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Comparative study of activity of cerium oxide


at thermal reduction temperatures of 1300e1550  C
for solar thermochemical two-step water-splitting
cycle

Nobuyuki Gokon a,*, Sachi Sagawa b, Tatsuya Kodama c


a
Center for Transdisciplinary Research, Niigata University, 8050 Ikarashi 2-nocho, Nishi-ku, Niigata 950-2181,
Japan
b
Graduate School of Science and Technology, Niigata University, 8050 Ikarashi 2-nocho, Niigata 950-2181, Japan
c
Department of Chemistry & Chemical Engineering, Faculty of Engineering, Niigata University,
8050 Ikarashi 2-nocho, Niigata 950-2181, Japan

article info abstract

Article history: Thermochemical two-step water-splitting using CeO2 (cerium oxide) particles was
Received 5 July 2013 studied to examine oxygen and hydrogen productivity and repeatability at thermal
Received in revised form reduction (T-R) temperatures of 1300e1550  C and water decomposition (W-D) temper-
13 August 2013 atures of 400e1000  C for the production of hydrogen from water using concentrated
Accepted 26 August 2013 solar radiation as the energy source. The temperature dependency of oxygen and
Available online 2 October 2013 hydrogen productivity and the cyclic repeatability of CeO2 are reported in this paper. The
characteristic features of CeO2 particles in the thermochemical two-step water-splitting
Keywords: cycle are compared with the well-known highly active reactive mediums of zirconia-
Solar heat supported Ni-ferrites (NiFe2O4/m-ZrO2 and NiFe2O4/c-YSZ) and unsupported NiFe2O4.
Energy conversion Copyright 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
Hydrogen production reserved.
Thermochemical water splitting
Cerium oxide
Redox cycle

1. Introduction advantages such as transportability and long-term storage


capability of solar energy [1,2]. Direct water-splitting by solar
Hydrogen production by solar thermochemical water-splitting thermal energy requires over 2000  C to obtain sufficient
uses concentrated solar radiation as its energy source. amounts of hydrogen [3]. Thus, a simpler method is the two-
Various multi-step thermochemical water-splitting cycles step water-splitting cycle operating at technically manageable
operating at high temperatures have been proposed and temperatures by use of a metal oxide as a redox medium for the
demonstrated by researchers around the world. The solar cycle [2,3]. The two-step cycle can eliminate the need for in situ
thermochemical water-splitting cycles are capable of convert- gaseous separation of oxygen and hydrogen. In addition, it
ing high-temperature heat from concentrated solar radiation leads to alleviating material constraints for the solar chemical
into clean hydrogen energy [1,2]. This technology offers reactor operating at high temperatures.

* Corresponding author. Tel./fax: 81 25 262 6820.


E-mail address: ngokon@eng.niigata-u.ac.jp (N. Gokon).
0360-3199/$ e see front matter Copyright 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ijhydene.2013.08.108
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 4 4 0 2 e1 4 4 1 4 14403

A thermochemical two-step water-splitting cycle using a and cyclic reactivity by itself without any support materials at
metal oxide as a redox pair is generally represented by the high temperatures. Although solar energy input will completely
following chemical reactions [2,3]. reduce CeO2 into Ce2O3, the redox pair CeO2/Ce2O3 requires a
very high temperature of 2000  C for the T-R step [4]. This leads
MxOy / MxOyd d/2O2 (Thermal Reduction or T-R step) (1) to significant loss of reactive mass due to volatilization. In
addition, it is difficult to reach such a high temperature using
MxOyd d H2O / MxOy d H2 (Water Decomposition the solar concentrating system. It was reported that CeO2 can
or W-D step) (2) form a compound at thermal reduction (T-R) temperatures less
than 2000  C in a non-stoichiometric state between CeO2 and
In the first step, oxygen evolution occurs when a metal oxide Ce2O3, requiring a relatively lower reduction temperature, and
is thermally reduced by high temperature, and oxygen is thereby decreasing volatility [4,28e33]. A repeatable two-step
released from the oxide. Then, in the second step, the reduced water-splitting cycle using CeO2/CeO2d is represented by:
metal oxide reacts with steam to be oxidized at relatively low
temperature, and hydrogen is produced. The metal oxide is CeO2 / CeO2d d/2 O2 (T-R step) (7)
then recycled to the first step. Two distinct types of redox pairs
are extensively studied for thermochemical water-splitting: the CeO2d d H2O / CeO2 d H2 (W-D step) (8)
volatile redox pair of zinc or tin oxide that produces metallic
gaseous species during the T-R step; and the non-volatile redox CeO2d represents a non-stoichiometric state of CeO2 that
pair of ferrite or cerium oxide that remains in the condensed is formed during the T-R step when oxygen is released from
state during the two-step reaction [2e4]. The present study fo- CeO2. In the second step, the W-D step, the CeO2d reacts with
cuses on the non-volatile redox pair of CeO2 (cerium oxide), and steam at temperatures less than 1000  C to produce hydrogen
the characteristic features of the CeO2 redox pair in cyclic re- [4,29e33].
actions are examined and evaluated by comparison with Hydrogen and oxygen productivity and cyclic reactivity of
NiFe2O4, which is known as a highly active redox material for thermochemical two-step water-splitting using CeO2/CeO2d
the solar thermochemical two-step water-splitting cycle. has been investigated by some researchers [4,29e33]. How-
The present authors have demonstrated a hydrogen/oxy- ever, in general, the production rates and amounts of oxygen
gen productivity and repeatability of the thermochemical two- generated during the T-R step depend on reduction tempera-
step water-splitting cycle using NiFe2O4/m-ZrO2 operating at tures, and the non-stoichiometry d of the resulting reduced
1400  C in the T-R step and at 1000  C in the W-D step [3,5e8]. phase of CeO2d vary on the basis of thermodynamic re-
strictions toward the stoichiometric Ce2O3. The reduced phase
NiFe2O4/m-ZrO2 / NiyFe1yO/m-ZrO2 1/2O2 (T-R step) (3) of CeO2d dominates the production rates and amounts of
hydrogen produced during the subsequent W-D step. In this
NiyFe1yO/m-ZrO2 H2O /NiFe2O4/m-ZrO2 H2 (W-D step)(4) study, we examined oxygen and hydrogen productivity at
each step and repeatability of the two-step water-splitting
The m-ZrO2 support is characterized by a melting point cycle using CeO2/CeO2d at wide temperature ranges in the T-
higher than 2000  C and causes a repeatable volume expan- R and W-D steps, and we elucidated the reaction contribution
sion/shrinkage of the ZrO2 crystal lattice involving phase of the non-stoichiometric state of CeO2 to hydrogen produc-
transition of monoclinic into tetragonal crystal structures at tion in the W-D step.
T > 1170  C [9]. Thus, the m-ZrO2 support has good resistance to The objective of this work is to examine oxygen and
agglomeration or sintering at temperatures of 1000e1400  C. In hydrogen productivity and repeatability of thermochemical
addition, partially-stabilized tetragonal zirconia (t-PSZ) and two-step water-splitting using CeO2/CeO2d as a reactive
yttria-stabilized cubic zirconia (c-YSZ) can be used as a support redox material. The thermochemical two-step water-splitting
[10e13]. Unsupported NiFe2O4 particles have also been tested cycle is repeated at relatively low temperatures of
for repeatable two-step water-splitting [7]. Solar chemical re- 1300e1550  C for the T-R step and in the range of 400e1000  C
ceivers/absorbers or reactors operating at temperatures of for the W-D step. The effects of different temperatures on the
800e1500  C are being developed and tested for hydrogen production rate and amount of oxygen released from CeO2
production from water via the two-step water-splitting cycle and the reactivity with steam of the reduced phase of CeO2d
using ferrite redox materials [14e27]. after the T-R step are compared and discussed. The charac-
CeO2 has recently emerged as a promising reactive redox teristic features of CeO2 particles are compared with the well-
material for the thermochemical two-step water-splitting known highly active reactive mediums of zirconia-supported
cycle [4]. Ni-ferrites (NiFe2O4/m-ZrO2 and NiFe2O4/c-YSZ) and unsup-
ported NiFe2O4.
CeO2 / 1/2Ce2O3 1/4 O2 (T-R step) (5)

1/2Ce2O3 1/2H2O / CeO2 1/2H2 (W-D step) (6) 2. Experimental section

The application of CeO2 to the thermochemical cycle ap- 2.1. Preparation of redox materials
pears to have a great advantage over the ferrite process, as
described above. The redox cycle of CeO2 involves a higher Ceria (CeO2) particles were prepared as redox materials. For
melting point of the oxide, leading to good sintering resistance comparison, monoclinic and cubic zirconia-supported Ni-
14404 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 4 4 0 2 e1 4 4 1 4

Table 1 e Tested redox materials and testing temperatures.


Redox material Chemical composition Testing temperature

T-R step W-D step



Unsupported CeO2 100wt%CeO2 1300, 1350, 1400, 1450 C 400, 600, 800  C, 1000  C
1500, 1550  C
NiFe2O4/m-ZrO2 20wt%NiFe2O4/80wt%m-ZrO2 1400, 1450, 1500, 1550  C 1000  C
NiFe2O4/c-YSZ 20wt%NiFe2O4/80wt%c-YSZ 1400, 1450, 1500  C 1000  C
Unsupported NiFe2O4 100wt%NiFe2O4 1300, 1350, 1400  C 1000  C

ferrites (NiFe2O4/m-ZrO2 and NiFe2O4/c-YSZ), and unsup- NiFe2O4 was set to approximately 20 wt%. The prepared
ported NiFe2O4 were also prepared. The redox materials tested NiFe2O4/m-ZrO2 was then calcined at 1200  C for 2 h in a N2
in this study are listed in Table 1. atmosphere before the high-temperature cyclic reactions
CeO2 particles were synthesized by a wet process using a were conducted.
method involving the co-precipitation of the CeO2 precursor c-YSZ-supported NiFe2O4 (NiFe2O4/c-YSZ) particles were
from the aqueous solution of Ce(NO3)3$6H2O. Oxygen- and also prepared by coating the c-YSZ particles with NiFe2O4
CO2-free distilled water was prepared by passing N2 through using a method involving the aerial oxidation of an aqueous
the distilled water for a few hours. Ce(NO3)3$6H2O was then suspension of Fe(II) and Ni(II) hydroxides.
dissolved in the distilled water. The pH of the solution was Unsupported NiFe2O4 particles (i.e., without zirconia sup-
adjusted to 8.5 by adding 0.15 mol dm3 NaOH solution, thus port) were prepared by a co-precipitation method as follows
resulting in the formation of the CeO2 precursor. After heating [7]. 12.15 g of FeCl3$6H2O was dissolved in distilled water
the solution to 65  C, air was bubbled into the suspension (150 dm3) previously degassed by passing N2 gas through it.
during 2 h while the pH was continually maintained at 8.5 by Appropriate proportions of NiCl2$4H2O were dissolved in the
addition of NaOH solution. The solid product was collected by FeCl3 solution at 60  C. 1.67-mol dm-3 NaOH solution was
centrifugation at 3000 rpm (KS-4000, Kubota), washed with also degassed by passing N2 gas through it, and the solution
distilled water and then acetone, and dried in vacuo at 100  C was kept at 60  C. The mixed metal chloride solution was
for one day. The CeO2 particles were then calcined at 900  C for added to the NaOH solution at 60  C with vigorous stirring for
2 h in air atmosphere before performing the high-temperature co-precipitation. The co-precipitate obtained was aged in the
cyclic reactions. mother solution at 60  C for 2 h. The co-precipitate was
ZrO2 particles with a monoclinic crystal structure (m-ZrO2) collected by centrifugation at 4000 rpm (Kubota, KS-4000),
and zirconium doped with 8 mol% Y2O3 (c-YSZ or YSZ; Tosoh washed with distilled water and then with acetone, and
TZ-8YS) with cubic crystal structure were used to support dried at room temperature for 3 days. The dried co-precipitate
NiFe2O4. The m-ZrO2 support had a purity of 98%, particle size was then pulverized using a mortar and pestle, and then
smaller than 1 mm, and Brunauer-Emmett-Teller (BET) surface packed into a quartz tube reactor with an inner diameter of
area of 12.6 m2 g1 (Shimadzu, TriStar 3000). The c-YSZ sup- 25 mm. The dried co-precipitate was calcined for 1 h at
port was characterized as having a purity of 99%, particle size 900e1000  C in a N2 atmosphere in order to further crystallize
smaller than 1 mm, and a relative surface area of 7  2 m2 g1. it before performing the high-temperature cyclic reactions.
m-ZrO2-supported NiFe2O4 (NiFe2O4/m-ZrO2) particles were The synthesized powder materials were characterized
prepared by coating the m-ZrO2 particles with NiFe2O4 using a using X-Ray Powder Diffraction (XRD) with CuKa radiation
method involving the aerial oxidation of an aqueous suspen- (MXeLabo, MAC Science) for identification of the phases
sion of Fe(II) and Ni(II) hydroxides [5e8]. The loading of formed. In order to determine the loadings of NiFe2O4 on the

(a) Thermal Reduction (T-R) Step (b) Water Decomposition (W-D) Step

Mass Sampl GC analysis


Quartz chamber e Sample Infrared furnace (TCD)
spectrometer Outlet
Infrared furnace
N2
(Purity 99.999%) N2
Capillary Heater Thermocouple
1dm3 min-1

Exhaust Distilled water


Platinum cup Thermocouple water trap
Vacuum
Stirrer
pump Oil bath (95C )

Fig. 1 e Experimental apparatus of thermochemical two-step water-splitting for (a) the thermal reduction (T-R) step and (b)
the water decomposition (W-D) step using redox material.
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 4 4 0 2 e1 4 4 1 4 14405

m-ZrO2 and YSZ supports and the chemical composition of the crucible, and placed in the quartz reaction chamber (Fig. 1(a))
synthesized materials, part of the powder materials were to perform the T-R step again. The T-R and W-D steps were
sampled and dissolved in an aqueous HCl solution, and alternately repeated upto six times.
the resulting solutions were analyzed using Inductively The powder sample was pulverized after each step in order
Coupled Plasma-Atomic Emission Spectrometry (ICP-AES; to evaluate hydrogen productivity at each cycle and the
SPSe1500PV, Seiko Instruments). reactivity of the powder material throughout the cyclic reac-
tion. The NiFe2O4/m-ZrO2 and NiFe2O4/c-YSZ samples
2.2. Activity test of the redox materials appeared to be sintered after the T-R step and became a
porous pellet of fine sintered particles. This is due to high-
The powder samples of CeO2, NiFe2O4/m-ZrO2, NiFe2O4/c-YSZ, temperature sintering of unreacted NiFe2O4 on the surface of
and unsupported NiFe2O4 were tested for activity in the two- the m-ZrO2 or c-YSZ supports. The sample was easily pulver-
step water-splitting cycle under the same reaction condi- ized using a mortar and pestle, so that the subsequent W-D
tions. Approximately 1 g of the powder sample was packed step to generate hydrogen could be performed. After the W-D
into a platinum crucible (10 mm in diameter and 7 mm in step, the sample did not appear to be sintered, but remained
depth) and mounted on the ceramic bar in a quartz reaction as a powder. On the other hand, the samples of CeO2 particles
chamber (SSAeE45, UlvaceRico) with an inner diameter of did not show any sintering, neither after the T-R step at
45 mm (Fig. 1(a)). The powder sample was heated to 1300e1550  C nor the subsequent W-D step at 400e1000  C.
1300e1550  C of the thermal reduction (T-R) step within 1 min
using an infrared furnace (RHLeVHTeE44, UlvaceRico) while
passing N2 gas (purity 99.999%) through the reactor at a flow 3. Results and discussion
rate of 1.0 Ndm3 min1. The temperature of the sample pow-
der was controlled using an R-type thermocouple in contact 3.1. Activity of CeO2 particles under various T-R
with the platinum crucible. The powder sample was cooled to temperatures of 1300e1550  C
room temperature after being heated at constant tempera-
tures of 1300e1550  C for 30 min. An aliquot of the effluent gas Thermochemical two-step water-splitting with unsupported
from the reaction chamber was led through a capillary tube CeO2 particles was repeated six times to examine the stoi-
and introduced into a Residual Gas Analyzer Mass Spec- chiometric productivity and repeatability of the redox cycle on
trometer (RGe102P, Ulvac) to determine the composition of the basis of the reaction mechanism described in Eqs. (7)e(8).
product gases and measure the production rates of oxygen. Fig. 2(a) shows the oxygen evolution rate of the 1ste6th runs
During the T-R step, variations in oxygen partial pressure in per gram of CeO2 material over time during the T-R step at
the product gases were measured with respect to reaction temperatures of 1300e1550  C. The oxygen evolution rate
time, and the amounts of oxygen evolved were determined during the T-R step of the 1st run rapidly increased beyond
from the spectrum of oxygen partial pressures. The mass 1000  C and attained to a maximum rate of about
spectrometer used is equipped with a standard oxygen gas 1.0e2.5 Ncm3/min per gram of CeO2 material. The maximum
tank that can supply oxygen gas at a constant flow rate of rate of oxygen evolution was obtained for each T-R step at
1.3  1010 mol/s. The oxygen releasing equipment was used temperatures of 1300e1550  C. The maximum rate of oxygen
to calibrate the relationship between partial pressure and the evolution drastically increased at T-R step temperatures from
amount of oxygen evolved. 1300 to 1400  C but remained almost the same at
The thermally reduced powder sample was pulverized 1450e1550  C. After reaching the maximum rate, the oxygen
using a mortar and pestle and then packed into a quartz tube evolution during the T-R step gradually decreased and
reactor (Fig. 1(b)) with an inner diameter of 7 mm in order to concluded within 10 min. The oxygen evolution at T-R tem-
perform the W-D step. A gas mixture containing H2O and N2 peratures of 1450e1550  C were repeatedly observed with a
was introduced into the reactor. This mixture was produced rate of about 2.0e3.8 Ncm3/min per gram of CeO2 material.
by bubbling N2 gas at a flow rate of 4 Ncm3 min1 through a The oxygen evolution at the T-R temperature of 1550  C
glass tube into distilled water at 80  C. The partial pressure of continued during a prolonged period of time in comparison to
steam in the H2O/N2 mixture was estimated to be 47%, by that of 1300e1500  C. The slight oxygen evolution at 1550  C
considering the steam vapor pressure at 80  C and 1 bar. The after the major oxygen release obtained at 1550  C that was
powder sample was heated at the given temperatures of reproducibly observed in the profile of the 1st run and during
400e1000  C within 10 min in an infrared furnace (RHLeE45P, each T-R step until the 6th run, indicates that oxygen evolution
Ulvac-Rico), and the W-D step was performed for 60 min. The continues to proceed slowly in the CeO2 powder after reaching
temperature of the powder sample was controlled using a K- a temperature of 1550  C. It can be considered that this ongoing
type thermocouple in contact with the sample bed located oxygen evolution is related to the characteristic formation of
inside the reactor. To determine the amount of hydrogen the reduced phase (CeO2d) in the CeO2 redox system. Ac-
produced during the W-D step, the effluent gas was collected cording to the reaction mechanism of the CeO2 redox system,
in a bottle by the water displacement method, and the gas oxygen evolution during the T-R step is associated with a redox
compositions were determined using a Gas Chromatograph transition of Ce4 into Ce3 in the cubic CeO2 lattice. The
(GCe8A, Shimadzu) with a Thermal Conductivity Detector transition of Ce4 into Ce3 in the cubic CeO2 lattice involves
(TCD). The powder sample was then characterized using XRD. oxygen diffusion inside the particles, and the higher T-R tem-
After the W-D step, the powder sample was again pulver- peratures will enhance oxygen diffusion and lead to contin-
ized using a mortar and pestle, mounted in the platinum uous slight oxygen evolution over a prolonged period.
14406 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 4 4 0 2 e1 4 4 1 4

(a)
1st 2nd 3rd

4th 5th 6th

(b) 1st 2nd 3rd

4th 5th 6th

Fig. 2 e (a) Oxygen evolution rate per gram of CeO2 redox material over time during the T-R steps of the 1ste6th runs at
temperatures of 1300e1550  C. The solid curve shows the oxygen evolution profile (b) Hydrogen production rate per gram of
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 4 4 0 2 e1 4 4 1 4 14407

Table 2 e Evolved amount of oxygen and hydrogen in each cycle at various T-R temperatures of 1300e1550  C.
T-R temperature Evolved amount of H2 and O2/Ncm3 g1-material H2/O2

1st 2nd 3rd 4th 5th 6th Ave.



1300 C O2 1.84 1.87 1.48 1.74 1.59 1.63 1.69 2.11
H2 3.56 3.38 3.76 3.86 3.48 3.32 3.56
1350  C O2 2.10 2.21 2.48 2.40 2.46 3.08 2.46 1.99
H2 4.32 5.14 4.79 5.07 4.66 5.33 4.89
1400  C O2 4.37 4.06 5.13 5.14 4.54 4.48 4.62 1.99
H2 9.56 9.44 10.03 8.49 8.91 8.40 9.14
1450  C O2 5.29 5.00 4.74 5.35 5.56 5.39 5.22 1.91
H2 10.49 10.24 9.76 9.70 10.20 9.37 9.96
1500  C O2 4.79 5.86 6.25 5.83 6.47 6.01 5.87 2.00
H2 12.06 10.48 11.92 11.35 12.12 11.70 11.61
1550  C O2 6.40 7.08 7.54 6.94 6.88 7.25 7.02 2.00
H2 13.82 13.53 14.53 14.19 13.65 14.33 14.01

Fig. 2(b) shows the hydrogen production rate per gram of and 3.6 Ncm3 per gram of material on average, respectively. As
CeO2 material over time during the W-D step of the 1ste6th the T-R temperature increased, the average amounts of oxygen
runs at the temperature of 1000  C. The hydrogen production and hydrogen monotonically enhanced and reached 7.0 and
rate during the W-D step rapidly increased beyond 200  C and 14.0 Ncm3 per gram of material, respectively, for the material
was almost diminished to zero within 15 min through all runs. reduced at T-R temperature of 1550  C. From the results of the
The solid materials that underwent T-R step at 1300e1350  C, evolved amounts, the ratio of evolved hydrogen/oxygen was
being represented as black and orange curves in this figure, calculated to be approximately 2.0 at all T-R temperatures.
showed lower rates of hydrogen production with less than These results indicate that the CeO2 material has a reproduc-
1.5 Ncm3/min per gram of material. However, the solid ma- ible stoichiometric productivity of oxygen and hydrogen in the
terials reduced at higher temperatures than 1400  C were thermochemical two-step water-splitting cycle.
rapidly reacted with steam and provided higher rates of Fig. 3(a) shows the XRD pattern of the original CeO2 parti-
hydrogen production with 2.5e6.8 Ncm3/min per gram of cles. Peaks due to CeO2 initially appeared in the XRD pattern.
material. Especially, the reduced materials subjected to T-R After the T-R step of the sample at 1400  C in a N2 atmosphere,
step temperatures of 1500e1550  C, being represented as red the relative intensity of the CeO2 peaks decreased, while two
and blue curves in this figure, showed exceptionally high rates additional series of peaks were observed in the XRD pattern at
of hydrogen production among the samples tested. lower diffraction angle compared to the original CeO2 peaks,
The profiles of oxygen and hydrogen production did not as shown in Fig. 3(b). The two series of new peaks can be
fluctuate but were reproduced with nearly the same produc- assigned to the reduced phases of CeO2d1 and CeO2d2 that
tion levels through the 6 runs. The maximum rate of oxygen have the same crystal structure as the original CeO2. The XRD
production in the 6th run was greater for the relatively high T- pattern after the subsequent W-D step of the reduced mate-
R step temperatures of 1400e1550  C than that in the 1st run rials at 1000  C in a N2/steam atmosphere showed that the
(Fig. 2(a)). It can be assumed that the reason the maximum series of peaks due to the reduced phase disappeared, as
rate was enhanced after the 1st run was due to crushing of the shown in Fig. 3(c). These results suggest that the reduced
redox material every time after implementation of each step. phases of CeO2d formed by the T-R step contribute to water-
The hydrogen production in the 6th run was almost the same splitting via the Ce3eCe4 transition.
as in the 1st run (Fig. 2(b)). The results showed in Fig. 2(a) and In general, the relationship between the lattice parameter
(b) indicate that stable production of both oxygen and and the chemical composition of a solid material is commonly
hydrogen are realized with CeO2 through the cyclic reaction. known as Vegards law [34]. According to Vegards law, the
The evolved amount of oxygen and hydrogen per gram of lattice parameters should vary linearly with a continuous
CeO2 material in the 1ste6th runs of the two-step water- chemical composition without changing crystal structure at
splitting cycle are shown in Table 2. The T-R step was per- constant temperature. Vegards law was applied to the CeO2
formed with CeO2 powder at temperatures of 1300e1550  C, and the reduced phases of CeO2d to estimate the chemical
while the subsequent W-D step was conducted with the composition of CeO2d. Phase information for various non-
reduced powder samples at a constant temperature of 1000  C. stoichiometric CeO2d materials was obtained from the Inor-
As shown in this table, the amounts of oxygen and hydrogen ganic Crystal Structure Database (ICSD) [35]. A peak decon-
maintained nearly the same levels for the reduced material volution for the two series of the reduced phases was
subjected to each T-R step temperature throughout the conducted by Origin 7.5, and the reduced phases of CeO2d1
repeated 6 runs. The amounts of oxygen and hydrogen for the and CeO2d2 were identified as CeO1.966 and CeO1.890,
material reduced at the T-R temperature of 1300  C were 1.7 respectively.

CeO2 redox material over time during the subsequent W-D steps of the 1ste6th runs at the temperature of 1000  C. The solid
curve shows the hydrogen production profile while the dotted curve shows a typical temperature profile for the sample
during the W-D step.
14408 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 4 4 0 2 e1 4 4 1 4

(a) original of the powder changed into a homogeneous gray. After the W-
3000
D step, the color of the powder changed into yellow-white.
The variations in color of the powder materials were

Intensity / cps
4000 CeO2 2000
observed at each step through the 1ste6th runs of the ther-
Intensity / cps

1000
mochemical cycle, and the variations in color are independent
3000
of T-R temperatures.
2000 0
46 46.5 47 47.5 48
2(Cu-K )/deg 3.2. Activity of CeO2 particles under various W-D
1000 temperatures of 400e1000  C

0 Thermochemical two-step water-splitting using unsupported


20 30 40 50 60 70 80
CeO2 particles was repeated two times to examine the impacts
2(Cu-K)/deg
(b) After T-R step 3000 of W-D temperatures on hydrogen productivity and produc-
tion rate on the basis of the reaction mechanism described in
Intensity / cps

3000
CeO2 2000
Eqs. (6)e(7). In this section, the T-R step using unsupported
CeO2-
CeO2 particles was performed at a constant temperature of
Intensity / cps

1500  C during 30 min, and the subsequent W-D step using the
1000
2000 CeO CeO

reduced materials was conducted at various temperatures.


0
46 46.5 47 47.5 48 Fig. 6 shows the hydrogen production rate of the 1st run per
2(Cu-K )/deg
1000 gram of material over time during the W-D step at tempera-
tures of 400e1000  C. The maximum rate of hydrogen pro-
duction monotonically increased and the production profile
0
20 30 40 50 60 70 80
sharpened as the W-D temperature increased. The evolved
2(Cu-K)/deg amount of oxygen and hydrogen at each run are listed in Table
3. The amount of hydrogen produced was independent of W-D
(c) After W-D step 4000
temperature and almost identical at all temperatures,
Intensity / cps

3000 although the rate of production decreased with decreasing W-


5000
2000
D temperature. The ratio of the average amount of hydrogen/
4000 oxygen produced gave a stoichiometric value of approxi-
Intensity / cps

1000
3000 mately 2 in the W-D step at temperatures of 400e1000  C. The
0 resulting stoichiometric ratio indicates that the reduced phase
46 46.5 47 47.5 48
2000 2(Cu-K )/deg
formed during the T-R step at 1500  C was completely oxidized
1000 back to the original CeO2 at temperatures of 400e1000  C.

0
20 30 40 50 60 70 80 3.3. Characteristic features of CeO2 particles by
2(Cu-K)/deg comparison with zirconia-supported and unsupported
NiFe2O4
Fig. 3 e XRD patterns of (a) original CeO2 material, (b) that
after the T-R step of the 1st run at 1400  C, and (c) that after Reactivity and cyclicity of pure CeO2 in thermochemical two-
the subsequent W-D step of the 1st run at 1000  C. step water-splitting, is compared with that of unsupported Ni-
ferrite (NiFe2O4) and zirconia-supported Ni-ferrites (NiFe2O4/

Fig. 4 shows XRD patterns in the diffraction angles


2q 46e48 for the solid materials obtained after the T-R step
at 1300, 1400 and 1550  C. As the T-R step temperature in-
creases, the relative peak intensity of the original CeO2
decreased; and the relative peak intensity of the reduced
phases of CeO2d1 and CeO2d2 increased. In addition, the peak
positions were almost the same at all T-R temperatures. The
results of different T-R step temperatures indicate that the
d value representing non-stoichiometry of the reduced phases
is independent of the T-R step temperatures; the formation of
the non-stoichiometric CeO1.966 and CeO1.89 is not derived
from a continuous peak shift from the original CeO2 but may
come out with discrete d values as thermodynamically stable
phases.
Fig. 5 shows photographs of the original CeO2 powder, the
powder materials obtained after the T-R step at 1500  C, and Fig. 4 e XRD patterns in the vicinity of diffraction angles
those after the subsequent W-D step at 1000  C. The color of 2q [ 46 e48 for CeO2 after the T-R step at 1300  C, 1400  C,
the original powder is ivory white. After the T-R step, the color 1550  C.
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 4 4 0 2 e1 4 4 1 4 14409

Fig. 6 e Hydrogen production profiles for CeO2 particles in


the T-R step of the 1st run at 1500  C and the subsequent
W-D step at various temperatures of 400e1000  C. The
solid curve shows the hydrogen production profile while
the dotted curve shows the temperature profile at the
different W-D step temperatures of 400e1000  C.

is selected as the representative reference of a highly active


Ni-ferrite [3,6]. As seen in the 1st run of Fig. 7(a), NiFe2O4/m-
ZrO2 started to release oxygen at lower temperatures in
comparison to pure CeO2, and the oxygen evolution rate of
NiFe2O4/m-ZrO2 was relatively higher than that of pure CeO2.
After reaching the maximum rate, the oxygen evolution of
both materials gradually decreased with time and nearly
stopped within 5 min. Among the three Ni-ferrite redox ma-
terials (unsupported NiFe2O4, NiFe2O4/m-ZrO2, and NiFe2O4/c-
YSZ), NiFe2O4/m-ZrO2 had the highest rate of oxygen evolution
in the 1st run of the two-step water-splitting. These results
indicate that NiFe2O4/m-ZrO2 is superior to pure CeO2 from the
prospect of oxygen production in the T-R step. If the oxygen
production rate of pure CeO2 is further enhanced by 1.5 times
without a prolongation of the production time, the pure CeO2
will be comparable to NiFe2O4/m-ZrO2. Fig. 7(b) shows a
comparison of the hydrogen production rate per gram of
redox materials of pure CeO2 and NiFe2O4/m-ZrO2 over time
during the W-D step of the 1st and 5th runs of the two-step
Fig. 5 e Photographs of (a) original CeO2 particles, (b)
material obtained after the T-R step of the 1st run at
1500  C, and (c) that obtained after the subsequent W-D Table 3 e Evolved amount of oxygen and hydrogen in
step of the 1st run at 1000  C. each cycle at various W-D temperatures of 400e1000  C.
W-D Evolved amount H2/O2
temperature of H2 and O2/Ncm3 g1-material

m-ZrO2 and NiFe2O4/c-YSZ), and the characteristic features of 1St 2nd Ave.
pure CeO2 are described in this section. Firstly, cyclic pro- 1000  C O2 4.8 5.9 5.3 2.1
ductivity of hydrogen and oxygen in two-step water-splitting H2 12.1 10.5 11.3
using pure CeO2 is compared with using unsupported NiFe2O4 800  C O2 4.2 5.9 5.1 2.0
and zirconia-supported Ni-ferrites (NiFe2O4/m-ZrO2 and H2 10.1 10.2 10.2
NiFe2O4/c-YSZ). Fig. 7(a) shows a comparison of the oxygen 600  C O2 4.5 5.3 4.9 21
H2 10.3 9.7 10.0
evolution rate per gram of redox materials over time during
400  C O2 4.4 5.9 5.1 19
the T-R step in the 1st and 5th runs of the two-step water-
H2 9.7 10.2 10.0
splitting cycle at the temperature of 1400  C. NiFe2O4/m-ZrO2
14410 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 4 4 0 2 e1 4 4 1 4

water-splitting at the temperature of 1000  C. As seen in the during the cyclic reaction. For hydrogen production, the peak
1st run of Fig. 7(b), the hydrogen production of pure CeO2 was rate is almost the same for CeO2 at 1st and 5th runs; however,
exceptionally faster than that of NiFe2O4/m-ZrO2. This is a the rate varies for NiFe2O4/m-ZrO2 at both runs. These results
characteristic feature of the reduced material of pure CeO2 indicate that the reproducibility of the profile for CeO2 is su-
from a prospect of hydrogen production in the W-D step. On perior to that of NiFe2O4/m-ZrO2 throughout the cyclic
the contrary, the profile of hydrogen production of the reaction.
reduced material of NiFe2O4/m-ZrO2 showed a very broad Fig. 8 shows (a) the oxygen evolution profiles in the T-R step
curve, which indicates that NiFe2O4/m-ZrO2 requires more at 1550  C and (b) the hydrogen production profiles in the
time to complete a cyclic reaction of two-step water-splitting subsequent W-D step at 1000  C in the 1st run of the two-step
in comparison to pure CeO2. water-splitting using CeO2 and NiFe2O4/m-ZrO2. As seen in
The oxygen and hydrogen production profiles of the 5th Fig. 8 (a), when T-R step temperature increases from 1400 to
run of the two-step water-splitting cycle are also shown in 1550  C, the peak rates of CeO2 and NiFe2O4/m-ZrO2 are
Fig. 7(a) and (b). The repeatability of the production rate can be enhanced. The characteristic behavior of NiFe2O4/m-ZrO2 is
evaluated by a comparison of the profiles of both materials. reflected in the slow oxygen production over a long-time after
For the oxygen production, the peak rate is decreased for the peak rate. This specific profile of NiFe2O4/m-ZrO2 indicates
NiFe2O4/m-ZrO2 but increased for CeO2. The reason for the that thermal reduction of NiFe2O4/m-ZrO2 at higher T-R step
lower rate is considered as follows: the high temperature temperatures requires longer time than that of CeO2. The
(1400  C) during the T-R step causes coagulation and sintering profile of oxygen production of CeO2, as mentioned in the
of NiFe2O4, which remarkably decreases the surface area of earlier section, shows that the time required to reduce CeO2 is
the material, and this effect is well documented in previous independent of T-R step temperature. As seen in Fig. 8 (b), the
reports [5e8]. However, as the densely-solidified material was hydrogen production of CeO2 proceeds rapidly, but that of
repeatedly crushed to powder in each step of the two-step NiFe2O4/m-ZrO2 continues at a slow rate for more than 60 min.
reaction, the surface area of the material would fluctuate These results indicate that CeO2 is a promising material from
every time due to the crushing. This effect creates instability a kinetic perspective in comparison to NiFe2O4/m-ZrO2 at
in the production rate of NiFe2O4/m-ZrO2 during the cyclic higher temperatures.
reaction. A specific characteristic of CeO2 is that it has a very Hydrogen and oxygen productivity and repeatability of
high melting point, 1950  C [4]. This means that CeO2 does not pure CeO2 through cyclic two-step water-splitting were
melt at the temperatures that prevail in the T-R step compared with that of zirconia-supported Ni-ferrites
(1300e1550  C). Thus, CeO2 can maintain its particle size (NiFe2O4/m-ZrO2 and NiFe2O4/c-YSZ) and unsupported
during the cyclic reaction, and it will not be decreased by NiFe2O4. The results are shown in Fig. 9. The T-R step was
crushing. This effect favors a stable production rate of CeO2 performed at 1400  C, and the subsequent W-D step was

Fig. 7 e (a) Oxygen production profile in the T-R step of the 1st and 5th runs at 1400  C, and (b) hydrogen production profile in
the subsequent W-D step at 1000  C using CeO2 and NiFe2O4/m-ZrO2 particles.
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 4 4 0 2 e1 4 4 1 4 14411

Fig. 8 e (a) Oxygen production profile in the T-R step of the


1st run at 1550  C, and (b) hydrogen production profile in
the subsequent W-D step at 1000  C using CeO2 and
NiFe2O4/m-ZrO2 particles.
Fig. 9 e (a) Amount of oxygen evolution in the T-R step at
1400  C, and (b) amount of hydrogen generation in the W-D
conducted at 1000  C. As seen in Fig. 9(a), the amount of ox- step at 1000  C using the CeO2 and NiFe2O4/m-ZrO2.
ygen production is greatest for unsupported NiFe2O4 in the 1st
run, but the productivity remarkably drops down to the same
level as with the other materials. The reason for deactivation
of unsupported NiFe2O4 is due to lowering of the surface area always conducted at a constant temperature of 1000  C. As
in the absence of support material due to high-temperature seen in Fig. 10(a), the amount of oxygen evolution generally
sintering and coagulation. The results of cyclic testing sug- increases with increasing T-R step temperatures. Pure CeO2
gest that the decreased surface area cannot be recovered by had a similar potential of oxygen evolution as NiFe2O4/m-ZrO2
crushing of the material after each run. CeO2 provides a stable at the T-R step temperatures of 1400e1550  C. With zirconia-
oxygen production without fluctuation as well as NiFe2O4/m- supported and unsupported Ni-ferrites, high-temperature
ZrO2 and NiFe2O4/c-YSZ. As seen in Fig. 9(b), the hydrogen sintering occurred during the T-R step above 1400  C for un-
production of NiFe2O4/m-ZrO2 and unsupported NiFe2O4 os- supported NiFe2O4 and above 1550  C for NiFe2O4/m-ZrO2.
cillates largely at every run. However, a characteristic feature Therefore, for performing cyclic reactions, pulverization of
of CeO2 is that it maintains a stable hydrogen production level these samples after the T-R step was necessary. On the other
throughout the cyclic reaction. hand, in the case of pure CeO2, the solid material formed after
The evolved amount of oxygen and hydrogen at each step the T-R step was easily pulverized using a mortar and pestle,
for all tested materials are listed in Table 4. The average so that the subsequent W-D step to generate hydrogen could
amount of oxygen produced by NiFe2O4/m-ZrO2, NiFe2O4/c- be performed. After the W-D step, the sample did not appear
YSZ, and unsupported NiFe2O4 are 5.0, 3.3, and 6.4 Ncm3-g1- to be sintered, but remained as a powder.
material, respectively, at T-R step temperature of 1400  C; and As illustrated in Fig. 10(b), hydrogen production also
the average amount of hydrogen are respectively 11.3, 6.4, and generally increases with increasing T-R step temperatures.
11.4 Ncm3-g1-material, respectively, at the subsequent W-D Hydrogen production for pure CeO2 increased monotonically;
step temperature of 1000  C. From these results, the ratio of while it appeared that hydrogen production for NiFe2O4/m-
evolved hydrogen/oxygen is estimated to be an approximately ZrO2 reached a ceiling at T-R step temperature of 1550  C. This
stoichiometric ratio (H2/O2 2). The stoichiometric produc- means that pure CeO2 has an advantage over NiFe2O4/m-ZrO2
tion of hydrogen and oxygen of CeO2 is also approved through in the productivity of oxygen and hydrogen at the higher
the cyclic reaction. temperature of 1550  C. Moreover, the repeatability of pure
The average amount of evolved oxygen and hydrogen for CeO2, as mentioned above, was superior to the Ni-ferrites
all tested redox materials are plotted against the T-R step (NiFe2O4/m-ZrO2, NiFe2O4/c-YSZ, and unsupported NiFe2O4)
temperatures of 1300e1550  C in Fig. 10. The W-D step was throughout the two-step water-splitting cycle. The CeO2 had
14412 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 4 4 0 2 e1 4 4 1 4

Table 4 e Evolved amount of oxygen and hydrogen for CeO2, NiFe2O4/m-ZrO2, NiFe2O4/c-YSZ, and unsupported NiFe2O4.
Sample Evolved amount of O2 and H2/Ncm3g1-material

1st 2nd 3rd 4th 5th 6th Ave.

CeO2 O2 4.4 4.1 5.1 5.1 4.5 4.5 4.6


H2 9.6 9.4 10.0 8.5 8.9 8.4 9.3
H2/O2 2.2 2.3 2.0 1.7 2.0 1.9 2.0
NiFe2O4/m-ZrO2 O2 5.1 6.1 4.4 5.4 4.2 e 5.0
H2 10.9 8.6 13.6 10.1 13.2 e 11.3
H2/O2 2.2 1.4 3.2 1.9 3.1 e 2.3
NiFe2O4/c-YSZ O2 3.8 3.0 3.2 e e e 3.3
H2 6.7 6.5 6.0 e e e 6.4
H2/O2 1.8 2.2 1.9 e e e 1.9
Unsupported NiFe2O4 O2 12.3 8.3 4.0 4.8 5.0 4.2 6.4
H2 10.0 10.8 15.0 10.5 10.7 11.5 11.4
H2/O2 0.8 1.3 3.75 2.2 2.1 2.7 1.8

good resistance to agglomeration or sintering at temperatures cyclic repeatability at thermal reduction (T-R) temperatures of
of 1000e1550  C, because it has a higher melting point than Ni- 1300e1550  C and water decomposition (W-D) temperatures of
ferrite. Therefore, CeO2 is a promising redox material for the 400e1000  C for the production of solar hydrogen from water.
thermochemical two-step water-splitting cycle at tempera- Hydrogen and oxygen productions of CeO2 particles under
tures higher than 1550  C. various T-R temperatures of 1300e1550  C and W-D tempera-
tures of 400e1000  C were experimentally examined, and the
cyclability of CeO2 in the thermochemical two-step water-
4. Summary splitting was evaluated. The characteristic features of CeO2
particles in thermochemical two-step water-splitting are
Thermochemical two-step water-splitting using CeO2 particles described by comparison with zirconia-supported Ni-ferrites
was studied to examine oxygen and hydrogen productivity and (NiFe2O4/m-ZrO2 and NiFe2O4/c-YSZ) and unsupported NiFe2O4.
The oxygen evolution rate drastically increased with
increasing T-R step temperatures from 1300 to 1400  C but
remained almost the same at 1450e1550  C. The CeO2 material
that was reduced at relatively higher temperatures during the
T-R step results in higher rate of hydrogen production during
the W-D step at a constant temperature of 1000  C. The profiles
of oxygen and hydrogen production did not fluctuate but were
reproducible with nearly the same production levels
throughout the 6 runs. Stable production of both oxygen and
hydrogen was realized through cyclic reaction. The CeO2 par-
ticles exhibit good reproducibility with a hydrogen/oxygen ratio
of approximately 2.0 at all T-R temperatures. These results
indicate that the CeO2 material has a reproducible stoichio-
metric productivity of oxygen and hydrogen in the thermo-
chemical two-step water-splitting cycle. At T-R temperatures of
1400e1550  C and W-D temperatures of 400e1000  C, the two-
step water-splitting repeatedly proceeds with a redox reaction
between the two kinds of non-stoichiometric ceria (CeO2d1 and
CeO2d2) and CeO2, and the reduced phases of CeO2d1 and
CeO2d2 were identified as CeO1.966 and CeO1.890, respectively.
The amount of hydrogen produced was independent of the
W-D temperatures 400e1000  C and showed almost identical
levels at all temperatures. However, the production rate
decreased with decreasing W-D temperature. The ratio of the
average amounts of hydrogen/oxygen produced was a stoi-
chiometric value of around 2 in the W-D step at temperatures
of 400e1000  C.
The characteristic features of CeO2 particles in terms of
Fig. 10 e (a) Average of oxygen generation in the T-R step at reactivity and cyclicity in thermochemical two-step water-
1300e1550  C, and (b) average of hydrogen generation in splitting are 1) extremely high rate of hydrogen production at
the W-D step at 1000  C using CeO2, NiFe2O4/m-ZrO2, temperatures less than 1000  C in comparison with NiFe2O4/
NiFe2O4/c-YSZ, and unsupported NiFe2O4. m-ZrO2, and stoichiometric hydrogen/oxygen production ratio
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 4 4 0 2 e1 4 4 1 4 14413

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