Solid State Ionics 288 (2016) 135–139

Contents lists available at ScienceDirect

Solid State Ionics

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

Iso-octane internal reforming in a solid oxide cell reactor

A. Al-Musa a, N. Kaklidis b, M. Al-Saleh a, A. Al-Zahrani a, V. Kyriakou c,d,⁎, G.E. Marnellos b,d,e
a
National Center for Combustion and Plasma Technologies, Water & Energy Research Institute, King Abdulaziz City for Science & Technology, 11442, Riyadh, Saudi Arabia
b
Department of Mechanical Engineering, University of Western Macedonia, 50100 Kozani, Greece
c
Department of Chemical Engineering, Aristotle University of Thessaloniki, Building E13, 54124, Greece
d
Chemical Process & Energy Resources Institute, Centre for Research & Technology Hellas, 57001 Thermi, Thessaloniki, Greece
e
Department of Environmental Engineering, University of Western Macedonia, 50100 Kozani, Greece

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

Article history: This study reports on the feasibility of internal iso-octane steam reforming process in an YSZ solid oxide fuel cell
Received 17 July 2015 reactor by employing Cu/CeO2 as catalyst/anodic electrode. The Cu/CeO2 anode is evaluated for its both catalytic
Received in revised form 27 November 2015 and electro-catalytic performance. In all cases, i-C8H18 was successfully reformed by H2O to syngas. In addition,
Accepted 6 December 2015
appreciable amounts of CO2 and CH4 were also produced. The distribution of products was also influenced by
Available online 30 December 2015
i-C8H18 thermal pyrolysis and catalytic decomposition processes leading mainly to olefins formation. At closed-
Keywords:
circuit operation, and by applying anodic overpotentials, mainly H2 and CO were electro-oxidized to H2O and
Iso-octane internal reforming CO2, while at cathodic polarization conditions the co-electrolysis of H2O and CO2 to H2 and CO was taking
SOFC place, affecting the equilibrium reactions at the anodic chamber. During fuel cell operation, the electrochemical
Cu/CeO2 anodic composite performance increased with cell temperature and i-C8H18/H2O feed ratio. The AC impedance spectroscopy anal-
YSZ ysis showed contributions both from charge and mass transfer processes, with the latter to dominate the overall
cell performance.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction The key-issue of liquid fuel-fed SOFCs development is the selection

of the anodic composite materials. An electro-catalyst for this applica-
The increasing energy demands are still mainly compensated by tion should mainly exhibit a) high catalytic activity for hydrocarbon ox-
fossil fuels employing thermodynamic limited conventional heat cycle idation and reforming, b) adequate electron conductivity and c) high
configurations [1]. In recent years great advances have been accom- tolerance to carbon deposition. The Ni-based anodes are currently the
plished in Renewable Energy Sources (RES) technologies. However, state of the art materials for SOFCs [2–6,8–13]. Nickel electrodes are
the high cost and complexity for RES adaptation and exploitation have fulfilling the first condition, but it has been proved that they are carbon
made them prohibitive to be implemented currently in stationary sensitive at low C/H2O ratios [14]. Furthermore, Ni in these cermets is
power plants. This “business as usual” scenario is leading to natural oxidized easily to NiO, due to its poor redox properties suffering an im-
sources depletion and significant environmental implications, which is portant decrease in electronic conductivity [15–18]. Hence, the devel-
in contrast with the strategies for a sustainable future imposed by opment of electro-catalytic active and conductive anodic materials,
international organizations. tolerant toward carbon poisoning, is of crucial importance [3,4].
Fuel cells are considered as a promising energy conversion technol- Among others, Cu-based cermets have been proved as the most
ogy, capable of satisfying the needs of high efficiency and low environ- promising candidates for direct hydrocarbon SOFCs, because they per-
mental footprint [1]. Although, H2 is the ideal fuel for fuel cells, several fectly fulfill all the aforementioned prerequisites. In a recent study it
obstacles related to its limited availability, the absence of relevant infra- was demonstrated that their performance is improved when a thin
structure and the difficulties associated with its storage and transport layer of carbonaceous compounds is deposited on their surface after
retard the market roll out of fuel cells [2]. In the meantime, the use of paraffin fuel treatment [3]. In addition, Gorte et al. also demonstrated
conventional fuels with established infrastructure, like gasoline, could that the Cu-CeO2 cermets show excellent stability in their relevant di-
be an alternative way to accelerate the commercialization of fuel cells. rect hydrocarbon SOFC works [6,7,15,19].
SOFCs, due to their high operating temperature can be potentially oper- In the present study, typical fuel cell measurements and AC imped-
ated directly on conventional hydrocarbon fuels [3–9]. ance spectroscopy studies are combined to investigate the performance
of an iso-octane internal steam reforming solid oxide reactor cell of the
⁎ Corresponding author at: Department of Chemical Engineering, Aristotle University of
type Cu-CeO2/YSZ/Pt. Iso-octane is used as fuel, because it is a common
Thessaloniki, Building E13, 54124, Greece. Tel.: +30 2310 996145. surrogate for gasoline and has lower tendency for cracking than other
E-mail address: [email protected] (V. Kyriakou). heavier hydrocarbons [20]. Furthermore, the catalytic and electro-

http://dx.doi.org/10.1016/j.ssi.2015.12.013
0167-2738/© 2015 Elsevier B.V. All rights reserved.
136 A. Al-Musa et al. / Solid State Ionics 288 (2016) 135–139

catalytic behavior of Cu-CeO2 anodic composite is also evaluated under 3. Results and discussion
open- and closed-circuit modes of operation.
3.1. Open-circuit studies

2. Experimental Open-circuit experiments were firstly carried out to demonstrate

the catalytic activity of Cu-CeO2 anodic electrode for iso-octane steam
The apparatus employed for the electrochemical measurements reforming (ISR). Fig. 1 shows the effect of temperature on the products'
during iso-octane internal reforming, has been described in detail in formation rate, open-circuit voltage (OCV) and reactants conversions.
previous communications [5,12]. The employed cell is consisted of an The inlet partial pressures of iso-octane and steam was 1.5 and 12 kPa,
8 mol% Y2O3-stabilized ZrO2 (YSZ) solid electrolyte tube (15 cm long, respectively, corresponding to a H2O/C feed ratio equal to unity. The re-
16 mm ID, 18 mm OD, 1.2 mm thickness, supplied by CERECO) closed actor cell effluent stream consisted mainly from H2, CO, CH4 and CO2,
at its one end and three electrodes applied on its both sides. On the while minor quantities of C2s (C2H4, C2H6), and C3 + olefins (C3H6,
outer surface of the closed-end, two porous Pt films were deposited C4H8) were also detected. Concerning the conversions of reactants, it
and served as counter and reference electrodes similarly to our seems that they both increase with cell temperature. However, iso-
previous works [5,11,12], while on the inside bottom surface a octane conversion is higher and its increase is more intense compared
70 wt.%Cu–30 wt.%CeO 2 mixed oxide composite was employed as to H2O consumption rate. The main reason is that H2O is also a product
anode. The Cu/CeO2 working electrode was prepared from cerium (IV) of the parallel running reverse water gas shift (1) reaction, which is fa-
oxide (99.9%, Alfa Aesar) and copper powders (99%, Alfa Aesar), respec- vored at elevated temperatures:
tively [5,12]. Appropriate quantities of both chemicals were diluted in
20 ml of ethyl glycol, fired at 200 °C and stirred at 400 rpm until half CO2 þ H2 ←→CO þ H2 O ð1Þ
of the volume was evaporated. The resulted viscous suspension was de-
posited on the inside bottom of the YSZ tube by painting. The tube was In addition, the catalytic decomposition and thermal pyrolysis of iso-
then heated up to 900 °C, and calcined for 4 h. The Cu/CeO2 electrode octane could also explain the observed differences in reactants conver-
thus formed had a superficial surface area of 1.7 cm2 and its morpholo- sions. The latter is confirmed by the formation of C2–C4 olefins which
gy, structure and composition was analyzed employing various charac- are derived as carbonaceous fragments via the scission reactions of
terization techniques, using a previously removed from the YSZ surface iso-octane [21]. Saunders and Kendall observed a similar product distri-
Cu/CeO2 electrode film [5,12]. The surface area was measured using the bution over Ni/YSZ electrodes which was assigned to the simultaneous
BET method, and was found equal to 2 m2/g. The elemental mapping polymerization and decomposition processes of produced olefins [17].
revealed that the microstructure is non-uniform, with the CeO2 and The observed H2/CO ratio is equal to 2.8 at 750 °C, a value higher
Cu phases randomly distributed. For XRD analysis, the Cu/CeO2 catalyst than the stoichiometric ratio (2.1) expected for ISR, and decreases
was first deposited as anodic electrode and it was treated with pure H2 with temperature becoming equal to 2 at 850 °C. At the same time,
under open circuit and anodic polarization conditions (η = 3000 mV) at the CO/CO2 ratio and methane production rate are also increasing
850 °C. Then, the electrode was removed from the solid electrolyte sur- with temperature. The above results clearly reveal the importance of re-
face and subjected to XRD analysis, where Cu, CeO2 and Cu2O phases verse water gas shift (RWGS) reaction at these operating conditions. A
were observed in the corresponding diffraction spectra [5]. The metallic similar H2/CO ratio equaled to 2.57 was observed in the work of
Pt counter and reference electrodes were prepared from an organome- Flores-Marin and Su [22], who proposed that the produced CO was con-
tallic paste (Metalor) after calcination in static air at 900 °C for 4 h. The sumed by one or more parallel reaction pathways carried out in the
heating and cooling rates in all steps were kept at 4 °C/min. reactor.
The experimental apparatus [5,12] is comprised of a liquid reactants Fig. 2 depicts the dependence of the formation rate of various prod-
feed unit equipped with the necessary heated saturators, the solid elec- ucts, reactants' conversion and OCV on the iso-octane (Fig. 2a) and H2O
trolyte cell reactor and the gas analysis system. The measurements were (Fig. 2b) inlet concentration. The partial pressures were ranged from
carried out in the temperature range of 750–850 °C under atmospheric 0.5–3 kPa for iso-octane under a constant PH2O = 12 kPa (Fig. 2a) and
pressure and a total flowrate of 75 cm3/min. Various mixtures of iso- from 3 to 24 kPa for H2O at Pi-C8H18 = 1.5 kPa (Fig. 2b), respectively.
octane and water vapors were fed into the cell reactor by bubbling The operation temperature was kept constant at 850 °C and the total
pure He (Air Liquide) through two different vessels containing i-C8H18 flowrate was remained always equal to 75 cm3/min. The observed
(99.5% purity, Riedel-de Haen) and twice-distilled water. Both vessels
were insulated and heated at specific temperatures in order to obtain
the desired amounts of iso-octane and water vapors, while the remain- Electromotive Force, mV
14 50
ing flow lines up to cell reactor inlet provisions and the GC were heated
- 908 - 905 - 900 - 898 - 897
Conversion of H 2O - i-C8H18, %

at 100 °C. The reactant and effluent composition was monitored with a
Production Rate, 107 mol/sec

12
SHIMADJU 14B gas chromatograph (GC) equipped with thermal 40
conductivity (TCD) and flame ionization (FID) detectors as well as 10
H2
with a Molecular Sieve 13X and a Porapack QS column for gas
30
separation. The carbon and water contents were always calculated 8

using the carbon, hydrogen and oxygen mass balances. CO

6 i-C8H18
The cell voltage and developed electrical current were controlled 20
and monitored by means of an AMEL model 2053 Potentiostat- 4
H2O
CH4
Galvanostat and two differential voltmeters (Digital Multimeter
CO2
10
DT9205A). For the fuel cell measurements, the cell characteristics 2 C3+
were acquired employing a resistance box 1051 by Time Electronics. C2s
AC electrochemical impedance spectra were acquired under open cir- 0 0
750 775 800 825 850
cuit conditions in the frequency range from 0.01 Hz to 1 MHz, with an oC
Temperature,
amplitude of 30 mV RMS, using the IVIUM technologies electrochemical
workstation and the corresponding software (IVIUMSOFT) for data pro- Fig. 1. Dependence of products' formation rates, i-C8H18 and H2O conversions and
cessing. Prior to each experiment the anodic electrode was pretreated developed OCV on cell temperature at open circuit conditions. Pi-C8H18 = 1.5 kPa,
with pure H2 at 850 °C for 3 h. PH2O = 12 kPa, FT = 75 cm3/min.
 A. Al-Musa et al. / Solid State Ionics 288 (2016) 135–139 137

of Wang and Gorte [24]. On the other hand, the apparent reaction orders
for i-C8H18 and H2O were found equal to 0.36 and 0.44, respectively.
These values, possibly suggest a rate determining step that involves
the dissociative adsorption and decomposition of both reactants on
the catalyst surface and the subsequent interaction of the resulted frag-
ments to final products.
The open literature contains only few works dealing with the ISR
process. Most of the studies agree that the ISR mechanism involves
several reactions carried out both on the catalytic surface and in the
gas-phase [21,25]. However, two are the most common reaction mech-
anisms. The first proposed by Savage, describes that hydrogen produc-
tion occurs through multiple pyrolysis reactions, including homolytic
dissociation of C–C bond, radicals recombination, beta scission, isomer-
ization and hydrogen removal with the distribution of products to be
determined by the strength of C–H and C–C bonds of the reactants
[21]. In the second, suggested by Kopasz et al., hydrogen production
occurs after iso-octane pyrolysis into lighter hydrocarbons and their
consequent catalytic reforming by Η2Ο [25].

3.2. Closed circuit operation

Fig. 3 contains results obtained under closed-circuit operation, i.e.

when an overpotential is applied to the cell in order to pump O2 −
through the electrolyte. A positive applied overpotential corresponds
to the electrochemical supply of oxygen anions (O2 −), according to
Faraday's Law, from the air exposed cathode (Pt) through the solid elec-
trolyte (YSZ) to the anode (Cu-CeO2). On the contrary, at cathodic polar-
ization conditions the opposite electrochemical flux is obtained; O2−
are removed from the anode chamber to cathode. The inlet partial pres-
sure of iso-octane and steam was 1.5 and 12 kPa, respectively, and the
operation temperature was kept at 850 °C. The applied overpotentials
Fig. 2. Dependence of products' formation rates, i-C8H18 and H2O conversions and ranged from −1 to +3 V with the current densities achieved to be rel-
developed OCV on a) Pi-C8H18 and b) PH2O feed partial pressures at open circuit atively low and took values from −29.3 to 25.3 mA/cm2, respectively.
conditions. T = 850 °C, FT = 75 cm3/min. During anodic polarization, the formation rates of H2, CO and CH4 are
decreasing as the applied overpotential and developed current increase,
due to their electro-oxidation at three phase boundary. As expected,
products and their distribution were similar as in Fig. 1, i.e., H2, CO, CO2, most of the applied current is consumed by H2 and CO to produce H2O
CH4 and small amounts of heavier hydrocarbons. and CO2, respectively, because they are both presenting higher
As the feed concentration of iso-octane increases, an important im- electro-oxidation kinetics and better diffusion characteristics compared
provement in H2 production is observed (Fig. 2a). However, the CO for- to methane. On the other hand, the effect of anodic overpotentials on
mation rate is only slightly affected, which leads to an increase of the higher hydrocarbons (C2s and C3 +) is less pronounced. At negative
H2/CO ratio from 2 to 2.35 at Pi-C8H18 = 0.5 kPa and Pi-C8H18 = 3 kPa, re- overpotentials, the hydrogen formation rate is increased due to water
spectively. In addition, the formation rates of CH4 and C2–C4 olefins electrolysis, while for the same reason the CO2 formation rate is de-
drastically increase at H2O/C ratios below unity indicating that at creasing leading to enhanced CO formation. As far as other products
steam deficient conditions iso-octane cracking is prevailing the reaction
system. The enriched atmosphere in H2, CO, CH4 and C2–C4 is the
reason for OCV increase from −850 to −925 mV at Pi-C8H18 = 0.5 kPa Current Density, mA/cm2
16 50
and Pi-C8H18 = 3 kPa, respectively. The effect of H2O partial pressure - 29.3 - 19.6 0 5.7 9.6 13.7 16.2 19.6 25.3
Conversion of H 2O - i-C8 H 18 , %

on the products' formation rates (Fig. 2b) is rather marginal for inlet
Production Rate, 10 7 mol/sec

14
H2
steams with steam to carbon ratio above the reaction stoichiometry 40
12
(H2O/C = 1). Hydrogen formation tends to stabilize over this value
i-C8H18
and at the same time H2/CO ratio slightly decreases due to the RWGS 10
30
reaction.
8
Of crucial importance is the coke formation on the catalyst which
CO
was calculated from the carbon balance. In all cases, this amount was 6
20
found to be negligible because of the H2O presence, which via gasifica- H 2O
4 CH4
tion prevents the accumulation of carbon deposits on the electrode, in CO2 10
contrast to what has been observed during the corresponding H2O- 2 C3+
free experiments [5]. In addition, it has been demonstrated that Cu cat- C2s
alysts on redox supports, such as CeO2, exhibit enhanced tolerance to 0 0
-1000 -500 0 500 1000 1500 2000 2500 3000
coke formation due to the high oxygen mobility of the support [23].
Overpotential, mV
Finally, by performing kinetic studies at differential conditions, the
apparent activation energy of the iso-octane steam reforming reaction
Fig. 3. Dependence of the products' formation rate, i-C8H18 and H2O conversions and
was calculated and was found equal to 24.1 ± 1.5 kcal/mol, a value developed current densities on the applied cell overpotential. Pi-C8H18 = 1.5 kPa,
slightly higher compared to 17.7 ± 2 kcal/mol estimated in the work PH2O. = 12 kPa, T = 850 °C, FT = 75 cm3/min.
138 A. Al-Musa et al. / Solid State Ionics 288 (2016) 135–139

-25
are concerned, the formation rates of CH4 is increasing at negative cur-
rents, while the formation rates of higher hydrocarbons are not notably
-20
affected under both anodic and cathodic polarization conditions.
The corresponding H2/CO ratio is close to stoichiometry and is not -15
essentially affected by the applied overpotentials. Thus, the supply or 0.03Hz

- Im (Ωcm2 )
removal of oxygen anions to or from the Cu/CeO2 electrode, respective- -10
6.3 Hz
2.5 Hz 0.63 Hz 750 oC
ly, does not influence the main reaction pathways occurring at open cir-
15.9 Hz
cuit catalytic operation but it does essentially affect the amounts of H2, -5 6.3 Hz 800 oC
39.8 Hz
CO, CO2 and H2O species, and thus the equilibrium of the RWGS reac- 850oC

Z
tion. At anodic polarization, H2 and CO are electro-oxidized to H2O 0
9.1
and CO2, while at cathodic overpotentials the co-electrolysis of H2O 3.6
and CO2 to H2 and CO is taking place. 5
1.9 12.7
10
0 5 10 15 20 25 30 35 40
3.3. Fuel cell & AC impedance spectroscopy studies
Z Re (Ωcm2)
Fig. 4 depicts the fuel cell characteristics at temperatures
Fig. 5. AC impedance spectra at different cell temperatures. Pi-C8H18 = 1.5 kPa, PH2O = 12
ranging from 750 to 850 °C, at a stoichiometric iso-octane to steam kPa, FT = 75 cm3/min.
ratio (H2O/C = 1). The absolute open circuit voltage values are decreas-
ing with temperature increase varying from 925 to 907 and 869 mV at
total electrode polarization resistance, a behavior which was also no-
750, 800 and 850 °C, respectively. The slopes of the voltage–current
ticed in similar experiments when acetic acid and H2O were co-fed to
density curves are decreasing with temperature, implying that the over-
the cell [12]. On the other hand, the contribution of charge transfer pro-
all cell resistance is reduced as cell temperature increases resulting to
cesses increases with temperature being ca. 20% at 850 °C.
higher achieved power output. The maximum power density is almost
Fig. 6 presents the voltage–current density and power density–cur-
doubled by increasing the cell temperature from 750 to 850 °C and it
rent density characteristics of the cell at three different iso-octane feed
was equal to 12.7 mW/cm2 at a cell voltage of 460 mV and a current
partial pressures (0.5, 1.5 and 3 kPa), at a constant PH2O = 12 kPa and
density of 23.4 mA/cm2.
cell temperature equal to 850 °C. It is obvious that as the iso-octane/
The corresponding open circuit AC impedance spectra are shown in
H2O ratio increases the achieved electrochemical performance is en-
Fig. 5. The ohmic resistance is decreased by increasing cell temperature
hanced reaching at Pi-C8H18 = 3 kPa a maximum power density value
from 4.1 Ωcm2 at 750 οC to 1.9 Ωcm2 at 850 οC. Furthermore, the
equal to 15.2 mW/cm2 at a cell voltage of 460 mV and a current density
electrode resistance is substantially reduced from 55.1 Ωcm2 at 750 °C
of 33.0 mA/cm2. Concerning the developed OCV, a clear increase in the
to 17.3 Ωcm2 at 850 °C with an apparent activation energy equal to
absolute OCV values is observed with increasing iso-octane feed partial
26.5 kcal/mol. The feature of the AC impedance spectra is comprised
pressure. Open-circuit voltage values of 834, 864 and 914 mV are re-
of two distinct arcs, one centered at high frequencies (HF) and the
corded at 850 °C for Pi-C8H18 equal to 0.5, 1.5 and 3 kPa, respectively.
other one at lower frequencies (LF), with the latter dominating the
The corresponding open circuit AC impedance spectra (data not
polarization resistance. Based on the pseudo-capacitance values,
shown) showed that as expected the ohmic resistance is almost similar
which are in the order of 10−3 and 10−1 F.cm−2 for the HF and LF
(ca. 2 Ωcm2) and independent from the reactants ratio. On the other
arcs, respectively, it can be assumed that the HF arc is attributed to
hand, the electrode resistance and specifically the mass transport part
charge transfer and surface reaction processes, while the LF arc is
is slightly improved upon increasing the iso-octane/H2O feed ratio.
reflecting mass transfer processes of charge and/or neutral chemical
species. By further analyzing the AC impedance data it was revealed
that the charge transfer and gas diffusion components of the overall 4. Conclusions
electrode resistance follow an Arrhenius-type behavior with activation
energies equal to 36.7 and 24.7 kcal/mol, respectively. In addition, it is In the present work, the performance of an iso-octane internal steam
evident that the diffusion of charge and/or neutral species seems to pre- reforming SOFC of the type Cu-CeO2/YSZ/Pt was examined. At open-
vail the overall process contributing with approximately 80–90% to the circuit studies, the results showed that i-C8H18 was successfully

1000 12 1000 16
FT = 75 ml/min
900 Pi-C8H18 = 1.5 kPa 900
14
10
800 PH2O = 12 kPa 800 Pi-C8H18 = 3 kPa
Power density, mW/cm2

12
Power density, mW/cm2

700 700
T = 850oC
8
Voltage, mV
Voltage, mV

10
600 600
FT = 75 ml/min
500 6 500 8
T = 850oC
400 T= 800 oC 400 PH2O = 12 kPa 6
4
300 300
4
200 T = 750 o C 200
2 Pi-C 8H18 = 0.5 kPa Pi-C8H18 = 1.5 kPa
100 2
100

0 0 0 0
0 5 10 15 20 25 30 35 40 45 0 10 20 30 40 50 60
Curremt density, mA/cm2 Current density, mA/cm2

Fig. 4. Effect of operation temperature on fuel cell characteristics. Pi-C8H18 = 1.5 kPa, Fig. 6. Effect of iso-octane feed partial pressure on fuel cell characteristics. T = 850 °C,
PH2O = 12 kPa, FT = 75 cm3/min. PH2O = 12 kPa, FT = 75 cm3/min.
 A. Al-Musa et al. / Solid State Ionics 288 (2016) 135–139 139

reformed by steam and effluent mixtures rich in Η2, CO, CO2 and CH4 Kingdom of Saudi Arabia through the Management Office of Research
were produced. The effluent distribution was dominated by i-C8H18 and Development Projects.
reforming reactions, but at the same time it was slightly affected
by the reactions of thermal pyrolysis and catalytic decomposition References
of i-C8H18, as well as, by the RWGS reaction. At electrocatalytic stud-
[1] BP Statistical Overview, 2014.
ies (overpotential effect) and when O2 − were pumped to Cu-CeO2 [2] Y. Zhao, C. Xia, L. Jia, Z. Wang, H. Li, J. Yu, Y. Li, Int. J. Hydrog. Energy 38 (36) (2013)
electrode (anodic polarization), the electro-oxidation of Η2 and 16498.
CO were the prevailing processes, while during O2 − removal from [3] X.-M. Ge, S.-H. Chan, Q.-L. Liu, Q. Sun, Adv. Energy Mater. 2 (10) (2012) 1156.
[4] M. Cimenti, J.M. Hill, Energies 2 (2) (2009) 377.
Cu-CeO2 (cathodic polarization) the co-electrolysis of H2O and CO2 [5] N. Kaklidis, G. Pekridis, C. Athanasiou, G.E. Marnellos, Solid State Ionics 192 (1)
dominated the reaction scheme, influencing the equilibrium reactions (2011) 435.
carried out at anode chamber. Under both open- and closed-circuit con- [6] S. Park, R. Cracium, J.M. Vohs, R.J. Gorte, J. Electrochem. Soc. 146 (10) (1999) 3603.
[7] S.D. Park, J.M. Vohs, R.J. Gorte, Nature 404 (6775) (2004) 265.
ditions at the cell reactor, insignificant carbon formation and conse- [8] D. Szymczewska, J. Karczewski, B. Bochentyn, A. Chrzan, M. Gazda, P. Jasiński, Solid
quently stable operation of the catalyst was observed. During fuel cell State Ionics 271 (2015) 109.
operation, the power output was increased with the cell temperature [9] S. McIntosh, M. van den Bossche, Solid State Ionics 192 (1) (2011) 453.
[10] G.E. Marnellos, C. Athanasiou, S.S. Makridis, E.S. Kikkinides, in Hydrogen based Au-
and the i-C8H18/H2O feed ratio. The AC impedance analysis showed con-
tonomous Power Systems, E.I. Zoulias and N. Lymberopoulos, Editors, p. 23 Springer
tributions, both from charge and mass transfer processes. The increase in Eds., London, UK (2008).
temperature reduced the ohmic and electrode resistances with the latter [11] N. Kaklidis, G. Pekridis, V. Besikiotis, C. Athanasiou, G.E. Marnellos, Solid State Ionics
having contributions both from charge transfer (Ea = 36.7 kcal/mol) 225 (2012) 398.
[12] N. Kaklidis, V. Besikiotis, G. Pekridis, G.E. Marnellos, Int. J. Hydrog. Energy 37 (21)
and mass transport (Ea = 24.7 kcal/mol) processes. On the other hand, (2012) 16722.
the i-C8H18/H2O feed ratio affected only the electrode resistance and [13] M.H. Pihlatie, A. Kaiser, M. Mogensen and M. Chen, 189(1), 82 (2011).
more notably the mass transfer component. Overall, the diffusion of [14] J. Zhang, Y. Wang, R. Ma, D. Wu, App. Catal., A 243 (2) (2003) 251.
[15] H. He, J.M. Vohs, R.J. Gorte, J. Power Sources 144 (2005) 135.
charged and/or neutral species at the electrode surface was possibly [16] R.M. Ormerod, Chem. Soc. Rev. 32 (1) (2003) 17.
the rate limiting step during fuel cell operation at all temperatures [17] G.J. Saunders, K. Kendall, J. Power Sources 106 (1–2) (2002) 258.
examined, with the charge transfer processes being significant at higher [18] A. Faes, J.M. Fuerbringer, D. Mohamedi, A. Hessler-Wyser, G. Caboche, J. Van herle, J.
Power Sources 196 (17) (2011) 7058.
operation temperatures. [19] X. Wang, R.J. Gorte, Appl. Catal. A Gen. 224 (1–2) (2002) 209.
[20] I. Kang, J. Bae, G. Bae, J. Power Sources 163 (1) (2006) 538.
[21] P.E. Savage, J. Anal. Appl. Pyrolysis 54 (1) (2000) 109.
Acknowledgments [22] G.O. Flores Marin, H. Su, Catal. Today 136 (3–4) (2008) 235.
[23] J.J. Spivey, K.M. Dooley, Catal. 22 (2010) 279.
The authors would like to acknowledge the financial support [24] X. Wang, R.J. Gorte, Appl. Catal. A Gen. 224 (1–2) (2002) 209.
[25] J.P. Kopasz, R. Wilkenhoener, S. Ahmed, J.D. Carter, M. Krumpelt, Prepr. Symp. - Am.
provided by King Abdulaziz City for Science and Technology (KACST Chem. Soc., Div. Fuel Chem. 44 (1999) 899–908.
Grant number 671-32: Novel anodes for solid oxide fuel cells)