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Rapid Microwave Assisted Sol-Gel Synthesis of

CeO2 and CexSm1-xO2 Nanoparticle Catalysts
for CO Oxidation

Article in Journal of Molecular Catalysis A Chemical · November 2016

DOI: 10.1016/j.molcata.2016.11.039

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 Journal of Molecular Catalysis A: Chemical 428 (2017) 41–55

Contents lists available at ScienceDirect

Journal of Molecular Catalysis A: Chemical

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

Rapid microwave assisted sol-gel synthesis of CeO2 and Cex Sm1-x O2

nanoparticle catalysts for CO oxidation
K. Polychronopoulou a,∗ , Abdallah F. Zedan b , M.S. Katsiotis c , M.A. Baker d , A.A. AlKhoori a ,
Siham Y. AlQaradawi b , S.J. Hinder d , Saeed AlHassan c
a
Department of Mechanical Engineering, Khalifa University of Science, Technology and Research, Abu Dhabi, P.O. Box 127788, UAE
b
Department of Chemistry and Earth Sciences, Qatar University, Doha 2713, Qatar
c
Chemical Engineering Department, The Petroleum Institute, Abu Dhabi, UAE
d
The Surface Analysis Laboratory, Faculty of Engineering and Physical Sciences, University of Surrey, Guildford GU2 4DL, UK

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

Article history: CeO2 and Cex Sm1-x O2 nanoparticle mixed oxides have been synthesized by microwave assisted sol-
Received 8 August 2016 gel (MW sol-gel) and conventional sol-gel synthesis carried out at 60 ◦ C (typical sol-gel) and 100 ◦ C
Received in revised form (approaching the MW temperature). Different characterization techniques, namely, XRD, BET, Raman,
15 November 2016
SEM, FTIR, TEM, XPS, H2 -TPR, CO2 -TPD, and XPS have been employed to understand the process-structure-
Accepted 29 November 2016
properties relationship of the catalysts. The CO oxidation performance has been determined both in the
Available online 30 November 2016
absence and in the presence of H2 in the feed gas stream. Microwave heating yields a more thermally
stable precursor material, which preserves 75% of its mass up to 600 ◦ C, attributable to the different
Keywords:
Microwave
chemical nature of the precursor, compared to the typical sol-gel material with the same composition.
Sol-gel Varying the synthesis method has no profound effect on the surface area of the materials, which is in
CeO2 the range 4–35m2 /g. Conventional sol-gel synthesis performed at 60 and 100 ◦ C yields CeO2 particles
Cex Sm1-x O2 with a crystallite size of 29 nm and 24 nm compared to 21–27 nm for MW sol-gel synthesis (at different
Sm-doped ceria power values). The MW sol-gel Cex Sm1-x O2 catalysts exhibit a smaller crystallite size (12–18 nm). The
CO oxidation pure ceria nanoparticles were shown to have a stoichiometry of approximately CeO1.95 . The presence of
XPS Ce3+ and Sm3+ in the mixed oxide particles facilitates the presence of oxygen vacant sites, confirmed by
XRD
Raman. Oxygen mobile species have been traced using H2 -TPR studies and a compressive lattice strain
H2 -TPR
in the 0.45–1.9% range of the cubic Cex Sm1-x O2 lattice were found to be strongly correlated with the CO
Redox properties
Kinetc studies oxidation performance in the presence and absence of H2 in the oxidation feed stream. MW sol-gel syn-
thesis led to more active CeO2 and Ce0.5 Sm0.5 O2 catalysts, demonstrated by T50 (temperature where 50%
CO conversion is achieved), being reduced by 131 ◦ C and 47 ◦ C, respectively, compared to typical sol-gel
catalysts. Conventional synthesis performed at 100 ◦ C leads to a CeO2 catalyst of initially higher activity
at a certain temperature window (220–420 ◦ C), though with a slower increase of XCO as a function of
temperature compared to the MW synthesized catalyst. MW sol-gel synthesized Ce0.8 Sm0.2 O2 exhibited
a high performance (∼90%) for CO oxidation over a period of more than 20 h in stream. In addition the
effect of reaction temperature and contact time (W/F) on the activity of the CeO2 -based materials for CO
oxidation kinetics were investigated. The activation energy of the reaction was found to be in the range
36–43 kJ/mole depending on the catalyst composition.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction
Metal oxides are of interest to many scientific fields and techno-
logical areas, such as environmental remediation, capacitors, fuel
cells, catalysis, etc. [1]. In particular, CeO2 is an important nanoma-
∗ Corresponding author.
E-mail address: kyriaki.polychrono@kustar.ac.ae (K. Polychronopoulou).
terial due to its wide range of applications, including but not limited
to catalysis [2], fuel cells [3] and sensors [4], due to its unique redox
capacity (Ce4+ /Ce3+ couple). However, CeO2 suffers from limited
thermal stability as CeO2 is subjected to sintering equally along
the x, y and z axes [5]. Several studies have reported improve-
ments in the thermal stability and reduction/oxidation behavior
of CeO2 , especially in the lower temperature regime (<300 ◦ C); the
latter being strongly facilitated by the presence of isovalent (Zr4+ )
or trivalent (e.g. La3+ , Eu3+ , Mn3+ , Sm3+ ) dopants [6–10]. The ceria-

http://dx.doi.org/10.1016/j.molcata.2016.11.039
1381-1169/© 2016 Elsevier B.V. All rights reserved.
42 K. Polychronopoulou et al. / Journal of Molecular Catalysis A: Chemical 428 (2017) 41–55

0.12
1.0
Ce0.50Sm0.50O2 1360
0.10
1550 1420 0.8
(a)

Normalized Mass
Absorption (a.u)

0.08
0.6
0.06

MW 1036 0.4 MW_CeO2

0.04 CONV_Ce0.5Sm0.5O2
MW_Ce0.8Sm0.2O2
CONV 0.2
0.02 MW_Ce0.5Sm0.5O2
CONV2_Ce0.5Sm0.5O2
0.00 0.0
3000 2000 1000 0 150 300 450 600
Temperature (oC)
-1
Wavelength (cm )

Fig. 1. FTIR absorption spectra obtained over the Ce0.5 Sm0.5 O2 materials synthesized
by using Conv and MW sol-gel methods.
40
(b)
based mixed metal oxides were found to perform much better
compared to pure ceria due to the doping induced modifications

of the fluorite-type lattice (increased lattice strain, more oxygen
vacancy sites, etc.). In particular, after introduction of such dopants,
the change in the oxygen local environment causes a change in
the Oxygen Storage Capacity (OSC) of the mixed oxide [11] which
is directly linked with the material’s performance in technologi-
cally important catalytic reactions such as Water Gas Shift (WGS)
[12,13], hydrocarbon steam reforming [14–16] and CO oxidation
[17]. There are many studies regarding the preferred elements for
doping ceria. Among them, [18,19] reported that high radii def-
erence between Ce and the dopant can enhance the reducibility
and hence boost the CO oxidation. Sm seems to be one of the best
dopants for inducing changes in the structure and chemical prop-
erties of ceria because of the values of the ionic radii (107 pm for
Sm3+ and 97 pm for Ce4+ ) and electronegativity (1.17 for Sm3+
and 1.12 for Ce4+ ) of the two elements. It has been reported that
Sm induces the largest increase in ionic conductivity in ceria [20].
The proximity in ionic radii is essential criterion for solid solution
formation. Also, Sm cations are soluble to ceria lattice. Sm-doped
ceria has been extensively studied for oxidation reactions such as
allylic oxidation, methane oxidation and diesel soot combustion
[21]. Several synthesis methods of CeO2 or CeO2 -related materials
have been proposed in the literature, such as hydrothermal [22],
sol-gel [23], co-precipitation [24], microwave-hydrothermal [25],
urea-nitrate combustion [26], microemulsion [27], metal organic
chemical vapor deposition (MOCVD) [28], electrospinning [29],
hard-template mediated methods [30] etc. The surface area of the
mixed metal oxides obtained from the above techniques does not
exceed 150 m2 /g. Other synthesis methods involving surfactants
may result in a higher surface area (235 m2 /g) [31]; however, the
requirement for longer aging times and the removal of surfactants
by a number of washing cycles renders these methods unattractive
for industrial implementation.
Microwave-hydrothermal synthesis belongs to the family of
low-temperature methods for the preparation of nanophase mate-
rials with a wide range of size and shape [32]. These methods
are considered energy and time efficient as well as environmen-
tally friendly. Microwave chemistry has been proved an excellent
approach to achieving higher reaction rates (hence significantly
shorter reaction times of several minutes to hours) compared
to conventional heating hydro/solvothermal methods. The proce-
dures and benefits of microwave synthesis have been presented
in a number of good reviews [33–35]. Given the prominent role
of the synthesis method on the intrinsic properties of a cata-
lyst (including OSC, mobile oxygen species, defects, crystallite
size and shape, surface acidity/basicity and others), it is of great
Heat Flow
0
MW_CeO2
CONV_Ce0.5Sm0.5O2
MW_Ce0.8Sm0.2O2
MW_Ce0.5Sm0.5O2
-40
CONV2_Ce0.5Sm0.5O2
125 250 375 500 625
Temperature (oC)
Fig. 2. (a) TGA and (b) DSC profiles obtained over the Cex Sm1-x O2 , (x = 0.5, 0.8, 1)
catalysts synthesized using MW sol-gel method. Ce0.5 Sm0.5 O2 Conv and Conv2 sol-
gel catalysts (synthesized at 60 ◦ C and 100 ◦ C) TGA/DSC profiles are provided for
comparison.
interest to the scientific community to explore non-conventional
preparation methods of active and selective catalytic materials.
Microwave synthesis has also been applied for the synthesis of
CeO2 and Ce-Sm-O materials. In particular, Riccardi et al. [36]
reported on a microwave-hydrothermal method of forming CeO2
rhombus-shape microplates employing a temperature of 150 ◦ C for
30 min [36]. Dos Santos et al. [37] discussed the rapid microwave
preparation of CeO2 . However, their research work is confined
only to preparation and the characterization of the material. The
authors discussed the potential applications of these materials in
catalysis. Li et al. [38] reported on the preparation of Ce1-x Smx O2-␦ -
attapulgite nanocomposites using a low power (160 W) microwave
synthesis and showed its capability in the methylene blue degrada-
tion. They reported an optimum amount of Sm dopant to increase
the catalytic activity, but after introducing Sm to an amount corre-
sponding to x = 0.4, formation of agglomerates causes a drop in the
activity.
CO removal is a highly valuable process both in the automo-
tive industry (three way catalytic converters) and the technology
of fuel cells [39]. For the latter application, the methods proposed
for CO removal from the hydrogen stream include purification with
hydrogen selective membranes, CO methanation, pressure swing
adsorption, and preferential oxidation (PROX) of CO. From these
methods, CO methanation and CO-PROX are considered to be the
most promising for small-scale fuel processor applications [39]. In
addition, CO oxidation can be considered as a benchmark catalytic
reaction due to its simplicity in terms of stoichiometry and thus
can be used as a diagnostic tool for the evaluation of new materi-
als or new material preparation routes. In addition, the CO-PROX

(a) CeO2
(220)
(111)
Intensity (a.u)
(200)
20 30 40 50
2theta (degrees)
2theta
(b)
Intensity (a.u)
20 30 40 50
2theta
Fig. 3. (a) XRD profiles of the CeO2 catalyst synthesized using sol-gel (Conv) and MW
sol-gel (130 ◦ C–800 W and 150 ◦ C–1200 W) methods, (b)Ce0.5 Sm0.5 O2 synthesized
using Conv sol-gel and MW sol-gel.
process is one of the most effective methods for the removal of CO
trace from reformate stream. Therefore, preferential oxidation is
an indispensable step to reduce the concentration of CO to 10 ppm
level in a H2 generation process [39]. The types of catalysts which
have been used for CO oxidation and CO-PROX include Pt- and Pd-
based catalysts [40], nano-gold catalysts and mixed oxide catalysts
with the main focus being on the CeO2 -CuO system [41]. Though it
has to be mentioned here that noble metal catalysts can operate in
the presence of moisture but need temperatures higher than 100 ◦ C,
whereas gold catalysts can function only in the form of supported
nanoparticles on a metal oxide support. Finding an active catalyst
for CO oxidation at ambient and sub-ambient conditions is chal-
lenging. Xie et al. [42] reported relatively recently for CO oxidation,
that the active and stable Co3 O4 system in the form of nanorods out-
performs at temperatures as low as −77 ◦ C and the system exposes
the 110 planes where Co3+ is the active center for the CO reaction.
Lou et al. [43,44] reported an enhancement in the catalytic activ-
ity in the case of In2 O3 -Co2 O3 . In particular, they demonstrated
that In2 O3 -Co2 O3 catalyst presents high CO conversion activity at
temperature as low as −105 ◦ C, whereas single Co2 O3 is an active
catalyst at only −40 ◦ C. It was discussed by the authors that tun-
ing the CO adsorption sites along with tuning the oxygen vacant
sites were the main factors contributing to the outstanding catalytic
performance.
In the present study, CeO2 and Cex Sm1-x O2 mixed metal oxides
have been synthesized by microwave assisted sol-gel (MW sol-
gel) synthesis and compared to materials of the same compositions
prepared by conventional synthesis. The latter was carried out at
temperatures chosen in a way to simulate both a typical sol-gel pro-
cedure (60 ◦ C) and the MW temperature (100 ◦ C). The synthesized
K. Polychronopoulou et al. / Journal of Molecular Catalysis A: Chemical 428 (2017) 41–55 43
Conv
MW-130-800
MW-150-1200
(311)
(331)
(422)
(420)
(400)
(222)
60 70 80 90
Fig. 4. XRD profiles of the (a) Cex Sm1-x O2 (x = 0.2, 0.5, 0.8, 1) catalysts synthesized
Ce0.5Sm0.5O2_Conv
Ce0.5Sm0.5O2_MW
using MW sol-gel method and Ce0.5 Sm0.5 O2 Conv2 for comparison.
catalysts were characterized in terms of their microstructure, mor-
phology, texture, surface properties (acidity, basicity, reducibility)
Conv and the catalytic performance towards CO oxidation both in the
absence and presence of H2 . A correlation of their catalytic perfor-
mance with their intrinsic properties was sought. Kinetic studies
were performed and Eact values are reported for the MW catalysts
MW in order to show their behavior under reaction conditions.
2. Experimental
60 70 80 90 100 2.1. Catalyst preparation
(a) Conventional sol-gel synthesis: The precursor salts,
Ce(NO3 )3 ·6H2 O and Sm(NO3 )3 ·6H2 O (Sigma-Aldrich) were
dissolved with the appropriate molar ratios in distilled water. The
total metal loading [Ce + Sm] was kept at 0.03 mol in all cases. Citric
acid (the complexing agent) was dissolved in distilled water, main-
taining the total metal loading to citric acid ratio (Mtot /citric acid)
at 0.75, yielding an excess of citric acid. The metal salt and citric
acid solutions were then mixed and the final solution subjected to
conventional heating (60 ◦ C) and stirring until a yellowish gel was
formed (duration ∼2 h, materials’ code: Conv). This conventional
synthesis protocol was used to prepare CeO2 and Ce0.5 Sm0.5 O2
mixed oxide compositions only, for critical comparison purposes.
However, in order to achieve a temperature closer to that one used
in the MW synthesis, the conventional synthesis was selectively
performed for CeO2 and Ce0.5 Sm0.5 O2 catalysts, at using the same
conditions, except the temperature was raised to 100 ◦ C (duration
∼20 min, materials’ code: Conv2).
(b) Microwave Assisted Synthesis. A Microwave accelerated reac-
tion system (MARS-6) is a microwave power system with a
power output of 0–1800 W ± 5% (IEC 705 Method-1988). The major
components of the reaction system include a magnetron, isola-
tor, waveguide, cavity, and mode stirrer. Microwave energy is
generated by the magnetron, propagated down the waveguide
and introduced into the cavity. The mode stirrer causes multi-
directional distribution of the energy and the cavity acts as a
containment housing for the energy until it is absorbed by the
sample load within the cavity. The isolator protects the mag-
netron from energy not absorbed by the sample load. The isolator
allows energy to propagate from the magnetron to the cavity
but will not allow it to propagate from the cavity back to the
magnetron. This feature is desirable because the magnetron can
be damaged when exposed to this reflected energy. A turntable
is used to rotate the sample load within the cavity to ensure a
uniform energy distribution. The materials were prepared by dis-
solving the precursor salts (Ce(NO3 )3 ·6H2 O and Sm(NO3 )3 ·6H2 O)
44 K. Polychronopoulou et al. / Journal of Molecular Catalysis A: Chemical 428 (2017) 41–55

Table 1
Textural and structural parameters of the CeO2 and Cex Sm1-x O2 catalysts prepared by Conv and MW sol-gel methods.

Oxide System BET (m2 /g) Dd (nm) Pore size (nm) ´

Lattice Parameter (Å) Lattice Strain, ␧e

Sm2 O3 -MW 0.5 – 10–300 – –

Ce0.2 Sm0.8 O2 -MW 4.1 12.5 3.4–184 5.32
Ce0.5 Sm0.5 -MW 12.2 14.8 3.1–206 5.29 −0.01068
Ce0.80 Sm0.2 O2 -MW 17.8 18.8 3.19–181 5.29 −0.01964
CeO2 -MWa 14.8 27 2.8–318 5.26 −0.00457
CeO2 -MWb 21 5.19
CeO2 CONV 35.1 29 2.9–198 5.22
CeO2 CONV(2)c 6.7 24 3.5–193 5.21
Ce0.50 Sm0.50 O2 CONV 11.3 3–89 5.29 −0.00511
Ce0.50 Sm0.50 O2 CONV(2) 35 17 9–205 5.29
a
130 ◦ C–800 W.
b
150 ◦ C–1200 W.
c
Conventional sol-gel synthesis carried out at 100 ◦ C.
d
Calculated based on Scherrer formula (XRD studies).
e
Calculated based on Williamson-Hall method.

in distilled water with the molar ratios for final compositions
of Cex Sm1-x O2 , where x = 0, 0.2, 0.5, 0.8 and 1. As for the Conv
sol-gel route, an aqueous citric acid solution was prepared in
molar excess (Mtot /citric acid = 0.75). The two solutions were
mixed and then heated in the microwave reactor. Two microwave
heating conditions were employed, namely 130 ◦ C–800 W (mild)
and 130 ◦ C–1200 W (severe). Following microwave heating (dura-
tion <10 min, materials’code: MW), all synthesized materials were
calcined at 500 ◦ C for 6 h under atmospheric conditions to form the
mixed oxide catalyst.
2.2. Characterization
2.2.1. X-ray diffraction
The crystal structure of the calcined catalysts was analyzed by
®
X-ray diffraction (XRD) with a D2-Phaser apparatus (Bruker, MA,
USA), using an excitation wavelength Cu K␣ of 1.5418 Å. The X-ray
generator was operated at 30 kV and 20 mA. A -2 scan range of
10–100◦ with a 0.02◦ step size was employed. The average crystal-
lite size was calculated from line broadening of (111) peak using the
Scherrer equation. The lattice parameter was estimated by apply-
ing a standard cubic indexation method, using the predominant
(111) peak. Williamson-Hall plots (ˇcos /␭ vs. sin /␭) were used
to estimate the lattice strain [45].
2.2.2. Porosimetry
Porosimetry measurements were carried out using a high-
resolution 3Flex Micromeritics (Atlanta, USA) adsorption instru-
ment equipped with high-vacuum system and three 0.1 Torr
pressure transducers. Before performing the analysis, the materials
were degassed at 150 ◦ C for 2 h to remove any residual moisture.
The BET surface area was calculated from the adsorption data in
the relative pressure range of P/Po = 0.04–0.25, where the Barrett-
Joyner-Halenda (BJH) method was applied so to estimate the pore
size and pore volume.
2.2.5. FT-IR studies
FITR analysis was performed on the as-synthesized catalysts
using a Nicolet 740 FT-IR spectrometer at ambient conditions with
a nominal resolution of 4 cm−1 and averaging of 100 spectra.
2.2.6. Thermal studies
The thermal stability of the mixed oxides catalyst precursors
was investigated by a TA SDT 600 simultaneous thermogravimetry
and differential scanning calorimetry (TG-DSC) instrument.
2.2.7. H2 temperature-Programmed reduction (TPR) studies
H2 temperature-programmed reduction (H2 -TPR) experiments
were conducted by passing a 10 vol%/H2 /Ar gas mixture
(30 NmL/min) over ∼0.2 g of the pre-calcined (20 vol% O2 /He,
500 ◦ C, 2 h) solid and using a temperature ramp of 30 ◦ C/min while
the Thermal Conductivity Detector (TCD) signal was recorded con-
tinuously. The material was mounted on a U-shaped quartz sample
tube plugged with quartz wool and placed in a flow through reac-
tor (Autochem 2920, Micromeritics, Atlanta, USA). The H2 (m/z = 2)
and H2 O (m/z = 18) signals were monitored using an online Cirrus
mass spectrometer to follow the kinetics of the process.
2.2.8. CO2 temperature-Programmed desorption (TPD) studies
CO2 -TPD experiments were conducted using Autochem 2920,
(Micromeritics, Atlanta, USA). In particular, the material was
mounted on a U-shaped quartz sample tube plugged with quartz
wool and placed in a flow through reactor. CO2 -TPD experiments
were conducted by passing a 5 vol%/CO2 /Ar gas mixture for 30 min
(30 NmL/min) over ∼0.2 g of the pre-calcined (20 vol%O2 /He,
1800
CeO2_MW
F2g band of CeO2 Ce0.8Sm0.2O2 _MW
Raman Intensity (a.u)

1200
2.2.3. Scanning electron microscopy (SEM)
The morphology of the catalysts was examined with JSM 7610F-
Field Emission Scanning Electron Microscope (JEOL Ltd., Tokyo,
600
JPN), using both secondary and low-angle-backscattered imaging.

2.2.4. Transmission electron microscopy (TEM)

Information regarding the crystallinity and elemental com-
0
position of the catalysts was obtained with an FEI Tecnai G20
Transmission Electron Microscope (TEM) coupled with a post 200 300 400 500 600 700 800
-1
Raman Shift (cm )
column energy filtered camera (Gatan Quantum 963–energy reso-
lution 0.9 eV full width at half maximum at zero loss peak), and an Fig. 5. Raman spectra of the CeO2 single oxide and Ce0.8 Sm0.2 O2 mixed oxide syn-
EDAX energy dispersive X-ray (EDX) analyser. thesized using MW sol-gel method.
 K. Polychronopoulou et al. / Journal of Molecular Catalysis A: Chemical 428 (2017) 41–55
Fig. 6. (a) TEM microphotograph and (b) HRTEM microphotograph obtained over the MW sol-gel synthesized Ce0.8 Sm0.2 O2 catalyst.
Fig. 7. (a) TEM microphotograph, (b) HRTEM microphotograph, obtained over the MW sol-gel synthesized CeO2 catalyst.
500 ◦ C, 2 h) solid and using a temperature ramp of 30 ◦ C/min while
the TCD signal was recorded continuously. The mass numbers (m/z)
28 and 44 were used for CO and CO2 , respectively, during CO2 -TPDs.
2.2.9. X-ray photoelectron spectroscopy
Surface elemental concentrations and chemical states were
studied via X-ray Photoelectron Spectroscopy (XPS). XPS analy-
ses were performed on a ThermoFisher Scientific (East Grinstead,
UK) Theta Probe spectrometer. XPS spectra were acquired using a
monochromated Al K␣ X-ray source (h = 1486.6 eV). An X-ray spot
of ∼400 ␮m radius was employed. Survey spectra were acquired
using a pass energy of 300 eV. High resolution, core level spec-
tra were acquired using a pass energy of 50 eV. All spectra were
charge referenced against the C 1s peak at 285.0 eV to correct for
charging effects during acquisition. Quantitative surface chemical
analyses were calculated from the high resolution, core level spec-
tra following the removal of a non-linear (Shirley) background. The
manufacturer’s Avantage software was used which incorporates
the appropriate sensitivity factors and corrects for the electron
energy analyser transmission function.
2.2.10. Catalytic studies
The catalytic activity of the as-prepared catalysts for CO oxida-
tion was measured in a continuous flow fixed-bed feed reactor.
The feed gas mixture contained 4% CO, 20% O2 and balance He
45
and 1% CO, 1% O2 , 4% H2 and balance He for CO oxidation in the
absence and presence of H2 measurements, respectively. The reac-
tor was equipped with a 9 mm ID quartz tube placed in the middle
of a programmable split tube furnace (Lindberg/Blue M Mini-Mite
Tube Furnace − Thermo). In all experiments, unless otherwise men-
tioned, the feed gas was passed over 50 mg of the catalysts at a
flow rate of 50 ml/min (60,000 cm3 g−1 h−1 WHSV). The flow rate
was controlled by a set of digital mass flow controllers (HI-TEC
Model F-201CV-10K-AGD-22-V Multi-Bus DMFC; Bronkhorst). The
temperature was ramped at a heating rate of 5 ◦ C/min and the
catalyst temperature was measured by a thermocouple placed in
contact with the catalyst bed. The signal from the thermocouple
was acquired using USB--6008 Multifunction I/O and NI-DAQmx
(National Instruments) data acquisition board. The effluent gas was
fed into an inline multichannel infrared gas analyzer (IR200, Yoko-
gawa) to analyze the exit gas reactants and products. The volume
percent of CO, CO2 and O2 gases were determined simultaneously
and logged along with the catalyst temperature during the course of
the conversion experiment using Labview-configured data acqui-
sition software. The long-term stability of selected catalysts was
studied under a continuous stream of feed gas for 20 h at 530 ◦ C.
The catalytic activity was expressed by the conversion of CO in the
effluent gas and indicated as a CO conversion percentage by the
[CO]in −[CO]out
formula, XCO (%) = [CO]
x100 where X represents the per-
in
46
Adsorbed Amount (cm3/g)
(a)
60
30
0 Fig. 2 shows plots of mass loss (Fig. 2a) and heat flow (Fig. 2b)
0.0 0.2 0.4
Relative Pressure (P/Po)
40
(b)
Absorbed Amount (cm3/g)
20
0
0.0 0.2 0.4
Relative Pressure (P/Po)
Fig. 8. N2 adsorption isotherms at 77 K obtained over (a) CeO2 and (b) Ce0.5 Sm0.5 O2
synthesized by Conv sol-gel and MW sol-gel methods.
centage conversion and [CO] is the CO molar flow in the inlet and
outlet feed gas.
2.2.11. Kinetic studies
For kinetic measurements, the catalyst loading for CO oxidation
experiments was varied as 15, 30, 50, 75 or 100 mg while keeping
the GHSV of the feed fixed (3000 cm3 h−1 ). The CO oxidation
 reac- 
tion rates were calculated using the formula rCO = XCO / W/FCO ,
where XCO is the fractional CO conversion, W is the mass of the cat-
alyst in g and FCO is the CO molar flow rate. The apparent activation
energies of selected catalysts were determined from the Arrhenius
plots using data from the linear region of <15% CO conversion.
3. Results and discussion
3.1. Mixed metal oxide precursor
Fig. 1 presents the FTIR absorption spectra obtained for
Ce0.50 Sm0.50 O2 samples synthesized by microwave and conven-
tional methods (Conv/60 ◦ C), in the as-synthesized form (before
calcination). The peaks at 1420 and 1360 cm−1 can be observed
in both spectra, indicative of the formation of cerium formate in a
bidentate configuration [46]. The peak at 1036 cm−1 corresponds
to the C O single bond [47]. The peak at 1550 cm−1 was of much
higher intensity for the MW sol-gel compared to the Conv sol-gel
synthesized nanoparticles. This peak corresponds to carboxylate
salts [47] and it clearly demonstrates a change in the synthesis
pathway, showing that different intermediate species and/or dif-
ferent population of intermediate species with different structural
features are formed under microwave radiation/heating. This is in
agreement with the literature where the reaction selectivity under
microwave radiation differs from the conventional route mainly as
K. Polychronopoulou et al. / Journal of Molecular Catalysis A: Chemical 428 (2017) 41–55
a result of the direct interaction of the microwave radiation with
CeO2_Conv
CeO2_MW
the material inducing a different degree of supersaturation in the
solution and a different nucleation rate [48]. Microwave radiation
is non-ionizing electromagnetic radiation with high penetration
depth which leads to the formation of crystallites with higher
dimensional uniformity due to the absence of thermal gradients
during the synthesis [49]. Water is an ideal solvent for microwave
synthesis due to its high dipole moment. The dipole moment of the
solvent interacts with the electromagnetic radiation. The creation
of ‘hot spots’, evenly distribution over the precursor surface, for a
short period of time leads to enhanced mass transport of species
from the solution to the nuclei [49].
0.6 0.8 1.0
versus temperature for all the materials synthesized using both
microwave and conventional (at 60 and 95 ◦ C) methods. All the MW
sol-gel materials (Fig. 2a) exhibited a greater thermal stability com-
Ce0.5Sm0.5O2_MW pared to the Conv sol-gel material synthesized at 60 ◦ C, whereas
Ce0.5Sm0.5O2_Conv the Conv2 sol-gel material appears to show less mass loss than
the Conv sol-gel. This can be due to the temperature effect in the
solution, where Conv2 sol-gel material is closer to the MW tem-
perature conditions (100 vs. 130 ◦ C), though at slower ramp rate.
So, it is anticipated that an enhanced mass transport of species is
taking place from the solution to the first-formed nuclei at this high
temperature and nucleation of different precursor entities is being
favored which are more stable in the MW and Conv2 cases. In par-
ticular, the mixed oxide Conv sol-gel material lost 40% of its mass
at a temperature lower than 150 ◦ C, whereas all the MW sol-gel
materials preserved 75% of their mass even at temperatures higher
0.6 0.8 1.0
than 600 ◦ C. In the DSC profiles shown in Fig. 2b, the Conv sol-gel
material exhibits a strong endothermic peak at 100–125 ◦ C due
to the loss of water of hydration. An exothermic peak due to the
solid–solid transition (from the precursor state to the crystalline
structure) appeared at 365 ◦ C. For the MW sol-gel catalysts, this
endothermic peak appeared at a lower temperature (ca. 80–100 ◦ C),
whereas two additional exothermic peaks appear at 270 and 500 ◦ C,
corresponding to the decomposition of different intermediates and
lattice formation, respectively.
3.2. Micro/nano-structure
Fig. 3a presents the XRD diffractograms of CeO2 for the MW and
Conv sol-gel materials. For the MW sol-gel material, two different
set of conditions were adopted, namely 130 ◦ C, 800 W and 130 ◦ C,
1500 W, for synthesis under mild and severe microwave condi-
tions, respectively. The (111), (200), (220), (311), (222), (400), and
(331) peaks of the CeO2 fluorite structure are observed in both sam-
ples [50], whereas some peaks corresponding to the Ce(OH)x (CO3 )y
were traced too (JPDS No. 41-0013) [50]. The intensity of the lat-
ter peaks is becoming smaller in the case of MW sol-gel method.
The crystallite size of the Conv sol-gel material was found to be
29 nm, compared to 27 and 21 nm for the MW (mild) MW (severe)
sol-gel material respectively (Table 1). More severe microwave
heating leads to a higher vaporization rate in the solution and a
dramatic increase in the reactant concentration in the liquid phase.
Condensation reactions and crystallization processes continue in a
vapor-soaked slurry solid, which give rise to the observed smaller
crystallite size for the MW (severe) sol-gel material. Fig. 3b presents
the effect of synthesis method (microwave vs. conventional at
60 ◦ C) on the crystalline structure of the Ce0.5 Sm0.5 O2 mixed oxide.
Microwave heating gives rise to a particle size of 14 nm compared
to 28 nm for the conventional process (at 60 ◦ C). This difference is
caused by the much shorter microwave processing time and the
fundamental differences between MW and conventional heating
(such as quenching, homogeneous distribution of temperature in
the MW conditions) [49].
 K. Polychronopoulou et al. / Journal of Molecular Catalysis A: Chemical 428 (2017) 41–55
Fig. 9. SEM microphotographs of (a) Conv sol-gel Ce0.5 Sm0.5 O2 , (b) MW sol-gel Ce0.8 Sm0.2 O2 , (c) MW sol-gel Sm2 O3 , (d) MW sol-gel CeO2 , (e) Conv sol-gel CeO2 and (f) Conv2
sol-gel Ce0.5 Sm0.5 O2.
Fig. 4 presents the XRD patterns obtained for the MW sol-gel
Cex Sm1-x O2 mixed oxides (x = 0, 0.2, 0.5, 0.8 and 1) along with the
CeO2 Conv2 and Ce0.5 Sm0.5 O2 Conv2 both synthesized at 100 ◦ C for
comparison purposes. Again, the CeO2 fluorite peaks are observed
in all samples. No XRD peaks corresponding to Sm oxide phases
are identified for the Ce–Sm mixed oxides, showing the forma-
tion of (Ce,Sm)O2 solid solutions in all cases. There is a progressive
broadening of the XRD peaks as Sm is introduced and its concentra-
tion increased in the CeO2 structure. The calculated crystallite sizes
for CeO2 , Ce0.8 Sm0.2 O2 , Ce0.5 Sm0.5 O2 and Ce0.2 Sm0.8 O2 are 27, 19,
15 and 13 nm respectively (Table 1). These crystallite sizes are in
good agreement with Sm-doped CeO2 mixed oxides prepared by
mechanochemical synthesis (10–30 nm) [51] and in all cases (MW
and conventional methods) a Sm-induced drop in the crystallite
size was measured. The XRD peak maxima are also observed to
progressively shift to lower 2 values with increased Sm doping
indicative of a lattice parameter expansion. This is expected consid-
ering the larger ionic radius of the Sm3+ cations (107 pm) compared
to the Ce4+ cations (97 pm).
Raman spectra of the microwave assisted synthesized CeO2 and
Ce0.8 Sm0.2 O2 samples, are presented in Fig. 5. In agreement with
the XRD data, the Raman spectra reflect the formation of the cubic
fluorite lattice and confirm the (Ce,Sm)O2 solid solution forma-
tion. The band at 460–470 cm−1 corresponds to the allowed Raman
mode (F2 g) of the fluorite metal lattice. For pure CeO2 oxide, the
Raman spectrum was found to be symmetric around the band at
465 cm−1 and the F2 g mode corresponded to the symmetric vibra-
tion of oxygen ions around Ce4+ ions in the CeO6 octahedra [52]. In
the samarium doped CeO2 material, the F2 g band becomes asym-
metrical and slightly shifted to lower wavenumber values, due to
the cell expansion resulting from the substitution of Sm3+ ions in
the CeO2 lattice and the subsequent oxygen loss around the cation
sites. In addition, a weak broad band in the range of 530–620 cm−1
was observed in samarium doped CeO2 , attributed to the oxygen
vacancies in the lattice [52]. It should be mentioned here that the
high synthesis temperature during the MW preparation is believed
that enhance the formation of oxygen vacancies. This is linked with
the enhanced mass transport (e.g. Sm3+ species incorporating into
the CeO2 lattice) due to high temperature at short times. This mass
transport of Sm3+ species is anticipated to happen homogeneously,
due to the undistrurbed temperature field, in the synthesis solution
47
(from the walls of the vessel to the core of the solution) in the case of
MW conditions [49]. No Raman band corresponding to Sm2 O3 was
found (cubic 375 cm−1 ) which is consistent with the incorporation
of Sm3+ ions into the ceria cubic lattice.
The nanostructure and morphology of the materials was inves-
tigated using TEM. A careful examination of the bright field TEM
images for the MW sol-gel Ce0.8 Sm0.2 O2 and CeO2 materials (Fig. 6a
and Fig. 7a respectively) shows that the Ce0.8 Sm0.2 O2 mixed oxide
exhibits a smaller crystallite size than CeO2 , in agreement with
the XRD data. Both materials are well-crystallised and octahedral
in shape even though the terminating surfaces of the crystals are
not well-defined due to inherent limitations of the TEM. From the
HRTEM images (Fig. 6b and Fig. 7b), the lattice fringes of the crystal-
lites and their growth in many different orientations can be seen. It
has been reported that doping ceria oxide with lower valent cations,
such as La3+ , Sm3+ induces strain within the lattice, which results in
a better CO oxidation catalytic performance. In the present study,
Williamson-Hall plots were used in order to calculate the lattice
strain (see Table 1) [45]. The lattice strain was found to be compres-
sive in all cases, giving rise to a shorter Ce-O bond than expected.
In the case of Gd-doped Ceria, where Gd3+ ions have a similar ionic
radius to Sm3+ , it was found that a compressive strain of 0.3% results
in a Ce-O bond contraction of 1% [53]. In the materials reported here
the compressive strain was found to be in the range of 0.45-1.9%
depending on the composition (Table 1). The shorter Ce-O bond
length results in Ce4+ ions being shifted away from the oxygen
vacancies, making the vacancies more mobile and easier to migrate.
It is reasonable to expect that the distortion of the oxygen sub-
lattice would be higher closer to the vacancies migration pathway
[54].
3.3. Texture and morphology characteristics of the mixed metal
oxides
Figs. 8a and b present the low-pressure N2 adsorp-
tion/desorption isothermal curves at 77.3 K for MW and C
sol-gel synthesized CeO2 and Ce0.5 Sm0.5 O2 . All the synthesized
materials demonstrated a type IV sorption isotherm based on
IUPAC [55], typical of mesoporous materials (pore width 2–50 nm).
The hysteresis loop appearing above a relative pressure of 0.45
is clearly attributable to capillary condensation of nitrogen gas
48 K. Polychronopoulou et al. / Journal of Molecular Catalysis A: Chemical 428 (2017) 41–55
5.48
(a)
5.47 284oC
400oC
TCD Signal (a.u)
5.46
CeO2_MW
Ce0.5Sm0.5O2_MW
5.45
CeO2_Conv
Ce0.2Sm0.8O2_MW
Ce0.8Sm0.2O2_MW
5.44
150 300 450
o
Temperature ( C)
(b)
MS Signal (a.u)
150 300 450
Temperature (oC)
Fig. 10. (a) H2 -TPR profiles obtained over the CeO2 single oxide and Cex Sm1-x O2
(x = 0.2, 0.5, 0.8, 1) mixed oxide catalysts synthesized using Conv sol-gel and MW
sol-gel, respectively, (b) On line mass spectroscopy signal for H2 (m/z = 18) and H2 O
(m/z = 18) recorded during the H2 -TPR experiment as presented in (a).
inside the mesopores, while its H3-type classification indicates the
presence of pores with a slit-shape. Moreover, the characteristic
single-step observed next to the point of loop closure (P/P0 ≈ 0.5)
strongly implies that desorption is achieved through cavitation.
The mechanism is associated with the evaporation of N2 from
the mesopores through the spontaneous nucleation and growth
of gaseous bubbles inside the condensed nitrogen [56]. At higher
relative pressures (up to P/P0 ≈ 0.99) the adsorption curve does
not reach a saturation point, but instead extends indefinitely in
the vertical direction. This behavior represents the unrestricted
multilayer adsorption of N2 due to the presence of a macroporous
surface (pore width >50 nm). This is in agreement with the mor-
phology of these materials, as shown in the SEM images of Fig. 9.
At lower relative pressures, (P/P0 < 0.05) the MW sol-gel materials
demonstrate weak N2 physisorption most probably due to the lack
of microporosity (pore width <2 nm). The BET surface area values
presented in this work are in good agreement with the values in
[51], where they studied the synthesis of 20 mol% samarium-doped
cerium oxide nanoparticles from the mechanochemical reaction
between samarium trichloride, sodium hydroxide and cerium
hydroxide, in which a surface area of 48.7 m2 /g was obtained. By
comparing the porosity values of CeO2 Conv (35.1 m2 /g), CeO2
Conv2 (6.7 m2 /g) and CeO2 MW (14.8 m2 /g), an effect of the
synthesis method can be observed. This can be due to the higher
temperatures associated with the MW synthesis for a very short
period of time. Though, in MW CeO2 catalyst, the high temperature
is homogeneously distributed leading to less dramatic collapse
of the surface area compared to Conv2 CeO2 . In the case of
Ce0.5 Sm0.5 O2 catalyst composition, the BET values for the MW,
Ce0.8Sm0.2O2_MW
Ce0.2Sm0.8O2_MW
CeO2_MW
634oC CeO2_CONV
TCD Signal
600 750
150 300 450 600 750
Temperature (oC)
m/e 2
m/e 18
Fig. 11. CO2 -TPD profiles obtained over the CeO2 single oxide and Cex Sm1-x O2
(x = 0.2, 0.5, 0.8, 1) mixed oxide catalysts, synthesized using Conv sol-gel and MW
sol-gel methods, respectively.
Conv and Conv2 materials, Conv2 demonstrate a more profound
effect of Sm doping on the thermal stability. There was no clear
effect of the synthesis method on the porosity type.
3.4. Surface chemistry of the mixed metal oxides
Fig. 10a presents the H2 -TPR profiles obtained for the
600 750
Cex Sm1-x O2 materials. According to the literature, for a typical
reduction profile of CeO2 oxide, the peak at 247 ◦ C can be attributed
to the sub-surface reduction of CeO2 [57,58]. On the other hand, the
peaks at approximately 467 ◦ C and 1000 ◦ C are assigned to the for-
mation of non-stoichiometric Ce oxides and Ce respectively [57,58].
Concerning the pure CeO2 oxides, it appears that both the MW and
C sol-gel methods result in materials with very similar reduction
profiles. However, the introduction of Sm3+ ions significantly mod-
ifies the reduction patterns. In particular, it is observed that the
Ce0.8 Sm0.2 O2 mixed oxide exhibits a reduction peak at 284 ◦ C, this
being a lower reduction temperature compared to the other oxides,
whereas the Ce0.5 Sm0.5 O2 mixed oxide exhibits a reduction peak at
around 450 ◦ C, showing the presence of less reducible species (at
low temperature regime), which is in agreement with the different
CO oxidation performance of the microwave prepared materials
(Ce0.8 Sm0.2 O2 > Ce0.5 Sm0.5 O2 ). Also, in the case of Ce0.5 Sm0.5 O2 , the
high temperature (HT) peak for the reduction of the bulk mate-
rial appears shifted to higher temperatures > 750 ◦ C compared to
the Ce0.8 Sm0.2 O2 mixed oxide (around 630 ◦ C). The latter result is
indicative of a higher structural integrity of the particular mixed
oxide under a reducing atmosphere. This is of particular technologi-
cal interest for catalytic reactions where a reducing atmosphere and
thermal effects both impact on the material structure. The reduc-
tion of the catalytic oxides is accompanied by water production,
as it can be seen in Fig. 10b by the mass spectrometer signal at
m/z = 18.
It is well known that the CO oxidation product, CO2 , can partic-
ipate in competitive adsorption with CO (and H2 in the case of the
CO-PROX reaction) having a negative effect on the overall reaction
taking place on the catalyst surface. In this respect, the nature of the
support plays a crucial role in terms of stability in the presence of
CO2 in the feed. Acidic supports were reported to be more resistant
to deactivation than basic supports [59]. Ceria is a basic oxide and
as such has the tendency to adsorb CO2 and form carbonates. TPD-
MS profiles of CO2 show broad peaks (Fig. 11) which correspond
to several forms of adsorbed CO2 on the surfaces of the materials
studied here. CO2 is being desorbed from the catalyst surface in the
 K. Polychronopoulou et al. / Journal of Molecular Catalysis A: Chemical 428 (2017) 41–55 49

Ce 3d v’’’ 20Ce
O 1s 20Ce
50Ce 50Ce
u 80Ce v
(a) u’’’ 100Ce (b) 80Ce
100Ce
u’
u’’ v’

CPS
CPS v’’

930 915 900 885 870 540 535 530 525 520
XT Binding Energy (eV)
Binding Energy (eV)
Text Legend
Sm 3d 20Ce
50Ce
80Ce
(c)
CPS

YL

XB

1130 1120 1110 1100 1090 1080 1070 1060

Binding Energy
XB (eV)
Binding Energy (eV)
Fig. 12. (a) Ce3d, (b) O 1s and (c) Sm 3d XPS core level spectra obtained over the Cex Sm1-x O2 (x = 0.2, 0.5, 0.8, 1) catalysts synthesized by MW sol-gel method.

Table 2
Reduction temperature, activation energy of CO2 desorption and T50 for the CeO2 and Cex Sm1-x O2 catalysts, prepared by Conv and MW sol-gel methods, in the CO oxidation
reaction.

Oxide System Reduction Temperatures (◦ C) CO2 Edes T50 (◦ C)

Ce0.2 Sm0.8 O2 -MW 312, 473 11.3 553

Ce0.5 Sm0.5 -MW 469, 737 453
Ce0.80 -Sm0.2 O2 -MW 284, 400, 645 8.7 406
CeO2 -MWa 370/667 – 390
CeO2 -MWb – – –
CeO2 CONV 328, 405, 633 24.7 524
Ce0.50 -Sm0.50 O2 CONV 19.6 512
c
:First order kinetics analysis.
a
Microwave conditions: 130 ◦ C–800 W.
b
Microwave conditions: 150 ◦ C–1200 W.

molecular form. The calculated values of Edes at corresponding tem-
peratures of CO2 desorption are tabulated in Table 2. The values of
Edes correlate very well with the catalyst activity in CO oxidation,
namely: the lowest Edes corresponds to the most active catalyst
(due to competitive adsorption). This trend seems to be valid in
the case of the Cex Sm1-x O2 mixed metal oxides and aligned with
their catalytic activity, where Ce0.8 Sm0.2 O2 presents the lowest Edes
of CO2 desorption (8.7 kJ/mol) compared to CeO2 (11.2 kJ/mol) and
Ce0.5 Sm0.5 O2 (19.6 kJ/mol).
The XPS Ce 3d and O1 s core level spectra obtained for the
Cex Sm1-x O2 catalytic materials are given in Fig. 12(a & b). In accor-
dance with the nomenclature used in previous XPS work on cerium
oxide, the peaks in Fig. 12a are labeled as v and u, corresponding
to transitions associated with Ce 3d5/2 and Ce 3d3/2 , respectively
[60–62]. The stronger peaks are v, v”, v”’, u, u”, u”’ corresponding to
Ce4+ species, whereas the peaks labelled as vo , v’, u’, u0 correspond
to Ce3+ species. The Ce 3d spectra show that the cerium oxide is
predominantly a Ce4+ based oxide, in agreement with the XRD and
Raman data. In order to investigate in more detail the presence or
not of Ce3+ states in the XPS spectra, it is useful to compare the data
given here for the pure CeO2 calcined catalysts with that of Mullins
et al. [61] for CeO2 bulk samples and Pfau and Schierbaum [62]
and Henderson et al. [63] for CeO2 thin films. In comparison with
the data of these other workers [61–63], there is a clear increase
in photoelectron intensity between the v and v” Ce4+ peaks, at a
binding energy position expected for the v’ Ce3+ peak. Both Pfau
and Schierbaum [62] and Henderson et al. [63] have studied the
emergence of the v’ peak, as a result of heating the CeO2 in the
UHV environment, leading to surface reduction of the CeO2 . From
their results, both sets of authors have presented the changes in the
Ce 3d spectral shape for the v, v’ and v” peak region. Furthermore,
Henderson et al. have estimated the CeO2-x stoichiometry corre-
sponding to the different spectral shapes [63]. In comparing the
data recorded for our CeO2 calcined catalysts with the data given
by Henderson et al. [63], the spectral shape for our data corresponds
to a stoichiometry of CeO1.95 . If the O2− vacancies associated with
50 K. Polychronopoulou et al. / Journal of Molecular Catalysis A: Chemical 428 (2017) 41–55

the sub-stoichiometric CeO2 are located in the outer surface layer, Ce0.5Sm0.5O2-CONV2
100
then the O2− vacancy concentration in that layer would be 22% of CeO2-CONV2

% CO Conversion
Sm2O3-MW
the surface O2− sites [63]. This is an important finding given the 80 CeO2-MW
key role of oxygen vacancies in the CO oxidation reaction. The CO CeO2-CONV
oxidation reaction is based on the formation of oxygen vacant sites 60 Ce0.8Sm0.2O2-MW
which facilitate the reaction progress and they are restored by gas Ce0.5Sm0.5O2-MW

phase oxygen exposure. 40 Ce0.5Sm0.5O2-CONV

Ce0.2Sm0.8O2-MW
The Sm 3d5/2 peak for all of the Cex Sm1-x O2 mixed oxides are
shown in Fig. 12c. The commercial samaria powder exhibiting a 20
(a)
stoichiometry of Sm2 O2.9 was used as a reference and presented
0
only carbonaceous contaminant species, hence was considered to
100 200 300 400
o
500
be a good reference sample. The Sm 3d5/2 peak for the samaria Temperature ( C)
powder was observed at a binding energy of 1082.4 eV, in excellent CeO2-MW
agreement with the data of Elkins and Hagelin Weaver [64], and 100 Ce0.8Sm0.2O2-MW

% CO Conversion
the O 1s peak at a binding energy of 531.5 eV. The Sm 3d samaria Ce0.2Sm0.8O2-MW
80
peaks for the Cex Sm1-x O2 calcined catalysts show the same peak
shape as that of the samaria powder. Hence, in all of the Cex Sm1-x O2
60
samples, the Sm exists in a 3+ oxidation state. Interestingly, the Sm
3d5/2 peak progressively shifts to lower binding energies as the Sm 40
content in the Cex Sm1-x O2 catalysts is reduced. Thus, as the Sm (b)
content in Cex Sm1-x O2 is reduced, there is less charge transfer to 20
the neighboring O atoms.
The O 1s peak for the CeO2 and Cex Sm1-x O2 catalysts was com- 0
prised of two distinct peaks, one at ∼529 eV and the other at 100 200 300 400 500 600
o
∼531.5 eV. The lower binding energy peak corresponds to the lat- Temperature ( C)
tice oxygen [62,63,65]. The higher binding energy peak for CeO2
CO Conversion: Ce0.8Sm0.2O2-MW
has been ascribed to the presence of hydroxyl species, carbonate or 100 600
polarised O2− ions located adjacent to O vacancy sites [63,65,66].

Temperature ( C)
% CO Conversion 525
80

For all of the samples, there was a small C 1s peak at a binding
energy of approximately 289.5 eV, indicative of the presence of a
surface carbonate. It has been reported previously that carbonate
species are expected at the surface of rare earth oxide materials
[64]. The intensity of the 531.5 eV peak (compared to the 529 eV lat-
tice oxide peak) for CeO1.95 sample by Henderson et al. [63] is very
small (due to the low O2− vacancy concentration), whereas for our
CeO1.95 oxide, the 531.5 eV peak has a substantially greater inten-
sity. The ceria films were deposited in-situ by Henderson et al. [63],
compared to the samples studied here, which have been exposed
to atmosphere. The O 1 s binding energy of metal hydroxides and
metal carbonates are typically around 531.0-531.5 eV [67]. There-
fore, for the pure ceria catalysts reported here, the 531.5 eV peak
can be ascribed predominantly to the presence of surface hydrox-
ide/carbonate species, with a small contribution from polarised O2−
ions located adjacent to O vacancy sites.
In our O 1 s spectra, the intensity of the 531.5 eV peak progres-
sively increases with Sm content. This is in agreement with our
observation of the O 1 s peak for samaria occurring at 531.5 eV.
Furthermore, when a Sm3+ ion substitutes for a Ce4+ ion, one oxy-
gen ion vacancy is introduced for every two Sm3+ cations [68]. As
such, an increase in Sm3+ content will lead to a greater concen-
tration of O2− vacancies in the Cex Sm1-x O2 catalysts and hence an
increase in the number of low co-ordinated and polarized O2− ions,
located in the vicinity of O vacancy sites. In the O 1 s spectra for
the Cex Sm1-x O2 catalysts, the higher binding energy O 1 s peak is
broader than the lower binding energy component, indicating the
presence of multiple components. Hence, it appears that this peak
centered at around 521.5 eV comprises of components associated
with: (i) the substitution of Sm3+ for Ce4+ in Cex Sm1-x O2 ; (ii) surface
hydroxide/carbonate species and (iii) the presence of O2− vacancies
in CeO2 and Cex Sm1-x O2 materials.
3.5. CO oxidation studies
The CO oxidation catalytic performance of the different catalysts
was compared using a continuous flow fixed-bed catalytic reactor
in the absence and the presence of hydrogen in the feed gas. Fig. 13a
o
Catalyst Temperature
450
60 (c) 375
300
40
225
20 150
0 75
00 04 08 12 16 20
Time (h)
Fig. 13. Catalytic performance (expressed as%CO conversion) as a function of tem-
perature, towards the CO oxidation reaction in the (a) absence (4% CO/20% O2 /He)
and (b) presence (1% CO/1% O2 /4% H2 /He) of H2 in the feed stream, obtained over
the Cex Sm1-x O2 catalysts, (c) Catalytic stability (expressed as % CO conversion) at
530 ◦ C obtained over the Ce0.8 Sm0.2 O2 catalyst for 20 h in stream.
displays the catalytic activity under the feed gas containing 4% CO
and 20% O2 with a He balance. By comparing the T50 values (T50 is
the temperature at which 50% CO conversion is achieved) for the
different oxides, it can be seen that the MW sol-gel CeO2 demon-
strated higher catalytic activity, with a T50 = 392 ◦ C compared to a
T50 = 523 ◦ C for Conv sol-gel CeO2 . Though, performing the conven-
tional sol-gel synthesis at much higher temperature (100 ◦ C) gives
a CeO2 Conv2 catalyst with T50 = 372 ◦ C. The Conv2 CeO2 catalyst
presented a high activity with a slower increase of XCO as a function
of temperature compared to the MW CeO2 . This is most likely due to
the presence of more activated oxygen species and higher surface
area of the MW CeO2 . Similarly, the MW sol-gel Cex Sm1-x O2 mixed
oxides showed higher activities, demonstrated by the lower con-
version temperature of T50 = 407 ◦ C and 454 ◦ C for Ce0.8 Sm0.2 O2 and
the Ce0.5 Sm0.5 O2 , respectively, compared to T50 = 513 ◦ C for Conv
sol-gel Ce0.5 Sm0.5 O2 (Fig. 13 & Table 3). However, the conventional
synthesis performed at 100 ◦ C led to a Ce0.5 Sm0.5 O2 Conv2 catalyst
with T50 = 427 ◦ C, a system with much better catalytic activity than
the Ce0.5 Sm0.5 O2 synthesized at 60 ◦ C (T50 = 513 ◦ C). Microwave
prepared Sm2 O3 exhibited a conversion temperature of T50 = 401 ◦ C
but the activity deteriorates with the temperature. Overall, it is
 K. Polychronopoulou et al. / Journal of Molecular Catalysis A: Chemical 428 (2017) 41–55 51

Table 3
CO oxidation Catalytic Activity Results (% CO conversion) in the absence and presence of H2 , obtained over the CeO2 and Cex Sm1-x O2 catalysts, prepared by Conv and MW
sol-gel methods.

COOX1 COOX2 % CO @ 500 ◦ C

20% 50% 80% 100% 20% 50% 80% 100% COOX1 COOX2

CeO2 MW 341 392 440 518 330 382 432 496 98% 100%
CeO2 CONV 455 523 NA NA NA NA NA NA 38% NA
CeO2 CONV2 307 372 455 NA NA NA NA NA 89 NA
Ce0.8 Sm0.2 MW 356 407 457 533 353 403 452 516 94% 97%
Ce0.50 Sm0.50 O2 MW 400 454 509 NA 379 436 491 NA 76% 83%
Ce0.50 Sm0.50 O2 CONV 456 513 NA NA NA NA NA NA 42% NA
Ce0.50 Sm0.50 O2 CONV2 375 427 477 NA NA NA NA NA 89.3 NA
Ce0.20 Sm0.80 O2 MW 497 NA NA NA 513 NA NA NA 20% 18%

COOX1 : 4% CO/20% O2 /He.

COOX2 : 1% CO/1% O2 /4% H2 /He.

the nucleation rate and the smaller the critical sizes of the nuclei
that are needed to overcome the nucleation barrier. Furthermore,
it is known that MW leads to uniformity in the formed crystals
[49], whereas conventional heating, even when it is performed at
similar temperatures with the MW, leads to non uniformity due to
nucleation. MW can also give rise to Ostwald ripening phenomanon
while the growth process is taking place [70]. Also, in the case of the
MW prepared catalysts, efficient coupling of the microwave radi-
ation with the solution allows for volumetric heating and a more
homogeneous temperature field to be developed compared to both
of the traditional routes adopted herein [49]. The lower values of
porosity that have been presented earlier imply more dense MW
prepared catalysts, whereas the lower particle size implies sup-
pressed grain growth. It has been mentioned [71] that there is a
certain temperature range called ‘the kinetic window’where den-
sification is activated but grain growth is not activated. Another
important aspect of MW synthesis is the dielectric loss (␧)¨ of the
precursor material in the solution (metal citrates/nitrates in this
work) [49]. It seems that the low dielectric loss of the precursor
material suppresses any further effect of high temperature on the
grain growth of the material. In addition, the finer grain size is in
agreement with a higher surface/volume (S/V) ratio and a higher
number of active sites exposed on the surface, available for reac-
tion. In the case of conventional catalysts prepared at 60 ◦ C it seems
that low mass transport happens in the solution leading to limited
incorporation of Sm3+ into the CeO2 lattice and eventually giving
rise to a rather not so well-performed catalytic system. Also, it is
known that [72] the surface defects in CeO2 play the role of oxy-
gen adsorption sites. The MW quenching effect that is taking place
Fig. 14. XRD patterns obtained over the Cex Sm1-x O2 (x = 0.2, 0.5, 0.8, 1) catalysts
following the catalytic test described in Fig. 13a.
immediately after the end of the MW reaction (end of reaction
is linked with end of heating) facilitates the formation of a more
defective structure, thus leading to the creation of more oxygen
(reactant) adsorption sites.
observed that for CeO2 single oxide, in the case of MW and con-
Comparing the CO oxidation in the absence and presence of H2
ventional synthesis at 100 ◦ C an improvement of T50 is observed
(only for MW catalysts) in the feed gas, in terms of the T50 param-
by 26% and 29%, respectively, compared to the conventionally pre-
eter it can be stated that in the presence of H2 the reaction is being
pared CeO2 at 60 ◦ C. In the case of Ce0.5 Sm0.5 O2 composition when
facilitated by the drop in temperature. In the presence of H2 , oxi-
the conventional catalyst synthesized at 100 ◦ C outperfomes the
dation of H2 occurs, simultaneously with CO oxidation, leading to
MW and the conventional at 60 ◦ C by only 6% and 13%, respectively.
H2 O production. In the co-presence of H2 O, CO can react towards
Though the much faster MW reaction should kept in mind when a
the Water Gas Shift (WGS) and Reverse Water Gas Shift (RWGS)
meaningful comparison is soughtin terms of practical application.
reactions at T > 200 ◦ C. WGS can lead to an additional route in the
Consequently, there is a profound effect of the synthesis method
production of CO2 , which has been proved to exhibit an inhibiting
on the T50 value for both CeO2 and Cex Sm1-x O2 mixed oxides. This
effect on the CO oxidation reaction in the presence of H2 [73]. From
synthesis effect can be understood on the basis of parameters,
the CO2 TPD studies on these materials (Fig. 11) it is clear that CO2 is
such as solvent (water) used, temperature/temperature field in the
chemisorbed on the surface of CeO2 and Cex Sm1-x O2 mixed oxides
solution and time of synthesis. According to microwave chemistry
forming stable surface species. At this point, it is worthwhile con-
theory, the medium microwave radiation absorption capability is
sidering the oxide acidic character. It has been reported that acidic
described by the tan␦ parameter (0.123 for water) [69]. Hence,
oxides are more resistant to carbonate formation than basic oxides
water absorbs microwave radiation rather efficiently and rapid
[74]. In the case of Ce-containing materials, the acid-base proper-
heating occurs which leads to supersaturation of the metal precur-
ties vary with the cerium cation oxidation state, with Ce4+ being
sors’ solution. In general, the higher the supersaturation, the higher
52 K. Polychronopoulou et al. / Journal of Molecular Catalysis A: Chemical 428 (2017) 41–55
Fig. 15. (a–c) the variation of the CO fractional conversion (XCO ) with W/FCO ratio, (d–f) Arrhenius plots for the MW CeO2 , Ce0.8 Sm0.2 O2 , Ce0.2 Sm0.8 O2 catalysts, respectively.
The apparent activation energies calculated from Arrhenius plots for the MW CeO2 , Ce0.8 Sm0.2 O2 , Ce0.2 Sm0.8 O2 are 35.74 ± 1.27 kJ mol−1 (R2 = 0.9937); 37.57 ± 1.54 kJ mol−1
(R2 = 0.99159) and 42.82 ± 4.29 kJ mol−1 (R2 = 0.95164), respectively.
more acidic than Ce3+ (XPS showed the presence of Ce3+ ions). Ce3+
as a hard acidic entity tends to form stable carbonates with a hard
CO3 2− base [75]. The catalytic activity of CeO2 can be understood on
the basis of facile generation of oxygen vacant sites under reaction
conditions followed by the Ce4+ /Ce3+ redox cycle. A very impor-
tant finding from a technological viewpoint is the fact that for CO
oxidation the Ce0.8 Sm0.2 O2 catalyst is stable and very active (96%
conversion) in stream for 20 h with no deterioration of its catalytic
activity (Fig. 13c). This can be attributed to the fact that this cata-
lyst chemisorbs a lower amount of CO2 as indicated by the CO2 -TPD
experiment (see Fig. 11).
Also it is worthwhile commenting on the lowering of the cat-
alytic activity that accompanies the Sm-doped materials which can
be explained as follows: (i) The ‘surface-bulk’ oxygen exchange pro-
cess in Ceria begins at 650 K (337 ◦ C) according to Gorte et al. [21],
meaning that at lower temperatures only the ceria surface partic-
ipates, which limits the available pool of oxygen species for the
reaction at hand; (ii) Based on XPS studies (Fig. 12b) the lattice
oxygen binding energy (eV) is shifted to lower values when Sm is
introduced. This would be expected to facilitate the oxygen avail-
ability, but it seems that temperature is the determining factor
for suppressing the above (as will be discussed in the next sec-
tion). Also, from the H2 -TPR studies it can be seen that Sm-doping
increases the reducibility of the doped ceria in the low and mid-
temperature regime, whereas the undoped ceria presented a high
reducibility at T > 500 ◦ C. This proves that indeed the temperature
is a key factor for the release of the potentially mobile oxygen
species; (iii) Sm2 O3 does not belong to the easily reducible oxides
[76], and as such it is anticipated that the CO oxidation reaction,
that is basically happening through oxidation and reduction of the
contributing oxides (CeO2 and Sm2 O3 in the particular case) or by
increasing the oxygen mobility, is being suppressed with Sm doping
as the population of mobile oxygen species is diluted by Sm dop-
ing. It can also be speculated that CO induces a minor reduction of
samaria and the reduced species of samaria decorate CeO2 -related
active sites for the reaction, thus lowering the activity; (iv) From the
CO2 -TPD studies it can be seen that the amount of CO2 desorbed
from the Sm-doped ceria oxides is lower than that of CO2 desorbed
from the undoped ceria (conventional or microwave). This can be
due to an increase of the surface basicity of the Sm-modified oxides
[77] which present stronger adsorption sites for the CO2 (reaction
product).
These catalysts, compared to other combinations of CeO2
dopants, exhibit a less favourable conversion temperature where
the maximum catalytic activity is achieved; however, their perfor-
mance is still very promising, particularly as they can be produced
rapidly and at low cost. Comparing the materials studied here with
reported MOFs, e.g. ra-MOF where T50 and T100 (temperatures for
50% and 100% conversion) were 364 ◦ C and 500 ◦ C, respectively,
the superiority of the MW CeO2 and MW Cex Sm1-x O2 catalysts is
notable given other benefits such as thermal stability and ease of
preparation and handling [78]. MOF catalysts reported by Jin Yeong
Kim et al. [79] showed increased activity (T50 and T100 at 222 ◦ C and
250 ◦ C, respectively) only after Pd nanoparticles were loaded onto
them, a feature that elevates the overall cost of the material. The
MW sol-gel CeO2 and Cex Sm1-x O2 catalysts also show an improved
activity compared to similar citrate sol-gel synthesized Ce0.6 Zr0.4 O2
catalysts which exhibited a 10%CO conversion (T10 ) of 327 ◦ C [79].
Finally, it is important to note that the cubic fluorite structure of
the catalysts was preserved following the reaction as shown from
the XRD results given in Fig. 14. A shift of the peaks towards higher
diffraction angles was noticed after the reaction, although, no peaks
corresponding to carbonate species were identified. This peak shift
is indicative of reduction of the cubic ceria lattice [62], whereas the
 K. Polychronopoulou et al. / Journal of Molecular Catalysis A: Chemical 428 (2017) 41–55
absence of carbonate-relevant peaks shows the structural integrity
of the catalysts and their self-healing capability.
3.6. Kinetic studies
Kinetic studies were performed over selected catalytic systems
so to enlighten the promising catalytic behavior of the MW pre-
pared materials.
Effect of temperature. The plot of fractional CO convention
vs. W/F for different reaction temperatures in the 180–280 ◦ C
range is presented in Fig. 15(a)–(c) for CeO2 , Ce0.8 Sm0.2 O2 and
Ce0.2 Sm0.8 O2 , respectively. A monotonic increase of CO conversion
can be observed as the temperature is increased (for fixed W/F val-
ues), indicating that CO oxidation over CeO2 and CeO2 -based mixed
oxides is being favored by temperature. This is in good agreement
with research already reported [80]. The reason might be that above
a certain temperature (260–280 ◦ C), the oxygen that is chemically
adsorbed on the catalyst surface is activated leading to species par-
ticipating in the CO oxidation and subsequently creating oxygen
vacancies and hence, improving the activity, since oxygen vacan-
cies are a crucial parameter of the oxidation reaction. This trend for
the XCO increase, presented herein, coincides quite well with the
Raman and H2 -TPR studies which show easily reducible oxygen
species and oxygen vacant sites of these catalysts at low- and mid-
temperature regimes (Ce0.8 Sm0.2 O2 ) and high temperature regime
(CeO2 ).
Effect of contact time (W/F). The effect of contact time (W/F,
W = catalyst weight (g); F = flow rate of the reactant (mL/min)) on
the CO oxidation reaction is shown in Fig. 15(a)–(c) as well. A mono-
tonic increase in CO conversion was observed from W/F = 0.015 to
0.070 g s ␮mole. At a low contact time, the CO oxidation reaction
does not proceed sufficiently due to the high flow rate. It can be
stated that the catalyst active sites are covered with adsorbed
species and there is not enough time for them to be regenerated
and restore their activity for the CO oxidation reaction. As a result,
only a low conversion of CO was observed. Increasing contact time
or increasing catalyst loading, the regeneration and availability
of sufficient population of active sites can be achieved leading to
increase of the CO conversion. The apparent activation energies
calculated from Arrhenius plots (Fig. 15(d)–(f) for the CeO2 MW,
Ce0.8 Sm0.2 O2 , Ce0.2 Sm0.8 O2 are 35.74 ± 1.27 kJ mol−1 (R2 = 0.9937);
37.57 ± 1.54 kJ mol−1 (R2 = 0.99159) and 42.82 ± 4.29 kJ mol−1
(R2 = 0.95164), respectively. These results demonstrate as well the
superiority of the CeO2 MW and Ce0.8 Sm0.2 O2 MW for the reaction
at hand. The proximity of Eact values for the doped and undoped
ceria has also been reported [80] and has been attributed to the
oxygen vacant sites and grain growth among other parameters. The
comparable Eact values for the CeO2 and Ce0.8 Sm0.2 O2 catalysts,
along with the enhanced thermal stability induced by Sm doping,
make the Ce0.8 Sm0.2 O2 catalyst a very promising system for CO
oxidation.
4. Conclusions
In this study, microwave assisted and conventional sol-gel CeO2
and Cex Sm1-x O2 mixed oxides were synthesized and their activ-
ity towards CO catalytic oxidation in the absence and presence
of H2 was evaluated. FTIR studies showed that during the synthe-
sis intermediate species population is different for the microwave
assisted compared to the conventional sol-gel method, but there
is no significant effect of the synthesis method on the material
porosity. However, the different population of intermediate species
that develop during microwave assisted synthesis leads to precur-
sor materials which are overall more thermally stable, preserving
75% of their mass up to 600 ◦ C. The thermal stability of the con-
53
ventionally synthesized material improves significantly when the
preparation takes place at higher temperature (100 ◦ C). Microwave
assisted synthesis gives rise to a significant advantage over the
conventional sol-gel process by CO oxidation occurring at a signif-
icantly lower temperature, with T50 for the CeO2 and Ce0.5 Sm0.5 O2
materials being reduced by 131 ◦ C and 59 ◦ C, respectively, but
still maintaining a high CO conversion. Further benefits of the
microwave assisted synthesis are the enhanced presence of oxygen
vacant sites, giving rise to a lower temperature at which reducible
oxygen species can be provided and a refinement of the particle
size.
The affinity of the catalytic surface with CO2 (a product of both
the reactions under study) was studied using CO2 -TPD. A lower
affinity of the surface with CO2 (as shown by a lower calculated
Edes value) leads to higher activity of the catalyst. Of the microwave
assisted sol-gel synthesized materials, Ce0.8 Sm0.2 O2 shows the
lowest Edes of CO2 desorption (8.7 kJ/mol) and a higher catalytic
activity compared to CeO2 (Edes = 11.2 kJ/mol) and Ce0.5 Sm0.5 O2
(Edes = 19.6 kJ/mol). Kinetic studies for the MW catalysts have
demonstrated the monotic increase of CO conversion with tem-
perature and contact time. Similar values of Eact were obtained
for CeO2 and Ce0.8 Sm0.2 O2 catalysts which shows that both sys-
tems have reactive sites for the studied reaction. Though, the MW
Ce0.8 Sm0.2 O2 catalyst brings the beneficient combination of high
activity and thermal stability. Given the facile MW method, MW
Ce0.8 Sm0.2 O2 could be a scalable system of industrial interest.
Acknowledgements
KP would like to acknowledge the financial support from Abu
Dhabi Educational Council (ADEC B3111) and Khalifa University
Internal Research Fund (L1 KUIRF-210103) for supporting this
research. Part of work presented here (XRD, SEM) is done at Khalifa
University Core Nanocharacterization Facilities. We acknowledge
KU and CNCF staff support. Work by AFZ and SYA was made possi-
ble by the grant number NPRP 6-351-1-072 from the Qatar National
Research Fund (a member of Qatar Foundation).
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