Applied Catalysis A: General 467 (2013) 483–496

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Applied Catalysis A: General

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

Photocatalytic CO2 reduction and kinetic study over In/TiO2

nanoparticles supported microchannel monolith photoreactor
Muhammad Tahir 1 , NorAishah Saidina Amin ∗
Low Carbon Energy Group/Chemical Reaction Engineering Group (CREG), Faculty of Chemical Engineering, Universiti Teknologi Malaysia, 81310 UTM
Skudai, Johor Baharu, Johor, Malaysia

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

Article history: In this study, a microchannel monolith photoreactor was investigated for photocatalytic CO2 reduc-
Received 9 March 2013 tion with H2 O in gaseous phase using TiO2 and indium doped TiO2 nanoparticles. Effects of
Received in revised form 25 July 2013 operating parameters such as monolith geometry, reaction temperature, indium loading and feed
Accepted 27 July 2013
ratios were investigated to maximize yield rates. CO and CH4 were the main products with max-
Available online 17 August 2013
imum yield rates being 962 and 55.40 ␮mol g-catal.−1 h−1 , respectively and selectivity being 94.39
and 5.44%, respectively. The performance of the photoreactor for CO production was in the order
Keywords:
of In/TiO2 -monolith (962 ␮mol g-catal.−1 h−1 ) > TiO2 -monolith (43 ␮mol g-catal.−1 h−1 ) > TiO2 -SS cell
Photocatalysis
Monolith photoreactor
(5.2 ␮mol g-catal.−1 h−1 ). More importantly, the quantum efficiency in microchannel monolith reactor
CO2 reduction was much higher (0.10%) than that of the cell type reactor (0.0005%) and previously reported internally
In/TiO2 nanoparticles illuminated monolith reactor (0.012%). The significantly improved quantum efficiency indicated pho-
Kinetic model ton energy was efficiently utilized in the microchannel monolith reactor. A simple kinetic model based
on Langmuir-Hinshelwood model, developed to incorporate coupled effect of adsorptive photocatalytic
reduction and oxidation process, fitted-well with the experimental data.
© 2013 Elsevier B.V. All rights reserved.

1. Introduction perfect candidate for the photocatalytic processes, are reasonably

Global warming, primarily due to increasing level of carbon
dioxide (CO2 ) emission from fossil fuels combustion, has aroused
considerable concerns [1,2]. Therefore, technologies pertinent to
carbon management, which not only mitigate global tempera-
ture, but also meet increasing energy demands, are high in the
priority list [3]. Photocatalytic CO2 reduction with H2 O is of signif-
icance importance for production of hydrocarbon fuels and value
added chemical such as CO, CH3 OH, CH4 , HCOOH and HCHO. It is
highly potential for reducing CO2 emissions and partly for resolving
energy crises [4,5]. However, lower photocatalytic CO2 reduction to
hydrocarbon fuels has been reported during the last decades. Under
such circumstances, efficient photocatalytic reactors that can emi-
nently enhance CO2 conversion and yield rates are inevitable.
Among various semiconductors available, the focus has been
on the extensively researched titanium dioxide (TiO2 ) as a photo-
catalyst. Some of the encouraging advantages of TiO2 , making it a
∗ Corresponding author. Tel.: +60 7 553 5579; fax: +60 7 5588166.
E-mail addresses: bttahir@yahoo.com (M. Tahir), noraishah@cheme.utm.my,
profnoraishah@yahoo.com (N.S. Amin).
1
Permanent address: Department of Chemical Engineering, COMSATS Institute
of Information Technology Lahore, Punjab, Pakistan.
cheap, good photoactivity, and widely available. It is also chem-
ically/thermally stable, non-toxic, and possesses higher oxidative
potential [6,7]. However, TiO2 is photoactive only under UV light
irradiations due to its wide band gap (3.2 eV). It also exhibits lower
CO2 conversion efficiency due to immediate recombination of pho-
togenerated charges. In order to enhance photocatalytic efficiency
of TiO2 , it is necessary to modify its surface to enhance recombi-
nation time of electron–hole pairs. The addition of metals and/or
sensitizers to TiO2 could alter TiO2 band gap to effectively prevent
recombination of photogenerated electron–hole pairs [8–10].
For the last few years, different types of metals and non-
metals together with lower band gap and/or mesoporous materials
have been investigated to improve TiO2 photocatalytic activ-
ity under UV and/or visible light irradiations. The most widely
researched materials include Ag/TiO2 [11], Pt/TiO2 [12] iodine/TiO2
[13], Cu/TiO2 [14], Rh/TiO2 [15], Cu-iodine/TiO2 [16], FeTiO3 /TiO2
[17], kaolinite/TiO2 [18], MMT/TiO2 [19], AgBr/TiO2 [20], Ti-
MCM-41 and Ti-MCM-48 [21], nitrogen-iron/TiO2 CoPc/TiO2
[22], N-TiO2 nanotubes [23], CeO2 -TiO2 [24], CdSe/Pt/TiO2 [25],
PbS/TiO2 [26], Cu-CdS-TiO2 /SiO2 [26,27], and CdS/Bi2 S3 /TiO2 nano-
tubes [3]. Furthermore, Poznyak et al. [28] investigated the
photo-electrochemical properties of nanocrystalline In2 O3 /TiO2
composites. It was observed that In2 O3 in TiO2 endorsed efficient
separation of photogenerated electron–hole pairs. In another study,

0926-860X/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.apcata.2013.07.056
484 M. Tahir, N.S. Amin / Applied Catalysis A: General 467 (2013) 483–496

it was observed that nitrogen doped In2 O3 thin film electrodes were developed to determine the kinetic parameters and to provide fun-
efficient for H2 O splitting [29]. Recently, Kuo et al. [30] reported damental insights on possible reaction mechanisms.
titanium–indium oxy (nitride) with RuO2 for H2 O splitting and
observed higher H2 yield rate over the In2 O3 /TiO2 catalyst. Due
2. Experimental
to indium ability to produce large number of electrons and hinder
their recombination, it is envisaged that indium is able to improve
2.1. Catalyst preparation and coating procedure
TiO2 photocatalytic activity for efficient CO2 conversion to value
added chemicals and fuels.
Fig. 1 describes the procedure of catalyst synthesis and coat-
In addition to an efficient semiconductor photocatalyst, the
ing on monolith channels. The sol–gel single step method was
design of photoreactor is also vital for improving product yield
used to prepare mesoporous TiO2 and In/TiO2 nanoparticles. The
rates. In the period of 1980–2000, slurry reactors have been
precursory of titanium solution was prepared with molar ratios:
employed excessively for the photocatalytic CO2 reduction [31–33].
Ti (C4 H9 O)4 :15C2 H5 OH:2CH3 COOH (1 M). Typically, 30 ml of iso-
However, slurry type reactors have several limitations includ-
propanol was added into 10 ml of titanium tetra iso-propoxide and
ing inefficient light distribution throughout the system, catalyst
stirred well for 30 min. The controlled hydrolysis was conducted by
attrition, and product separation challenges and fewer catalyst
adding drop wise a mixture of 6.37 ml acetic acid (1 M) and 10 ml
recycling possibilities.
isopropanol under vigorous stirring. The mixture was continuously
During the last 10 years, fixed-bed, catalyst supported and opti-
stirred for 24 h at 30 ◦ C. Subsequently, indium(III) nitrate dissolved
cal fiber reactors have been under investigation for photoreduction.
in isopropanol was added drop-wise and stirred for another 12 h
The fixed-bed with its lower surface to volume ratio, inefficient
until clear sol was produced. The sol obtained was poured into a
light distribution and lower interaction between reactant and cat-
glass container for monolith coating.
alyst [34] seem not suitable for the photoreduction process. The
The monolith was initially washed with acetone and iso-
optical fiber photoreactors, however, fall in the category of effi-
propanol to remove any organic material, and then dried at 80 ◦ C
cient photocatalytic reactors. These reactors have been explored
for 12 h. The SHIMADZU analytical balance ATY-224 with speci-
for photocatalytic CO2 reduction since the exposed surface area
fications: Max = 220 g, Min = 10 mg, d = 0.1 mg, e = 1 mg was used
to light ratio are larger, delivering light efficiently and uniformly
to measure the weight of the monoliths. For every sample, three
throughout the reactor [35,36]. However, several disadvantages
readings were noted for bare monolith as well as coated monoliths
such as lower adhesion strength, relatively low surface area and
and their average values are reported. For example, the weight of
only 20–30% of effective total reactor volume hindered the progress
the 2 cm 100 CPSI bare monolith was 46.8219 g, aggregated from
of the reactor toward commercialization [37,38].
three different readings, i.e. (a) 46.8214 g, (b) 46.8225 g, and (c)
Among photocatalytic reactors, the monoliths with large illu-
46.5218 g. After the weight of the dried monolith was recorded,
minated surface area to reactor volume ratio and efficient light
it was immersed slowly into the indium loaded TiO2 sol and kept
utilization/distribution over the catalyst surface are considerably
for a few minutes. The excess sol from the channels was blown off
effective for photocatalytic CO2 reduction applications. Basically,
using compressed air and dried with an air drier. To increase the
monoliths composed of large number of channels with catalyts
film thickness and catalyst loading, the monolith was dipped for
usually coated as thin layer along the walls to allow higher surface
the second time using the same procedure. The coated monolith
interaction with irradiation [39,40]. In addition, higher flow rates in
was then put into the oven, dried at 80 ◦ C for 12 h and finally cal-
the honeycomb monoliths give lower pressure drops, and its sub-
cined in a muffle furnace at a rate of 5 ◦ C min−1 up to a maximum of
strate can provide specific surface area 10–100 times more than
500 ◦ C and held for 5 h. After calcination, the average weight of the
other types of catalyst supports having the same outer dimensions
coated monolith was 47.3532 g calculated from three readings (a)
[34,41,42].
47.3539 g, (b) 47.3531 g, and (c) 47.3526 g. Therefore, the catalyst
Internally illuminated monolith photoreactor was tested by
coated over monolith channels was 0.5313 g calculated by subtrac-
Liou et al. [37] for photocatalyitc CO2 reduction in which optical
ting coated monolith weight (47.3532 g) from un-coated monolith
fibers were inserted inside the channels of the honeycomb sub-
weight (46.8219 g). In/TiO2 sol was dried and calcined with the
strate. Increased yield rates were observed using the monolith
same procedure as explained above to obtain In/TiO2 powder. For
reactor with optical fibers. However, such experimental system
comparison, bare TiO2 nanoparticles were also similarly prepared
needs higher aperture of channels to increase space for inserting
and coated inside the microchannels of the monolith.
the fibers. Consequently, using higher aperture of channels, light
could not be distributed efficiently over the catalyst surface. The
other disadvantages of larger aperture channels are decreased in 2.2. Characterization of nanocatalysts
mass transfer rates, non uniform gas distribution, and lower illu-
minated surface area per volume of reactor. However, recently it In order to determine the structure and crystallinity of the
has been reported that, higher efficiency of CO2 reduction pro- photocatalysts, powder X-ray diffraction (XRD) was performed on
cess is posssible using monolith of smaller aperture channels [43]. Bruker D8 advance diffractometer (Cu K␣ radiation, wavelength
Smaller channels with higher surface area per unit volume are use-  = 1.54 Å, operated at 40 kV and 40 mA). The surface morphology
ful for efficient light distribution and increasing mass transfer rate was examined using scanning electron microscopy (SEM) with JEOL
on the catalyst surface. In addition, light distributions along the JSM6390 LV SEM instrument. The particle size and lattice structure
axial length of the monolith decreases gradually and higher CO2 of the individual crystals was visualized by high resolution trans-
mass transfer coefficient can be achieved using shorter monolith mission electron microscope (HR-TEM) carried out with FEI-Tecni
length [44]. G2 Transmission Electron Microscope (TEM) at EFGO Scientific,
The objective of this study is to test the performance of a Kulim, Kedah, Malaysia. Textural characterization of the samples
microchannel monolith as photoreactor for the conversion of CO2 was carried out with a Micromeritics ASAP 2020. The nitrogen
using H2 O as the reducing agent over In/TiO2 nanoparticles. The adsorption–desorption properties were examined at 77 K. The spe-
catalyst samples were characterized using XRD, FE-SEM, TEM, cific surface area (SBET ) of monolayer coverage was determined
BET, and UV–vis spectroscopy. The monolith geometric and oper- using Brunauer–Emmett–Teller (BET) method. The pore size distri-
ating parameters effects were investigated to maximize yield bution was calculated using the adsorption branch of the isotherm
rates. Kinetic model based on Langmuir-Hinshelwood equation was by means of Barrett–Joyner–Halenda (BJH) method. Meanwhile,
 M. Tahir, N.S. Amin / Applied Catalysis A: General 467 (2013) 483–496
Fig. 1. Preparation of In/TiO2 nanoparticles and In/TiO2 coated over monolith.
the UV–vis absorption spectra of the samples were measured with
UV-Vis-NIR spectrophotometer, Shimadzu UV 3101pc.
2.3. Photocatalytic CO2 reduction
The schematic photocatalytic reaction system for reduction of
CO2 with H2 O in gaseous phase is illustrated in Fig. 2. The reactor
consisted of a stainless steel cylindrical vessel with 5.5 cm length
and a total volume of 150 cm3 . The monoliths were supplied by
Pingxiang Meitao Chemical Packing Co., Ltd., China. The dimen-
sions of the monolith are as follows: diameter = 6 cm; length = from
0.50 to 10 cm, channels per square inch (CPSI) = 100 and 400. After
coating with about 50 mg catalyst the monolith was placed at the
center of the cylindrical stainless steel reactor, equipped with a
quartz window for passing light irradiations from the reflector lamp
located above the reactor. The reactor temperature was adjusted
using heating and cooling jackets. The light source used to acti-
vate the photocatalytic reactions was a 200 W mercury lamp for UV
irradiations source, having non-collimated irradiations with max-
imum intensity at 252 nm. The lamp was equipped with a cooling
485
fan at the top and sides to remove lamp heat. The light intensity
was measured with an online optical process monitor ILT OPM-1D
and a SED008/W sensor. The average irradiation intensity passing
through the top of the reactor was 150 mW/cm2 . The reactor was
covered with aluminum foil to ensure lights for reactions came
through the quartz window only. In case of the cell type photore-
actor, the reactor chamber and the light source was the same with
the monolith reactor. Furthermore, 50 mg of nanocatalyst powder
was suspended uniformly at the bottom of the reactor to ensure
the light was efficiently distributed over the catalyst surface.
Prior to feeding, both reactors were purged using helium (He)
flow to remove air as well as to check for leakage under 2 bar pres-
sure for 10 h. Pure CO2 (purity = 99.995%) was bubbled through
deionized water saturator for 1 h to remove dissolved oxygen and
air. The temperature inside the water bubbler was controlled using
a temperature controller. The compressed CO2 regulated by a mass
flow controller (MFC), was bubbled through the deionized water
and its concentration was adjusted with helium regulated by the
MFC. The partial pressure of H2 O vapors was adjusted by changing
the temperature of the water saturator. The gases, CO2 , He and H2 O
486 M. Tahir, N.S. Amin / Applied Catalysis A: General 467 (2013) 483–496

Fig. 2. Schematic of experimental set-up using monolith photoreactor for photocatalytic CO2 reduction with H2 O vapors.

mixed well inside the gas mixer, continuously passed through the
reactor containing powdered catalyst or coated monolith for about
1 h prior to switching on the lamp. The pressure inside the reactor
was adjusted to 0.20 bars above atmospheric pressure while tem-
perature inside the reactor was controlled using a heating jacket.
The products were analyzed using an on-line gas chromatograph
(GC-Agilent Technologies 6890N, USA) equipped with thermal con-
ductivity detector (TCD) and flame ionized detector (FID). The
gaseous products from the reactor were also taken using gastight
syringe (Agilent, 1000 ␮l) for offline analysis using the same vol-
ume as in the online analysis. Furthermore, the FID detector was
connected with a HP-PLOT Q capillary column (Agilent, length
30 m. ID 0.53 mm, film 40 ␮m) for separation of C1 –C6 paraffins
and olefins hydrocarbons, alcohols and oxygenated compounds.
The TCD detector was connected to UCW982, DC-200, Porapak Q
and Mol Sieve 13X columns. The UCW-982 was used for back flush
and reversed flow to ensure C6 and higher compounds could be
detected earlier in the chromatogram. Meanwhile, C1 –C2 , C3 –C5
compounds and light gasses (H2 , O2 , N2 , CO) were separated using
Porapak Q, DC-200, and MS-13X columns, respectively.
associated with tetragonal anatase. The average crystallite sizes
of TiO2 and In/TiO2 nanoparticles were calculated using Scherer’s
equation (Eq. (1)) according to the (1 0 1) peak [45,46].
k
L= (1)
˛ cos 
where L is the thickness of crystallite (nm), k is a constant
depending on the crystallite shape (0.90 for this study),  is the
X-ray wavelength (nm), ˛ is full peak width at half max in radi-
ans and  is Bragg’s angle of the 2 peak. The calculated crystallite
sizes of TiO2 , 10% In/TiO2 and 20% In/TiO2 samples were 18.73,
13.8 and 11.32 nm, respectively. It was observed that the size of
the TiO2 nanoparticles decreased gradually, possibly due to indium
controlling the crystal growth in TiO2 .
The SEM micrographs of monoliths are depicted in Fig. 4. The
pore morphology of the bare and coated monolith is shown in
Fig. 4(a) and (b), respectively. It is obvious that catalyst was entirely
coated over the monolith channels with no broken layer observed.
Fig. 4(c) indicates smooth and thoroughly distributed uniform

3. Results and discussion

3.1. Characterization of monolith and catalysts

The X-ray diffraction (XRD) patterns of bare TiO2 and In/TiO2

coated monolith samples are shown in Fig. 3. All the TiO2 peaks cor-
responded to pure crystalline and anatase phases calcined at 500 ◦ C
for 5 h. The XRD data do not infer any presence of indium. How-
ever, the anatase peaks become wider while the intensities also
increase with indium loadings, with no shifts in the anatase peaks
observed. The wider anatase In/TiO2 peaks indicate the crystallite
size of TiO2 decreases with indium loading. In order to confirm bulk
compositions of each sample, the XRD peaks are compared with
the JCPDS-ICSD standards for anatase (89-4921). The diffraction
peaks for TiO2 and In/TiO2 are essentially equivalent, exhibiting 2
peaks at 25.54◦ , 38.02◦ , 48.26◦ , 55.29◦ , and 62.90◦ , which are consis-
tent with the (1 0 1), (0 0 4), (2 0 0), (1 0 5), (2 1 1) and (2 0 4) planes Fig. 3. XRD patterns of anatase TiO2 nanoparticles and In/TiO2 catalysts.
 M. Tahir, N.S. Amin / Applied Catalysis A: General 467 (2013) 483–496
Fig. 4. SEM micrographs of bare monolith and In/TiO2 coated monolith at different magnifications; (a) bare monolith channels, (b) catalyst coated monolith channels, (c) top
view image at magnification 1000 and scale 10 ␮m, and (d) mesroprous structure of coated catalyst at magnification 15,000 and scale 1 ␮m.
catalyst layer investigated at 10 ␮m of SEM magnification over
the monolith surface. At magnification of 1 ␮m, it is identified
that the catalyst nanoparticles are uniformly distributed on the
monolith surface, as shown in Fig. 4(d). It is also observed that
the indium-loaded TiO2 mesoporous particles are uniform in
size.
The TEM micrographs of mesoporous In/TiO2 catalyst are shown
in Fig. 5. From Fig. 5(a), TEM image revealed mesoporous anatase
TiO2 nanoparticles consisted of average particle size with diam-
eter less than 13 nm. The particle size is close to the estimated
crystallite size by Scherrer equation. It can be observed that the
nanoparticles have interparticle mesoporous structure. The growth
and aggregation of the small particles probably caused interparticle
mesoporosity. The HR-TEM image in Fig. 5(b) confirms the mor-
phology of TiO2 nanoparticles where 0.35 nm aligned anatase phase
grown along 1 0 1 directions is observed, as already confirmed with
XRD. These results are in good agreement with previous reports
[4,47].
Fig. 6 exhibits the N2 adsorption and desorption isotherms and
Barrett–Joyner–Halenda (BJH) pore-size distribution of TiO2 and
In/TiO2 samples. It is obvious from Fig. 6(a) that the hysteresis
loops increase with increasing indium loading, resulting obvious
increase in the N2 volume adsorbed. The isotherms of the samples
are similar to type IV curves with hysteresis loops, corresponding
to mesoporous materials [19].
Furthermore, the initial part of the isotherms (at low P/Po ) is
related to monolayer–multilayer adsorption on the internal sur-
face. However, at higher P/Po , there was a steep increment in the
adsorption volume, attributed to capillary condensation, then pores
saturated with liquid. The monolayer–multilayer is more dominant
in TiO2 in which capillary action starts at P/Po = 0.60. Both capillary
and condensation processes are more obvious in In/TiO2 samples
and eminent at P/Po of 0.55.
487
The pore size distribution of the samples is presented in
Fig. 6(b). The pore size distribution, calculated from adsorp-
tion branch, is based on the BJH model. The BJH adsorption
isotherms show that the interparticle pore size diameter falls in
the range of 2.5–25 and 2.4–14 nm for TiO2 and In/TiO2 samples,
respectively.
The BET surface area, pore volume and pore size of bare TiO2
and In/TiO2 samples are summarized in Table 1. Obviously, the
indium loading into TiO2 influences the surface area, pore vol-
ume and pore size. The BET surface areas for indium doped TiO2
samples are larger than bare TiO2 . Besides this, the t-plot exter-
nal and BJH adsorption surface areas also increased significantly.
The increase in surface area was probably due to suppression
of TiO2 crystal growth by indium and also due to increase in
mesoporosity. Furthermore, the BJH adsorption pore volume also
increased with indium loading. Conversely, the pore diameter grad-
ually decreased with indium loading. The increase in the pore
volume with reduced pore diameter is attributed to higher sam-
ple mesoporosity. The well-developed mesopores, larger surface
area and higher pore volume could enhance molecular transporta-
tion rates of reactants and products to increase CO2 conversion
efficiency.
3.2. UV–vis analysis
The UV–vis absorbance spectra of the TiO2 nanoparticles and
In/TiO2 samples are depicted in Fig. 7. The absorption band
edge of TiO2 is located at 400 nm, which indicates obvious red
shift in wavelength of TiO2 compared to standard anatase TiO2
( ∼ 380 nm). The peaks identified for 5, 10, 15 and 20 wt.% In/TiO2
are located at 401, 402, 403 and 404 nm respectively. It can be
seen that indium has no significant effect on shifting TiO2 band
488 M. Tahir, N.S. Amin / Applied Catalysis A: General 467 (2013) 483–496

Fig. 5. TEM and HR-TEM images of In/TiO2 sample.

Fig. 6. (a) N2 adsorption–desorption isotherms of TiO2 nanoparticles and In/TiO2 samples and (b) BJH pore size distribution of corresponding samples.

edge. The band gap of the samples was calculated according to 20 wt.% indium doped TiO2 samples, respectively. It is identified
Eq. (2). that loading indium into TiO2 decreased the band gap but not red
shift was observed as compared to TiO2 nanoparticles.
hc
Eg = (2)

3.3. Photocatalytic reduction of CO2 with H2 O
where Eg is the band gap energy (eV), h is the Planks constant, c
is the light velocity, and  the wavelength (m). The Ebg estimated Initially, a series of preliminary tests were conducted in the
were 3.105, 3.098, 3.090, 3.082 and 3.075 for TiO2 and 5, 10, 15 and absence of CO2 and H2 O under UV irradiations for 2 h at 373 K for

Table 1
Summary of physiochemical characteristics of TiO2 and In/TiO2 samples.

Type of catalyst Surface area (m2 /g) Pore volume (cm3 /g) Pore width (nm)

BET surface area t-Plot external surface area BJH adsorption surface area BJH adsorption pore volume BJH pore width

TiO2 42.98 34.05 52.19 0.14 10.33

5% In–TiO2 61.40 60.66 68.10 0.16 8.34
10% In–TiO2 98.01 95.16 113.04 0.22 7.67
20% In-–TiO2 123.04 123.32 170.20 0.31 7.38
 M. Tahir, N.S. Amin / Applied Catalysis A: General 467 (2013) 483–496 489

compared to 400 CPSI. The higher yield rate was probably due to
efficient harvesting and utilization of light irradiations inside 100
CPSI channels compared to very dense channels (400 CPSI) [43].
Conversely, further increase in yield rates possibility exist over 150
and/or 200 CPSI channels, as smaller apertures support more illu-
minated surface area to volume ratio of reactor granting further
investigation for optimum channel aperture.
Fig. 8(b) shows the effect of monolith channel lengths on
photocatalytic CO2 reduction over TiO2 photocatalyst at differ-
ent irradiation times. It was found that CO2 reduction with H2 O
vapors to CH4 improved using longer monolith. As the channel
length increased beyond 2 cm, a gradual reduction in CH4 yield
was observed. Although the same amount of irradiation penetrated
inside the channels yet only small portion of light probably passes
through longer channels because of non-collimated light source.
Besides, there is higher catalyst loading and lower CO2 mass trans-
fer on the catalyst surface at prolonged monolith length, resulting
Fig. 7. UV–vis absorption spectra of TiO2 and In/TiO2 samples.
in lower yield rate [44]. Furthermore, only the front part of the
monolith was efficiently irradiated and after a certain length there
was probably inefficient light being distributed over the catalyst
the following cases; (1) empty reactor with helium, (2) reactor with
required for photocatalysis. Therefore, the monolith geometry is
monolith without coating and helium, (3) reactor with TiO2 coated
vital and optimum monolith dimensions are critical to enhance CO2
monolith and helium and (4) monolith coated with In/TiO2 cata-
reduction efficiency. Based on such observations, it is obvious that
lyst with helium. In all cases, no reaction products were detected.
photon flux distribution inside reactor is very important, since it
This confirmed that no products were due to photodecomposition
directly influences reactor performance [48].
of organic residues in catalyst, if any. In addition, other prelimi-
Fig. 9 illustrates the effect of reaction temperature on photo-
nary tests were also conducted using H2 O vapors and helium in
catalytic CO2 reduction at three different temperatures (70, 80 and
presence of photocatalyst. The results again confirmed in either
100 ◦ C) using 10 wt.% In/TiO2 catalyst. In all the three temperatures
case no carbon containing compounds were produced. Therefore,
investigated, the reaction rate exhibits similar behavior, which
it can be reiterated that photocatalytic reduction process require
is slow initially for CO production, but becomes considerably
all three components, i.e. catalyst coated monolith and/or catalyst,
faster after 2 h of irradiations. The other products observed were
feed (CO2 , H2 O), and light source. Meanwhile any carbon containing
CH4 and traces of C2 –C3 alkanes and alkenes (figure not shown).
compounds should be produced from CO2 through photocatalytic
The increased in yield rates at elevated temperature can be
reactions. Furthermore, all the experiments were repeated three to
explained on the basis of adsorption–desorption phenomenon. In
five times and aggregated results have been reported.
heterogeneous photocatalysis process, especially in gaseous phase,
The effect of cell density on photocatalytic CO2 reduction over
simultaneous adsorption and desorption processes occurred over
different irradiation time is illustrated in Fig. 8(a). Higher CH4 yield
the catalyst surface. The rate of reaction depends on the efficiency
rate observed over TiO2 using monolith with cell density of 100

Fig. 8. Effects of channel length on performance of monolith photoreactor for photocatalytic CO2 reduction with H2 O vapors.over TiO2 catalyst (T = 373 K, PH2 O = 0.074 bar
and PCO2 = 0.020 bar).
490 M. Tahir, N.S. Amin / Applied Catalysis A: General 467 (2013) 483–496
Fig. 9. Effect of reaction temperature on yield rate of CO (L = 2 cm, CPSI = 100, 10%
In–TiO2 , CO2 = 0.02 bar, PH2 O = 0.074 bar).
of these processes. Therefore, at elevated temperature, the CO2
mass transfer rate on the catalyst surface can be increased, thus the
probability of CO2 adsorption increases which can result in higher
reaction rate [41]. Furthermore, at higher reaction temperature, the
possibility of species desorption at the catalyst surface increased.
In this way, the chances of efficient collisions between the charge
transfer excited state species and reactant molecules also increased
[10]. Besides this, the increase in reaction rate at higher tempera-
ture may be possibly due to a decrease in activation energy during
the course of reaction. Similar observations have been reported in
other studies during the investigations of the effect of temperature
on the reduction of CO2 with H2 O in gaseous phase [19,49].
Fig. 10 illustrates the effect of indium loading on TiO2 photo-
catalytic activity for transformation of CO2 with H2 O to CO and
CH4 . By using un-doped TiO2 nanoparticles, small amount of CO
was produced, while CO yield increased significantly by the dis-
persion of indium into the TiO2 structure. The higher yield rate is
an evidence that photocatalytic activity of TiO2 can be enhanced
by increasing indium content to an optimum loading of 10 wt.%.
Beyond the 10 wt.% loading, the CO2 reduction rate slowed down
probably due to increase in recombination rate of charges. The
Fig. 10. Effect of indium loading into TiO2 for photocatalytic CO2 reduction over
monolith keeping all the parameters fixed (L = 2 cm, CPSI = 100, T = 373 K, PH2 O =
0.074 bar, PCO2 = 0.02 bar).
difference in the photocatalytic activity of bare TiO2 with doped
TiO2 may be attributed to reduced crystal size and increased surface
area, resulting in efficient charge production and separations over
the mesoporous In/TiO2 samples. Similar observations are reported
in literature using doped TiO2 catalysts [13,35,50].
The effects of partial pressure of CO2 and irradiation time for
photocatalytic CO2 reduction over 10 wt.% indium doped TiO2 sup-
ported microchannel monolith are investigated for a period of
0–10 h as depicted in Fig. 11. There is continuous production of
CO and CH4 over the entire irradiation period. CO was identified as
the major product and its higher yield over In/TiO2 catalyst con-
firmed higher CO2 reduction efficiency using this process. Initially
CO yield was very low, but gradually increased over the time. The
lower yield rate at the start of reaction was supposedly due to
higher CO2 adsorption and lower CO desorption. The yield of CH4
increased continuously with irradiation time; due to surface reac-
tion and efficient desorption of hydrocarbon based products. Trace
distribution of C2 H4 , C2 H6 , and C3 H6 with time was also observed
in the product mixture. However, yield of CH4 was lower than CO
and this was probably attributed to the conductance band (CB) of
the thermodynamic reduction potential.
Furthermore, the concentrations of CO and CH4 increased with
increasing CO2 partial pressure at fixed water vapor pressure
(0.074 bar) (Fig. 11). This phenomenon is likely due to adsorp-
tion competition between CO2 and H2 O molecules on the active
sites of In/TiO2 catalyst during photoreduction process. At lower
CO2 concentration, large amount of H2 O molecules could adsorb
over the catalyst surface to react with CO2 resulting in higher CO2
photoreduction. However, at higher CO2 concentration, it covers
supposedly maximum active sites and H2 O would have to com-
pete with CO2 for the active sites resulting in lower reaction rate.
Therefore, an optimum concentration of both reactants would be
favorable for higher CO2 conversion. Similar findings have been
reported in literature during photocatalytic CO2 with H2 O vapors
using various TiO2 based photocatalysts [19,51]. The photocatalytic
performance of In/TiO2 supported over microchannels with respect
to the product yield is in the following order (␮mol g-catal.−1 ):
CO > CH4 > C2 H6 > C2 H4 > C3 H6 . The higher yield of CO and hydro-
carbons was likely due to significant increase in the number of
electron–hole pairs and inhibited recombination times over In/TiO2
supported microchannels.
Fig. 12 compares photocatalytic CO2 reduction with H2 O vapors
using stainless steel (SS) cell and monolith photoreactor. Inter-
estingly, the yield rate of CO obtained was much higher over
In/TiO2 supported microchannels and this reveals indium enhances
rate of reaction for CO production. Under the same experimen-
tal conditions, the CO yield rate over indium modified TiO2 was
962 ␮mol g-catal.−1 h−1 22.4-fold higher compared to TiO2 sup-
ported monolith photoreactor and 185-fold higher compared to
SS cell reactor. Overall, the presence of monolith enhanced the
photoactivity of TiO2 . These results confirmed indium is efficient
to inhibit recombination of electrons–hole pairs. Furthermore, in
TiO2 coated monolith, the CO yield was 8.3 times higher than cell
type reactor. This was also probably due to increased light irradia-
tion utilization and better contact efficiency between reactants and
catalyst coated monolith due to the microchannels. Basically, hon-
eycomb configuration of monolith provides a higher geometrical
surface area to support catalyst over microchannels and to increase
mass transfer; thus, higher reactor volume could be used for pho-
tocatalytic reactions. It is also inferred that electrons produced
were immediately utilized over thin film coated microchannel, thus
reducing the rate of electron–hole pair recombination as similarly
observed previously [52].
The product compositions of photoreactors are usually quanti-
fied based on quantum efficiency. Table 2 highlights the operating
parameters used in both type of reactors to calculate quantum
 M. Tahir, N.S. Amin / Applied Catalysis A: General 467 (2013) 483–496 491

Fig. 11. Photocatalytic CO2 reduction with H2 O over 10% In/TiO2 catalyst at different irradiations time and CO2 partial pressures (L = 2 cm, CPSI = 100, In = 10 wt.%, T = 373 K,
and PH2 O = 0.074 bar).

efficiency, calculated for each experiment, as the ratio of product
rate (mol per s) with photonic flux (mol per s) [38]. The quantum
efficiency of the microchannel monolith photoreactor coated with
In/TiO2 for CO production was 0.10%, 24 times higher than that of
TiO2 coated monolith and 198 times higher than catalyst suspended
cell type photoreactor. Liou et al. [37] reported quantum efficiency
of internally illuminated monolith photoreactor for methanol pro-
duction during CO2 reduction with H2 O vapors which was 0.012%,
8.33 times lower than the value reported above for CO produc-
tion. Significantly higher quantum efficiency was observed using
microchannel monolith photoreactor, which may be attributed to
higher photons absorption inside the microchannels due to larger
illuminated active surface area. The significant improvement in
the performance of the monolith is due to more catalyst being
exposed to incoming irradiation flux. In this way, a much larger
fraction of the reactor volume was effectively used to convert CO2
to products, thus resulting in higher quantum efficiency. The lower
efficiency in TiO2 is related to higher probability of electron–holes
recombination over TiO2 where large number of photons remained
unproductive.

Fig. 12. Comparison of photocatalytic CO2 reduction with H2 O using cell type and monolith photoreactor (V = 150 cm3 , T = 373 K, PH2 O = 0.074 bar, PCO2 = 0.04 bar).
492 M. Tahir, N.S. Amin / Applied Catalysis A: General 467 (2013) 483–496

Table 2
Summary of operating parameters used for cell type and microchannel monolith photoreactor and calculated quantum efficiencies.

System Cell type photoreactor Monolitha photoreactor coated with TiO2 Monolitha photoreactor coated with In/TiO2
3 3
Volume 150 cm 150 cm 150 cm3
Catalyst loading 0.5000 g TiO2 0.5341 g TiO2 0.5520 g 10% In/TiO2
Light source 200 W Hg,  = 252 nm, I = 150 mW/cm2 200 W Hg,  = 252 nm, I = 150 mW/cm2 200 W Hg,  = 252 nm, I = 150 mW/cm2
Temperature 373 K 373 K 373 K
Pressure 0.20 bar 0.20 bar 0.20 bar
Main product CO/CH4 CO/CH4 CO/CH4
Yield rateb (␮mol g-catal.−1 h−1 ) 5.2/7.7 43.0/78.0 962.0/55.40
Quantum efficiency for COc 0.0005% 0.0042% 0.10%
Quantum efficiency for CH4 c 0.0028% 0.0301% 0.022%
a
The dimensions of monolith were length = 2 cm, CPSI = 100, diameter = 6 cm.
b
Yield rates were calculated at 10 h irradiation basis, PH2 O = 0.074 bar and PCO2 = 0.040 bar.
c
Quantum efficiency = (number of electrons × moles of production rate)/(moles of UV photons flux) × 100%.

Table 3 summarizes the yields over various catalysts used • CO− radicals. On the other hand, holes (h+ ) were transferred to
2
in cell type and monolith photoreactor with 10 h irradiation H2 O initiating its photooxidation yielding hydrogen ions (H+ ) and
time. The presence of mesoporous In/TiO2 and microchan- hydroxyal radical (• OH) and further oxidized with • OH radicals for
nel monolith played important roles and CO2 reduction was the production of O2 and H+ [53]. The • H radicals originated during
obviously increased. The performance of the photoreactor for CO reduction of proton were reacted with carbon radicals on the cata-
production was in the order of In/TiO2 -monolith (962 ␮mol g- lyst surface to produce intermediate • CH2 , • CH3 and finally CH4 and
catal.−1 h−1 ) > TiO2 -monolith (43 ␮mol g-catal.−1 h−1 ) > TiO2 -SS higher hydrocarbons (C2 H4 , C2 H6 and C3 H6 ). All possible reaction
−1 −1
cell (5.2 ␮mol g-catal. h ). Similarly, the yield rates of CH4 steps during photocatalytic CO2 reduction with H2 O are explained
produced were 55.4, 78.0 and 7.7 ␮mol g-catal.−1 h−1 , for In/TiO2 - by Eqs. (3)–(11).
monolith, TiO2 -monolith and TiO2 cell type, respectively. In E ≥E
−→bg e−
TiO2 ph (TiO2 ) + h+
vb (TiO2 ) (3)
addition, less concentrations of C2 H4 , C2 H6 , and C3 H6 were also cb
produced over TiO2 and In/TiO2 coated monoliths. Based on these In + e−
cb
→ In − e−
cb
(4)
results, it is obvious that mesoporous In/TiO2 catalyst with higher
e− ,H2 O
surface area and lower particle size is more favorable for efficient H2 O + h+ → • OH + H+ −→ • H + O2 (5)
reduction of CO2 to CO. In general, higher efficiency of the catalysts •H
and reactors may be attributed to the followings: CO2 + e− → • CO−
2 −→CO + OH
−
(6)
•H
CO + e− → • CO− −→• C + OH− (7)
(1) Larger illuminated surface area, higher light utilization, efficient
•H •H •H
adsorption–desorption process and higher catalyst interparti- •C + •H → • CH−→• CH2 −→• CH3 −→CH4 (8)
cle mesoporosity are probably the important factors to improve
• CH + • CH2 → C2 H4 (9)
the yield rates in monolith photoreactor. Conversely, in cell type 2
photoreactor, there is lower light utilization and mass transfer • CH + • CH3 → C2 H6 (10)
3
rates.
• CH + • CH3 + • CH → C3 H6 (11)
(2) Indium in TiO2 controls the crystal growth, increases the meso- 2
porosity and the surface area, and reduced the particle size.
Since all the above products were detected experimentally, there-
Indium doped TiO2 catalysts with smaller particle sizes coated
fore, CH4 was confirmed to be produced from methyl radicals
over microchannels have higher photocatalytic activity because
(• CH3 ) through Eq. (8). Similarly, CO was probably produced
electrons are more mobile over the photocatalysts. Further-
according to Eq. (6). The higher yield rate of CO production also con-
more, indium trapped electrons and hindered recombination
firmed that there were significant productions of electrons which
of electrons–hole pairs during TiO2 photocatalysis, and possibly
were efficiently trapped by indium and then transferred to CO2 for
enhanced TiO2 photocatalytic activity.
its reduction to CO. However, there are many possible routes for
the production of C2 –C3 hydrocarbons and most possible routes
3.4. Mechanism of photocatalytic CO2 reduction are explained in Eqs. (9)–(11). According to above reaction mecha-
nism, all the possible products are dependent on the production of
During photocatalytic CO2 reduction with water vapors the first intermediate product, CO and its further reduction to C1 –C3 hydro-
step was the production of electrion–holes pairs when light striked carbons through Eqs. (7)–(11). The possibility for production of
on the TiO2 surface. The electrons (e− ) were transferred from the C2 –C3 compounds enhanced if there are series of reaction taking
conduction band of TiO2 for the photoreduction of CO2 yielding place over catalyst surface. Similar observations have been reported

Table 3
Summary of products from photocatalytic CO2 reduction with H2 O for different type of reactors and catalysts.

Products Yield rates (␮mol g-catal.−1 h−1 )a Selectivity (%)

TiO2 -cell TiO2 -monolith In/TiO2 -monolith TiO2 -monolith In/TiO2 -monolith

CO 5.2 43.0 962.0 34.87 94.39

CH4 7.7 78.0 55.40 63.27 5.44
C2 H4 0.79 1.50 0.34 1.22 0.034
C2 H6 0.00 0.79 1.50 0.64 0.147
C3 H6 0.00 0.00 0.068 0.00 0.00

Operating conditions: PCO2 = 0.040 bar, PH2 O = 0.074 bar, T = 373 K.

a
Yield rates calculated on 10 h irradiation basis.
 M. Tahir, N.S. Amin / Applied Catalysis A: General 467 (2013) 483–496
Fig. 13. (a) Schematic reaction scheme for photocatalytic CO2 reduction and H2 O oxidation to hydrocarbons using CO as intermediate over In/TiO2 and (b) thermodynamic
reduction based mechanism of CO2 reduction with H2 O vapors to CO and CH4 over In/TiO2 catalyst.
in other studies using TiO2 based photocatalysts [19,49]. The reac-
tion scheme for the production of CO, CH4 and higher hydrocarbons
using In-loaded TiO2 is elaborated further in Fig. 13(a).
The photocatalytic CO2 transformation to CO and CH4 as main
products over In/TiO2 catalyst could be further explained using
energy band theory, which is based on the relative positions of con-
ductance band, valance band and oxidation potentials. In general,
photo-excited electrons could consume effectively, if the reduction
potential of reaction is lower than the conductance band potential
of the semiconductor [54]. The mechanims for photocatalytic CO2
reduction in terms of thermodynamic reduction potentials versus
normal hydrogen electrode (NHE) at pH 7 is explained in Fig. 13(b)
[17]. The possible reactions that can occur during photocatalytic
CO2 with H2 O to produce CO and CH4 in terms of thermodynamic
reduction potentials versus normal hydrogen electrode (NHE) at
pH 7 can be described by reactions (12)–(15) [11,55,56].
CO2 + 2H+ + 2e− → CO + H2 O E o = −0.48 V
2H+ + 2e− → H2 E o = −0.41 V
+ − o
CO2 + 8H + 8e → CH4 + 2H2 O E = −0.24 V
2H2 O + 4h+ → 4H+ + O2 E o = +0.82 V
The conductance band potential of TiO2 is ECB = −0.50 V at pH 7,
which is higher than reduction potential of Eo (CO2 /CO) = −0.48 V,
thus reduction of CO2 to CO is possible. On the other hand, produc-
tion of CH4 was also posisble because of lower reduction potential
difference (Eo (CO2 /CH4 ) = −0.24 V). However, higher production
rate of CO is possible since two electrons are required for CO
production compared to eight electrons to produce CH4 . Besides,
there was possible higher production of electrons than holes due
to indium loading which enhanced CO production. On the other
493
hand, traces amount C2 to C3 were possible due to a series of reac-
tion that occured ove rthe catalyst surface. Using bare TiO2 , CH4
was found as the major product which revealed TiO2 coated over
microchannel is more feasible for CH4 production than CO. Thus, the
CO production over In/TiO2 was probably due to a more negative
conductance band and possibility of CH4 reduction to CO. How-
ever, further investigations are needed to find out the exact reaction
mechanism of CO and hydrocarbons production. In other studies,
CO was also observed as the main product during CO2 reduction
with H2 O vapors using TiO2 and the modified TiO2 catalysts [13,14].
3.5. Development of kinetic model
In heterogeneous photocatalytic processes, rates are usually
proportional to adsorption of reactants with efficient desorption of
products on the catalyst surface. When the two reactants compet-
itively adsorbed on the same catalyst surface active sites, but with
(12)
different adsorption and desorption rate constants, and undergoes
(13) a reaction to yield different products, the reaction could be repre-
sented by Langmuir-Hinshelwood mechanism, as explained by Eq.
(14) (16) [44].
(15) KA PA KB PB
Rate = kA B = k (16)
(1 + KA PA + KB PB )2
where  A and  B represent the fractional surface coverage of
each reactant while PA and PB are the partial pressures of each
species. The rate constant k and adsorption equilibrium constant
parameters KA and KB are all temperature dependent. If the adsorp-
tion is random, the probability of adsorption would be taken as the
fraction of the surface not covered (1 − ) and desorption taken
as the surface covered . By employing these assumptions, the
kinetic model for photocatalytic CO2 reduction with H2 O could be
494 M. Tahir, N.S. Amin / Applied Catalysis A: General 467 (2013) 483–496

developed. The results from previous section could enable kinetic the L–H mechanism could be written as in Eq. (21) [44]. The rate of
model development for photocatalytic reduction of CO2 and H2 O. product formation can be obtained by subtracting rate of oxidation
In general, the CO2 with H2 O was photocatalytically reduced to from rate of reduction as explained in Eq. (22) where, k2 = (koxd Ia )
CH4 and CO as the main products through the following reaction is dependent on reaction temperature and light intensity factor.
scheme as illustrated in Eq. (17). 
KO2 PO2
hv, In2 O3 /TiO2
3CO2 + 2H2 O −→ CH4 + 2CO + 3O2 (17) Rate of oxidation = k2 (21)
(KCO PCO )
Some of the products would photo-adsorb on the catalyst sur-  
KH2 O PH2 O KCO2 PCO2 KO2 PO2
face, blocked the active sites and slowed down the CO2 reduction Rate of formation = k1 − k2 (22)
process. There is also possibility some of these products recom- (KCO PCO ) KCO PCO
bined in a reversed reaction. For example, when CO and oxygen Under constant temperature and pressure, partial pressure of CO2
produced were not effectively desorbed from the catalyst surface, and H2 O vapors will be constant. Similarly, partial pressures of CO
these products would undergo photo-oxidation back to CO2 in and oxygen would be proportional to partial pressure of desired
the reversed reaction. The kinetic model is developed using these product, i.e. PCO = PO2 = P. Based on these assumptions, product
assumptions to investigate the coupled effect of adsorptive photo- formation Eq. (22) in simplified form can be expressed by Eqs. (23)
catalytic reduction and oxidation processes. By assuming reactants and (24).
and products are adsorbed on same active sites, rate of reaction
dP
k   k 
3 4
can be explained by using Langmuir-Hinshelwood mechanism as = − (23)
dt P P 1/2
described in Eq. (18).  
P
KH2 O KCO2 (PH2 O PCO2 ) dt = dP (24)
Rate of reduction = kI a 2
k3 − k4 P 1/2
(1 + KH2 O PH2 O + KCO2 PCO2 + KCO PCO + KO2 PO2 + KCH4 PCH4 )
where
(18)
  
KH2 O PH2 O KCO2 PCO2 KO2
k3 = k1 , k 4 = k2
where ‘k’ is the rate constant, I is UV light flux intensity for which KCO KCO
kinetic constants is evaluated, ‘a’ is the reaction order of light inten-
The differential equation (Eq. (24)) was solved using integral
sity, having value 1 or less depending on the light intensity [57].
approach as shown in Eq. (25).
KH2 O , KCO2 , KCO , KO2 , and KCH4 are the ratios of adsorption to
desorption equilibrium rate constants for H2 O, CO2 , CO, O2 and CH4 , 2k33 2P 3/2 k3 P 2k32 P 1/2
respectively. During photocatalytic CO2 reduction over the catalyst t=− ln(k3 − k4 P 1/2 ) − − 2 − +C (25)
3k44 3k4 k4 k42
surface the rate equation can be determined with the assumptions:
(a) reaction rate is proportional to the fraction of surface covered Applying initial boundary condition (t → to , Po = 0), constant C
by CO2 ; (b) H2 O, CH4 and O2 are weakly adsorbed over the cata- could be calculated, where, to is the reaction start up time or time
lyst; (c) while CO2 and CO are moderately adsorbed, then the rate delay of photo-activities due to transient state at which Po = 0. After
equation becomes Eq. (19) [44]. inserting the value of C in Eqs. (25) and (26) is obtained which was
further simplified to get Eq. (27)
KH2 O KCO2 (PH2 O PCO2 ) 
Rate of reduction = kI a (19)    1/2   
(1 + KCO2 PCO2 + KCO PCO )2 2k33 P 2
t − to = − ln 1− − P 3/2
A simple kinetic model incorporating the coupled effect of the 3k44 (k3 /k4 )
2 3k4
adsorptive photocatalytic reduction and oxidation could be devel-    
oped using the modified Langmuir-Hinshelwood model (Eq. (19)) k3 2k32
− P− P 1/2 (26)
using the following assumptions: k42 k42

(1) The surface reactions occurred at the outer surface of the mono-
  P 1/2   
k8 k9
lith channel where the catalyst is coated as thin layer. t − to = −k5 ln 1− − (P 3/2 ) k7 + √ + (27)
k6 P P
(2) The reduction of CO2 on the surface produced CO, which
strongly adsorbed and overall rate of reaction may be limited where
by the rate of CO desorption.  3
  k 2  2   
2k3 3 k3
(3) Initially reaction rate was very fast but the rate decreased as k5 = 4
, k6 = , k7 = , k8 = 2
,
3k4 k4 3k4 k4
CO accumulated on the surface, strongly adsorbed and the
surface was nearly completely covered by CO, i.e. KCO PCO   2

2k3
1 + KCO2 PCO2 . k9 = 2
k4
The rate of reduction in Eq. (19) is simplified to Eq. (20).
Eq. (27) is known as the kinetic equation and it could be used
KH2 O PH2 O KCO2 PCO2 to evaluate experimental data. However, it is further simplified by
Rate of reduction = k1 (20)
(KCO PCO ) applying assumption that k5  (k7 + (k8 /P1/2 ) + (k9 /P)) as described
where k1 = (kred Ia ) is the photoreduction rate constant affected by in Eq. (28).
  P 1/2 
temperature and light intensity. The rate of formation of the prod-
ucts is dependent on CO conversion and/or desorption over the t − to = −k5 ln 1− (28)
k6
catalyst surface. During photocatalytic CO2 reduction, when CO
entirely covers the catalyst surface, it also undergoes partial oxi- Eq. (28) is the simplified kinetic model equation while, k5 and k6 are
dation with oxygen. The Langmuir-Hinshelwood model could also constants related to reaction rate constants, adsorption–desorption
be used to evaluate rate of photo-oxidation. When CO oxidation ratio constants, light intensity, and experimental conditions. By
reaction with oxygen undergoes dissociative adsorption process, assuming ideal gas law, P can be assumed to be the yield of the
 M. Tahir, N.S. Amin / Applied Catalysis A: General 467 (2013) 483–496 495

Table 4
Summary of kinetic constants for model fitting (Eq. (28)) with experimental data.

Catalyst PCO2 (bar) PH2 O (bar) Product k5 k6 Error

In/TiO2 0.02 0.074 CO 250 9650 ±5%

In/TiO2 0.04 0.074 CO 250 11,700 ±5%
In/TiO2 0.06 0.074 CO 250 10,500 ±5%
In/TiO2 0.02 0.074 CH4 260 490 ±3%
In/TiO2 0.04 0.074 CH4 220 600 ±3%
In/TiO2 0.06 0.074 CH4 220 530 ±3%
TiO2 0.04 0.074 CO 220 500 ±2%
TiO2 0.04 0.074 CH4 210 840 ±2%

desired product at any interval of time t. This kinetic model would

be suitable for most of the photocatalytic CO2 reduction processes
in gaseous phase in which there will be strong movement of elec-
trons at the catalyst surface and efficient conversion of CO to other
products or desorption of CO from the catalyst surface. The kinetic
equation should be useful for optimization purposes and can also be
used to deduce the rate and product yield at any particular reaction
time. Fig. 15. Comparison of model fitting with the experimental data for formation of
The curves representing the profiles of CO production could CH4 and CO on TiO2 supported monolith photoreactor.
be generated as a function of irradiation time using the proposed
kinetic model (Eq. (28)) to fit with the experimental data using the
the catalyst surface as compared to other products. It may also be
values of k5 and k6 as summarized in Table 4. CO and CH4 formation
attributed to the possibility of strong mobility of electrons, and
profiles for proposed model and experimental data are illustrated
efficient desorption of products over the catalyst coated monolith
in Figs. 14 and 15. After inserting the constants, the model fitted-
surface.
well with the experimental data. The good fitting of the model
with experimental data confirmed CO to be strongly adsorbed over
4. Conclusions

A microchannel monolith photoreactor with catalysts coated as

very thin film on the walls of the channels is presented for higher
CO2 reduction rate. By doping TiO2 with indium, pure anatase phase
of TiO2 was achieved with smaller particle size, larger surface area
and mesoporous structure. The geometric of the monolith pro-
foundly improved product yield rates. Furthermore, the effect of
temperature, catalyst loading and partial pressure of CO2 were also
investigated. CO and CH4 were observed as the main products with
yield rate 962 and 55.4 ␮mol g-catal.−1 h−1 , respectively and selec-
tivity of 94.39 and 5.44%, respectively over 10 wt.% indium doped
TiO2 supported over microchannels at 373 K and 0.20 bars. The
other products observed were C2 H4 , C2 H6 , and C3 H6 . The perfor-
mance comparison between the photoreactors revealed 183-fold
higher yield of CO in the monolith compared to cell type reac-
tor. The quantum efficiency achieved in the cell type reactor was
also much lower (0.0005%) compared to the microchannel mono-
lith reactor (0.10%). More importantly, the quantum efficiency was
significantly improved using microchannels compared to internally
illuminated monolith as reported previously. The higher efficiency
of the monolith photoreactor was supposedly due to higher illu-
minated surface area, higher photon energy consumption and
better utilization of reactor volume. The kinetic equation based on
L–H mechanism could effectively estimate the reaction rate and
product formation during photocatalytic CO2 reduction with H2 O.
Therefore, a new monolith photoreactor design is eminent in the
photocatalytic reactor research field while indium doped TiO2 is a
highly efficient catalyst for maximizing CO yield rates and selectiv-
ity.

Acknowledgments

The authors would like to extend their deepest appreciation to

Fig. 14. Comparison of model fitting with the experimental using data for the for-
mation of CH4 on 10% In/TiO2 supported monolith at different CO2 partial pressure;
(a) for the formation of CO and (b) for the formation of CH4 .
the Ministry of Higher Education (MOHE), Malaysia and Univer-
siti Teknologi Malaysia for financial support of this research under
LRGS (Long-term Research Grant Scheme) and RUG (Research Uni-
versity Grant).
496 M. Tahir, N.S. Amin / Applied Catalysis A: General 467 (2013) 483–496
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