Mohammed Jaber F.

Al Marri and Fadwa El Jack (Editors), Proceedings of the

4th International Gas Processing Symposium, October 26–27, 2014 , Doha, Qatar.
© 2015 Elsevier B.V. All rights reserved.

Thermochemical Conversion of CO2 into Solar

Fuels Using Ferrite Nanomaterials
Rahul R. Bhosale,a,* Dareen Dardor,a Shahd S. Gharbia,a Jamila Folady,a
Mehak Jilani,a Anand Kumar,a Leo L. P. van den Broeke,a Fangjian Lin,b
Ivo Alxneitb
a
Department of Chemical Engineering, College of Engineering, Qatar University,
PO Box 2713, Doha, Qatar.
b
Solar Technology Laboratory, Paul Scherrer Institute, CH-5232 Villigen PSI,
Switzerland.
*Corresponding Author: rahul.bhosale@qu.edu.qa

Abstract
This paper reports the synthesis of NixFe3-xO4 nanoparticles via sol-gel
method. For NixFe3-xO4 synthesis, the Ni and Fe precursor salts were
dissolved in ethanol and propylene oxide (PO) was added dropwise to
the well mixed solution achieve gel formation. As-prepared gels
were aged, dried and subsequently calcined upto 600oC in air. The calcined
powders were characterized by powder x-ray diffractometer (XRD), BET
surface area, as well as scanning (SEM) and transmission (TEM) electron
microscopy. The derived NixFe3-xO4 nanoparticles were further examined
towards thermochemical conversion of CO2 into solar fuels by performing
several reduction/re-oxidation cycles using a thermogravimetric analyzer
(TGA).

Keywords: Solar Fuels, CO2 Conversion, Sol-Gel Method, Ferrites,

Nanomaterial, and Thermochemical Reactions

1. Introduction
The extensive utilization of fossil fuels led to a rapid depletion of the
easily accessible oil reserves resulting in continuously rising oil prices.
Furthermore, combustion of fossil fuels is believed to be one of the major
causes of increase in the CO2 concentration level in the environment.
The increase in CO 2 emission into the environment is of serious concern
for future because of CO 2 being a major contributor to the greenhouse
gases [1-2]. Since the atmospheric concentration of CO2 is shown to
directly affect the climate temperature [3 -4], search for carbon neutral
142 Bhosale et al.

alternative energy sources is growing along with ways to reduce the

atmospheric CO 2 concentration.
To overcome the problems related to the continuously rising of oil
prices and global warming due to the CO2 induced greenhouse effect, as one
of the promising alternatives, the liberated CO 2 can be re-energized into
CO via metal oxide (MO) based thermochemical looping process using
concentrated solar energy. The C O produced via solar thermochemical
CO 2-splitting can be combined with H2 derived from MO based solar
thermochemical H 2O-splitting process to produce solar syngas which can
be further processed to liquid fuels such as methanol, diesel, and jet fuel
via the Fischer-Tropsch process [5]. Production of solar fuels via MO
based thermochemical reactions is a two-step process. In the first step, the
MO is reduced into a lower valence MO or metal with the help of solar
energy. The reduced MO is further re-oxidized in the second step via
H2O and/or CO2 splitting reactions.
Among the many MOs investigated so far for solar fuel production,
in recent years, research has been focused towards non-volatile mixed
MOs such as ferrites [6-19]. Ferrites are particularly appealing as their
reduced form is a solid and hence the separation of a gaseous metal
(or MO) and O 2, a challenging and compulsory step in cycles based
on ZnO/Zn or SnO2/SnO/Sn, can be eliminated. Previously, ferrites were
considerably used for solar H 2 production [6-16], while their utilization for
solar CO or syngas production is very limited [17-19].
In this paper, synthesis of NixFe3-xO4 (where, x = 0.2 to 1)
nanoparticles using sol-gel method is presented. Sol-gel synthesized
NixFe3-xO4 powders were further characterized by using powder x-ray
diffractometer (XRD), BET surface area analyzer, scanning (SEM) and
transmission electron microscopy (TEM), and an inductively coupled
plasma spectrometer (ICP). Furthermore, NixFe3-xO4 powders were
examined towards their thermal reduction and CO 2 splitting ability by
performing successive thermochemical cycles using a thermogravimetric
analyzer (TGA). A typical Ni xFe3-xO4 based two-step solar thermochemical
CO2 splitting process is depicted in Figure 1.
Thermochemical Conversion of CO2 into Solar Fuels 143

Figure 1. NixFe3-xO4 based solar thermochemical CO2 splitting process.

2. Experimental
2.1 Synthesis of NixFe3-xO4
For the synthesis of NixFe3-xO4 via sol-gel method, the nitrate salts of Ni
and Fe were added in ethanol and this mixture was sonicated to dissolve the
metal salts in the solvent. To this solution obtained after sonication,
predetermined amount of propylene oxide (PO) was added dropwise and the gel
formation was achieved. For instance, a picture of a typical NixFe3-xO4 gel
prepared via sol-gel method is shown in Figure 2. As-prepared gels were aged
for 24 h, dried at 100oC, and then heated up to 600oC and cooled down
rapidly in air. Various combinations of NixFe3-xO4 were synthesized such as
Ni0.2Fe2.8O4 (NF2), Ni0.4Fe2.6O4 (NF4), Ni0.5Fe2.5O4 (NF5), Ni0.6Fe2.4O4 (NF6),
Ni0.8Fe2.2O4 (NF8), and NiFe2O4 (NF10).
144 Bhosale et al.

Figure 2. NixFe3-xO4 gel synthesized via sol-gel method.

2.2 Characterization of Ni xFe3-xO4

Phase purity, crystallite size, morphology, specific surface area, and
elemental composition of the sol-gel derived ferrite powders were
analyzed using a Panalytical XPert MPD/DY636 powder X-ray diffractometer,
a Zeiss Supra 55VP field-emission scanning electron microscope (SEM), a FEI –
Tecnai G2 200kV transmission electron microscope (TEM), a BET surface area
analyzer (Micromeritics, ASAP 2420), and an ICP (Thermo, iCAP 6500).

2.3 Thermochemical CO2 Splitting Set-ups and Operating Procedure

Thermal reduction and CO2 splitting ability of the sol-gel derived
NixFe3-xO4 materials was examined by using a thermogravimetric analyzer
(TGA, Netzsch STA 409). Approximately 50 mg of ferrite powder was
placed inside an Al2O3 crucible and was subjected to multiple thermal
reduction (1400oC) and CO2 splitting (1000oC) cycles. During the thermal
reduction step, the ferrite powder was heated upto 1400oC and maintained
at this temperature for 60 min in an inert Ar atmosphere (100 ml/min). The
mass loss observed after 1000oC was directly correlated towards O2 released
by the ferrite material due to the thermal reduction. Once the thermal
reduction was carried out for 1h, the temperature was lowered to 1000oC to
perform the CO2 splitting reaction. CO2 was injected (100 ml/min,
Ar : CO2 = 1:1) once the targeted reaction temperature was reached and the
CO2 splitting reaction was performed at isothermal conditions for 30 min. The
variation in the mass of the sample was directly correlated to the O2
release (mass loss) during thermal reduction step or to CO produced
Thermochemical Conversion of CO2 into Solar Fuels 145

(mass gain) during the CO2 splitting step. Furthermore, the gases exiting the
TGA were continuously analyzed via a gas chromatograph (GC, VARIAN,
CP-4900, Micro GC 2 channel system).

3. Results and Discussion

The compositional purity of the synthesized Ni x Fe3-xO4 materials was
analyzed using a powder XRD and the corresponding XRD patterns
are shown in Figure 3. Sol-gel derived Nix Fe3-xO4 materials indicate strong
reflections and a well-defined spinel cubic structure with high degree of
crystallinity. Reflections that could be attributed to impurities such as
precursors, NiO, or metallic Ni were absent which further confirm
the formation of phase pure NixFe3-xO4 materials. Due to the substitution of the
Ni ions in the Fe3O4 spinel structure, a successive shift in the diffraction
patterns of the NixFe3-xO4 materials was observed. The elemental composition
of the synthesized NixFe3-xO4 materials was further confirmed with the help of
ICP analysis.
Intensity Counts (a.u.)

NF10
NF8
NF6
NF5
NF4
NF2

2θ
Figure 3. XRD patterns of sol-gel derived Nix Fe3-x O4.

Size of the single crystalline domains of sol-gel derived NixFe3-xO4 redox

materials were calculated by using Scherrer equation. This quantitative analysis
indicate slight decrease in the crystallite size of the Ni xFe3-xO4 with the
increase in the degree of substitution of Ni in the ferrite spinel structure.
Typically, the crystallite size for different Ni xFe3-xO4 materials was observed to
be in the range 24 to 34 nm. The SEM and TEM analysis further confirm the
nanoparticle morphology of the sol -gel derived NixFe3-xO4 materials. As an
example, SEM and TEM pictures of NF10 are shown in Figure 4. The
146 Bhosale et al.

specific surface area of the sol -gel derived NixFe3-xO4 obtained after
calcination at 600oC was observed to be in the range of 35 to 40 m2/g.
Thermochemical CO production ability of the derived Ni xFe3-xO4 redox
materials was investigated by performing multiple thermal reduction and
CO2-splitting cycles using a high temperature thermogravimetric analyzer.
Befor performing the thermochemical experiments by using the derived NixFe3-xO4
materials, a baseline run was conducted under identical experimental
conditions in absence of the ferrite powder (using empty Al2O3 crucible). This
allows subtracting artifacts due to buoyancy effects or caused by changing the
gas composition.

a) b)

20 nm

Figure 4. a) SEM and b) TEM image of sol-gel derived NF10 redox material.

Figure 5. CO2 -splitting experiments performed using sol-gel derived NF8.

Thermochemical Conversion of CO2 into Solar Fuels 147

Thermal reduction and thermochemical CO 2 -splitting ability of the

sol-gel derived Nix Fe3-xO4 materials was examined by performing four
successive thermochemical cycles in the temperature range of 1000 oC to
1400o C. For instance, the thermogravimetric mass loss during thermal
reduction step and as gain during CO2 -splitting step in case of NF8
material is shown in Figure 5. The temperature is reported as blue line
while the weight change of the NF8 sample is reported in red color. As
shown in Figure 5, the redox capacity of the NF8 material does not
deteriorate i.e. approximately the same mass loss and mass gain is
observed in all cycles. During first th e r ma l reduction step, a
disproportionally large weight loss occurs due to the desorption of
physisorbed water from the NF8 sample

According to the results obtained via TGA experiments, the % mass loss
during the 1st thermal reduction step was much higher in case of NF2, NF4,
and NF5 as compared to the other Ni xFe3-xO4 materials. However, the
thermal reduction ability of NF10 (% mass loss) was observed to be the
highest and constant during the 2 nd, 3rd, and 4th thermochemical cycles.
Likewise, the re - oxidation ability (% mass gain) was again observed to be
maximum in case of NF10 material as compared to other NixFe3-xO4
materials. The average thermal reduction and CO 2-splitting ability of the
derived NixFe3-xO4 redox materials during 2 nd, 3rd, and 4th thermochemical
cycles was observed to be in the order of NF10 > NF8 > NF6 > NF5 > NF4 >
NF2. The obtained results indicate that the NF10 material performs best
when compared with the other sol-gel derived NixFe3-xO4 materials and also
with ceria based redox materials investigated previously [20-23].

4. Conclusions
In this investigation, Ni x Fe3-xO4 (where, x = 0.2 to 1) redox
materials were successfully synthesized via sol -gel method by using
nitrate salts of Ni, and Fe, ethanol as solvent, and PO as gelation
agent. The XRD analysis confirms the phase pure formation of Ni xFe3-
x O4 materials with high degree of dopant incorporation in the ferrite
spinel structure and with no impurities. Quantitative XRD and SEM/TEM
analysis reveal nanocrystalline morphology of the derived Ni xFe3-xO4. As-
synthesized ferrite powders were further investigated for their use in
thermochemical CO2 -splitting and thermal reduction cycles in the
temperature range 1000 oC to 1400oC using a Thermogravimetricv
analyzer. The results obtained indicate that the stoichiometric NiFe 2 O4
(NF10) generates the highest amounts of O 2 and CO when compared to
the other ferrites examined in this study and other nonvolatile redox
materials such as ceria based oxides investigated previously.
148 Bhosale et al.

5. Acknowledgements
The authors gratefully acknowledge the financial support provided by the
Qatar University Internal Grant (QUUG-CENG-CHE-13/14-4), Indo-Swiss
Joint Research Program (ISJRP, grant #138852), and the Swiss Federal
Office of Energy (SFOE).

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