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Solar Energy 97 (2013) 186–194
www.elsevier.com/locate/solener

Photoreduction of carbon dioxide in the presence of H2, H2O and

CH4 over TiO2 and ZnO photocatalysts
Ghader Mahmodi a, Shahram Sharifnia a,⇑, Mohammad Madani b, Vahid Vatanpour c
a
Catalyst Research Center, Chem. Eng. Dept., Razi Univ., Kermanshah 67149-67246, Iran
b
Chem. Eng. Dept., Amirkabir University of Technology, Tehran, Iran
c
Young Researcher Club, Ardabil Branch, Islamic Azad University, Ardabil, Iran

Received 2 February 2013; received in revised form 11 August 2013; accepted 18 August 2013
Available online 12 September 2013

Communicated by: Associate Editor Gion Calzaferri

Abstract

In this study, efficiency of the prepared photocatalysts (TiO2 and ZnO) on stainless steel mesh network was examined for photore-
duction of CO2 gas. The experiments were performed under direct UV irradiation in a self-designed batch reactor. UV–visible spectra
and XRD pattern showed that crystalline structure of the particles did not change in calcinations process. Also, SEM images indicated
that semiconductors were well coated on the surface of the mesh. Conversion results showed that photoreduction of CO2 in the presence
of TiO2 photocatalyst with H2O reductant had highest conversion. However, the best conversion efficiency for ZnO was achieved in the
presence of CH4 molecules. The conversion products in the presence of CH4 as reductant can be formate and acetate derivatives, whereas
the conversion products in the presence of H2 can be assigned to the production of methane and formic derivatives.
Ó 2013 Elsevier Ltd. All rights reserved.

Keywords: Photoreduction; CO2; Zinc oxide; Titanium dioxide

1. Introduction Recent innovations in photocatalysis technology have

Carbon dioxide plays a significant role as the main con-
tributor of the greenhouse effect. The global concentration
of CO2 in the atmosphere is mainly due to the emissions
from fossil fuel combustion and its influence on climate
has recently received much attention (Lo et al., 2007).
Therefore, effective utilization of carbon dioxide and its
conversion to high-value products is one of the important
subjects which nowadays receive enough attention in order
to be developed. However, it is not easy to convert CO2 sta-
ble molecule to other useful chemicals at moderate reaction
conditions.
⇑ Corresponding author. Tel.: +98 831 4274539x284; fax: +98 831
4274542.
E-mail address: sharif@razi.ac.ir (S. Sharifnia).
made CO2 conversion a potentially promising application.
The reduction of CO2 by photocatalysts is one of the most
promising methods since CO2 can be reduced to useful
compounds by irradiating it with ultraviolet (UV) light at
the room temperature and the ambient pressure (Adachi
et al., 1994; Aurian-Blajeni et al., 1980; Koci et al., 2009;
Tseng et al., 2002). This process uses UV and/or visible
light as the excitation source for semiconductor catalysts,
and the photoexcited electrons reduce CO2 with reductants
on the catalyst surface and form energy-bearing products
(Li et al., 2010).
Several semiconductors were used as photocatalysts that
their band gap energies are suitable for the photocatalytic
reduction of carbon dioxide such as ZnS (Yoneyama,
1997), CdS (Liu et al., 1998), ZrO2 (Kohno et al., 2000),
Ga2O3 (Tsuneoka et al., 2010), MgO (Teramura et al.,
2004), NiO/InTaO4 (Wang et al., 2010) and ZnO (Gokon

0038-092X/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.solener.2013.08.027
 G. Mahmodi et al. / Solar Energy 97 (2013) 186–194
et al., 2003). These catalysts are suitable for this conversion
due to the fact that their conduction band energy (Ecb) is
sufficiently negative compared to the reduction potentials
of CO2. Although TiO2 conduction band energy is almost
equal to the reduction potentials of CO2 (e.g., the latter
is 0.24 eV for reduction of CO2 toward CH4), TiO2 is
one of the most widely employed photocatalytic semicon-
ducting materials (Osathaphan et al., 2008; Wong and
Malati, 1986; Wu et al., 2005). ZnO is a direct band gap
semiconductor with similar band gap and band edge posi-
tions as TiO2 (Gratzel, 2001). It is reported that ZnO can
reduce CO2 to oxygenated compounds using irradiation
in the presence of a reductant such as H2O under high pres-
sures of 25–35 kg/cm2 of CO2 gas (Watanabe, 1992).
The photocatalytic reduction of CO2 to CO and hydro-
carbons (such as CH4, C2H6, HCHO, CH3OH, and
HCOOH) has attracted the interest of many researchers
(Chen et al., 2013; Guo et al., 2013; Johne and Kisch,
1997; Teramura et al., 2008; Torabi Merajin et al., 2013;
Truong et al., 2012). Several researchers have reported that
the photocatalytic reduction of CO2 using gaseous H2O acts
on powdered TiO2 at the room temperature to form CO and
CH4, simultaneously (Anpo, 2013; Ikeue et al., 2002; Izumi,
2013; Lo et al., 2005; Wang et al., 2013; Yamashita et al.,
1998). When H2 is used as a reductant, the photoreduction
of CO2 forms only CO (Kohno et al., 1999).
The main aim of this work is improving the photoreduc-
tion efficiency by using TiO2 and ZnO particles coated on
stainless steel mesh as a support for conversion of CO2 to
valuable products. The net structure makes possible large
surface area for the catalyst film, allows the gas to pass
through the voids of the mesh and also good use of UV
light. The webnet was coated with particles of catalyst using
very simple and inexpensive method by immersion in slurry
of the particles. CO2 conversion was occurred in the surface
of coated mesh network in the self-designed reactor, which
UV lamp irradiated directly to the catalyst surface. Also,
the influence of different reductants (H2, H2O and CH4)
on the conversion percentage was investigated.
2. Experiment
2.1. Materials
Titanium dioxide P25 was supplied by Degussa com-
pany and ZnO (wurtzite hexagonal structure) was pur-
chased from Merck company. Stainless steel mesh with
mesh sizes of 120 was used as support. The used CO2,
H2, CH4 and He gases were ultra-high pure (99.9%). Nitric
acid (65%), ethanol (96%), hydrochloric acid (37%) and
acetone were purchased from Merck. The deionized water
was used in catalyst preparation.
2.2. Preparation of ZnO coated meshes
Immobilization of ZnO and TiO2 particles on stainless
steel meshes with minor changes was done using a simple
187
and efficient method which is ideal for industrial applica-
tion. This technique was originally developed by the scien-
tists at ECN (Netherlands Energy Research Foundation)
for deposition of TiO2 on quartz slides to prepare solar
cells (Hosseini et al., 2007). Previously, stainless steel has
been reported to be used as support for TiO2 nanoparticles
(Fernandez et al., 1995; Shang et al., 2003) which was
selected here because of its large surface area, flexibility
to be engineering, good ventilation for gases passing and
its resistance to various corrosions.
In order to coat support with titanium dioxide, first
2.5 g (±0.001 g) TiO2 powder was added to 15 mL
(±0.01 mL) ethanol as the base medium of the slurry. Eth-
anol was select as solvent due to good dispersion of TiO2
and ZnO in this solvent in a cloud-shape manner. Then,
5 mL of dilute nitric acid with a pH of 3.5 (±0.01) was
added to the slurry to supply a suitable acidity in the slurry.
As the acid is added, the slurry becomes more uniform and
its cloudiness starts to disappear.
To coat supports with ZnO, the same above mentioned
method was applied with difference in amount of precur-
sor. 1.7 g (±0.001 g) of zinc oxide was added to 20 mL eth-
anol and, at the second step, 7 mL (+0.01 mL) of dilute
nitric acid with a pH of 3.5 (±0.01) was added to the slurry.
Because of the higher density of ZnO than TiO2 nanopar-
ticles, amount of coating of ZnO in the same concentration
will be more than TiO2 and comparison of photocatalysts
will be incorrect. Therefore, we used less amount of ZnO
than TiO2. In both prepared catalyst, 0.4 g (±0.001 g) par-
ticles were coated on the surface of 415 cm2 (±0.1 cm2)
mesh network.
The prepared slurry was sonicated for 30 min for suit-
able dispersion of powders and obtaining more uniform
slurry. Next, stainless steel mesh was immersed into the
slurry. The mesh was previously formed in cylindrical
shape and cleaned with hydrochloric acid, acetone and dis-
tilled water to remove any organic and inorganic material
attached to or adsorbed on the surface and dried under
atmospheric conditions. Contact time for slurry adsorption
by stainless steel mesh was 1 min. Then, the mesh was put
in an oven for 12 h at 120 °C (±1.0 °C) for drying. In the
final stage of coating process, calcination was done through
furnace at 350 °C (±1.0 °C) for 30 min.
2.3. Instruments and analytical procedures
Fourier-transform infrared spectroscopy (FTIR) was
recorded using MB160 FTIR spectrometer (ABB Bomem
Inc., Canada) with special designed cell to characterize
photoreduction products in gas phase. The designed cell
made of cylindrical quartz with 3.5 cm (±0.01 cm) diameter
and 10 cm (±0.01 cm) in length was closed with two Pyrex
disks, which had two KBr tablets with 1.2 cm (±0.01 cm)
diameter in center. Two inlet and outlet valves were
adapted to filling the cell with gas. For analysis of the prod-
ucts, after certain period of time, the converted gas output
photoreactor was directed to the spectrophotometer.
188 G. Mahmodi et al. / Solar Energy 97 (2013) 186–194
XRD patterns of samples were recorded using EQUI-
NOX diffractometer (Inel Company) operating with a Cu
anode and a sealed X-ray tube. The 2h scans were recorded
at several resolutions using Cu Ka radiation of wavelength
1.548 Å in the range 20–80 with 0.05 step size. Also, scan-
ning electron microscope (SEM) was utilized (Philips, XL-
30), in order to probe ZnO coated on the surface of stain-
less steel meshes. The coated mesh samples were coated
with a thin layer of gold before scanning for producing
electric conductivity and viewed with the microscope at
17 kV.
A Hewlett–Packard 8453 diode-array UV–vis spectro-
photometer equipped with a 1.0 mm (±0.1 mm) path
length quartz micro-cell and controlled by a computer
was applied for ultraviolet spectra acquisition. And, quan-
titative determination of photocatalyst products was done
using on-line commercial gas chromatograph GC-CGCA-
1 apparatus equipped with a thermal conductivity detector
(TCD). These analyses were performed isothermally at
50 °C using a parallel setup of two packed columns (Molec-
ular sieve and Porapak Q).
2.4. Photocatalytic reaction test
In order to assess the photocatalytic efficiency of the
prepared catalysts, photoreduction of the CO2 gas under
UV illumination was investigated. Experiments were car-
ried out in photocatalytic reactor made of steel. Batch pho-
tocatalytic reactor was designed and built in the
laboratory. The photoreactor, comprised of coated parti-
cles over the stainless steel mesh, was assembled to transmit
and spread light uniformly. The schematic of experimental
set-up is shown in Fig. 1.
The cap of mesh photoreactor was scaled using O-rings
and checked if there was leakage. At the next step, the reac-
tor was vacuumed and then it was filled in by gaseous feed
(CO2, CH4, H2 and He). Total inner volume of reactor was
1.0 L (±0.01 L). Before starting the reaction, the gas feed
concentration was analyzed through using on-line GC
(equipped with a TCD detector), and then it was illumi-
nated by UV lamp for 5 h continuously. After that, it
was illuminated by UV lamp for maximum 5 h continu-
ously and the products were analyzed through using on-
line GC and gas cell. A 125 W high pressure mercury lamp
was used as the light source. The photocatalytic activity
was calculated on the basis of CO2 conversion, formulated
as follows (Eq. (1)):
ðMole of COi2  Mole of CO2 Þ
Conversion of CO2 ð%Þ ¼
Mole of COi2
 100
ð1Þ
where COi2 and CO2 are the concentration of CO2 at the
beginning and in different time of the reaction, respectively.
Based on the calculation of the carbon balance, the abso-
lute error of the CO2 conversion is less than 3.7%.
3. Results and discussions
3.1. Characterization of the prepared photocatalysts
The stainless steel mesh were coated with ZnO and TiO2
particles by a very simple and inexpensive method. For
suitable immobilization and to increase durability of ZnO
on the support, particles were calcinated after coating on
the mesh surface. The optimum calcination temperature
(350 °C) was selected from literature that showed more
increasing of temperature with increasing of the particle
size (Hariharan, 2006; Jing et al., 2001).
It is reported that size of particles can be reduced
depending on the calcination method (Jing et al., 2001),
which it increases surface area of catalyst. The calcination
leads to decrease in agglomeration and uniform distribu-
tion of particles, and consequently, increase in the active
surface of catalysts (Suna et al., 2009).
Fig. 2 shows the UV–vis absorption spectra of the ZnO
and TiO2 at room temperature. These calcinations lead to
improvement of absorption intensity of the calcinated
photocatalysts. Also, the calcinations cause shifting of
absorption peak to visible area, especially in TiO2 particles.
It can be concluded that the calcinated ZnO photocatalyst
had a broad absorption band from ultraviolet to visible
region. The maximum absorption peak was found at 330
and 387 nm for TiO2 and ZnO, respectively. However,
the commercial ZnO and TiO2 showed weaker absorption
in the whole region.
The good performance for the absorption of UV–vis
light by the calcinated photocatalysts can be attributed to
its uniform structure (Suna et al., 2009). The uniform sur-
faces of calcinated photocatalysts can enhance the light
absorption but the commercial ZnO and TiO2 are easy to
agglomerate. The uniform structures of calcinated photo-
catalysts were shown in Fig. 3 using SEM images. Compar-
ison of the calcinated ZnO (Fig. 3(a)) and TiO2 (Fig. 3(c))
structures with commercial ZnO (Fig. 3(b)) and TiO2
(Fig. 3(d)) showed that agglomeration of the particles
was reduced by the calcination technique.
On the basis of the maximum absorption wave, the band
gap of the prepared calcinated ZnO and TiO2 photocata-
lysts can be estimated to be 3.204 and 3.758 eV, respec-
tively, according to Eq. (2) (Suna et al., 2009):
1240
Ebg ¼ ðeVÞ ð2Þ
k
where Ebg is the band-gap energy of the photocatalyst and
k is the maximum wavelength in nanometer.
To investigate the quality of coatings from the structural
aspect, i.e. whether or not ZnO and TiO2 crystals have
found obvious changes in structural properties and crystal-
lite size during the calcination process, X-ray diffraction
(XRD) patterns of the coated samples was assessed.
Fig. 4 shows XRD patterns of photocatalysts before and
after calcinations. The XRD results did not show any
 G. Mahmodi et al. / Solar Energy 97 (2013) 186–194
Fig. 1. Schematic of experimental set-up.
Fig. 2. UV–vis spectra of commercial and calcinated photocatalysts (a)
ZnO and (b) TiO2.
significant changes in the structure of photocatalysts as a
consequence of the calcination and coating processes.
It was concluded that the calcination process did not
have significant influence on crystalline morphologies of
189
photocatalysts particles. No perceptible impurities can be
recognized in the graphs. This is important for the stainless
steel mesh coating, since iron impurities caused by heating
the steel could have a negative effect on the photocatalytic
efficiency of the catalyst. It has been reported that Fe3+ ions
present in TiO2 coated steel plates heated at 600 °C and
more, but not at lower temperatures (Chan et al., 2002).
Morphology of prepared catalysts and stainless steel
mesh were determined by SEM. The images were used to
show how photocatalysts were coated on/in mesh network.
As shown in Fig. 5, uncoated mesh (Fig. 5(a)), and cata-
lysts coated on mesh of TiO2 (Fig. 5(b)) and ZnO
(Fig. 5(c)) were immobilized in a good state between woven
fabrics of mesh, and gases could easily pass from
photocatalysts.
3.2. Photocatalytic activity
The photoreduction of CO2 was performed in the self-
designed gas-phase batch reactor system to investigate
the influence of the reductant types on the efficiency of
CO2 conversion (Fig. 6). Comparison of photocatalyst
types shows that titanium dioxide has better photoreduc-
tion activity. In addition, in TiO2 coated mesh, the best
conversion percentage of CO2 was reached in the presence
of H2O molecules. However, the best results for ZnO cata-
lyst was obtained in the presence of methane molecules.
3.3. Characterization of converted products
Direct conversion of carbon dioxide in the presence of
H2, H2O and CH4 to oxygenated compounds was carried
190 G. Mahmodi et al. / Solar Energy 97 (2013) 186–194
Fig. 3. Surface SEM images of (a) calcinated ZnO, (b) commercial ZnO, (c) calcinated TiO2, and (d) commercial TiO2.
(a)
Calcinated ZnO
Commercial ZnO
(b)
Calcinated TiO 2
Commercial TiO2
Fig. 4. The XRD of commercial and calcinated photocatalysts: (a) ZnO
and (b) TiO2.
out over immobilized ZnO coated on stainless steel meshes
(Fig. 7). The converted products were characterized using
FTIR with special designed cell to identify photoconverted
products in gas phase. Fig. 7(a) shows the IR spectra in the
presence of CH4 as reductant for conversion of CO2 over
immobilized ZnO coated on stainless steel meshes. For
gas feed, only three distinct peaks were observed. The
peaks at 1303 and 3016 cm1 correspond to the CAH
stretch in methane (Huang et al., 2001). The peak at
2360 cm1 corresponds to the O@C@O stretch in carbon
dioxide (Zhang et al., 2010). No other peaks were observed,
indicating that no reaction occurred between CH4 and CO2
in the presence of photocatalysts without irradiation. In the
case of using CH4 as a reductant new bands in the region of
2600–3000 and 1200–2000 cm1, and in the range of 2600–
3000 cm1, and six bands at 2958, 2927, 2885, 2825, 2806,
and 2738 cm1 were observed. These peaks can be assigned
to characteristic absorption band of methyl symmetric
CAH stretching (2958 cm1), methyl asymmetric CAH
stretching (2885 cm1), and the bands between 2700 and
2900 cm1 can be attributed to aldehyde and ketone
CAH stretching or methylene symmetric and asymmetric
CAH stretching (He and Ekerdt, 1984; Silverstein et al.,
1991; Teramura et al., 2004).
In the range of 1200–2000 cm1, new bands appeared at
1754, 1716, 1683, 1652, 1616, 1575, 1558, 1541, 1458, 1436,
1396, 1365, 1355, and 1342 cm1. Appearance of these var-
ious peaks can be attributed to different compound groups
such as aldehyde, ketone and carboxylic acid. However,
with regarding presented mechanisms in literature (Shi
et al., 2004; Kohno et al., 2000; Tanaka et al., 2000; Teram-
ura et al., 2004; Yuliati et al., 2008) for conversion of CO2
using CH4 as a reductant on the semiconductor photocat-
alysts, the peaks can be assigned to production of formic
and acetic acid derivatives.
The bands at 1616, 1541, 1458, 1396, 1355 cm1 are
assigned to tas(OCO), r(CH), and ts(OCO), respectively,
indicating the formation of formate species (Kiss et al.,
2004; Martin et al., 1992; Shi et al., 2004) . The band at
1683 cm1 can be assigned to the stretching of HCO3 (Kiss
et al., 2004). In contrast, it was anticipated that the other
bands were derived from the acetate. The spectra related
 G. Mahmodi et al. / Solar Energy 97 (2013) 186–194
Fig. 5. SEM images of photocatalysts coated on mesh: (a) uncoated mesh,
(b) TiO2, and (c) ZnO.
to acetic acid were observed at 1558 and 1436 cm1. The
band at 1558 cm1 can be correlated to a CAO symmetric
vibration mode (Teramura et al., 2004). The bands at 1436,
1365, and 1342 cm1 are assigned to a CAH deformation
vibration mode: ras(CH3), r(CH), and ra(CH3), respec-
tively (Natal-Santiago et al., 1999). Consequently, the spe-
cies produced on the surface of ZnO can be formate and
acetate derivatives. Similar to the ZnO photocatalyst, the
efficiency of TiO2 coated mesh in photoreduction of CO2
and CH4 and the conversion products in gas phase were
studied by Torabi Merajin et al. (2013). Similar results have
been reported from the identified products (Torabi Merajin
et al., 2013).
191
H2 H2 O (H2O+H2) CH4
Fig. 6. Conversion percentage of CO2 in the presence of different
reductants after 5 h.
Fig. 7(b) shows the IR spectra in the presence of H2 as a
reductant for the conversion of CO2 over immobilized ZnO
coated on the stainless steel meshes. For gas feed, only
three distinct peaks were observed. The peaks at 1340
and 2865 cm1 can be corresponded to the HAH stretch
in hydrogen (Tsuneoka et al., 2010). The peak at
2360 cm1 can be related to the O = C = O stretch in car-
bon dioxide (Zhang et al., 2010). No other peaks were
observed, indicating that no reaction occurred between
H2 and CO2 in the presence of photocatalysts without
irradiation.
New bands at 2951, 2832, and 2741 cm1 appeared in
the region of 2700–3000 cm1 under photoirradiation.
These bands are assigned to a CAH stretching vibration
band t(CH) which can be related to the produced methane
(Lo et al., 2007; Natal-Santiago et al., 1999; Teramura
et al., 2004). In the region of 1800–1250 cm1, the new
bands appeared at 1682, 1662, 1639, 1591, 1454, 1442,
1387, 1362, 1316 cm1. The bands at 1591, 1442,
1362 cm1 are assigned to tas(OCO), r(CH) and ts(OCO),
respectively (Kiss et al., 2004; Martin et al., 1992; Teram-
ura et al., 2004), whereas the bands at 1662, 1639, and
1316 cm1 are assigned to a bidentate carbonate and the
bands at 1682, 1454, and 1387 cm1 are corresponded to
a bicarbonate (Teramura et al., 2004). Consequently,
regarding the presented mechanisms in literatures (Tanaka
et al., 2000; Teramura et al., 2004; Tsuneoka et al., 2010),
for the conversion of CO2 using H2 as a reductant on the
surface ZnO, the peaks can be assigned to the production
of formic (formate) derivatives.
The reason for more conversion of CO2 with CH4 in
comparison with its conversion with H2 can be related to
the production of acetate in addition to formate deriva-
tives, while, only formate derivatives are produced in appli-
cation of H2 as a reductant. Fig. 7(c) shows the IR spectra
in the presence of H2O as reductant. The variations illus-
trates that new bands appears in 1560, 1540, 1510, 1480,
1340, 1120, 1050, 1750, 1718, 1687, 1652 and 1770 cm1.
These peaks could be attributed to carbonyl groups com-
ponent like aldehyde, ketone and aliphatic ether. Also, in
192 G. Mahmodi et al. / Solar Energy 97 (2013) 186–194
(a)
240 min
120 min
30 min
Feed
(c)
240 min
120 min
30 min
Feed
Fig. 7. FTIR spectra of CO2 photoreduction in the presence of (a) CH4, (b) H2, (c) H2O, and (d) (H2O + H2) on calcinated ZnO coated on stainless steel
mesh under UV irradiation.
the region of 2800–3000 cm1 new bands appears at 2865
and 2960 cm1. These bands are assigned to alkane groups
(methyl) methyl symmetric CAH stretching (2958 cm1)
and methyl asymmetric CAH stretching (2865 cm1). The
CAH bonds attraction is a function of hybridization type
(Teramura et al., 2004). However, paying attention to the
presented mechanisms in literature (Lo et al., 2007; Slamet
et al., 2009; Wu and Huang; 2010) for conversion of CO2
using H2O as a reductant on the semiconductor photocat-
alysts, the peaks can be assigned to production of formate
and methoxy derivatives.
Furthermore, in the range of 3000–3500 cm1, the new
band appeared at 3300 cm1 can be attributed to the triple
bond of acetylene. In the range of 3300–3400 cm1 a broad
peak appeared can be attributed to the bond OAH, as the
hydrogen bond is very strong (Slamet et al., 2009). A very
weak band in 3430 cm1 can be seen that is related to the
carbonyl group. Considering this peak, it is predicted that
the final product can be methanol (Slamet et al., 2009; Wu
and Huang, 2010).
Fig. 7(d) shows the IR spectra in the presence of
(H2O + H2) as a reductant. New bands at 2965 and
2858 cm1 appeared in the region of 2700–3000 cm1
under photoirradiation. The bands at 2965 cm1 is
assigned to a CAH stretching vibration band t(CH), and
its higher intensity can be related to the produced methane
(Lo et al., 2007; Martin et al., 1992; Natal-Santiago et al.,
(b)
240 min
120 min
30 min
Feed
(d)
240 min
120 min
30 min
Feed
1999; Teramura et al., 2004), while the weak peak at
2858 cm1 is assigned to t(CH3) that can lead to the pro-
duction of C2H6 (Lo et al., 2007).
In the region 1800–1250 cm1, new bands appeared at
1687, 1666, 1637, 1594, 1451, 1440, 1389, 1366, and
1319 cm1. The bands at 1594, 1440, 1366 cm1 are
assigned to: ras(CH3), r(CH), and rs(CH3), respectively
(Martin et al., 1992; Natal-Santiago et al., 1999), whereas
the bands at 1666, 1637, and 1319 cm1 are assigned to a
bidentate carbonate and the bands at 1687, 1451, and
1389 cm1 are assigned to a bicarbonate (Teramura
et al., 2004). It is clear that the peaks are almost similar
to the peaks when using H2 as reductant and the only dif-
ference is that the utilized H2O increases acceleration in
products achievement.
4. Conclusion
In this study, the ZnO and TiO2 particles were coated
on mesh as a support by a very simple and inexpensive
method. The calcination leads to decrease in agglomera-
tion and uniform distribution of particles, and conse-
quently, increases the active surface of catalysts. The
XRD results did not show any significant changes in the
structure of photocatalysts as a consequence of the calci-
nation and coating processes. It was concluded that the
calcination process has not significant influence on
 G. Mahmodi et al. / Solar Energy 97 (2013) 186–194
crystalline morphologies of photocatalysts particles. The
obtained CO2 conversion percentage shows that titanium
dioxide has better photoreduction activity. In addition, in
TiO2 coated mesh, the best conversion percentage of CO2
was reached in the presence of H2O molecules. However,
the best results for ZnO catalyst was obtained in the pres-
ence of methane molecules. The conversion products in
the presence of CH4 as reductant can be formate and ace-
tate derivatives. The converted products in the presence of
H2 as reductant can be assigned to the production of
methane and formic (formate) derivatives. Also, for con-
version of CO2 through using H2O as a reductant on
the semiconductor photocatalysts, the peaks can be
assigned to the production of methanol, formate and
methoxy derivatives. The IR spectra showed that the con-
verted products in the presence of (H2O + H2) as reduc-
tant can be methane and ethane.
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