejo de Desarrollo Científico y
Humanístico of La Universidad del Zulia (CONDES-
LUZ) and Fondo Nacional de Ciencia, Tecnología e Inno-
vación (FONACIT-Project PEI2011001345). Dr. Francesco
Giordano (ISMN-CNR) is acknowledged for XRD
measurements.
3871
Influence of Thermal Treatments on the Reducibility and Catalytic Properties
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Received: 20 May 2016. Accepted: 19 August 2016.
J. Nanosci. Nanotechnol. 17, 3864–3872, 2017