Article

pubs.acs.org/EF

Tailoring Hybrid Nonstoichiometric Ceria Redox Cycle for Combined

Solar Methane Reforming and Thermochemical Conversion of H2O/
CO2
Mahesh M. Nair and Stéphane Abanades*
Processes, Materials and Solar Energy Laboratory, PROMES-CNRS (UPR 8521), 7 Rue du Four Solaire, 66120 Font-Romeu, France
*
S Supporting Information

ABSTRACT: Combining partial oxidation of methane with H2O/CO2 splitting under solar thermal conditions presents a very
promising strategy for producing solar fuels. In order to achieve this, the development of stable and efficient redox catalysts is
necessary, among which ceria (CeO2) seems to be one of the most promising for lattice oxygen transfer. In this study, CeO2 was
used for splitting CO2 and H2O using concentrated solar energy with reaction temperatures in the range 900−1100 °C. The
experimental studies in a solar-driven thermogravimetric system indicated that both CH4 induced reduction and CO2 induced
oxidation of CeO2−δ followed close reaction orders with activation energies of 109 and 36 kJ mol−1, respectively. The results were
compared with those obtained from hydrothermal templating and surfactant induced self-assembly. To our knowledge, such
materials are studied for the first time for CH4 induced fuel production via solar thermochemical redox cycles. Enhanced reaction
rates and stability upon cycling were observed for materials synthesized by hydrothermal and self-assembly methods. Experiments
were also carried out to deduce the effect of various inert materials (MgO and Al2O3) as promotional agents. Higher reduction
rate and maximum nonstoichiometry (δ = 0.431) during reduction at 1000 °C were observed in the case of MgO promoted
CeO2. In addition, the amount of evolved CO was found to be the highest (δ = 0.402), indicating almost complete reoxidation.
The achieved nonstoichiometry and the resulting fuel productivity are more than 10 times higher than the reported values for
thermal reduction of ceria. Studies were also performed in a solar reactor prototype, enabling both partial ceria reduction with
methane, followed by oxidation with H2O/CO2. Typically, MgO and Al2O3 promoted ceria were tested under packed bed
conditions and compared with commercial ceria for syngas production. In this case, significant enhancement in the system
efficiency was observed for MgO promoted CeO2.

1. INTRODUCTION Several aspects are to be considered for selecting appropriate

Solar energy is the largest exploitable alternative to fossil fuels
with enormous potential. However, it must be harnessed and
converted into storable and transportable forms such as high-
temperature heat (thermal storage), power (photovoltaics or
solar thermal), or chemical fuels (H2, syngas, liquid fuels). A
wide variety of strategies are being explored on this regard
including solar cells, semiconductor photocatalysis, etc.1,2 The
efficiency of these methods mostly relies on the visible region
of the solar spectrum. Besides, thermochemical conversion of
solar energy into fuels or feedstock such as syngas (CO + H2)
has gained considerable interest over recent years.3−5 In this
method, the entire solar spectrum can be effectively utilized
while the redox properties of metal oxides are exploited to
convert H2O and CO2 into H2, CO, or syngas.6 Two-step redox
processes for splitting H2O and/or CO2 can be divided into
two categories, namely, stoichiometric and nonstoichiometric
cycles. Thermochemical redox reactions proceed via discrete
transition between two valence states for stoichiometric oxides
(which generally occurs with phase transitions), while
formation of oxygen vacancies in the oxide lattice during
solid-state reactions occurs for nonstoichiometric oxides. Thus,
the development of efficient and stable redox materials remains
one of the major bottle necks for the effective commercializa-
tion of this technology. Alternatively, the maximum temper-
ature of the redox cycles can be decreased by using a
carbonaceous reducing agent (such as carbon or methane).7−9
redox materials such as solid phase stability during the
operating conditions, resistance to carbon deposition, for-
mation of metal carbide during the reduction step with CH4 in
the case of a carbothermal process, etc.
One of the most widely investigated materials for solar
thermochemical fuel production is ceria (CeO2).3,10−13 The
inbuilt unique redox properties of CeO2 make it an extremely
promising material for solar thermochemical fuel production,
with high potential for commercial applications.14 The
additional advantages encompass high oxygen storage and
release capacities, crystallographic stability during Ce4+ to Ce3+
reduction, and rapid kinetics during thermochemical cycles.
First, ceria is partially reduced to a nonstoichiometric oxide at
high temperatures exceeding 1400 °C, in an endothermic
thermal reduction step. In a subsequent low temperature
exothermic oxidation, the reduced ceria is oxidized with H2O
and/or CO2, producing H2 and/or CO, along with the
stoichiometric oxide. Recent studies indicated that significant
attention must be paid with regard to the stoichiometry of
chemical reactions involved and the presence of volatile
compounds in the gas phase at equilibrium.15 One way to
enhance the fuel production is to increase the extent of
Received: May 3, 2016
Revised: June 23, 2016
Published: June 26, 2016

© 2016 American Chemical Society 6050 DOI: 10.1021/acs.energyfuels.6b01063

Energy Fuels 2016, 30, 6050−6058
Energy & Fuels
reduction (δ) at a lower temperature. Introduction of 4+
valence dopants (Zr, Hf) with a lower ionic radius than Ce4+ in
the CeO2 fluorite structure significantly helped to overcome
this issue by improving the reducibility of ceria.16−20 However,
slower reoxidation kinetics compared to pure CeO2 was also
observed in this case. Studies performed by Le Gal et al.
indicated that ceria with dopant concentration of 25 mol % Zr4+
was the optimal composition for reoxidation with steam.21 The
structural modifications induced by the substitution of Ce4+ by
Zr4+ appear to be responsible for the enhancement of the
reduction processes. The reduction/oxidation processes induce
expansion/contraction of the lattice parameter and strongly
modify the material microstructure. The sintering process
induces a structural modification of the ceria-zirconia solid
solution, which promotes the reduction in the bulk and induces
formation of mesoporosity, resulting in a high efficiency of the
Ce4+-Ce3+ redox cycle at moderate temperatures.22 The
reduction occurs concurrently at the surface and in the bulk
of the solid solution. The availability of bulk Ce(IV) sites for
the redox processes at moderate temperatures, even after
extensive sintering, makes these materials highly attractive for
processes requiring an efficient redox couple with a high
thermal stability. A computer simulation study of the Ce4+/
Ce3+ reduction process in CeO2-MO (M = Ca, Mn, Ni, Zn)
and CeO2-M2O3 (M = Sc, Mn, Y, Gd, La) mixed oxides showed
that the process is enhanced with increasing metal dopant
content (the enhancement being more pronounced for divalent
dopants).23 For a fixed dopant content, larger dopant ions favor
the reduction of cerium. These results are explained by the
higher oxygen vacancy concentration and the larger dopant size
being effective in accommodating the greater relaxation or
elastic strain associated with the larger Ce3+ species formed
upon reduction.
Alternatively, performing ceria reduction in the presence of a
reducing agent such as methane is found to be effective.24−27
This highly endothermic process is expressed as
CeO2 + δCH4 → CeO2 − δ + δCO + 2δ H 2 (1)
The reduced metal oxide thus produced can be used for
splitting H2O or CO2 in the second step.
CeO2 − δ + δCO2 (H 2O) → CeO2 + δCO (H 2) (2)
Hence, this two-step cyclic process has a noticeable incentive
for the production of carbon-free hydrogen for fuel cells and/or
syngas. The coupling of partial oxidation of CH4 with CeO2
redox cycle enables one to perform the entire reactions under
isothermal or near isothermal conditions because the temper-
ature of the reduction step is greatly decreased and both
reactions can thus proceed at the same temperature. Also,
additional H2 and CO are produced during the CeO2 reduction
step in the presence of CH4 with a 2:1 ratio desired for
conversion to liquid fuels via Fischer−Tropsch reactions or
methanol synthesis.
So far, few studies were performed by coupling partial
oxidation of CH4 with H2O/CO2 splitting over CeO2.24−27
Most of these studies focused on using pure or doped CeO2.
However, the effects of surface structure, morphology, and
porosity on the performance of these materials are rarely
exploited, especially in the case of CeO2 redox cycles coupled
with partial oxidation of CH4. In the present study, the kinetic
analysis of the reduction and reoxidation of commercial CeO2
in the presence of CH4 and CO2, respectively, was performed
using a customized solar thermogravimetric device in order to
6051
Article
monitor continuously the amount of oxygen released/absorbed
by the material during redox reactions. The experimental setup
used is depicted in Figure 1. In comparison, studies were also
Figure 1. Schematic representation of the experimental setup used for
solar-driven thermogravimetric analysis of CeO2 redox cycles and
photograph of solar concentrating system and reactor.
performed under similar conditions using CeO2 synthesized via
hydrothermal and self-assembly methods and clearly indicated
that such differences in the synthesis strategies modified the
redox performance of the materials. This performance
modification can be attributed to the variations in structure
and morphology. Such materials were previously found to be
advantageous for a variety of applications in comparison with
their bulk counterparts.28−32 Further, the effect of various inert
promotional agents, such as Al2O3 and MgO, on the redox
properties of CeO2 was studied. Finally, a different reactor
configuration consisting of a porous SiC packed bed to support
CeO2 and MgO or Al2O3 promoted CeO2 was also used for
H2O and CO2 splitting redox cycles.
2. EXPERIMENTAL SECTION
2.1. Materials Synthesis. CeO2, MgO, and Al2O3 were purchased
from Aldrich (99.9%). CeO2 was used as received, and for MgO and
Al2O3 promoted materials, appropriate quantities of materials (50 wt
%) were ground well in a mortar before performing the tests for
promoting the mixture homogenization. All of these materials were
calcined at 1000 °C for 2 h in air before the solar experiments to
warrant their structural and chemical stability after this pretreatment
step and to remove the impurities such as moisture that got adsorbed
on the surface of the material. A recently developed one-pot
hydrothermal templating method was also used for the synthesis of
CeO2 (CeO2-HT in the following).33,34 Typically, 3.5 g of glucose was
dissolved in 20 mL of water. Next, 1.4 g of Ce(NO3)3·6H2O (CeO2
purity > 99.5%, total remaining rare earth oxides < 0.05%) was added
to this solution and kept stirring for 1 h. The entire homogeneous
solution was transferred to a Teflon-lined stainless steel autoclave and
was hydrothermally treated at 180 °C for 24 h. The resulting black
precipitate was filtered, dried at 80 °C, and calcined under air at 1000
°C for 2 h.
CeO2 was also synthesized by following the self-assembly method
(CeO2-SA in the following) as described by Yuan et al. for the
synthesis of ordered mesoporous (Ce,Zr)O2.35 Nonionic surfactant
Pluronic P123 was used as the soft template. In a typical synthesis, 1 g
of P123 and 4.34 g of Ce(NO3)3·6H2O were dissolved in 10 mL of
DOI: 10.1021/acs.energyfuels.6b01063
Energy Fuels 2016, 30, 6050−6058
Energy & Fuels Article

ethanol and stirred for 2 h at room temperature. The clear

homogeneous solution was aged at 40 °C for 48 h and subsequently
dried at 100 °C for 24 h. The resultant dried gel was ground well and
calcined at 1000 °C for 2 h, under air.
2.2. Characterization. Structural and morphological character-
izations of the synthesized materials before and after redox cycles were
performed. X-ray diffraction (XRD) patterns were recorded with a
Philips PW 1820 diffractometer with the Cu Kα radiation (αCu =
0.15418 nm, angular range = 20−100 2θ, steps = 0.02 2θ, recording
time = 2 s). For the used/cycled materials, the whole sample powder
was collected after thermochemical cycles and mixed in a mortar
before XRD analysis. The powder morphology and pore structure
were studied by using SEM (FESEM, Hitachi S4800).
2.3. Thermochemical Activity Measurements. The exper-
imental setup is shown schematically in Figure 1 and was previously
developed for investigating high-temperature solid−gas thermochem-
ical reactions in a controlled atmosphere.36 Concentrated solar energy
is used to drive the thermochemical reactions. The high-temperature
process heat is supplied by a horizontal axis solar furnace consisting of
a sun-tracking heliostat reflecting the incident solar irradiation toward
a 2 m diameter parabolic dish concentrator. The solar thermogravi-
metric reactor consists of a cavity receiver with the aperture (15 mm
diameter) positioned at the focal point of the concentrator for the
optimal access and absorption of concentrated solar radiation. The
cavity made of graphite is lined with a surrounding insulation layer and
separated from the atmosphere using a glass window. Concerning the
solar thermogravimetric measurements, the sample to be analyzed was
placed in an alumina crucible (12 mm i.d., 15 mm o.d., 10 mm height)
connected to a microbalance inside a cylindrical lining tube made of
alumina (25 × 20 mm diameter). Temperature above the reacting
sample during redox cycles was measured by placing a B-type
thermocouple inside the alumina tube. It corresponds to the reaction
temperature because the cavity-type solar reactor configuration
provides homogeneous temperature distribution in the reacting zone
inside the absorber tube where the sample is placed.36 The sample is
mainly heated by radiation from the nearby hot tube walls (radiative
heat transfers are prevailing because of the high temperatures) with a
radiative thermal equilibrium established in this zone. The absence of
thermal gradient inside the reacting powder is presumed given the very
limited size of the crucible. Purge gas (Ar, 99.999% purity, O2 content
below 2 ppm), CH4 (99.95% purity), and CO2 (99.995% purity) flow
rates were regulated by using electronic mass flow controllers. Total
flow rate was maintained constant (0.5 L·min−1) to keep the gas
residence time constant. The reduction extent (δ) in eq 1 is calculated
as follows

δ = (Δm/m)· (MCeO2 /MO)
where Δm is the mass loss (or gain) obtained during ceria reduction
(or oxidation), m is the initial amount of sample used for analysis,
MCeO2 is the molecular weight of CeO2, and MO is the molecular
weight of the oxygen atom. The same equation is used for estimating
the amount of CO evolved in eq 2 with the mass loss replaced with
mass gain during oxidation.
3. RESULTS AND DISCUSSION
3.1. Physicochemical Characterization. Initial studies
were dedicated to perform the physicochemical characterization
of the fresh/used materials. Wide angle X-ray diffraction
patterns of the materials used in this study are provided in
Figure 2. All the observed reflections for the commercial,
hydrothermal, and self-assembled materials match well with the
highly crystallized and pure phase of the cubic fluorite-type
CeO2 structure. XRD patterns for CeO2 reduced in the
presence of CH4 and CeO2 after three successive redox cycles
reveal that, while partial structural changes resulting from the
formation of Ce2O3 phase took place during reduction, the
structure returned back to the initial cubic fluorite structure
(3) Figure 2. Representative wide angle powder XRD patterns of (a) fresh
CeO2, CeO2−δ after CH4 induced reduction, and CeO2 after 2 redox
cycles; (b) Al2O3 and MgO promoted CeO2 before and after 3 redox
cycles; (c) CeO2-HT and CeO2-SA before and after 3 redox cycles.
after oxidation. Thus, complete reoxidation was evidenced for
the cycled material. Part of ceria was completely converted into
the Ce2O3 phase after reduction, as confirmed by the XRD
pattern of the reduced ceria, while a fraction of CeO2 was
partially reduced to nonstoichiometric ceria. The concomitant
presence of partially reduced CeO2 and Ce2O3 in the recovered
sample after reduction yields global composition CeO2−δ (with
δ < 0.5). In the case of MgO and Al2O3 promoted materials (50
wt %), respective diffraction peaks of the inert material were
also observed. This confirms that the interactions between the
individual compounds remained negligible and the materials
retained their phase composition during the initial precalcina-
tion process. For these materials, diffraction patterns matching
well with the fresh materials were also observed after cycling. It
can be concluded that the phase purity of these materials was
unaffected under the thermochemical reaction conditions that
involved reduction in the presence of CH4 and oxidation in the
6052 DOI: 10.1021/acs.energyfuels.6b01063
Energy Fuels 2016, 30, 6050−6058
Energy & Fuels
presence of CO2 at 1000 °C. Similar results were observed in
the case of CeO2 redox materials synthesized by hydrothermal
and self-assembly methods.
The scanning electron microscopy (SEM) images of
commercial CeO2 along with the ones synthesized by
hydrothermal and self-assembly methods are provided in
Figure 3. In the case of commercial CeO2, closely agglomerated
Figure 3. Representative SEM images of fresh CeO2 materials
depicting the structural and morphological variations based on the
differences in synthesis methods.
dense particles with uneven morphologies and a nearly uniform
size distribution were observed. In the case of hydrothermally
synthesized CeO2 (CeO2-HT), even though agglomerated
domains were visible, the particles were uniformly sized with a
more or less spherical morphology. Regions containing broken
particles were also visible, indicating that the interior of these
particles was hollow to some extent. This was also confirmed by
the fact that a similar mass of these CeO2-HT materials
occupied almost twice the volume occupied by commercial
CeO2. The synthesis of these hollow CeO2 particles involved
the use of carbonaceous spheres obtained from glucose, as hard
templates. CeO2 formation took place on the surface of these
carbon spheres under hydrothermal conditions. Thermal
removal of the carbon templates generally results in the
formation of well-defined oxide hollow spheres, as observed in
various studies for a variety of oxide compositions.33,34 The
deviations, however, observed in the present study can be
attributed to the high temperature treatment (1000 °C) aimed
at the stabilization of the CeO2 structure. It must be noted that
such high temperature pretreatment cannot be avoided in the
present study because it corresponds to the temperature chosen
for performing redox experiments.
SEM analyses were also performed to determine the
morphology of CeO2 synthesized by the template assisted
self-assembly method using pluronic P123 as soft template
(CeO2-SA). In this case, extremely small-sized particles were
agglomerated, leading to the formation of largely porous
material with a pore size distribution in the macro/meso range.
Two types of macropores were observed with larger pores of
∼300 nm and smaller pores of ∼150 nm. In addition,
mesopores of ∼40 nm were observed throughout the material.
This porous CeO2 was synthesized by following the cooperative
self-assembly method as reported by Yuan et al., for the
synthesis of ordered mesoporous (Ce,Zr)O2.35 As mentioned
above, the deviation of structural order in the present study
resulted from the inevitable higher calcination temperature
during materials synthesis (1000 °C).
3.2. Parametric Analysis of Ceria Redox Cycles via
Solar Thermogravimetry. Regarding the redox performance
6053
Article
of the ceria-based materials, commercial CeO2 was investigated
initially. Reduction of CeO2 was first monitored as a function of
temperature during a nonisothermal run in the presence of CH4
(40% in Ar, CH4 injection at about 400 °C during temperature
rise) in order to identify the temperature at which the reaction
commences. As a result, ceria reduction with CH4 occurs
slightly from ∼600 °C with a steep rate increase from ∼800 °C
as the temperature rises. The obtained reduction profile after a
blank run correction is provided in the Supporting Information
(Figure SI1). Isothermal redox cycles were then performed.
The two-step cycle consists of partial oxidation of CH4,
resulting in the formation of reduced CeO2−δ, followed by CO2
induced reoxidation. Heat delivered from concentrated solar
energy was used to increase the temperature of the reaction
chamber where the sample is placed, under a flow of Ar (0.5 L·
min−1). Purging was done with Ar to avoid ceria reduction
during heating up to the operation temperature (at ∼80−100
°C/min) before introducing CH4 under isothermal conditions.
This was confirmed by the mass loss that remained negligible
until CH4 was injected. When the temperature reached 1000
°C, a continuous flow of CH4 (0.2 L·min−1, 40% CH4 in Ar)
was introduced under isothermal conditions and was retained
until the oxygen releasing step from ceria was completed, as
evidenced by the steep mass loss curve as a function of time.
Afterward, the entire CH4 remaining in the reactor was
removed using a vacuum pump and Ar refilling, and CO2 was
subsequently introduced (0.2 L·min−1, 40% CO2 in Ar) at the
same temperature (1000 °C) in order to reoxidize the partially
reduced ceria (CeO2−δ), thereby completing the cycle as shown
in Figure 4a. On the whole, CO and H2 are produced from
CH4 and CO2. In order to check the stability of this material,
the entire process of reduction and reoxidation was performed
again as mentioned above. During the initial reduction step in
the first cycle, approximately 3.5% mass loss was observed,
corresponding to a δ value of 0.378 (which also corresponds to
the amount of released O from ceria in mol·mol−1). The
resulting global ceria reduction yield is thus 76% assuming that
a δ of 0.5 corresponds to complete ceria reduction into Ce2O3.
The quantity of CO produced during the CO2-splitting step
was calculated from the mass gain observed during the
reoxidation of CeO2−δ, which amounted to 0.365 mol·mol−1.
Clearly, the negligible difference observed between the mole
values of O and CO evolved during reduction and reoxidation,
respectively, indicated almost 100% reoxidation for this
material. Even though significant variation in the reduction
extent was not observed during the reduction in the presence of
CH4 in the second cycle (δ = 0.372), the amount of CO
evolved was found to decrease to 0.322 mol·mol−1 during the
reoxidation step. From this observation, it can be concluded
that stability of commercial CeO2 will be diminished during the
long run. The amounts of evolved product gases during each
cycle are compiled in Table 1, along with the reduction yields
(δ corresponds to oxygen nonstoichiometry in CeO2−δ).
In order to investigate the reaction kinetics for commercial
CeO2 during CH4 induced reduction and reoxidation in the
presence of CO2, the kinetics of both reduction and reoxidation
over this material were monitored as a function of the
temperature and reacting gas concentration. The corresponding
reduction and reoxidation profiles as a function of time are
shown in Figure 5. Reduction was carried out at 900, 1000, and
1050 °C, and the concentration of CH4 in the feed was 20, 40,
and 60% (balanced with Ar and using a total flow rate of 0.5 L·
min−1). The values of reaction rates for each temperature were
DOI: 10.1021/acs.energyfuels.6b01063
Energy Fuels 2016, 30, 6050−6058
Energy & Fuels Article

Figure 4. Time-dependent solar thermochemical reduction and

reoxidation profiles for (a) CeO2 (black), CeO2-HT (red), and
CeO2-SA (blue), and (b) CeO2-MgO (green) and CeO2-Al2O3
(yellow). Temperature was fixed at 1000 °C. Reduction experiments
were performed in the presence of CH4 and oxidation in the presence
of CO2 (with reacting gas mole fractions of 40% in Ar).
Figure 5. (a) CeO2 reduction (CO2 was used as the oxidizing agent,
40% in Ar at 1000 °C) and (b) reoxidation (CH4 was used as the
reducing agent, 40% in Ar at 1000 °C) profiles as a function of time
with varying temperature and concentration of CH4/CO2 in the feed.

determined from the slope of the curves provided in Figure 5a

in the part corresponding to constant reaction rate (almost
linear evolution of the mass loss). The reaction order (α) with
respect to CH4 was obtained from a logarithm plot of the
reaction rate versus the partial pressure of CH4. The reaction
rates were further plotted against the partial pressure of CH4
raised to the power α, and a linear dependence was observed
between the reaction rates and the partial pressure of CH4, as
shown in eq 4 and the Supporting Information (Figure SI2).
r = k(PCH4)0.62 (4)
Rate constants (k = A·exp(−Ea/RT)) were determined by
performing the linear regression of eq 4, the values of which
were found to vary directly with the inverse temperature. The Figure 6. Arrhenius plot for CH4 induced reduction and CO2 induced
reoxidation of CeO2 under solar thermochemical conditions.
values of activation energy (Ea) and pre-exponential factor (A)
were thus obtained from the Arrhenius plot as given in Figure
6. The values are compiled in Table 2.

Table 1. Reduction Extent (δ) and CO Released during Isothermal Solar Redox Cycling of CeO2 at 1000 °C

δ (O) evolved (mol·mol−1) δ (CO) evolved (mol·mol−1) reduction yield (%)

sample cycle I cycle II cycle III cycle I cycle II cycle III time (s) cycle I cycle II cycle III
commercial CeO2 0.378 0.372 0.365 0.322 2984 76 74
CeO2-Al2O3 0.331 0.264 0.333 0.320 0.236 0.350 4232 66 53 66
CeO2-MgO 0.431 0.394 0.350 0.402 0.346 0.344 2560 86 79 70
CeO2-HT 0.346 0.349 0.338 0.341 0.347 0.342 2010 69 70 68
CeO2-SA 0.379 0.363 0.369 0.374 0.367 0.360 2998 76 73 74

6054 DOI: 10.1021/acs.energyfuels.6b01063

Energy Fuels 2016, 30, 6050−6058
Energy & Fuels
Table 2. Kinetic Parameters Obtained for CH4 Induced
Reduction and CO2 Induced Reoxidation over CeO2 under
Solar Thermochemical Conditions
Ea (kJ mol−1) A (g·s−1)
step
reduction 109 ± 6 6 × 10−2
reoxidation 36 ± 4 5 × 10−5
Similar studies were performed to elucidate the kinetics of
the reoxidation step in the presence of CO2. In this case,
temperature of initial reduction in the presence of CH4 was
fixed at 1000 °C. Reoxidation was also performed at 900, 1000,
and 1070 °C and a CO2 concentration of 20, 40, and 60%, as
shown in Figure 5b. The reaction rate was determined as the
slope of the mass increase evolution, which is almost linear
before slowing down when the oxidation reaction approaches
completion (Figure 5b). The reaction order (α) with respect to
CO2 was obtained from a logarithm plot of the reaction rate
versus the partial pressure of CO2. The rate equation used to
determine the rate constants is given below:
r = k(PCO2)0.53
(5)
The values of activation energy (Ea) and pre-exponential
factor (A) were determined as mentioned before in the case of
reduction (Figure 6 and Table 2). A noticeable difference
between the values of Ea and pre-exponential factors was
observed for reduction and reoxidation. Activation energy for
oxidation is consistently lower than that for reduction. The
values of activation energies obtained in the present study were
compared with the ones previously observed for CeO 2
reduction and reoxidation. The value for reduction was found
to be significantly lower when compared with the thermal
reduction of CeO2 (reduction with CH4 is consistently easier
than purely thermal reduction), and the activation energy for
reoxidation was found to be similar.37
As mentioned above, these initial experiments with
commercial CeO2 indicated loss of stability during multiple
cycles. In particular, the amount of evolved CO decreased
during the reoxidation step in the second cycle, most probably
due to sintering. Therefore, in order to improve the resistance
to sintering, the effect of the presence of promotional agents
along with CeO2 was studied first. Hence, MgO and Al2O3,
which are inert under the operating conditions, were used. The
presence of such inert materials could hinder the high
temperature sintering during prolonged exposure, by reducing
the contact between the active phases. First, 50 wt % of MgO
was mixed with CeO2 by grinding and was used for CH4
induced solar thermochemical CO2 splitting. The reduction and
reoxidation profile obtained during three successive cycles is
shown in Figure 4b. The weight loss during the reduction step
for these materials was found to be higher (4%) compared to
commercial CeO2. Reduction extent and CO evolution
amounts of about 0.431 and 0.402 mol·mol−1 were obtained
during the first reduction and reoxidation steps, respectively.
These values were higher than that observed in the case of pure
CeO2, indicating that the reduction extent and amount of
evolved CO increased in the presence of MgO. Interestingly,
this high δ value approaches the theoretical maximum value of
0.5 for complete reduction and the reduction extent is
approximately 10 times higher than that observed previously
for ceria-based materials under solar thermal reduction.10,38
Even though the reduction extent and CO amounts decreased
slightly to 0.394 and 0.346 mol·mol−1 during the second redox
6055
Article
cycle, it was still higher than that observed in the case of pure
CeO2. Interestingly, during the third cycle, the reduction extent
further reduced to 0.350 mol·mol−1, but, however, the
reoxidation step yielded a stable CO amount (0.344 mol·
mol−1) that agrees well with the oxidation step during the
second cycle, confirming complete oxygen replenishment
during ceria oxidation.
In addition, Al2O3 (50 wt %) was used as a promotional
agent for CeO2 (Figure 4b). However, differently from the case
of MgO, the presence of Al2O3 lowered the reactivity of pure
CeO2, which can be attributed to sintering. The rates of
reduction and reoxidation were found to be the lowest in this
case among the series of materials considered in the present
study. However, the reduction extent and the amount of
evolved CO were similar to those observed for other materials,
except during the second cycle as given in Table 1. After
completing the first cycle, the system was not purged, leaving
some CO2 in the system, which hindered the CH4 induced
reduction in the second cycle. This explains the lower values of
evolved O and CO during the second cycle. The system was
purged with Ar before the third cycle, and hence values of
evolved O and CO in the third cycle became higher than the
ones observed during the first cycle. The ceria reduction
capability and amount of CO production during cycles were
not significantly altered by Al2O3 addition, which denotes the
negligible interaction between individual compounds (in
particular, the possible formation of the stable CeAlO3
compound that keeps Ce in its Ce(III) oxidation state was
not detected, although it may alter the long-term redox activity
of ceria). The results obtained in this study clearly indicate that
addition of MgO significantly enhanced the extent of CeO2
reduction and hence the amount of CO released. Also, the rates
of reduction and reoxidation were found to be improved
markedly.
Further experiments were performed to investigate the effect
of structural and morphological variations in the redox
performance of CeO2 under solar thermochemical conditions.
Agglomerated CeO2 particles with near spherical morphology
were obtained by performing one-pot hydrothermal templating
(CeO2-HT). Here, carbonaceous spheres synthesized from
glucose acted as a hard template, on the surface of which CeO2
was formed under hydrothermal conditions. The template was
further removed by performing calcination at 1000 °C. This
method was previously employed for the successful synthesis of
various hollow oxide compositions.33,34 To our knowledge,
such CeO2 particles are studied for CH4 induced solar
thermochemical fuel production for the first time. The extent
of reduction and reoxidation was found to be slightly lower
than that for pure CeO2 and MgO promoted CeO2, with
comparable amounts of released oxygen and CO as evidenced
from Figure 4 and Table 1. Interestingly, this material was
found to be highly stable with respect to the amount of O and
CO evolved, as evidenced by the three cycles of reduction and
reoxidation performed in this study. Additionally, even though
the reaction rate during the first cycle was comparable with
MgO promoted CeO2, the rate was enhanced during the
subsequent cycles of operation and the highest among the
series of materials used in this study. These results indicate that
the morphology of the materials plays an important role in
determining the redox cycling efficiency of CeO2. To further
elucidate the effect of porosity on the performance of CeO2,
reduction and reoxidation experiments were performed using
porous CeO2 (CeO2-SA) synthesized by following the
DOI: 10.1021/acs.energyfuels.6b01063
Energy Fuels 2016, 30, 6050−6058
Energy & Fuels
cooperative self-assembly method using P123 as the soft
template as reported by Yuan et al.35 Here again, such materials
are utilized for the first time for CH4 induced solar
thermochemical fuel production. The CH4 induced reduction
and reoxidation in the presence of CO2 were found to proceed
with higher rates when compared to the case of commercial
CeO2 as shown in Figure 4. The reduction extent was found to
be closely similar to the one of commercial CeO2 materials,
however, with improved stability. Even though the reaction
rates were lower than those for hollow materials, these
materials outperformed the commercial counterpart with
reaction rates similar to MgO promoted CeO2.
SEM analysis was performed over the materials recovered
after redox cycles (Figure 7). Commercial CeO2 was found to
Figure 7. Representative SEM images of various CeO2 materials after
reduction and reoxidation cycles at 1000 °C.
undergo extensive sintering during the two redox cycles,
resulting in the formation of very large particles in comparison
with the fresh ones. Even though sintering was observed to a
smaller extent in the case of CeO2-HT, this material mostly
retained its particle size and morphology during the three
cycles. Probably, the observed sintering might have occurred
among the broken particles. In the case of CeO2-SA, no
significant variation in the particle size and porosity was
observed. Accordingly, the superior performance of this
material can be attributed to the enhanced structural stability.
Also, the presence of larger pores provided easier access of gas
species to active sites and enabled faster diffusion of reactants
and products. In the case of Al2O3 promoted material, large
CeO2 particles were observed, which denotes sintering similar
to the case of commercial CeO2. In contrast, for MgO
promoted materials, the CeO 2 particle size remained
considerably lower in comparison with pure CeO2 and Al2O3
promoted CeO2.
3.3. Experimental Study in a Packed Bed Solar
Reactor. Solar thermochemical fuel production over ceria
was performed in a packed bed solar reactor configuration with
online gas analysis for gas species detection and identification.
This reactor was heated by concentrated solar energy delivered
by a 2 m diameter parabolic concentrator. The reactor was
based on a cavity receiver (45 mm height, 40 mm width, and 55
mm depth) crossed by a vertical alumina tube and closed at the
front by a glass window.39 Inside the tube, a porous SiC foam
(20 mm diameter, 20 mm length, 30 ppi) was used to support
the redox material with minimal pressure drop. Regarding the
packed bed experimental setup (Figure 8), the SiC reticulated
porous foam was settled inside the alumina absorber tube,
above which a packed bed was placed. This packed bed consists
of a bottom layer of inert SiC particles (about 2.5 g, 1 mm
mean diameter) and an upper layer of the reactive ceria sample
6056
Article
Figure 8. Schematic representation of the packed bed solar reactor
used for solar thermochemical analysis of CeO2 redox cycles.
mixed with SiC particles (about 3.5 g of CeO2 powder mixed
with 8.8 g of SiC particles). This layout was used in order to
increase heat transfer within the particle bed, facilitate gas
circulation through the bed, and alleviate bed densification
resulting from downward gas flow. The reaction temperature
(temperature of the particle bed) was measured directly via a
Pt−Rh thermocouple settled within the tube and immersed in
the particle bed. The bed was first heated in Ar up to the
targeted operation temperature (1000 °C). The feed gas
consisting of reactant gases (40% CH4 in Ar during reduction)
was fed from the top of the tube, and the product gases exiting
from the reactor outlet at the bottom were monitored using a
gas analyzer (GEIT GAS 3100P SYNGAS analyzer). A total gas
flow rate of 0.5 L·min−1 (0.3 L·min−1 Ar and 0.2 L·min−1 CH4
or CO2) was used during cycles. Liquid water (0.2 mL·min−1)
was injected with a peristaltic pump via a capillary stainless steel
tube to supply steam during the water-splitting redox cycles.
First experiments were performed with commercial CeO2
using H2O and CO2 as the oxidants at a constant bed
temperature of 1000 °C. Representative gas evolution profiles
observed during the reduction step under CH4 and reoxidation
using H2O during the first cycle are provided in the Supporting
Information (Figure SI3). During all the reduction steps of
ceria with CH4, H2 and CO were the main gaseous products,
but small quantities (approximately 1%) of CO2 and acetylene
were also observed. This indicates the occurrence of some
unwanted side reactions to a small extent. During the reduction
steps, peak concentrations of about 18% H2 and 6% CO were
measured. These values remained definitely constant during the
second and third cycles when using CH4 as the reducing agent
of ceria (Figure 9a). Likewise, H2 was the main species
measured during ceria oxidation with H2O (Figure 9b), but side
products including mainly CO and CO2 were detected (Figure
SI3). This denotes the presence of solid carbon that is oxidized
when H 2 O is injected. The plateau region in the H 2
concentration profile after 300 s (Figure 9a) can be attributed
to the thermal decomposition of CH4 leading to the formation
of residual H2 and deposition of carbon. This side reaction also
explains the presence of acetylene in the gas products during
ceria reduction with CH4 and the CO/CO2 formation during
ceria oxidation with H2O. The reaction of CH4 decomposition
DOI: 10.1021/acs.energyfuels.6b01063
Energy Fuels 2016, 30, 6050−6058
Energy & Fuels
Figure 9. H2 and CO evolution profiles as a function of time over
commercial CeO2 in a packed bed reactor under solar thermochemical
reaction conditions (solid lines for H2, dotted lines for CO). (a) CH4
was used as the reducing agent and (b) H2O was used as the oxidizing
agent. Both reduction and reoxidation were performed at 1000 °C.
yielding H2 and solid carbon along with acetylene byproduct
formation was previously observed using the same solar reactor
configuration with a packed bed of SiC particles.39 During the
reoxidation step, the H2 evolution started when H2O was
injected and lasted about 3 min, which indicates that the
reaction was rapid. Further tests using CO2 as the oxidant
indicated high yield to CO (Figure 10). However, in this case,
the reaction took a longer time to reach completion, suggesting
that ceria oxidation with CO2 is slower in comparison with
H2O.
Similarly to the solar thermogravimetry analysis, experiments
were performed using MgO and Al2O3 promoted CeO2 under
packed bed reactor conditions at 1000 °C. The corresponding
H2 and CO production profiles per unit mass of CeO2 are given
in the Supporting Information (Figure SI4). During the
oxidation step with H2O, the maximum CO concentration
was about 1%/g in the case of MgO promoted ceria, with a
peak H2 concentration of about 7%/g. When MgO was used as
a promoter, the amounts of CO and H2 produced during the
redox cycles were significantly higher than those for pure ceria.
Regarding the use of Al2O3 as the promotional agent, the
amount of H2 decreased and the amount of CO remained the
same as for pure ceria. These results indicate that addition of
MgO significantly favored the undesirable CH4 decomposition
reaction during the reduction step. CH4 decomposition is a
heterogeneous reaction generally favored by the presence of
active sites offered by the reactive ceria particles and by the high
surface area offered by inert supports such as SiC porous foam,
SiC particles, and promoting agents used in this study.
6057
Article
Figure 10. CO evolution profiles as a function of time over
commercial CeO2 in a packed bed reactor under solar thermochemical
reaction conditions. CH4 was used as the reducing agent, and CO2 was
used as the oxidizing agent. Both reduction and reoxidation were
performed at 1000 °C.
However, this side reaction is not a detrimental issue for the
whole cycle since the oxidation step with H2O/CO2 produces
further H2/CO from solid carbon. Decreasing the temperature
of ceria reduction with CH4 would be one possible solution to
lower the carbon deposition and to favor the syngas
production, at the expense of slower reaction kinetics. In
short, this study showed the relevant coupling of partial
oxidation of methane with ceria redox cycle for syngas
production in a solar reactor prototype.
4. CONCLUSIONS
Ceria-based materials appear to be promising for producing
syngas by coupling partial oxidation of methane with CO2/H2O
splitting during solar thermochemical redox cycles. In this
study, different strategies to modify the reactivity of CeO2 were
analyzed. The results clearly indicate that MgO can be used as a
promotional agent to enhance the efficiency of CeO2 for CO2
splitting. Significant enhancement regarding the extent of
evolved oxygen, reaction rate, and stability was observed for
MgO promoted CeO2. In addition, structural and morpho-
logical variations modified the efficiency of CeO2. Typically,
CeO2 synthesized by self-assembly and hydrothermal methods
were more reactive and stable than their commercial bulk
counterpart. Among the series of the materials used in this
study, CeO2 synthesized via hydrothermal and self-assembly
and MgO promoted CeO2 were the most active with regard to
the reaction rate and amount of CO evolved. Finally,
experiments performed in a packed bed solar reactor indicated
repeatable syngas production through redox cycling, and the
occurrence of side reactions and carbon deposition ascribed to
CH4 decomposition. However, such a solar reactor prototype
can be optimized for the production of syngas. On the basis of
the enhanced performance of porous CeO2 evidenced in this
study, it would be interesting to utilize mesostructured CeO2
synthesized by a hard templating method. Since these materials
exhibit well ordered mesoporosity, their implementation in a
packed bed configuration could be relevant with replacement of
inert SiC surface promoting CH4 decomposition, by such active
materials promoting partial oxidation of CH4 to syngas via ceria
redox cycle.
DOI: 10.1021/acs.energyfuels.6b01063
Energy Fuels 2016, 30, 6050−6058
Energy & Fuels Article

■
*
ASSOCIATED CONTENT
S Supporting Information
(21) Le Gal, A.; Abanades, S.; Bion, N.; Le Mercier, T.; Harlé, V.
Energy Fuels 2013, 27, 6068−6078.
(22) Fornasiero, P.; Balducci, G.; Di Monte, R.; Kašpar, J.; Sergo, V.;
The Supporting Information is available free of charge on the Gubitosa, G.; Ferrero, A.; Graziani, M. J. Catal. 1996, 164, 173−183.
ACS Publications website at DOI: 10.1021/acs.energy- (23) Balducci, G.; Islam, M. S.; Kašpar, J.; Fornasiero, P.; Graziani,
fuels.6b01063. M. Chem. Mater. 2003, 15 (20), 3781−3785.
CeO2 reduction profile as a function of temperature and (24) Krenzke, P. T.; Davidson, J. H. Energy Fuels 2014, 28, 4088−
4095.
time, reaction rates as a function of partial pressures, gas
(25) Jeong, H. H.; Kwak, J. H.; Han, G. Y.; Yoon, K. J. Int. J.
evolution profiles of CeO2 in a packed bed reactor, and Hydrogen Energy 2011, 36, 15221−15230.
gas evolution profiles of Al2O3 and MgO promoted CeO2 (26) Otsuka, K.; Wang, Y.; Nakamura, M. Appl. Catal., A 1999, 183,
in a packed bed reactor (PDF) 317−324.

■
(27) Otsuka, K.; Wang, Y.; Sunada, E.; Yamanaka, I. J. Catal. 1998,
AUTHOR INFORMATION 175, 152−160.
(28) Xu, M.; Kong, L.; Zhou, W.; Li, H. J. Phys. Chem. C 2007, 111,
Corresponding Author 19141−19147.
*E-mail: stephane.abanades@promes.cnrs.fr. (29) Yen, H.; Kleitz, F. J. Mater. Chem. A 2013, 1, 14790−14796.
Author Contributions (30) Nair, M. M.; Kaliaguine, S.; Kleitz, F. ACS Catal. 2014, 4, 3837−
3846.
All authors have given approval to the final version of the
(31) Rudisill, S. G.; Venstrom, L. J.; Petkovich, N. D.; Quan, T.;
manuscript. Hein, N.; Boman, D. B.; Davidson, J. H.; Stein, A. J. Phys. Chem. C
Notes 2013, 117, 1692−1700.
The authors declare no competing financial interest. (32) Malonzo, C. D.; De Smith, R. M.; Rudisill, S. G.; Petkovich, N.

■
D.; Davidson, J. H.; Stein, A. J. Phys. Chem. C 2014, 118, 26172−
ACKNOWLEDGMENTS 26181.
(33) Titirici, M. M.; Antonietti, M.; Thomas, A. Chem. Mater. 2006,
This study was supported by Airbus Foundation. The authors 18, 3808−3812.
also thank E. Beche for technical support in XRD analysis and (34) Cui, X.; Antonietti, M.; Yu, S. H. Small 2006, 2, 756−759.
O. Prevost for technical support during solar reactors design (35) Yuan, Q.; Liu, Q.; Song, W. G.; Feng, W.; Pu, W. L.; Sun, L. D.;
and manufacturing. Zhang, Y. W.; Yan, C. H. J. Am. Chem. Soc. 2007, 129, 6698−6699.

■
(36) Levêque, G.; Abanades, S. Sol. Energy 2014, 105, 225−235.
REFERENCES (37) Le Gal, A.; Abanades, S. Int. J. Hydrogen Energy 2011, 36, 4739−
4748.
(1) Kubacka, A.; Fernandez-García, M.; Colon, G. Chem. Rev. 2012, (38) Ackermann, S.; Sauvin, L.; Castiglioni, R.; Rupp, J. L. M.;
112, 1555−1614. Scheffe, J. R.; Steinfeld, A. J. Phys. Chem. C 2015, 119, 16452−16461.
(2) Roldan-Carmona, C.; Malinkiewicz, O.; Soriano, A.; Espallargas, (39) Abanades, S.; Kimura, H.; Otsuka, H. Int. J. Hydrogen Energy
G. M.; Garcia, A.; Reinecke, P.; Kroyer, T.; Dar, M. I.; Nazeeruddin, 2014, 39, 18770−18783.
M. K.; Bolink, H. J. Energy Environ. Sci. 2014, 7, 994−997.
(3) Chueh, W. C.; Falter, C.; Abbott, M.; Scipio, D.; Furler, P.; Haile,
S. M.; Steinfeld, A. Science 2010, 330, 1797−1801.
(4) McDaniel, A. H.; Miller, E. C.; Arifin, D.; Ambrosini, A.; Coker,
E. N.; O’Hayre, R.; Chueh, W. C.; Tong, J. Energy Environ. Sci. 2013, 6,
2424−2428.
(5) Demont, A.; Abanades, S. J. Mater. Chem. A 2015, 3, 3536−3546.
(6) Kodama, T.; Gokon, N. Chem. Rev. 2007, 107, 4048−4077.
(7) Levêque, G.; Abanades, S. Energy Fuels 2014, 28, 1396−1405.
(8) Aoki, A.; Ohtake, H.; Shimizu, T.; Kitayama, Y.; Kodama, T.
Energy 2000, 25, 201−218.
(9) Adinberg, R.; Epstein, M. Energy 2004, 29, 757−769.
(10) Furler, P.; Scheffe, J.R.; Steinfeld, A. Energy Environ. Sci. 2012, 5,
6098−6103.
(11) Gibbons, W. T.; Venstrom, L. J.; De Smith, R. M.; Davidson, J.
H.; Jackson, G. S. Phys. Chem. Chem. Phys. 2014, 16, 14271−14280.
(12) Hao, Y.; Yang, C. K.; Haile, S. M. Phys. Chem. Chem. Phys. 2013,
15, 17084−17092.
(13) Furler, P.; Scheffe, J. R.; Marxer, D.; Gorbar, M.; Bonk, A.; Vogt,
U.; Steinfeld, A. Phys. Chem. Chem. Phys. 2014, 16, 10503−10511.
(14) Montini, T.; Melchionna, M.; Monai, M.; Fornasiero, P. Chem.
Rev. 2016, 116 (10), 5987−6041.
(15) Rager, T. Chem. Commun. 2012, 48, 10520−10522.
(16) Scheffe, J. R.; Jacot, R.; Patzke, G. R.; Steinfeld, A. J. Phys. Chem.
C 2013, 117, 24104−24114.
(17) Hao, Y.; Yang, C. K.; Haile, S. M. Chem. Mater. 2014, 26, 6073−
6082.
(18) Abanades, S.; Le Gal, A.; Cordier, A.; Peraudeau, G.; Flamant,
G.; Julbe, A. J. Mater. Sci. 2010, 45, 4163−4173.
(19) Meng, Q. L.; Lee, C. I.; Ishihara, T.; Kaneko, H.; Tamaura, Y.
Int. J. Hydrogen Energy 2011, 36, 13435−13441.
(20) Le Gal, A.; Abanades, S. J. Phys. Chem. C 2012, 116, 13516−
13523.

6058 DOI: 10.1021/acs.energyfuels.6b01063

Energy Fuels 2016, 30, 6050−6058