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Application of TiO2 Photocatalysis

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 NESAJ Patra, Vol. 9, March

Application of TiO2 Photocatalysis for the Treatment of NOx

-Ananta Kumar Karki

Mr. Karki has completed Master degree in Environmental Science from Tribhuvan
University in 2007 and Masters of Philosophy in Environmental Technology from The Joint
Graduate school of Energy and Environment, Bangkok in 2010. He is currently working at
DEMCO Public Company Ltd Bangkok as an Environmental Manager at West Huay Bong 02,
03 Wind Farm, Nakhornratashima Province, Thailand. His research interest includes Environ-
mental Nanotechnology, Photocatalysis, Renewable Energy Development, Environmental
Management, Climate Change, Waste Management, and Water Resource Management.

Abstract
As air pollution is increasing problem in every
urban area, photocatalytic oxidation of these
inorganic pollutants by TiO2 under UV and visi-
ble light has become a promising field for future
pollution control technology. NOx can easily be
degraded into less harmful products such as
HNO3 and water by TiO2 photocatalytic reac-
tion. Various researches regarding effective
treatment of NOx under UV and visible light
with the application of TiO2 have been reviewed
in this paper.
Keywords: TiO2, Photocatalysis, NOx
1. Introduction
1.1 Air pollution
The increased air pollution is one of the serious
problems of urban areas and cause of many hu-
man health related problems. It is particularly
affected by environmental conditions such as
high population density, large traffic volume,
poor wind condition and roadside surrounded
by high-rise buildings. This leads to a poorer
dispersion of the pollutants such that the rapid
pollutants generation rate outweighs the disper-
sion rate. Nitrogen oxides (NOx), carbon mon-
oxide (CO), sulphur oxides (Sox) and volatile
organic compounds (VOC) are the main compo-
nents in polluted air.
Various processes such as combustion modifica-
tion, dry processes and wet processes are availa-
ble for pollution control but they require rela-
tively high operating temperature and good
maintenance to ensure good abatement on pol-
lutant emissions (Devahasdin, et al, 2003). Pho-
to-catalytic process can be potential means in a
long-run pollutant treatment strategy because of
its ability to oxidize low concentration pollu-
tants at ambient temperature and pressure, com-
plete mineralization of hydrocarbon, byproducts
amenable to bio-remediation and potential utili-
zation of solar energy. Photocatalytic oxidation
(PCO) is shown to be more cost effective than
incineration, carbon adsorption and bio-filtration
for flow rates up to 20000 ft3/min for treating
500 parts per million (ppm) VOC laden com-
pounds. (Devahasdin, et al, 2003).
1.2 Photocatalysis
Photocatalytic oxidation (PCO) of volatile or-
ganic compounds (VOCs) and a microorganism
is a highly attractive alternative technology for
purification and deodorization of air and water.
Heterogeneous photocatalytic oxidation is an
effective technique for reducing the concentra-
tions of pollutants at low concentrations. It has
been demonstrated that organic compounds can
be oxidized to carbon dioxide, water and simple
mineral acids at room temperature using Titani-
um dioxide (TiO2) catalysts in the presence of
UV or near-UV illumination (Ahmed and Ollis,
1984).
TiO2 is a metal oxide semiconductor with high
band gap energy, 3.2 electron volt (eV). The
mechanism of the photocatalytic oxidation is
simple. Its capacity in oxidizing pollutants arises
from the generation of highly oxidizing hydroxyl
radicals (•OH). Under UV radiation (wavelength
< 387.5 nm), which exceeds the TiO2 band gap
energy level of 3.2 eV, an electron (e-CB) in the
valence band is excited to the conduction band
(CB) leaving behind the positive hole (h+VB) in
the valence band (VB). The mechanism is shown
in (Fig. 1). The positive hole reacts with water
or hydroxide ion to generate hydroxyl radical
(•OH)
h+VB + OH- •OH (1)
+ +
h VB+ H2O •OH + H (2)

7
 NESAJ Patra, Vol. 9, March
If the oxygen is present, the electron will react with N2, O2 and N2O. But under the same condition pure
them and form superoxide ions (O2•-) TiO2 catalyst did not exhibit any photocatalytic ac-
e-CB + O2 O2•- (3) tivity (Kumar et at., 2005). The main objective of
Then the water molecule reacts with O2•- and gen- the paper is to study how TiO2 has been applied for
erates additional •OH. degradation of NOx and its effectiveness in treating
2 O2•- + 2H2O H2O2 + 2OH- + O2 (4) it under UV and visible light.
-
H2O2 + e CB OH- + •OH (5)
The generated •OH can then oxidize pollutants on 2. Methodology
the catalyst surface. For example, Oxidation of For this study, recent research papers on TiO2 pho-
NOx leads to the formation of NO3- on the surface tocatalysis of various pollutants were widely stud-
of catalyst. The sequence is: ied. However, about a dozen of research papers
NO NO2 HNO3 (6) were relevant to our objective and they were re-
viewed in detail and reported in this review.

Figure 1: Illustration of the major processes occurring on a semiconductor particle following

electronic excitation. Electron-hole recombination can occur at the surface (reaction (a)) or
in the bulk (reaction (b)) of the semiconductor. At the surface of the particle, photo generat-
ed electrons can reduce an electron acceptor A (reaction (c)) and photo generated holes can
oxidize an electron donor D (reaction (d)). (Mills and Hunte, 1997)

The widespread technological use of a TiO2 photo- 3. Results and discussion

catalyst has been hampered by its wide band gap
(3.2 eV for anatase TiO2), resulting generally in the
requirement of ultraviolet radiation (λ=380 nm) for
photocatalytic activation. Thus, the development of
visible light active TiO2 is of paramount importance
to the development of photocatalysts active under
solar radiation or even interior room lighting
(Kumar et at., 2005). Metal ion implantation such
as V, Cr, Mn, Fe and Ni enable a pronounced lower-
ing of energy of the conduction band edge of TiO2
catalyst thus facilitating visible light photocatalysis.
Visible light irradiation (λ=450nm) of the Cr ion
implanted TiO2 catalyst degraded NO at 275 K into
8
In general, TiO2 is immobilized on beads, hollow
tubes, woven fabric, silica gel, and so on using the
methods such as the dip coated method and sol–gel
method (Zhao and Yang, 2003). Generally either
UV light or visible light is used for photocatalytic
reaction. In the case of visible light, TiO2 is doped
with various transitional metals (Fe, Ni, V, or Cr),
non metals (C, F, N, S) or organic compounds or
dyes to make it visible light sensitive. Fix concen-
tration of pollutants is injected into the reactor to be
adsorbed on the immobilized TiO2 surface and irra-
diated with appropriate radiation to initiate the
treatment process. Three main types of reactors;

honeycomb monolith, fluidized-bed and annular
have been widely used. In order to get higher con-
version rate, the reactors are designed so as to pro-
vide efficient contact among UV photons, solid cat-
alyst and gaseous reactants (Zhao and Yang, 2003).
NESAJ Patra, Vol. 9, March
Better PCO of NO can be achieved by using TiO2
immobilized on an activated carbon (AC) filter.
Higher removal efficiency of NO can be achieved
by using TiO2/AC than using TiO2 alone (Fig. 3).
The higher removal efficiency is mainly due to the

Fig. 2: Schematic diagram of the photocatalytic oxidation equipment. 1 –NO; 2 – N2; 3 – pu-
rified air; 4 – flow meter; 5 – water saturator; 6 – Hg-arc lamp; 7 – hollow chamber; 8 –
thermocouple; 9 – Pyrex reactor; 10 – catalyst; 11 – fan; 12 – drier; 13 – gas analyzer; 14 –
wet scrubber.

large adsorption area provided by AC. Similarly

3.1 Photocatalytic degradation NOx under UV higher removal efficiency can be achieved using
light short wave UV (Ao and Lee, 2005).
Emission of nitrogen oxides is the result of high
temperature combustion. Concentration near con-
gested roadways and in tunnels can exceed 1-2 ppm
of NOx, mostly in the form of NO. At locations
away from immediate sources, the NOx is present
mostly in the form of NO2 (Berdahl
et al. 2008). Long-term exposure to NO2 can irritate
lungs and lower resistance to respiratory infections.
Moreover, NOx is attributed to the formation photo-
chemical smog and peroxy acetyl nitrates (PAN).
Wang et el. (2007) studied the photocatalytic oxida-
tion of nitrogen oxides using TiO2 loading on wo-
ven glass fabric. The photo-catalytic oxidation
(PCO) efficiency reached 27% when the inlet con-
Figure 3: NO removal using TiO2 filter and TiO2/
centration of NO was 147 ppm. The reaction rate
AC filter
depended on several factors such as relative humid-
ity, space time, inlet concentration and oxygen con-
The PCO of NO involves a series of oxidation steps
centration. During the reaction hydroxyl radical and
by OH● radical: NO to HNO2 to NO2 and finally to
active oxides play an important role in the oxida-
HNO3. The product NO2 can be collected in an ad-
tion. Deactivation of catalyst is due to the accumu-
sorbent bed or as HNO3 (Devahasdin et al., 2003).
lation of nitric acid and nitrous acid on the TiO2 sur-
Photocatalytic properties of TiO2 Degussa P25 pow-
face. But it can be easily recovered by simple heat
der (commercial TiO2 powder) with respect to nitro-
treatment. Schematic diagram of the photocatalytic
gen oxides removal was higher when anatase and
oxidation equipment used is shown below (Fig. 2).
rutile structure were present than only the rutile
9

structure was present in TiO2 powder. Anatase and
rutile are two most common polymorph of TiO2
crystal. Generally the anatase structure shows better
efficiency for the photocatalytic degredation of the
nitrogen oxides. (Toma et al. 2004).
3.2 Photocatalytic degradation NOx under visi-
ble light
TiO2 can utilize UV light well for photocatalytic
oxidation of various pollutants. But because of its
high band gap (3.2 eV), it cannot be sensitized by
visible light. So it is to be modified by doping with
various transitional metals such as Cr, V, Fe
(Hwang et al., 2003 and Zhan et al., 2006). A signif-
icant shift of adsorption edge to a lower energy and
a higher absorption in the visible light reaction is
obtained by nitrogen doping method (Asahi et al.,
2001). Degradation of NOx by N-doped TiO2 was
found to be significant. 100% removal ability was
obtained within 5 hr of reaction. Then the removal
rate decreased over time. But the catalyst can be
recovered by rinsing with water (Fig. 4) (Zhou et
al., 2007).
Fig. 4: Lifetime and regeneration of N-codoped
TiO2 for oxidation of NOx (Catalyst loading=3 g,
relative humidity=90%, feeding concentration of
NO2=2.0 ppm, feeding flow rate=0.5 L/min).
4. Conclusion
Application of TiO2 for the degradation of air pollu-
tants especially NOX, can be promising technology
for pollution control. NOx can easily be degraded
into less harmful products such as HNO3 and water
by TiO2 photocatalysis. However the wide applica-
tion of TiO2 is limited because of its negligible ac-
tivity under visible light. Many researches are going
on to modify UV sensitive TiO2 to visible light ef-
fective TiO2 by transitional metal doping or anion
doping. Nitrogen doping is one of the best ways to
make TiO2 react under visible light.
10
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NESAJ Patra, Vol. 9, March
References
Ahmed, S. & Ollis, D.F. (1984). Sol. Energy, 32 (5),
597.
Ao, C.H. & Lee, S.C. (2005). Indoor air purification by
photocatalyst TiO2 immobilized on an activated car-
bon filter installed in an air cleaner. Chemical Engi-
neering Science 60, 103 – 109.
Asahi, R., Morikawa, T., Ohwaki, T., Aoki, K., & Taga,
Y. (2001). Science 293, 269.
Ber-
dahl, P., & Akbari,H. (2008). Evaluation of Titanium
Dioxide as a Photocatalyst for Removing AirPolluta
nts. California Energy Commission, PIER EnergyRe
lated Environmental Research program.
Devahasdin, S., Fan, C., Li, J.K., & Chen, D. H. (2003).
TiO2 photocatalytic oxidation of nitric oxide: transi-
ent behavior and reaction kinetics. Journal of Photo-
chemistry and Photobiology A: Chemistry 156, 161–
170.
Hwang, S., Lee M.C., & Choi W. (2003). Highly en-
hanced photocatalytic oxidation of CO on titania
deposited with Pt nanoparticles: kinetics and mecha-
nism. Applied Catalysis B: Environmental 46, 49–
63.
Kumar, S., Fedorova, A.G., & Golea, J. L. (2005).
Photodegradation of ethylene using visible light
responsive surfaces prepared from titania
nanoparticle slurries. Applied Catalysis B:
Environmental 57, 93–107.
Mills, A., & Hunte, S.L. (1997). An overview of semi-
conductor photocatalysis. Journal of Photochemistry
and Photobiology A: Chemistry 108, 1-35.
Toma, F. L., Bertrand, G., Klein, D., & Coddet, C.
(2004). Photocatalytic removal of nitrogen oxides
via titanium dioxide. Environ Chem Lett 2, 117–121.
DOI 10.1007/s10311-004-0087-2.
Wang, H., Wu, Z., Zhao, W. & Guan, B. (2007).
Photocatalytic oxidation of nitrogen oxides using
TiO2 loading on woven glass fabric. Chemosphere
66, 185–190.
Zhao, J. & Yang, X ( 2003). Photocatalytic oxidation for
indoor air purification: a literature review. Building
and Environment 38, 645 – 654.
Zhou, L., Tan, X., Zhao, L. & Sun, M. (2007).
Photocatalytic oxidation of NOx over visible-light-
responsive nitrogen-doped TiO2. Korean J. Chem.
Eng., 24(6), 1017-1021.