2558 Ind. Eng. Chem. Res.

2006, 45, 2558-2568

Photocatalytic Process for CO2 Emission Reduction from Industrial Flue Gas
Streams
Phairat Usubharatana, Dena McMartin,* Amornvadee Veawab, and Paitoon Tontiwachwuthikul
Faculty of Engineering, UniVersity of Regina, Regina, SK, S4S 0A2 Canada

At present, carbon dioxide (CO2) is the largest contributor among greenhouse gases. This article addresses
the potential application of photocatalysis to the reduction of CO2 emissions from industrial flue gas streams.
Not only does this process remove CO2, but it can also convert CO2 into other chemical commodities such
as methane, methanol, and ethanol. In addition, the photocatalytic process can consume less energy than
conventional methods by harnessing solar energy. Given these advantages, photocatalysis is an attractive
alternative for CO2 capture. This article reviews the principle of photocatalysis; existing literature related to
photocatalytic CO2 reduction; and the effects of important parameters on process performance, including
light wavelength and intensity, type of reductant, metal-modified surface, temperature, and pressure. Finally,
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we discuss various system configurations for UV and solar photocatalytic reactors. The advances in
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photocatalysis technology indicate a promising application potential for significant reductions of CO2 emissions
and a positive impact on climate change effects.

1. Introduction Nevertheless, chemical absorption is costly, with significant

According to the Intergovernmental Panel on Climate Change
(IPCC 2001),1 the Earth’s surface temperature has risen by
approximately 0.6 K in the past century, with particularly
significant warming trends over the past two decades. The
primary contributor to this phenomenon is carbon dioxide (CO2)
emissions from fossil fuel combustion. A great deal of effort
has been expended to reduce CO2 emissions from the industries
where the largest percentages of fossil fuels are used. The
reduction of CO2 emissions can be achieved by three ap-
proaches: (1) efficient use of carbon-based energy sources, (2)
use of alternative or carbon-free energy sources, and (3) use of
a posttreatment carbon-capture technology.2 With the abundance
of fossil fuels, the continued reliance of global markets on this
energy source, and the current absence of a cost-effective
alternative energy source, posttreatment carbon-capture technol-
ogy is a viable means of reducing CO2 releases into the
atmosphere.
Carbon capture refers to the removal of CO2 from industrial
flue gas by a gas separation process prior to release to the
atmosphere. The captured CO2 can be stored in depleted oil
and gas wells, the deep ocean, or aquifers. It can also be utilized
in one of two ways. First, the captured CO2 can be used as a
chemical commodity for meat freezing, a component of carbon-
ated beverages, or a reactant for methanol production. Second,
the captured CO2 can be injected into geological formations
for the enhanced recovery of fossil fuel products in processes
such as enhanced oil recovery (EOR), enhanced coal bed
methane recovery (ECBM), and enhanced gas recovery (EGR).
Currently, many technologies are available for the capture
of CO2 from flue gas. Such technologies include gas absorption
into chemical solvents, permeation through membranes, cryo-
genic distillation, and gas adsorption onto a solid sorbent (Table
1). Gas absorption into chemical solvents refers primarily to
chemical absorption. This is the most promising technology
because of its capacity to handle a large volume of flue gas
and its efficiency in CO2 capture at atmospheric pressure.
* To whom correspondence should be addressed. E-mail:
dena.mcmartin@uregina.ca.
10.1021/ie0505763 CCC: $33.50 © 2006 American Chemical Society
Published on Web 01/12/2006
energy required for CO2 stripping and solvent regeneration. Gas
absorption membranes are also available for flue gas treatment.
By combining chemical absorption with membrane separation
techniques, the efficiency of CO2 capture can be improved.
However, the development of effective membranes with high
CO2 selectivity and permeability presents a great challenge.
Cryogenic processes, although technically feasible, are not
economically viable because of the considerable energy input
required for phase transformation from gas to liquid. Further-
more, the cryogenic process must be operated at high CO2 partial
pressure, which is not applicable for a typical flue gas. The
option of sorption on a solid sorbent is also not currently viable
for CO2 capture, and despite its simplicity of operation, the
adsorption process is costly.
The recent innovations in photocatalytic processes have
introduced CO2 capture as a potential application. These
processes can be applied for CO2 removal while simultaneously
converting CO2 to marketable products such as methane,
methanol, and ethanol. Another potential feature of the photo-
catalytic reduction of CO2 is the use of solar energy for the
reaction. This article reviews the principles of the photocatalytic
process and its potential application to the capture of CO2 from
fossil fuel combustion emission sources.
2. Photocatalytic Method
Photocatalysis makes use of semiconductors to promote
reactions in the presence of light radiation.8 Unlike metals, which
have a continuum of electronic states, semiconductors exhibit
a void energy region, or band gap, that extends from the top of
the filled valance band to the bottom of the vacant conduction
band when exposed to light radiation (Figure 1). The generation
of electron-hole pairs (e--h+) and its reverse process are
shown in eqs 1 and 2, respectively
hV
photocatalyst 98 e- + h+ (1)
e- + h+ f heat (2)
e-
where hV is the photon energy, represents a conduction band
electron, and h+ represents a hole in the valence band.
 Ind. Eng. Chem. Res., Vol. 45, No. 8, 2006 2559

Table 1. Advantages and Disadvantages of Alternative CO2-Capture Techniques

technique advantages
chemical absorption (i) effective for dilute CO2 stream
(typically flue gas contains only0-12% CO2 by volume)
(ii) commercially available and currently in use
(iii) operated at low temperature and pressure
(Rao and Rubin3)
membrane gas (i) compact because of a high packing
absorption density
(ii) operation of the contactor is independent of gas
and liquid flow rates
(iii) no foaming, channeling, entrainment, or flooding
(Falk-Pedersen and Dannström4)
cryogenics (i) use for high partial pressure of CO2
(ii) use for gas contained more than 90% CO2
solid adsorption (i) uncomplicated technology
(ii) relative ease of operation
disadvantages
(i) requires significant energy for regeneration because of the strong bond
between CO2 and the absorbent (ii) limited CO2 loadings result from the
reaction stoichiometry
(i) development of a CO2-selective membrane is challenging because
each gas component has its own solubility and permeability through
membrane material (Wolsky et al.5)
(i) high energy consumption associated with gas compression and cooling
(Plasynski and Chen6)
(i) low efficiency (ii) expensive (Meisen et al.7)

The lifetime of this excited electron-hole pair is a few

nanoseconds,10 but this is adequate for promoting redox reac-
tions. The initial excitation and electron transfer make chemical
reactions in the photocatalytic process possible. Figure 2
illustrates the excitation of an electron from the valence band
to the conduction band initiated by light absorption with energy
equal to or greater than the band gap of the semiconductor. The
separated electron and hole can be followed by one of several
pathways. Migration of electrons and holes to the semiconductor
surface is followed by transfer of photoinduced electrons to Figure 1. Schematic representation of band-gap formation (adapted from
adsorbed molecules or to solvent. The electron-transfer process Kabra et al.9).
is more efficient if the species are adsorbed on the surface.11
At the surface, the semiconductor can donate electrons to
acceptors (pathway A). In turn, holes can migrate to the surface,
where they can combine with electrons from donor species
(pathway B). The rate of charge transfer depends on the band-
edge position of the band gap and the redox potential of the
adsorbate species, respectively. Electron and hole recombination
prevents them from transferring to the surface to react with
adsorbed molecules. Recombination can occur in the volume
of the semiconductor particle (pathway C) or on the surface
(pathway D).
The optimal characteristics required for photocatalysts include
the following:8 (1) The redox potential of the photogenerated
valence-band hole must be sufficiently positive for the hole to
act as an acceptor. (2) The redox potential of the photogenerated
conductance-band electron must be sufficiently negative for the
Figure 2. Photoexcitation in solid followed by deexcitation.
electron to act as a donor. (3) The material must not be prone
to photocorrosion or produce toxic byproducts. (4) The material Table 2. Band-Gap Energies of Semiconductors Used for
should be commercially and economically available. Photocatalytic Processesa
Table 2lists band-gap energies of semiconductors used for band-gap band-gap
photocatalytic processes. photocatalyst energy (eV) photocatalyst energy (eV)
Si 1.1 TiO2 rutile 3.02
3. Photocatalytic Reduction of CO2 WSe2 1.2 Fe2O3 3.1
R-Fe2O3 2.2 TiO2 anatase 3.23
Because CO2 is a relatively inert and stable compound, its CdS 2.4 ZnO 3.2
V2O5 2.7 SrTiO3 3.4
reduction is quite challenging. The majority of conversion and WO3 2.8 SnO2 3.5
removal methods rely on high-energy input for high-temperature SiC 3.0 ZnS 3.7
and/or -pressure conditions.12 Conversely, photocatalysis occurs a Kabra et al.9
under relatively mild conditions with lower energy input,
especially where the reaction is activated by solar energy or (HCHO), formic acid (HCOOH), methyl alcohol (CH3OH), and
other easily obtained light sources. The use of solar energy is trace amounts of methane (CH4) using various semiconductors,
a particular advantage, as it relies on a continuous and readily such as tungsten trioxide (WO3), titanium dioxide (TiO2), zinc
available power supply. In addition to reducing CO2 emissions oxide (ZnO), cadmium sulfide (CdS), gallium phosphide (GaP),
into the atmosphere, photocatalytic methods can also produce and silicon carbide (SiC). These semiconductors were activated
valuable chemicals that make such approaches an appealing by both xenon- and mercury-lamp irradiation. In later years,
option to conventional CO2 removal methods. many research groups have studied the mechanism and ef-
In 1979, Inoue et al.13 first reported the photocatalytic ficiency of CO2 photocatalytic reduction using a variety of
reduction of CO2 in aqueous solution to produce formaldehyde semiconductors.14,15 This literature demonstrates that products
2560 Ind. Eng. Chem. Res., Vol. 45, No. 8, 2006

such as ethyl alcohol (C2H5OH) and ethane (C2H6) can also be Although the cadmium sulfide (CdS) semiconductor has a
obtained through the use of specific semiconductor materials.16 smaller band gap (∼2.4 eV) and works in the visible range, it
Tennakone et al. conducted many studies of CO2 reduction by is not sufficiently positive to act as an acceptor. This causes
photocatalysts over various supported TiO2 materials including the photocatalyst to decompose with hole formation.57
platinum (Pt), gold (Au), silver (Ag), cobalt (Co), lead (Pb),
and mercury (Hg); reduction with hydrous cuprous oxide (Cu2O‚ 5. Effect of Reductant on Pathway Mechanism and
H2O); and reduction of carbonate and bicarbonate to form Selectivity
formaldehyde with TiO2 powder.17-19
Investigations related to the photosynthesis reaction of CO2 The photoreduction of CO2 by water is readily available and
with water vapor to form CH4 over metal-loaded SrTiO3 have inexpensive. Two important species involved in CO2 photore-
also been conducted.20 Through the development of nanopho- duction are H• (hydrogen atom) and •CO2- (carbon dioxide
tocatalysts on SiO2,21,22 Vycor glass, γ-zeolite, and β-zeolite, anion radical) produced by electron transfer from the conduction
improved reactivity and selectivity for CO2 reduction to CH4 band as follows:
and CH3OH can be achieved. The use of nanoparticle semi-
conductors can provide a higher activity for CO2 reduction H+ + e- f H• (5)
compared to the corresponding bulk semiconductor.23
CO2 + e- f •CO2- (6)
When water is used as a reductant, the amount of organic
products is very low. Other researchers have observed that the
These radicals will also form other stable substances58 (mech-
polarity of solvents exerts a significant influence on the
anisms and pathways are not indicated):
reduction pathways of CO2.24 Therefore, improving the ef-
ficiency using sacrificial electron donors such as trimethylamine, Carbon monoxide formation
triethanolamine,25 dimethyformamide,26 and isopropyl alcohol27
has also been extensively studied. Beyond the use of water as CO2 + 2H+ + 2e- f CO + H2O (7)
a reductant, CO2 photocatalysis can be achieved in the presence
of gas-phase H2S,28 H2,29,30 and CH4.31 Furthermore, CO2 Formic acid formation
photoreduction via the hydrogenation process, using an Fe-based
CO2 + 2H+ + 2e- f HCO2H (8)
Fischer-Tropsch catalyst, has been used to produce H2 via the
water-splitting reaction.32 A chronological compilation of the
Formaldehyde formation
CO2 photocatalysis literature between 1997 and 2005 is
presented in Table 3. CO2 + 4H+ + 4e- f CH2O + H2O (9)

4. Effects of Wavelength, Light Intensity, and Band Gap Methanol formation

Semiconductors absorb light radiation with a threshold CO2 + 6H+ + 6e- f CH3OH + H2O (10)
wavelength that provides sufficient photon energy to overcome
the band gap between the valence and conduction bands. The Methane formation
minimum wavelength required to promote the excited state
depends on the band-gap energy given by52 CO2 + 8H+ + 8e- f CH4 + 2H2O (11)

1240 However, the solubility of CO2 in water is particularly low, and

λmin ) (3)
band-gap energy
Electron excited states are produced via electronic transitions.
The probability of an electronic transition is proportional to the
square of the amplitude of the radiation field, E0, and the square
of the transition dipole moment, |µif|53,54
P ∝ E0 |µif|
2 2
(4)
The amplitude of the radiation field, E0, can be controlled by
varying the light intensity. Matthews et al.55 demonstrated that
shorter-wavelength (254-nm) radiation is significantly more
effective for CO2 degradation using TiO2 than 350-nm radiation.
At low light intensities, the degradation rate increases linearly
with light intensity;56 at midrange light intensities, the rate is
dependent on the square root of intensity; and at high intensities,
the degradation rate is independent of intensity.
Large-band-gap semiconductors are the most suitable pho-
tocatalysts for CO2 reduction, because they provide sufficient
negative and positive redox potentials in conductance bands and
valence bands, respectively. The disadvantage of using wide
band-gap semiconductors is the requirement for high energy
input. For example, TiO2 anatase, a stable photocatalyst with a
large band-gap energy (∼3.2 eV), is active only in the ultraviolet
region of the solar spectrum (Figure 3).
the CO2 photoreduction process is competing with H2 and H2O2
formation, which consumes H+ and e- as follows:
photocatalyst + 4hV T 4e- + 4h+ (12)
Water decomposition
2H2O + 4h+ f O2 + 4H+ (13)
Hydrogen formation
4H+ + 4e- f 2H2 (14)
Hydrogen peroxide formation
O2 + 2H+ + 2e- f H2O2 (15)
Because of these limitations, some researchers have attempted
to replace water with other reductants. This provides a high
reaction yield and high selectivity to desired products by
changing the mechanism. Liu et al.24 conducted an experiment
with CdS in various solvents including water, methanol, ethanol,
and 1-propanol with dielectric constants of 80, 33, 24.3, and
20.1, respectively. The results indicated that, if low-dielectric-
constant solvents or low-polarity solvents are used, •CO2- anion
radicals can be strongly adsorbed on the surface through the
carbon atom of another •CO2- anion radical because these
 Ind. Eng. Chem. Res., Vol. 45, No. 8, 2006 2561

Table 3. Summary of the CO2 Photocatalysis Literature

photocatalyst primary
used reductant light source product(s) comments ref
TiO2/zeolite water 75-W high-pressure Hg lamp, CH4 high selectivity to methanol formation Anpo et al.33
λ > 280 nm
CdS surface- TEA 300-W halogen tungsten lamp, not reported improved photocatalytic activity through the Fujiwara
modified by DMF λ > 400 nm formation of sulfur vacancies et al.26
ZrO2 H2 500-W ultrahigh-pressure Hg lamp CO intermediates exist on the catalyst surface Kohno et al.29
under irradiation, and reaction is expected to
proceed to yield CO
CdS surface- propanol 500-W high pressure Hg arc lamp formate, CO, ratio of formate to CO is greater with thiol Liu et al.24
modified by thiol with 300-nm cutoff filter H2, acetone solution
TiO2 (P-25) isopropyl alcolhol 4.2-kW Xe lamp CH4, HCOOH high-pressure CO2 is more efficient in the Kaneco et al.27
formation of CH4
Ti-MCM-41 and water vapor high-pressure Hg lamp, λ > 280 nm CH4, CH3OH catalysts exhibited high efficiency and Anpo et al.21
Ti-MCM-48 selectivity for CH3OH formation; larger pore
sizes gave higher reactivity and selectivity
TiO2 nanocrystals lithium nitrate/ 500-W high pressure Hg arc lamp formate, CO, reaction of nitrate is rate-determining step in Liu et al.34
in SiO2 2-propanol with 280-nm band-pass filter NH3, urea photoformation of urea
TiO2/zeolite, water vapor high-pressure Hg lamp, λ > 280 nm CH3OH zeolite and molecular sieve catalysts with TiO2 Yamashita
TiO2/molecular species highly dispersed in their cavities are et al.35
sieves promising as efficient photocatalysts
Rh/TiO2 H2 Toshiba UV-29, UV-37 Y-45 CO, CH4 when Rh is fully reduced, the main product Kohno et al.12
changes from CO to CH4
TiO2/Pd/Al2O3, water 250-mW Hg arc lamp acetone, noteworthy selectivity exhibited by Subrahmanyam
TiO2/Pd/SiO2 ethanol, TiO2/Pd/Al2O3; basic nature of support was et al.16
CuO/ZnO and methanol, more suitable for the activity and selectivity
Li2O/TiO2 formaldehyde, of C1-C3
supported over formic acid,
MgO, Al2O3 methane,
ethane
[fac-Re(bpy)- TEOA/DMF 500-W Hg lamp with 365-nm CO, H2 indicated the mechanism of these complexes Hori et al.36
(CO)3(4-Xpy)]+ band-pass filter
TiO2 methanol; ethanol; 0.96-kW Xe lamp formic acid reduction of CO2 carried out in supercritical CO2; Kaneco et al.37
2-propanol; protonation after irradiation with acid
nitric, hydrochloric, preferred over pure water
phosphoric
acids
(protonation)
ZrO2 H2 500-W ultrahigh-pressure Hg lamp CO CO2 adsorbed on surface produces CO2- Kohno et al.30
anion radical upon irradiation; hydrogen
then reacts with this radical in dark in the
rate-determining step
ZrO2 CH4 500-W ultrahigh-pressure Hg lamp CO reaction mechanism is similar to that of CO2 Kohno et al.31
photoreduction by H2, except that carbonaceous
residue is formed by the reaction of CO2 and CH4
Ti-β zeolite water vapor 100-W high-pressure Hg lamp, CH4, CH3OH H2O molecules can more easily gain access Ikeue et al.22
λ > 250 nm to the tetrahedrally coordinated titanium
oxide species, Ti-β(OH), but high selectivity for
the formation of CH3OH was observed on Ti-β(F).
Ti silicalite methanol 266-nm emission of a pulsed HCO2H, CO, formic acid is primary two-electron reduction Ulagappan
(TS-1) molecular Nd:YAG laser at 10 Hz HCO2CH3 product; C-H bond formation implied to et al.38
sieve occur in the initial step
Pd/RuO2/TiO2, NaOH, aqueous 450-W Xe short-arc lamp formate activity of CO2 photoreduction improved Xie et al.39
Pd/TiO2 Na2SO3 after surface noble-metal deposition
MgO H2 500-W ultrahigh-pressure Hg lamp CO surface formate acts as a reductant and converts Kohno et al.40
CO2 to CO upon irradiation
Ti-containing water vapor 100-W high-pressure Hg lamp CH4, CH3OH Ti-containing mesoporous silica thin films Ikeue et al.41
porous silica exhibited significantly higher activity than powdered
thin films Ti-MCM-41 and high selectivity for CH3OH
formation; high reactivity attributed to their high
transparency
Cu/TiO2, sol-gel- water, NaOH 8-W Hg lamp methanol, methanol favorably produced in CO2/NaOH Tseng et al.42
prepared Cu/P-25 oxygen
[fac-Re(bpy)- TEOA/DMF 500-W Hg lamp with 365-nm CO, H2 moderate CO2 pressure (1.36 MPa) desirable for Hori et al.43
i
(CO)3P(O Pr)3] + band-pass filter efficient CO formation
Pt/K2Ti6O13 with water 300-W Xe lamp, 150-W Hg lamp H2, CH4, methanol and ethanol produced when hybrid Guan et al.32
Fe-based catalyst HCHO, catalyst was used
HCOOH,
CH3OH,
C2H5OH
transparent Ti- water vapor 100-W high- CH4, CH3OH Ti-containing mesoporous silica thin films Shioya et al.44
containing pressure Hg lamp exhibited significantly higher activity than
mesoporous powdered Ti-MCM-41 and high selectivity
silica thin film for CH3OH formation
Co(bpy)32+ DMF/TEOA, Xe lamp with IR-cut filter CO, H2 system allowed easy handling and recovery of Hirose et al.45
sensitized with DMF/H2O/TEOA Ru complex, and CO production was largely
Ru(bpy)3 2+ improved for the partially heterogeneous
system
ZnO on activated - Xe lamp CO, H2 used high temperature (>873 K) via Boudouard Gokon et al.46
carbon reaction; improved gasification occurs by
photocatalysis
[fac-Re(bpy)- Et3N/DMF 500-W Hg lamp with 365-nm CO, H2 use of high CO2 pressure was much more effective Hori et al.47
(CO)3Cl] band-pass filter than addition of excess Cl- ions; turnover number
for CO was 5.1 times that at normal pressure
sol-gel-prepared water, NaOH Hg lamp; UV-C (254 nm), methanol higher copper dispersion and smaller copper Tseng et al.48
Cu/TiO2 UV-A (365 nm) particles on the titania surface correspond to a
greater improvement in CO2 photoreduction
performance
2562 Ind. Eng. Chem. Res., Vol. 45, No. 8, 2006

Table 3. (Continued)
photocatalyst primary
used reductant light source product(s) comments ref
MgO H2, CH4 250-W ultrahigh-pressure Hg lamp CO revealed mechanism of CO2 photocatalytic Teramura
reduction in the presence of H2 or CH4 et al.49
P-25 aqueous 15-W (maximum) source at 365 nm CH4, CH3OH adsorption-controlled reaction rate; reaction Ku et al.50
NaHCO3 can be modeled by Langmuir-Hinshelwood-
type mechanism; more effective at higher acidity
Ti-MCM-41 water vapor 266-nm emission of a pulsed CO, O2 CO2 reduced to CO as a single-photon two- Lin et al.51
Nd:YAG laser at 10 Hz electron-transfer product, with O2 as a coproduct.

radicals are not well dissolved in low-polarity solvents. Here,

CO is produced as the major reduction product of CO2. If a
high-dielectric-constant solvent is used (e.g., water), the •CO2-
anion radicals can be greatly stabilized by the solvent, resulting
in weak interactions with the photocatalyst surface. Subse-
quently, the carbon atom of the radical tends to react with a
proton to produce formic acid.37

•CO2- + •CO2- f CO + CO32- (16)

•CO2- + 2H+ + e- f HCO2H (17)

A study of CO2 photocatalysis in the absence of a reductant

made use of TiO2 powder continuously dispersed in supercritical
CO2 during irradiation with a Xe lamp.37 Following irradiation,
degassed aqueous solution was added to protonate the reaction
intermediates on the TiO2 powder. The results showed that CO2
molecules interact with the excited-state photocatalyst surface, Figure 3. Solar spectrum at sea level with the sun at the zenith.
resulting in the formation of •CO2- radicals. During irradiation,
no gaseous reduction products were identified. It was inferred
that the •CO2- anion radicals cannot be adsorbed on another
•CO2- anion radical, because the excited surface of the
photocatalyst is more active than the •CO2- radical. However,
following a washing process with several solvents, formic acid
was detected. The amount of formic acid increased with the
pH of the solution. From these studies, it was noted that the
amount of H+ in the reductant controls the direction and
selectivity of the CO2 photoreduction products. Nevertheless,
the use of an additional reductant is not commonly employed
in practice because it increases the cost of CO2 reduction. Water
remains the primary hole scavenger used in most applications.
The use of hydrogen as an alternative for CO2 photoreduction Figure 4. Mechanism of photocatalytic reduction of CO2 in the presence
of H2 on ZrO2 (adapted from Kohno et al.37).
results in CO as the major product in a two-step process (Figure
4). Although CO is more toxic than CO2, it is a valuable
substrate for many industrial processes, such as Fischer-
Tropsch synthesis or methanol synthesis. The first step in CO
formation produces formate from CO2 and H2. The second is
the reduction of CO2 to CO on the formate radical.

6. Recombination and Effect of Metal-Modified Surface

Recombination of the photoexcited electron-hole pair retards
an efficient CO2 photoreduction process. Previous photocatalytic
studies have been performed on the loading of the photocatalyst
with metals that function as “charge-carrier traps”. Charge-
carrier traps suppress recombination and increase the lifetime
of the separated electrons and holes. An illustration of electron
trapping with metal in contact with the semiconductor surface
is shown in Figure 5.
Several researchers have investigated the efficiency and
selectivity of processes by modifying the photocatalyst surface
with metal. Hirano et al.59 observed CH4 production from CO2
photoreduction when using a Cu/TiO2 suspension in water. This
was confirmed by Tseng et al.48 for Cu/TiO2 prepared by sol-
gel procedures. They noted that a high copper dispersion on
the photocatalyst surface corresponds to greater improvement
Figure 5. Metal-modified surface photocatalyst.
in the performance of CO2 photoreduction. The presence of Hg
and Pt on TiO2 can accelerate the rate of formation of
formaldehyde.17 Another report claims that photoreduction using
Pd, Rh, Pt, Au, Cu, and Ru deposited on TiO2 photocatalyst
produces methane and acetic acid.60 Pd/TiO2 exhibits a very
high selectivity for methane from CO2 photoreduction. The
effect of Pt loading on the photocatalytic reactivity of Ti-
containing zeolite increased methane and methanol production.61
Metal-loaded surfaces also enhance the efficiency of CO2
photoreduction using hydrogen as a reductant. In 1987, Thampi

et al.62 reported that Rh/TiO2 resulted in a high activity for CO2
photoreduction using hydrogen. In this experiment, the methane
product was selectively obtained, although CO is a more
preferable product.12 In the references mentioned above, it was
noted that the performance of CO2 photoreduction to produce
formaldehyde, methanol, and methane, which consumes more
electrons (eq 9-11), was increased. Because the metal contacts
the semiconductor surface, the electrons can easily flow from
the semiconductor to the metal and distribute on the surface.
Additionally, the holes are then free to diffuse to the semicon-
ductor surface, where oxidation of organic species can occur.
The metal loading must be optimized and uniformly dispersed
over the photocatalyst. An excess metal loading results in a
decreased illuminated photocatalyst surface, as photons cannot
be absorbed because of reflection.
7. Effect of Temperature
Generally, for photocatalysts, photon irradiation is the primary
source of energy for electron-hole pair formation at ambient
temperature, because the band-gap energy is too high for thermal
excitation to overcome. However, at high temperatures, the
reaction rate can be increased by raising the collision frequency
and diffusion rate. Fox et al.63 stated that, like most photore-
actions, photocatalytic reactions are not significantly sensitive
to small variations of temperature.
Gokon et al.46 studied the effect of ZnO on carbon gasification
with CO2 at high temperature and observed that the presence
of ZnO enhanced the CO evolution rate at the lower temperature
of 873 K. However, the photocatalytic effect cannot be induced
at higher temperatures (>1037 K), where the carbothermal
reduction of ZnO dominates. This phenomenon occurs because
the band-gap energy, chemical potential, and excited electron-
hole pair lifetime of ZnO decrease with increased temperature.
In addition, the luminescence quantum yield of ZnO (ratio of
the number of photons emitted to the number of photons
absorbed by the substance) is reduced. This translates into lost
potential for providing energy to stimulate molecules to the
excited state.64
Guan et al.32 attempted to photodegrade CO2 with water under
concentrated sunlight using Pt/K2Ti6O13 photocatalyst combined
with an Fe-based catalyst at high temperature. In this experiment,
the Fe-Cu-k/Day catalyst had no effect on CO2 reduction at
room temperature. However, the yields of HCOOH, CH3OH,
and C2H5OH significantly increased with temperature between
534 and 590 K. Guan’s research group demonstrated that water
decomposition by the photocatalyst is remarkably improved,
because high temperatures enhance the rate of hydrogen
production. The hydrogen from water decomposition was used
in the CO2 hydrogenation process in which Fe-Cu-k/Day acts
as the catalyst.
Photoreduction at high temperatures also was attempted using
TiO2 to photodegrade CO2 with water.65 The products CO, H2,
CH4, and some longer-chain hydrocarbons were detected in
small quantities at temperatures up to 700 K. This investigation
concluded that high temperatures are beneficial to the rate of
thermally activated steps such as desorption, which occur after
photochemical reactions. Some literature reports state that
photocatalytic reactions at high temperature generally suffer
from a decreased excited-state lifetime. Kohno et al.30 noted
that the photoexcitation step of CO2 with hydrogen over ZrO2
can be deactivated with increased temperature. However, the
photoexcitation step does not limit the reaction rate. Many
researchers have concluded that the improved reaction rate must
be due to the thermal step involved in entire reaction process.
Ind. Eng. Chem. Res., Vol. 45, No. 8, 2006 2563
8. Effect of Pressure
Increasing the CO2 pressure is one method for increasing the
concentration of CO2 in aqueous solvent and improving the
reduction selectivity. In fact, investigations have reported the
use of high pressure in both water66,67 and other organic
media.68,69
Saeki et al.68 studied the electrochemical reduction of CO2
under various pressures galvanostatically at 200 mA/cm2 in a
methanol medium. The results show that the current efficiency
(ratio of the electrochemical equivalent current density for a
specific reaction to the total applied current density) of CO2
reduction increased from 23% at 1 atm (0.1 MPa) to 92% at 20
atm (2 MPa). High pressure enhances the reaction, as reflected
in the increased equivalent current density. This effect can be
applied to photocatalysis with the same amount of energy
supplied to the identical system. The difference between
electrochemical reduction and photocatalysis is the source of
electrons. Electrons from the electrochemical process are
supplied by an applied current; electrons for photocatalysis are
supplied by a semiconductor exposed to light radiation.
A similar effect was anticipated for the photoreduction of
CO2 in aqueous solutions when the Mizuno research group
investigated the use of TiO2 powder at high pressure.70,71
Hydrocarbons, such as methane and ethylene, which were not
produced at ambient CO2 pressure, were obtained under high
CO2 pressure (2.5 MPa). However, a long retention time was
required. This can be attributed to the rate of adsorption of CO2
on the surface TiO2 being overcome by the rate of adsorption
of H2 with increasing pressure. Hydrogen species then proceed
to form lower-mass hydrocarbons, such as methane and ethyl-
ene.
The effect of pressure on the photocatalytic reduction of CO2
using TiO2 suspension in isopropyl alcohol solution was also
investigated.27 The results illustrate that the formation of
methane increases with increasing pressure to 2.8 MPa, similarly
to the behavior observed in aqueous solution.71 In isopropyl
alcohol, ethylene cannot be produced even at relatively high
pressure, as no dimerization takes place because of the acceler-
ated formation of methane.
Rhenium bipyridine complexes have received a great deal
of attention for their photochemical properties. Past researchers
have focused primarily on modifying the chemical structure to
improve the catalytic performance. Increasing the CO2 pressure
is another potential approach. Current researchers have dem-
onstrated that CO2 reduction can be achieved at high pressure
using a CO2-soluble rhenium complex without an organic
solvent in a one-phase (up to 7.3 MPa) system of liquid CO2.72
However, the one-phase system had no advantage for the
production of CO. The presence of the gas phase (at pressures
between 1.4 and 5.6 MPa) might be required for efficient CO
formation. Therefore, photoreduction of CO2 to CO is conducted
in a high-pressure two-phase system using [fac-Re(bpy)-
(CO)3P(OiPr)3]+ in dimethylfomamide (DMF) solvent with
triethanolamine (TEOA) reducing agent (reductant).43 The CO
formation rate greatly increased with pressure from 0.10 to 1.36
MPa and gradually increased between 1.36 and 5.57 MPa. The
increased CO formation rate is a result of the increase in CO2
solubility with increasing pressure. This result can also be
observed with triethylamine (TEA) in place of TEOA, although
the CO formation rate is slightly reduced. CO2 is more soluble
in DMF/TEA, and TEA is a more efficient electron donor than
TEOA. Thus, the lower CO formation rate occurs because the
reduction of CO2 to CO requires not only two electrons but
also two protons (Figure 6). TEOA can act as both an electron
2564 Ind. Eng. Chem. Res., Vol. 45, No. 8, 2006
Figure 6. CO-to-CO2 photocatalysis at high pressure using [fac-Re(bpy)-
(CO)3P(OiPr)3]+ (adapted from Hori et al.43).
donor and a proton donor, whereas the stronger base TEA acts
only as an electron donor. The same effect of pressure can be
seen when [fac-Re(bpy)(CO)3Cl] is used in DMF/trimethylamine
(Et3N) under high pressure (2.45 MPa).47
9. Effect of Dispersed Photocatalyst within Zeolites and
Mesoporous Molecular Sieve
Because of the low water solubility of CO2, some researchers
have attempted to perform CO2 photocatalysis in a gas-solid
system. Several reports have shown that the photocatalytic
reduction of CO2 with gaseous water processed on powdered
TiO2 at room temperature forms trace amounts of methane.73-75
The results further show that extremely small TiO2 particles
have higher activities.76 Additionally, highly dispersed TiO2
exhibits a higher reactivity than bulk catalyst powder.33
Because zeolite or silicate frameworks offer unique nano-
scaled pore reaction fields, unusual internal surface topologies,
and ion-exchange capacities, photocatalysts prepared within the
zeolite cavity and framework have a unique local structure and
high selectivity in photoreduction. The photocatalytic reaction
rate and selectivity for the formation of CH3OH depend strongly
on the degree of dispersion of titanium species. The distances
between the two atom centers (atomic distance) of Ti-MCM-
48, Ti-MCM-41, and TS-1 (1.88, 1.86, and 1.8 Å, respectively)
are much shorter than that of bulk TiO2 (1.96 Å) and show
higher dispersion, making them more active in CH3OH forma-
tion. Additional distinguishing features of Ti-MCM-48 that
produce higher reactivity and higher selectivity are three-
dimensional channels and a large pore size (>20 Å).
Highly dispersed TiO2 catalysts prepared within zeolite
cavities as photocatalysts (titanium oxide/Y-zeolite) for CO2
photoreduction increase CH3OH formation.35 Moreover, the
effect of catalyst preparation was studied for both the ion-
exchange and impregnation methods. Those results clearly
indicate that the titanium oxide/Y-zeolite prepared by ion
exchange consists of highly dispersed isolated tetrahedral
titanium oxide species, whereas that prepared by the impregna-
tion method and bulk TiO2 are aggregated octahedral species
that tend to form CH4. The conclusion is that, with bulk TiO2
or aggregated octahedral photocatalyst, the holes and electrons
rapidly separate and move apart. This prevents the reaction
between the carbon radicals and OH• radicals on the same sites
and results in the formation of methane through the reaction
between the H atoms and carbon radicals at the electron
trap.21,33,35,75 Although the synthetic zeolite and mesoporous
molecular sieve produce highly efficient photocatalysis, the
morphology of these materials in powdered form is difficult to
handle in practical applications.
In this context, the synthesis of transparent porous silica thin
films is a subject of current interest.77,79 Transparent porous silica
Table 4. CO2 Photoreduction Three-Phase System Reactors
two-phase systems three-phase systems
fluidized bed trickle bed
packed bed bubble-flow fixed bed
liquid or gas catalysts high-velocity flow
CSTR slurry
bubble slurry
thin films have a larger surface area and efficient light
absorption. The reactivities of titanium-containing porous silica
thin-film mesostructures, Ti-PS(h, 25), Ti-PS(h, 50), and Ti-
PS(c, 50), were studied for CO2 photoreduction by Ikeue et
al.41,44 The results indicated that both Ti-PS(h, 50) and its
powdered form exhibit higher photocatalytic reactivities than
powdered Ti-MCM-41, even with the same pore structure.
Unlike Ti-PS(h, 50), which is tetrahedral, Ti-PS(h, 25) has
an aggregated octahedral structure similar to that of bulk TiO2.
Ti-PS(c, 50) displays a higher selectivity for CH3OH formation,
whereas Ti-PS(h, 25) displays a higher selectivity for CH4
formation. High yields observed with these TiO2-containing
mesoporous photocatalysts can be attributed to their high
transparency and large amount of surface OH•, which lead to a
high selectivity for CH3OH formation.44
10. UV Photocatalytic Reactor for CO2 Reduction
Both solar and UV radiation can be used for CO2 photocata-
lytic reduction. Approximately 10% of the solar flux that reaches
Earth’s surface is useful for photocatalysis, whereas high-energy
UV-light radiation tends to be based on wavelengths that do
not reach Earth’s surface (UV-C range).
Studies of UV photocatalytic reactor designs for CO2 reduc-
tion are limited and have generally been conducted as batch
processes. Conversely, heterogeneous catalytic reactor design
is well researched within the context of wastewater treatment
and air cleansing. Table 4 identifies the variety of heterogeneous
catalytic reactors that can be applied for CO2 photocatalysis
within two major system types: (1) two-phase and (2) three-
phase.
Two-phase systems can be either gas-catalyst or liquid-
catalyst and are typically either fluidized or fixed beds. The
chief advantage of the fluidized bed is that vigorous agitation
of the solid by passing fluids can reduce temperature gradients
within the bed.80 The violent motion of solids also provides
high heat- and mass-transfer rates. The disadvantages of
fluidized beds are erosion by abrasion of catalyst particles and
attrition of the catalyst. Therefore, filters or scrubbers (in gas-
catalyst systems) are required.
For fixed beds, the fluid flow regime approaches plug flow,
so high conversion per unit mass of catalyst can be achieved.
Another advantage of fixed-bed reactors is the low pressure
drop, which enables such systems to be operated at reduced
operating costs.
Among fixed-bed designs, honeycomb monoliths and annular
reactors are the most common because of their higher volumes
and lower pressure drops. These designs are required for gas-
solid systems, which have particularly high gas feed rates.81
Honeycomb monolith reactors have been utilized for automobile
exhaust emission control and NOx reduction in power plant
gases.
The reactor configuration in Figure 7 is an example of a
beneficial design for CO2 photocatalytic reduction. Here, the
channel cross section is typically square or circular. UV lamps
irradiate the monolith from the front and back. Air containing
CO2 is forced through the photocatalyst-coated monolith chan-
 Ind. Eng. Chem. Res., Vol. 45, No. 8, 2006 2565

Figure 7. Schematic diagram of a scale-up honeycomb photocatalytic

reactor for CO2 reduction in the gaseous phase.

Figure 9. Three-phase-system photocatalytic reactor.

Figure 8. Schematic diagram of the annular reactor.

nels.82 A prefilter is typically installed upstream to block large

particles from entering the system and damaging the UV lamps
or reducing the radiation penetration because of turbidity. This
filter might or might not be impregnated with the active
photocatalyst.
An annular reactor is composed of two concentric cylinders
that form an annular region. The interior wall of the tube is
coated with photocatalyst. The UV light source can be located
at the center or around the reactor (Figure 8). In general, the
cross section of the reactor is small, inducing a high gas velocity
to ensure that products desorbed from the surface are removed.83
In three-phase systems, the reactor is operated in one of two
ways (Figure 9): Fixed-bed contactors use large photocatalyst
particles, whereas suspended reactors use very fine suspended
photocatalyst particles. Because of the higher active surface area
and beneficial mass-transfer conditions, suspended systems are
the more efficient of the two.84-86 However, separation and Figure 10. Possible layout of multiple-lamp packed beds for CO2
retrieval of the catalyst is more complex than in fixed-bed photoreduction.
systems, and there is the potential for reduced light penetration
into the slurry. In the past decade, low-cost supported catalysts tochemical, electrochemical, and membrane processes (Figure
consisting of photoactive materials that deposit on transparent 11). One half-cell of this reactor is a proton anode that splits
and inert bodies have been developed significantly. This water into one proton (H+) plus diatomic oxygen and consists
improves not only the surface area of the fixed-bed reactor of sol-gel-deposited TiO2 coated on a Ti metal substrate.
design but also the UV light penetration (Figure 10).87,88 The Electrons transfer directly to another half-cell, whereas protons
proposed design is a bubble-flow fixed-bed column that is are transported through a Nafion membrane. The photons,
cylindrical and contains a bed of catalytic particles and a coaxial electrons, and CO2 molecules react at the electrocatalyst
UV-lamp radiation source. The catalytic bed is a random (platinum modified by zinc oxide) to form new products. Not
packing of relatively small particles made of a UV-transparent only can this reactor convert CO2 into valuable products, but it
material (typically quartz glass) coated with a thin layer of also produces hydrogen, a carbon-free energy source. This
photocatalyst. The reductant flows via gravity countercurrent system works with an efficiency of about 12% under UV
with the CO2 to enhance mass transfer. The product at the irradiation, but only 0.3% with solar radiation.89
bottom of the reactor is separated for reductant reuse. Separation
of the treated gas stream might be necessary to capture beneficial
11. Solar Photocatalytic Reactor for CO2 Reduction
gaseous products.
In addition to the above reactors, a new photoelectrochemical Several comprehensive articles have been published discuss-
cell has been designed that integrates three techniques: pho- ing the design of solar photocatalytic reactors and wastewater
2566 Ind. Eng. Chem. Res., Vol. 45, No. 8, 2006
Figure 11. Hitachi Research Laboratory schematic for a CO2 photoreduc-
tion reactor.
Table 5. Reactor Configurations for Solar Photocatalytic Reactionsa
suspended photocatalyst supported photocatalyst
Concentrating Reactors
parabolic trough reactor parabolic trough reactor
falling-film reactor
Nonconcentrating Reactors with Reflectors
compound parabolic collecting reactor tubular reactor
fiber-optic-cable reactor
Nonconcentrating Reactors without Reflectors
solar pond flat-plate reactor
tubular reactors trickle-down flat-plate reactor
inflatable tube reactor thin-film fixed-bed reactor
pressurized tube reactor
flat-plate reactor
trickle-down flat-plate reactor
double-skin sheet reactor
falling-film reactor
a (NSERC) of Canada is gratefully acknowledged for partial
Adapted from Alfano et al.88
treatment plants. The design concepts for those applications can
potentially be applied for CO2 photoreduction (Table 5). Two
key design issues for solar photoreactor systems include the
options of (i) suspended or supported photocatalysts and (ii)
concentrated or nonconcentrated sunlight.90 The advantages and
disadvantages of each suspended and supported photoreactors
are similar to those under UV photocatalysis. To concentrate
solar radiation, light is gathered and concentrated in a photo-
catalytic reactor by a reflecting surface. The volume of this
reactor type is smaller than that of the nonconcentrating type
for the same light-harvesting area. Nonconcentrating systems
can use more sunlight because they capture diffuse UV light,
as well as direct solar beams. They also use light more efficiently
than concentrating systems.91 However, nonconcentrating sys-
tems function as both solar collectors and photocatalytic reactors,
translating into much larger systems than required for the
concentrating configuration.
The key design differences between wastewater and CO2
treatment systems are that wastewater systems are designed for
organic and biological destruction in an aqueous solution,
whereas CO2 systems must first dissolve CO2 in water or another
solvent prior to the destruction of the gas into beneficial
byproducts. Therefore, CO2-capture plants that use chemical
absorption can divert CO2-rich solvents through photocatalytic
reactors rather than directly to regeneration units.
12. Conclusion
The use of photocatalysis for the reduction of CO2 emissions
is an innovative alternative technology. Although there are few
current options for the application of this technology, photo-
catalysis is a potentially economical and environmental CO2
removal process. Understanding the parameters that influence
photocatalysis is essential to developing this technology for
practical use.
There are three general methods for improving the efficiency
of a photocatalytic process. The first is choosing semiconductors
with appropriate band-gap energies. The proper structure of the
photocatalyst can improve the product selectivity and yield and
increase the rate of reaction. Therefore, photocatalyst preparation
is one of the most important steps that can enhance the capacity
of a photoreduction system.
The second improvement method involves reductant develop-
ment. The effectiveness and product selectivity of photocatalytic
reactions are obtained using the appropriate reductant. Water
is the most common reductant, although the solubility of CO2
in water is particularly low, and the reaction is in competition
with H2 and H2O2 formation. By performing the photocatalytic
reaction in the gas phase, this difficulty can be eliminated.
Hydrogen and some organic solvent are alternative reductants,
but they are too costly to replace water.
The third and last method is to optimize operating conditions
including temperature, pressure, light intensity, and operating
wavelength. These will not only provide a high reaction activity
but can also improve the selectivity to and yield of products.
Photocatalytic systems using solar energy for CO2 reduction ar
eone attractive option for CO2 emissions reductions. Further
research should focus on the potential and economics of solar
reactors and their design.
Acknowledgment
The Natural Sciences and Engineering Research Council
financial support of this project.
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ReceiVed for reView May 16, 2005
ReVised manuscript receiVed November 24, 2005
Accepted November 29, 2005
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