ECS Transactions, 57 (1) 1235-1244 (2013)

10.1149/05701.1235ecst ©The Electrochemical Society

Ni-Zr0.75Ce0.25O2-δ Composite as Steam Methane Reformable SOFC Anode

Snehashis Biswasa, A. Das Sharmaa, Amlan Buragohainb, C. V. Stayanarayanab

and R. N. Basua
a
Fuel Cell & Battery Division, CSIR-Central Glass & Ceramic Research Institute,
Kolkata 700 032, India
b
Catalysis Division, CSIR-National Chemical Laboratory, Pune 411008, India

The feasibility of Ni supported Zr0.75Ce0.25O2-δ (ZCO) composites

as steam methane reformable anode has been studied. ZCO powder
was prepared by combustion synthesis technique using L-alanine
as fuel. Phase pure material with average particle size below 1 µm
was obtained upon calcination at 700oC for 6 h. Thermal expansion
behaviour and electrical characterization of bulk samples of such
Ni-ZCO composite anodes (Ni content between 20 and 40 vol%)
have been carried out. Steam methane reforming (SMR) activity of
the samples was also evaluated. The composite anodes were found
to be quite promising in terms of matching thermal expansion
coefficient, electrical conductivity and SMR activity. Anode
supported single cells having configuration Ni-ZCO/YSZ/LSM
have been fabricated and tested using methane as fuel.

Introduction

Direct catalytic reforming of hydrocarbons in solid oxide fuel cell (SOFC) offers the
possibility to generate electricity without any upstream fuel reforming (1). Methane,
which is the main component of natural gas, is suitable as SOFC fuel (2). Methane has
the least possibility to form coke on anode side of SOFC due to only one carbon in the
structure. As the pure methane enters into the anode side, it forms mainly H2, CO2 and
CO due to the catalytic oxidation by Ni catalyst. This gas is formed by the partial
oxidation and steam reforming of methane. These oxidation reactions also produce
electrons which generate electricity. The direct oxidation of methane (DOM) on SOFC
anode helps to prevent carbon deposition (3).

CH4 + 4O2- = CO2 + 2H2O + 8e- [1]

Partial oxidation of methane (POM) leads to the formation of H2 and CO; these gases
also enhance power generation.

CH4 + ½ O2 = CO + H2 [2]

Direct oxidation of fuel has some major obstacles. Due to high temperatures, it leads
to coke formation on Ni-YSZ anode side of conventional SOFC.

CH4 + Ni = C-Ni + 2H2 [3]

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 ECS Transactions, 57 (1) 1235-1244 (2013)

From thermodynamics, it can be predicted that, for methane as fuel, carbon should
form at 8000C and 1 atm pressure unless steam:carbon ratio is very high (4). Coke
formation is more probable with higher hydrocarbons. This study is aimed at replacing
the conventional SOFC anode material with suitable cermet having high resistivity to
coke formation as well as the other compatibility factors. Zirconium doped cerium oxide
is reported to have high catalytic activity and high carbon tolerance (5-6). ZCO structure
has high oxygen vacancy due to the ZrO2 doping which increases the mobility of O2 ions.
Due to availability of oxygen ions, the carbon formed on Ni oxidizes as soon it forms.

Ni-C + O2 = Ni +CO2 [4]

The stability of zirconia-ceria composition is also quite high at high temperatures.

Even its stability is higher than pure ceria catalyst. That is why such zirconia doped ceria
is widely used in automobile industry as catalytic converter.

In the present investigation, nano-crystalline zirconia doped ceria, Zr0.75Ce0.25O2-δ

(ZCO) has been synthesized by combustion synthesis technique and composites of Ni-
ZCO having different Ni contents have been studied to find the suitability of such Ni-
ZCO composites as steam methane reformable anodes for SOFC application. Powder and
bulk samples have been thoroughly characterized for studying the structural, thermal and
electrical properties. Steam methane reforming (SMR) activities of the composite anodes
have also been studied to optimize the composition for suitable catalytic activity. Finally
anode-supported single cells have been fabricated using the optimized Ni-ZCO composite
as the anode support. Electrochemical performance of such anode-supported coupon cells
have been evaluated using both hydrogen and methane as fuel.

Experimental

ZCO (Zr0.75Ce0.25O2-δ) powder was prepared by combustion synthesis method.

Reagent grade Ce(NO3)3.6H2O, 99.5% (Acros Organic) and ZrO(NO3)2.H2O, 99.5%
(Acros Organic) were used as the starting raw materials and dissolved in minimum
volume of water in stoichiometric amounts. L-alanine (C3H7NO2), 99% (SRL India), used
as fuel in this combustion reaction, was added to the above mixed solution in calculated
amount so as to have a nitrate to fuel ratio of unity. The solution mixture, taken in a glass
beaker, was allowed to evaporate slowly on a hot plate at around 200oC with continuous
stirring. The liquid slowly turned viscous and began to turn into a deep yellowish-white
gel and finally auto ignited, leaving behind a light and fragile yellowish powder. The as-
synthesized powder, thus obtained, was calcined at a temperature of 7000C for 6 h in air.
TG-DTA of precursor gel had been carried out using a Thermal Analyzer (STA 409C
Netzsch). X-ray crystallographic studies of the calcined powders were carried out using
an X-ray diffractometer (PW 1710, Phillips) with Cu-Kα radiation. Rietveld refinement
of the diffraction data was carried out by PANalytical X’Pert High Score software using a
pseudovoight function. BET surface area of the powder samples was determined using a
surface area analyzer (Quantachrome, Nova, USA). The morphology of the calcined
powders was observed under a transmission electron microscope (Tecnai G2 30 ST, FEI,
USA). For this purpose, the specimens were prepared by dispersing the ZCO powder in
isopropanol, deposition on carbon film, followed by drying under vacuum.

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 ECS Transactions, 57 (1) 1235-1244 (2013)

Bulk samples of NiO-ZCO having different Ni loading (in the range between 15 and
50 volume %) were prepared by mixing required amounts of NiO (JT Baker, USA) and
the synthesized ZCO (calcined at 700oC) powders for about 20 h. The mixing was carried
out in polypropylene bottles using zirconia balls as grinding media and isopropanol as the
liquid medium. After drying the mixture, rectangular bars of dimension 25 mm x 10 mm
x 3.5 mm were made through uniaxial pressing at 200 MPa. The green compacts of NiO-
ZCO, thus obtained were sintered in air at 1400oC for 6 h followed by reduction at 900oC
for 6h in the presence of mixture gas (5%H2 in Ar) so as to obtain the corresponding Ni-
ZCO cermet samples. Thermal expansion coefficient (TEC) of the sintered samples of
each composition was determined using a high temperature dilatometer (Netzsch DIL
402C). Experiments were conducted in an atmosphere of air for NiO-ZCO samples and in
inert atmosphere (Argon) for Ni-ZCO samples. Measurements of TCE were taken in the
range of room temperature to 8000C.

Electrical conductivity of the Ni-ZCO cermet composite samples, as a function of

temperature, was measured by four probe method using a DC power supply (Agilent
E3631A) and digital multimeter (Agilent 34401A). Pt wire was used as the electrode
leads. The conductivity was measured under a flowing stream of a reducing gas mixture
(5% H2 in Ar). The conductivity of pure ZCO was carried out by impedance
spectroscopy (ModuLab, Solartron, UK) in the frequency range 10 µHz to 1MHz.

Steam methane reforming (SMR) was carried out in a fixed bed down flow reactor
(Incolloy HT, 13 mm ID) using sieved (0.3-0.5 mm) catalyst placed at the centre of the
reactor sandwiched between quartz beads. Catalyst was diluted with equal volume of
quartz particles of the same mesh range. The catalyst was initially treated in air at 7500C
followed by reduction in presence of H2:N2 gas mixture (20:80 ratio) at 8000C for 6 h.
Activity of the catalysts was evaluated at different temperatures at a gas hourly space
velocities (GHSV’s) in the range of 15000-20000 using steam to carbon ratio of 2. Some
catalysts were also tested at S/C= 1.5 and 3. Catalytic stability was monitored on stream
for about 12-15 h.

Anode supported single cells (of diameter 16 mm and thickness 1.5 mm) having
configuration NiO-ZCO (anode-support)/NiO-ZCO-YSZ (anode active layer)/YSZ
(electrolyte)/LSM-YSZ (cathode active layer)/LSM (cathode current collector) were
fabricated by our standard tape casting and screen printing technique (7). Electrochemical
performance of such coupon cells at 800oC was measured using both H2 and CH4
(saturated with 3% moisture) as fuel and O2 as the oxidant. During testing, both oxygen
and hydrogen/methane flow rates were set and maintained at 100 ml min−1 with the help
of mass flow controllers (MKS Instruments, USA).

Results and Discussion

Thermal Decomposition of the Gel and Evolution of Phases

Thermal analysis results (Fig. 1a) show the thermal decomposition behaviour of
precursor gel of ZCO material prepared by combustion synthesis. It can be clearly
observed from figure 1a that there are different steps of decomposition of the gel. Mass
loss of about 38% below 2300C is generally due to removal of absorbed water which is
further manifested by a peak at the same temperature in the corresponding DTA curve.

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 ECS Transactions, 57 (1) 1235-1244 (2013)

Second significant weight loss at around 3000C is due to the decomposition of nitrates.
The corresponding DTA peak is observed at 294.60C. The third weight loss at a still
higher temperature of around 360oC may be due to the decomposition of metal-alanine
complex.

The XRD pattern of ZCO powder obtained upon calcinations of the as-synthesized
ashes at a temperature of 7000C for 6 h is presented in Fig. 1b. All the peaks of the XRD
pattern match well with the standard (JCPDS File No. 01-081-0792) indicating formation
of a phase pure material having a cubic structure (8).
110 2000
(a) (b) ZCO Calcined at 9000C
100 1.2
Peak: 294.60C
90 Peak: 362.40C
1.0 1500
80 Peak:0

DTA/(mW/mg)
227.7 C 111
70 0.8

Intensity
1000
TG/%

60
0.6
50
0.4 220
40 500
311
200
30 0.2
222 331
400 420
20
0.0 0
0 200 400 600 800 1000 10 20 30 40 50 60 70 80 90

Temperature ( C)O 2θ

Figure 1. (a) TG/DTA curve of precursor gel of ZCO and (b) XRD pattern of calcined
ZCO powder.

Microstructural Analysis of Powder

Transmission Electron Microscopic (TEM) images of such calcined powders reveal the
nano-crystalline nature of the synthesized particulates (Fig. 2). It is clear from the figure
that the size range of such synthesized powders is within 20 to 30 nm (Fig. 2a). The cubic
structure of the crystalline particulates is also confirmed from the corresponding selected
area diffraction (SAD) pattern (Fig. 2b) that shows the diffraction pattern from the first
five planes having different d spacing in the range of 1.52 Ao (reflection plane 222) to
3.07 Ao (reflection plane 111).

Figure 2. (a) TEM image of 700oC calcined powder and (b) the corresponding selected
area diffraction (SAD) pattern showing reflection from different planes.

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 ECS Transactions, 57 (1) 1235-1244 (2013)

Thermal Expansion Behaviour and Electrical Properties

The thermal compatibility of anode material with other cell component is one of the
most important concerns affecting cell fabrication. To ensure cell stability at high
temperatures, thermal expansion coefficient (TEC) of anode material should be made
similar to electrolyte material. The TEC value of Ni-ZCO cermet materials varies due to
different factors, such as volume % of components, porosity, sintering temperature etc.
(9). Table I summarizes the results of thermal expansion coefficient (TEC) measurements
on samples having different Ni content (15 to 50 vol. %). The TEC values of both the
NiO-ZCO (i.e. before reduction) and the corresponding Ni-ZCO cermet (i.e. after
reduction) are shown in Table I. It is observed that for all NiO-ZCO samples and the
corresponding Ni-ZCO cermets, a linear relationship exists between thermal expansion
and the temperature so that the TEC increases linearly with increasing temperature. Also,
the TEC value of the sample increases with increasing Ni loading. It can also be observed
from Table I that for any given Ni content, the TEC value of the Ni-ZCO cermet is lower
than the corresponding air-sintered NiO-ZCO composite. The decrease in TEC values for
reduced sample may be due to increase in porosity during reduction (9).

TABLE I. Thermal expansion coefficient of Ni-ZCO cermet samples

Sample Ni Volume % TEC of NiO-ZCO (X 10-6/K) TEC of Ni-ZCO ( X 10-6/K)
Ni-ZCO 50 50 14.31 13.86
Ni-ZCO 40 40 13.96 13.03
Ni-ZCO 30 30 13.95 12.35
Ni-ZCO 20 20 13.60 12.07
Ni-ZCO 15 15 13.45 12.27

Electrical conductivity of pure ZCO sample, the ceramic part of the cermet
composition, has been carried out by impedance spectroscopy and the results are shown
in Fig.3. It is found from figure 3a that the conductivity of ZCO increases exponentially
with increase in temperature in the range of 600-800oC. The highest conductivity as
observed from figure is 9.3 x 10-4 S/cm at 800oC. The temperature vs. conductivity plot
exhibits that the conduction is prevalently ionic and governed mostly by oxygen ion
which also resembles with the literature (10, 11). The Arrhenius plot of the electrical
conductivity of ZCO (Fig. 2b) also supports the higher electrical conduction observed at
the higher temperature. The activation energy for the ZCO sample is calculated from the
Arrhenius plot of electrical conductivity and is found to be ~ 208 kJ/mol.
700 -4
(a) Pure ZCO (b)
600 -5
ln(Conductivity/S.cm-1)

-6
500
Conductivity x 105 (S/cm)

-7
400
-8
300 -9

200 -10

100 -11

-12
0
-13
600 650 700 750 800 850 900 0.85 0.90 0.95 1.00 1.05 1.10 1.15
Temperature (oC)
1000/T (K-1)
Figure 3. (a) Electrical conductivity of pure ZCO sample and (b) Arrhenius plot of
conductivity of pure ZCO sample from 600-9000C.

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 ECS Transactions, 57 (1) 1235-1244 (2013)

The temperature dependent conductivity of the Ni-ZCO cermet samples prepared by

conventional solid state and sintered at 1400oC was measured under a flowing stream of a
reducing gas mixture (5% H2 in Ar).. The conductivity measurement was carried out for
various Ni contents ranging from 15-50 vol% of the metallic phase in the cermet. From
figure 4a, it is observed that the electrical conductivity of cermet sample with 15 vol% of
the metallic phase is predominantly ionic and found to be 0.068 S/cm at 8000C. The
temperature dependent conductivity of 15 Ni-ZCO exhibits the similar trend to that of the
pure ZCO sample indicating ionic nature (Fig. 4b). The onset of the metallic conductivity
of Ni-ZCO cermet resumes at metal content ≥ 20 vol%. Electrical conductivity decreases
with increase in temperature for such cermets. The typical metallic nature of the electrical
conductivity of the sintered cermets is thus exhibited for all the compositions ranging
from 20Ni-ZCO to 50Ni-ZCO. The highest electrical conductivity for such Ni-ZCO
cermets is found with 50Ni-ZCO (> 1000 S/cm). However, the required conductivity
percolation threshold for such cermet is found to be 35-40 Ni-ZCO and the range of
conductivity is observed to be ~265 S/cm to ~420 S/cm for the above mentioned cermet
composites (Fig. 4c). Temperature dependent Arrhenius plots for all the cermet
compositions (15Ni-ZCO through 50 Ni-ZCO) are shown in figure 4d. The calculated
activation energies for such cermets are tabulated in Table II.
0.10
15 Ni-ZCO 50 Ni-ZCO
. (a) 1400 (b)
40 Ni-ZCO
0.09
30 Ni-ZCO
1200 20 Ni-ZCO
0.08
Conductivity (S/cm)

1000
Conductivity (S/cm)

0.07
800
0.06
600
0.05
400
0.04
200
0.03
0
0.02
500 550 600 650 700 750 800 850 900 500 600 700 800 900
Temperature (OC) Temperature (0C)
1200 12
Conductivity at 8000C 50 % Ni-ZCO
(c) (d) 40 % Ni-ZCO
1000 10 30 % Ni-ZCO
20 % Ni-ZCO
8 15 % Ni-ZCO
ln(Conductivity/S.cm-1)
Conductivity (S/cm)

800
6
600 4

400 2
0
200
-2
0
-4
10 15 20 25 30 35 40 45 50 55 0.8 0.9 1.0 1.1 1.2 1.3
Volume % of Ni 1000/T (K-1)

Figure 4. Electrical conductivity of Ni/ZCO cermets: (a) electrical conductivity for 15Ni-
ZCO; (b) temperature dependent electrical conductivity for 15Ni-ZCO; (c) electrical
conductivity percolation curve; (d) Arrhenius plots of Ni-ZCO samples from 500-8000C.

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 ECS Transactions, 57 (1) 1235-1244 (2013)

TABLE II. Activation Energies for Electrical Conduction

Ni Vol % 15 20 30 40 50
Activation Energy 22.44 2.51 6.45 3.04 5.8
Ea(kJ/mol)

The activation energies of Ni-ZCO cermets are evaluated from 500-8000C. Though no
direct correlation between the activation energies with vol% of Ni in the cermet is
established, cermets having metallic conduction are found with lower activation energies
for electrical conduction compared to that of the cermets having prevalent ionic
conductivities.

Steam Methane Reforming (SMR) activity and Catalytic Behaviour

Since, Ni-ZCO cermets with Ni ≥ 20 vol% only showed good electrical conductivity
and matching TEC with YSZ, we have evaluated 20Ni-ZCO and 40Ni-ZCO anode
cermets for steam methane reforming activity and stream stability up to 12 h. The results
are shown in Fig. 5. As may be seen from Fig. 5, both 20 Ni-ZCO and 40 Ni-ZCO
samples gave quite stable activity during the period of their study. The reaction
parameters chosen were steam/carbon ratio of 2 and gas hourly space velocity 15,000 h-1.
A close look at the data shows that Ni-ZCO sample with 20 vol% Ni deactivates at a
slightly higher rate than Ni-ZCO sample with 40 vol% Ni. It is expected that availability
of catalytic sites are higher for the sample with 40% Ni compared to 20 vol% Ni, hence
its activity is expected to be high provided the sintering of Ni is to the same extent on
both the samples.

105

100

95
% CH4 Conversion

90

85 Ni-ZCO 40
Ni-ZCO 20
80

75

70

65

60
2 4 6 8 10 12
TOS (hours)
Figure 5. Steam methane reforming on Ni-ZCO samples. (Steam/carbon =2, Gas hourly
space velocity 15000 h-1).

To evaluate these catalysts further, we have investigated their catalytic activity at

different temperatures. The primary aim was to be away from equilibrium conditions by
conducting the methane steam reforming at lower temperatures (12). As mentioned in the
Experimental Section, these experiments have also been conducted at different
steam/carbon ratios. As may be seen from Fig. 6, conversion of methane increased with
increasing temperature on both 40 and 20 vol% Ni containing samples. At all

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 ECS Transactions, 57 (1) 1235-1244 (2013)

temperatures studied, the methane conversion was high on 40Ni-ZCO sample compared
to 20Ni-ZCO Similarly, methane conversion was high at higher steam/carbon ratio, as
one may anticipate due to shifting of equilibrium towards product formation according to
Le Chatelier's principle. Though results are on expected lines, 40Ni-ZCO sample showed
slightly lower conversion at 600oC, for steam/carbon ratio 2. It was also seen that
methane conversions are much closer at 800oC, as they reach equilibrium conversions.

Figure 6. Steam methane reforming on Ni-ZCO samples at different temperatures.

Steam/carbon =2 & 3, Gas hourly space velocity 15000 & 20000 h-1.

The catalysts with 20 and 40 vol% Ni have also been evaluated at close to
equilibrium conditions, to check their on stream stability for 10-12 h. Surprisingly, under
these conditions, more rapid deactivation was observed for the sample with 20 vol% Ni.
The reasons for deactivation as well as type of coke and wt% of coke formed during the
reaction are being investigated.

Electrochemical Performance of Anode-supported Cells

As mentioned under Experimental Section, anode-supported single cells in the form of

coupon cells (of dia 16 mm and thickness 1.5 mm) were fabricated using 40 Ni-ZCO as
the material for anode-support. In order to enhance the triple phase boundary (TPB)
length at the anode-electrolyte interphase and also to enhance thermal compatibility
between the anode and YSZ electrolyte, a thin (~10 µm) layer of Ni-ZCO-YSZ (50: 50
by weight) was put between the anode-support and YSZ electrolyte. Similarly, a thin
layer (~10 µm) of La0.6Sr0.35MnO3-δ (LSM)-YSZ (50:50 by weight) was put between the
YSZ electrolyte and the LSM cathode current collector. Fig. 7a shows the results of the
initial experiments which are quite encouraging. Thus, at an operating temperature of
800oC and 0.7 V, a current density of ~2.2 Acm-1 is obtained from such a cell with
hydrogen as fuel. Under similar conditions, the value drops to about 1.4 Acm-1 when
hydrogen is replaced with methane as the fuel. The microstructure of the cell after testing
in methane is shown in Fig. 7b.

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 ECS Transactions, 57 (1) 1235-1244 (2013)

Figure 7. (a) Comparative electrochemical performance of a single cell with 40 Ni- ZCO
composite anode using H2 and CH4 as fuel (operating temperature: 800oC) and (b)
Microstructure of the cell after testing in methane.

Conclusions

Nano-crystalline (20-30 nm) powder of Zr0.75Ce0.25O2-δ (ZCO) has been synthesized

by combustion synthesis technique. Phase pure powder having cubic crystal structure is
obtained upon calcination of the as-synthesized ash at 700oC for 6 h. Using such ZCO
powders, composites of Ni-ZCO with different Ni content (15 to 50 vol %) have been
fabricated and characterized thoroughly for thermal, electrical and steam methane
reforming activity studies. A composite anode with 40 vol % Ni is found to be suitable
for SOFC anode application having good steam methane reforming ability. At an
operating temperature of 800oC and 0.7 V, a current density of ~1.4 Acm-1 is obtained
from such a cell with methane as fuel.

Acknowledgments

The authors acknowledge Director, CGCRI for his kind permission to publish the
work. Financial support from CSIR-NMITLI project is also acknowledged. Two of the
authors (SB and AB) also acknowledge the financial support from CSIR for providing
fellowship. Technical assistance rendered by the Electron Microscope and XRD Sections
of the Institute is also gratefully acknowledged.

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