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Photocatalytic Applications of Micro- and
Nano-TiO
2
in Environmental Engineering
Soonchul Kwon
a
, Maohong Fan
b
, Adrienne T. Cooper
c
& Hongqun
Yang
d
a
School of Civil and Environmental Engineering, Georgia Institute of
Technology, Atlanta, Georgia, USA
b
School of Materials Science and Engineering, Georgia Institute of
Technology, Atlanta, Georgia, USA
c
Department of Civil and Environmental Engineering, Temple
University, Philadelphia, Pennsylvania, USA
d
Department of Chemical and Materials Engineering, University of
Alberta, Edmonton, Alberta, Canada
Version of record first published: 06 Mar 2008
To cite this article: Soonchul Kwon, Maohong Fan, Adrienne T. Cooper & Hongqun Yang (2008):
Photocatalytic Applications of Micro- and Nano-TiO
2
in Environmental Engineering, Critical Reviews in
Environmental Science and Technology, 38:3, 197-226
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Critical Reviews in Environmental Science and Technology, 38:197226, 2008
Copyright Taylor & Francis Group, LLC
ISSN: 1064-3389 print / 1547-6537 online
DOI: 10.1080/10643380701628933
Photocatalytic Applications of Micro- and
Nano-TiO
2
in Environmental Engineering
SOONCHUL KWON,
1
MAOHONG FAN,
2
ADRIENNE T. COOPER,
3
and HONGQUN YANG
4
1
School of Civil and Environmental Engineering and
2
School of Materials Science and
Engineering, Georgia Institute of Technology, Atlanta, Georgia, USA
3
Department of Civil and Environmental Engineering, Temple University, Philadelphia,
Pennsylvania, USA, and
4
Department of Chemical and Materials Engineering, University of
Alberta, Edmonton, Alberta, Canada
The photocatalytic activity of micro- and nano-titanium dioxide
(TiO
2
) has been utilized to signicantly improve the degradation
efciencies of various contaminants in both water treatment and
air pollution control. This article is a review of the literature cov-
ering current research on environmental applications of micro-
and nano-TiO
2
. The mechanisms of contaminant degradation of
nanoparticle TiO
2
are reviewed, and its special properties are com-
pared to micro-sized TiO
2
in air purication and water treatment.
1. INTRODUCTION
Because of their promise for a wide range of applications in catalysis, sensors,
and molecular electronics, much attention has been paid recently to research
on micro and nano materials.
1,2
Micro and nano materials evidence unusual
chemical, mechanical, optical, electrical, and magnetic properties compared
to traditional materials.
3
Since considerable research has shown that many
applications of micro- and nanomaterial properties depend on their specic
surface area, it is clear that a decrease in particle size will lead to improved
and expanded application.
4
For example, nanocatalysts having small particle
size, high surface area, and a high density of surface coordination unsaturated
sites offer improved catalytic performance over microscale catalysts. They are
Address correspondence to Mahong Fan, School of Materials Science and Engineering,
Georgia Institute of Technology, Atlanta, GA 30332, USA. E-mail: mfan3@mail.gatech.edu
197
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198 S. Kwon et al.
especially attractive candidates in applications where the degradation rates
of contaminants are of major concern.
512
The surface effects of micro and nanoparticles are extremely important.
13
For spherical nanoparticles with a diameter of 3 nm, about 50% of the
atoms or ions are on the surface, allowing both the possibility of manip-
ulating bulk properties by surface effects and near-stoichiometric chemical
reactions.
7
Due to their extreme sensitivity, the structural failure of nanoma-
terials frequently occurs on the material surface. Typically, optimization of
the nanoparticle structure is conducted under the condition that the particles
are larger than 5 nm.
14
The potential benets of photocatalysis have been reported in a large
number of studies published in recent decades. Heterogeneous photocataly-
sis has been applied in water treatment and air pollution control. A photocat-
alyst can facilitate the breakdown and removal of a variety of environmental
pollutants at room temperature by oxidation, using either sunlight or articial
light as an energy source. In the photo-oxidative removal of potentially toxic
organic or inorganic compounds present in the environment, primary atten-
tion has been given to the role of titanium dioxide (TiO
2
) over compounds
such as ZnO, CdS, and WO
3
. This attention is due to its high photocatalytic
activity, biological and chemical inertness and stability, resistance to pho-
tocorrosion, low cost, nontoxicity, and favorable band-gap energy.
11,1524
Indeed, laboratory studies have demonstrated that TiO
2
is the most suitable
photocatalyst of all these compounds for widespread environmental treat-
ment and other applications. These applications include the destruction of
microorganisms such as bacteria
2527
and viruses
28
the inactivation of can-
cer cel1s,
29,30
odor control,
31,32
the conversion of NO
x
,
3344
the removal of
mercury,
4553
the conversion of SO
2
,
40,5463
and the decomposition of oil
spills.
6471
Furthermore, a TiO
2
photocatalyst that exhibits high activity for
the oxidation of volatile organic compounds (VOCs) under ultraviolet (UV)
radiation offers an economically and technically practical means to clean air
and water. This article provides an overview of the underlying principles
governing environmental applications of TiO
2
as a photocatalyst.
2. MECHANISM OF THE TIO
2
-BASED PHOTOCATALYTIC
DEGRADATION PROCESS
The primary applications of TiO
2
fall in the areas of pigments, adsorbents,
and catalytic supports. The solgel route is regarded as a good method for
synthesizing ultrane metallic oxides,
73,74
and therefore has been widely used
to prepare TiO
2
particles. There are three different phases of TiO
2
: anatase,
rutile, and brookite.
81
Although all are expressed with the same chemical
formula (i.e., TiO
2
), their crystal structures are different. The anatase phase
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Photocatalytic Applications of Micro- and Nano-TiO
2
199
has a tetragonal structure and, in terms of thermodynamics, is a metastable
phase.
81
An anatase-to-rutile phase transformation occurs during heat treat-
ment at about 900 K, and has an energy band gap of 3.2 eV.
81
The rutile
phase has a tetragonal structure that is stable at high temperatures and has
an energy band gap of 3.0 eV.
81
The brookite phase has an orthorhombic
structure but, as it has many defects in its crystal structure,
81
has not been used
as a photocatalyst. Because the band gap energy of the rutile and anatase
phases is slightly greater than that of brookite, they both absorb primar-
ily ultraviolet rays. However, the rutile type can absorb some visible rays.
Among the three types of TiO
2
, the anatase form appears to be the most
photoactive
11,15,16,22,24,50,52,72,77,8284
and the most practical for widespread
environmental applications such as water purication, wastewater treatment,
and air pollution control, although anatase mixed with rutile has been found
to be highly photoactive as well.
81
Figure 1 illustrates the mechanism of the photocatalytic degradation pro-
cess. When TiO
2
photocatalyst is irradiated with energy equal to or greater
than the band gap (E), it is thought to undergo the mechanism described by
Eqs. (1)(5):
14,8587
TiO
2
+h h
+
vb
+e

cb
(1)
H
2
O+h
+
vb
OH +H
+
(2)
h
+
vb
+Pollutant
(ads)
Pollutant
+
(3)
OH +Pollutant
(sol)
CO
2
+H
2
O (4)
O
2
+e

cb
O

2
(5)
FIGURE 1. Primary mechanism of photocatalytic reaction. Path 1: formation of charge carries
by a photon. Path 2: charge carrier recombination to liberate heat. Path 3: production of
superoxide by a conduction band electron. Path 4: production of hydroxyl radical (OH).
14
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200 S. Kwon et al.
With the absorption of photons by TiO
2
, electrons (e

cb
) and positive holes
(h
+
vb
) are produced; electrons move to the conduction band (CB) to create
positive holes in the valence band (VB), which disperse on the surface of
TiO
2
. These charges either can recombine to produce heat or can be used
to reduce or oxidize species in solution at the TiO
2
surface. The positive
holes react with H
2
O [Eq. (2)] or the pollutants adsorbed at the TiO
2
surface
as shown in Eq. (3). Also, two highly reactive substances are formed, as
indicated in Eqs. (2) and (5): hydroxyl radicals (OH) and a super-oxide
anion (O

2
).
88
A possible second way of contaminant degradation occurs
at the liquid/solid interface by means of the hydroxyl radical [Eq. (2)],
87
which can initiate the degradation of the adsorbed chemical species by one
or more forms of electron transfer reactions at room temperature with a
UV light source [Eq. (4)]. Photocatalytic reactions provide not only photo-
excited holes and electrons, but also oxidatively and reductively generated
active oxygen species.
88
As an example, the photocatalytic degradation of
ethanol (CH
3
CH
2
OH) on TiO
2
is described next:
14
TiO
2
+h h
+
vb
+e

cb
(6)
H
2
O+h
+
vb
OH +H
+
(7)
CH
3
CH
2
OH +OH CH
3
C HOH +H
2
O (8)
CH
3
C HOH +O
2
CH3CH(OH)OO (9)
CH
3
CH(OH)OO +CH
3
CH2OH CH
3
CH(OH)OOH +CH
3
HOH (10)
CH
3
CH(OH)OOH CH
3
CHO+H
2
O
2
(11)
Ethanol reacts with O
2
on TiO
2
surfaces, and an organoperoxyl radical
(CH
3
CH(OH)OO) is subsequently formed as an intermediate step. Finally,
acetaldehyde (CH
3
CHO) and hydrogen peroxide (H
2
O
2
) are produced.
3. PHOTOCATALYTIC DEGRADATION REACTORS
As shown in Figure 2, various types of photocatalytic reactors have been
designed for water treatment. Well-mixed heterogeneous batch reactors have
been employed in laboratory experiments, for the most part. In most cases
(Figure 2c), UV sources from outside of the reactor illuminate on one side and
the photons from UV lamps (usually mercury lamps) are dispersed toward the
pollutant inside the reactor (Figure 2d). The reactor designs for photocatalytic
degradation with micro and nano-TiO
2
particles are similar.
19,24,70,78,89
3.1. Photoreactors for Water Treatment Systems
Photoreactors were employed in water treatment processes to per-
form photocatalytic reactions over nano-TiO
2
powder in liquid
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Photocatalytic Applications of Micro- and Nano-TiO
2
201
FIGURE 2. Photocatalytic laboratory reactor congurations: (a) jacketed batch photoreactor
for water degradation with center UV source;
24
(b) circulating ow photoreactor with UV lamp
at water phase;
11
(c) uidized-bed continuous-ow gas reactor illuminated from outside UV
source;
89
(d) continuous-ow gas photoreactor with center UV lamp.
78
suspensions.
19,50,70,72,75,80,90
Inside the reactor, the mixture of the pho-
tocatalytic reaction was maintained in suspension by means of a magnetic
stirrer. Synthesized nano-TiO
2
particles are known for their dispersion in
water.
77
The dispersion of nano-TiO
2
was irradiated with a UV lamp as the
UV source, placed in the center of the reactor, as shown in Figure 2, a and
b. Cooling water (Figure 2a) or continuous gas (Figure 2b) was circulated
through the inner sleeve to control the temperature in the reactor. Li et al.
19
used pure oxygen or ozone containing oxygen bubbled continuously into
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202 S. Kwon et al.
the solution to maintain a constant temperature, whereas Szab o-B ardos et
al.
11
have used continuous air or argon gas. Also, water can sometimes be
used to maintain a constant temperature.
The photoreactor illustrated in Figure 2a has an internal light source
contained in a cylinder of quartz glass; therefore, degradation of crude oil
could be initiated with illumination in the wavelength range of = 240375
nm without direct contact with the light source.
24
Toluene and asphaltene
were solubilized by 8 mM of anionic surfactant (sodium dodecyl sulfate, SDS)
in water and their photocatalytic degradation was performed using H
2
O
2
in
0.1% (w/v) aqueous suspension of TiO
2
.
24
The F2 crude oil was emulsied
into water under intensive cooling at 25 0.5

C with addition of H
2
O
2
during
10 h of irradiation.
24
The photochemical reactor shown in Figure 2b uses continuously fed
air, at a ow rate of 40 dm
3
/h, to provide circulation within the reactor. As in
the previously described reactor, the light source (40W,
max
= 350 nm) does
not come in contact with the water. The light source is placed at the center
of the reactor, and a glass tube between the internal (quartz) and external
(glass) walls separates the reactor of 3 dm
3
into two parts.
11
The outlet gas
ows out at the top of the reactor and a septum is located for sampling from
the bottom.
Initial TiO
2
photocatalytic reactor design research for water treatment
evaluated slurry reactors. In numerous photocatalytic water treatment studies,
both micro- and nano-TiO
2
particles have demonstrated excellent degrada-
tion capabilities,
11,15,1721,2325,30,31,33,34,38,45,46,5153,67,74,77,78,80,84,88,89,9199
sorption of contaminants,
35,54,55,5760,63,83
and load-carrying capacity.
1,3,100
However, the slurry reactor design requires additional steps, such as
ltration and/or centrifugation to separate the photocatalyst particles
from the water. The addition of these unit processes adds signicantly
to the process complexity and cost.
86
Alternative congurations provide
either uidized
11,89,96,98,99
or xed-bed reactors.
22,24,51,52,70,72,85,87,101
One
of the most practical applications of photocatalysis is the use of xed-
bed reactor congurations with immobilized particles or semiconductor
ceramic membranes.
86
Fixed-bed reactors for water or gas-type treat-
ment processes continuously use the photocatalyst, eliminate the need
for postprocess ltration and particle recovery, and facilitate catalyst
regeneration.
3.2. Photoreactors for Gas-Phase Treatment System
Contrary to the dispersion of micro and nano-TiO
2
powder in water treat-
ment processes, in the photocatalytic reaction of gas treatment systems the
uniform distribution of free-owing micro- and nano-TiO
2
inside the reac-
tor plays a key role. The distributed photocatalyst illuminated by UV light
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Photocatalytic Applications of Micro- and Nano-TiO
2
203
contacts the reactant pollutant as it ows continuously through the photore-
actor. Research for gas-phase photocatalytic reactions has been carried out
primarily in glass continuous-bed reactors, utilizing a UV lamp placed either
outside or inside the reactor, as shown in Figures 2, c and d, respectively.
78,89
A UV source from outside of the reactor, particularly if it is only from one
side, may not illuminate uniformly to the central location of the packed TiO
2
.
Thus, a UV lamp located in the middle of the reactor affords better photo-
catalyst performance.
11,78,89
The uidized-bed reactor shown schematically in Figure 2c is a at-wall,
parallel-plate reactor formed from 7042 Pyrex glass.
89
As light is transmitted
into this photoreactor from outside the reactor, coarse glass frit sealed in the
reactor feed tube maintains uniform gas distribution and provides support of
the catalyst bed. A single 4-W uorescent UV source (GE F4T5-BLB) aligned
parallel to the at reactor wall uniformly illuminates the uidized catalyst.
Inlet and outlet gases were sampled manually with a Carle valve and sub-
sequently analyzed for the concentration prole using gas chromatography
(GC) with ame ionization detection (FID).
89
The photoreactor represented in Figure 2d consists of a UV lamp, pro-
ducing 2.2 W (around
max
=365 nm), surrounded by several layers of TiO
2
immobilized on berglass mesh. The layers of catalyst screen are optimized
to completely absorb/diffract the light and induce turbulent air ow.
78
Mass
ow meters were used to insure a constant ow (624 L/h) of air contain-
ing a given concentration of the pollutant studied and, in some cases, of
ozone.
78
4. ORGANIC POLLUTANT DEGRADATION OVER TIO
2
Volatile organic compounds (VOCs) are emitted into the atmosphere, soil,
and water from a variety of anthropogenic activities, such as transportation
and discharges from residences, businesses, and industrial facilities. They
cause environmental degradation of soil and groundwater,
24,66
and the con-
tribute to air pollution.
15,83
The two main criteria for photocatalyst suitability
for the degradation of volatile organic compounds are (1) that the redox
potential of the H
2
O/OH (OH

= OH + e

; E
o
= 2.8 V) couple falls
within the appropriate band gap of the catalyst and (2) that the photocata-
lyst remains stable over long periods.
86
Photochemical reaction properties
of non-nano-sized TiO
2
is the same as that of nano-sized TiO
2
, but the
degradation capability of nano-TiO
2
is much greater because of the large
specic surface area and high density of surface coordination.
4
Recent stud-
ies have revealed the signicant photocatalytic degradation capability of
nano-TiO
2
for aromatic compounds such as benzene, toluene, phenol, and
catechol.
19,73,77,78,102
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4.1. Decontamination of Benzene
Benzene is an aromatic hydrocarbon resulting from burning of coal, gasoline,
and other fuels. Benzene is also used in the manufacture of plastics, deter-
gents, pesticides, and other chemical processes.
73
Fu et al.
73
used a glass
xed-bed reactor with a UV lamp in the middle and 19 g of 350-nm TiO
2
to investigate gas-phase mineralization of benzene. Utilizing benzene in air
at a concentration of 491 ppmv, experiments were carried out in the range
of 70140

C.
73
The concentrations of benzene and carbon dioxide were an-
alyzed by using the GC/FID and GC/TCD, respectively. Figure 3 shows the
results of these experiments as a function of temperature. Line 1 shows the
control, catalyst with no illumination, while line 2 illustrates the conversion
of benzene with UV illumination. With and without illumination, the mineral-
ization of benzene improved with increasing temperature. At 140

C, conver-
sion efciency attained its maximum of 30% for the thermocatalytic process
(line 1), while it reached 90% for photocatalytic reaction under UV irradia-
tion (line 2). This result indicates that TiO
2
photocatalysis is effective for the
mineralization of benzene. Because the initiation of photocatalytic energy
is dominated by photons, photocatalytic reactions are generally minimally
affected by increases in temperature;
103
however, this study was affected by
even small variations in low temperature (70140

C). This is likely due to the

high specic surface area and porosity of nanosized TiO
2
, which enhances
photocatalytic activity and improves initiation of the photoreaction at lower
temperatures.
FIGURE 3. The decontamination of 491 2% ppm benzene balanced with N
2
at a concen-
tration of (1) thermocatalytic control; (2) photocatalytic reaction with (350 nm) nano-TiO
2
catalyst (line 2); mass of catalyst 19 g;.
73
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Photocatalytic Applications of Micro- and Nano-TiO
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205
4.2. Degradation of BTX
Benzene, toluene, and xylene (BTX) are recognized as harmful VOCs be-
cause of their adverse effects on the human nervous system. Exposure to BTX
occurs via contact with gasoline, kerosene, heating oil, paints, and lacquers,
either via inhalation or skin contact, and through drinking contaminated well
water.
104
Pichat et al.
78
demonstrated the photocatalytic effect of TiO
2
on BTX
degradation using the photoreactor previously described in section 3.2 and
shown in Figure 2d. In the Pichat experiments a 9-W UV lamp is surrounded
by layers of xed TiO
2
mesh that maintain turbulent air ow inside the reac-
tor and completely absorb the radiant ux emitted by the UV lamp. Outside
air was introduced into the reactor before each experiment for 15 min. The
details of the experimental procedure are the same as those presented in
section 3.2. The results of photocatalytic BTX degradation in this study are
shown in Figure 4. This result clearly indicates that the concentrations of
benzene, toluene, and xylene each declined within 1 h by photocatalytic re-
action, with the removal efciencies of toluene and xylene over 60% and 50%,
respectively. However, although the conversion of benzene was almost 70%
within 1 h, removal efciency decreased to 25% at 15 ppb concentration in
this study. They found that in order to enhance photoreaction performance,
contact time between contaminants and the TiO
2
surface area should be
sustained by limiting the air ow rate (e.g., to 50 L/h). By comparison, a
conversion efciency of benzene greater than 90% was shown in the study
FIGURE 4. The degradation of BTX [benzene (x), toluene (), o-xylene (), and both m- and
p-xylene ()] by nano-TiO
2
-coated ber glass mesh (50 g/m
2
) in the prototype air purier.
78
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206 S. Kwon et al.
of Fu et al.
73
They used a higher initial benzene concentration (490 ppm)
than in the study of Pichat et al.
Several researchers have investigated the use of ozone to en-
hance photocatalytic degradation while preventing the generation of
intermediates.
19,72,78,86,94,96
Ozone is superior to oxygen in this regard as
ozone is a more powerful oxidant (E
o
= 2.07 V) when compared to oxygen
(E
o
= 0.82 V), and the electron transfer from TiO
2
to ozone is faster than the
electron transfer from TiO
2
to O
2
. Additionally, ozone has a strong electron-
withdrawing tendency that leads to a negative charge density and facilitates
reactions with the free radical (E
o
= 2.80 V).
19,78
4.3. Degradation of Phenol and Catechol
Phenol, used in a number of products such as nylon and other synthetic
bers, is a common contaminant in industrial wastewater. Exposure via skin
contact to high levels of phenol can cause liver damage, diarrhea, and discol-
oration of the urine.
19,77
Phenol poses a substantial challenge, because of its
high stability and solubility in water. The decontamination of phenol using
several different removal techniques has been studied.
Among various degradation methods, Nagaveni et al.
77
investigated
the photocatalytic degradation of phenol and catechol by combustion-
synthesized nano-TiO
2
with both articial UV and solar irradiation. More-
over, to improve the degradation efciency H
2
O
2
was added into reactor
and compared to combustion-synthesized nano-TiO
2
without H
2
O
2
. Solu-
tion combustion is a fast and simple one-step method applied to an aque-
ous redox mixture containing stoichiometric amounts of metal salts and
rapidly heated water-soluble fuel.
77
The articial light reactor used a medium-
pressure mercury vapor lamp (125 W,
max
= 365 nm) in a jacketed quartz
tube
77
in order to keep the constant light property. Cold water was cir-
culated continuously through the inner sleeve of the reactor to remove
heat from the solution. The samples were centrifuged and ltered through
0.45-m Millipore membrane lters to remove the catalyst particles prior to
analysis.
77
While the use of TiO
2
without a UV source had little or no effect on phe-
nol degradation, signicant degradation was realized through the application
of a photocatalyst in combination with UV. The experimental results in Figure
5 show the photocatalytic activity for phenol degradation over combustion-
synthesized and commercial TiO
2
(Degussa P-25) using both solar and arti-
cial UV illumination. Phenol degradation over combustion-synthesized TiO
2
is more effective than that over commercial TiO
2
for both solar and UV il-
lumination (0.1 g of 90% over combustion-synthesized TiO
2
and 35% over
commercial TiO
2
under solar irradiation at 200 min of exposure). This likely
is due to the special characteristics of combustion-synthesized TiO
2
(68 nm);
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Photocatalytic Applications of Micro- and Nano-TiO
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207
FIGURE 5. Phenol degradation with 68 nm of combustion-synthesized and 30 nm of com-
mercial nano-TiO
2
photocatalyst at 0.5 mmol/L initial concentration of phenol.
77
the small particle size results in a higher surface area, an anatase crystal struc-
ture, and higher surface density of the hydroxyl group than Degussa P-25,
which has a particle size in the 30 nm range. It has been reported that the
crystallinity of TiO
2
affects phenol degradation.
105
The use of hydrogen peroxide also enhances photocatalytic
efciency.
24,77
Pernyeszi et al.
24
described the effects of H
2
O
2
concentra-
tion for the photocatalytic process. For example, compared to photocatalytic
reaction without added H
2
O
2
, the addition of 0.1 M and 1 M H
2
O
2
improves
the phenol photocatalytic degradation by 14% and 30%, respectively. Photo-
catalysis with articial UV irradiation results in a more effective degradation
in comparison to solar irradiated photocatalysis under the same intensities.
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FIGURE 6. Degradation of phenol with of combustion-synthesized nano-TiO
2
photocatalyst
(68 nm) as a function of initial phenol concentration.
77
For example, at 120 min of exposure time, the completion of phenol de-
composition by combustion-synthesized TiO
2
under articial UV and solar
illumination was 80% and 70%, respectively. Figure 6 shows that degradation
rates depend on the phenol concentration, and that the rate of decrease in
the phenol concentration is slower as the initial concentrations increase, thus
indicating that lower concentrations of phenol are much easier to degrade.
Catechol, used as a developing agent for fur dyes and photography, is
recognized as a chemical hazard in wastewater.
106108
The U.S. Department
of Health and Human Services (HHS) has determined that catechol causes
depression of the central nervous system and skin disorders similar to those
caused by phenol,
107
thus making its oxidation a signicant objective of
wastewater treatment systems. Li et al.
19
investigated the photocatalytic oxi-
dation and the addition of ozonation with photocatalysis of catechol over car-
bon black-modied nano-TiO
2
(CB-nano-TiO
2
) supported by an aluminum
sheet.
19
CB-nano-TiO
2
thin lms, formed by a solgel method, prevent sep-
aration between the solid and liquid phases in wastewater treatment. The
space vacated by nano-sized carbon black (d = 18 nm) increases the poros-
ity of nanoparticle TiO
2
lm and the fraction of rutile, improving photocat-
alytic activity, both of which aid in light absorption.
19,95
Kang et al.
109
also
indicated that the carbon-black-incorporated TiO
2
has a more uniform pore
size than that of regular TiO
2
.
CB-nano-TiO
2
thin lms therefore yield photocatalytic activity 1.5 times
greater than unmodied nano-TiO
2
thin lms for the degradation of catechol.
Figure 7 shows that the efciency of photocatalytic catechol degradation
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Photocatalytic Applications of Micro- and Nano-TiO
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209
FIGURE 7. Catechol degradation at various ozone concentrations in the nano-TiO
2
(18
nm)/UV/O
3
process.
19
improved with the addition of ozone. At an ozone concentration of 50 mg/h
and 5 min of irradiation, catechol degradation was 90%. Efciencies de-
creased as ozone rates decreased and without the presence of ozone cat-
echol removal was only 10% after ve minutes of irradiation. These results
are consistent with those found for phenol, wherein the presence of ozone
improves photocatalytic efcacy.
5. NO
x
REMOVAL BY TiO
2
Another recently targeted source of environmental pollution is NO
x
, pro-
duced by the combustion and exhaust gases of motor vehicles. Of the various
FIGURE 8. Comparison of oxidative methods for catechol degradation.
19
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210 S. Kwon et al.
methods for removing NO
x
, photocatalytic reaction has received consider-
able focus, due to its high removal efciency and ease of use. There are two
types of photocatalytic processes for removing NO
x
, namely, photocatalytic
oxidation and the decomposition of NO. Both plants and microorganisms
use products of photocatalytic oxidation such as nitrite and nitrate ion. Pho-
tocatalytic oxidation occurs in the presence of both water and oxygen to
form nitrate, whereas photocatalytic decomposition occurs in the absence
of water and oxygen.
33,34,92
Hashimoto et al.
33
demonstrated that the pho-
tocatalytic oxidation of NO with UV irradiation can effectively remove NOx.
The experiment was carried out in a xed continuous-bed reactor at 1 atm
using 120 mg of nano-TiO
2
combined with zeolite (A- and Y-form zeolite:
TiO
2
-AZ and -YZ), which was used as a photocatalyst under uniform UV il-
lumination inside reactor. The concentrations of nitrogen oxide and nitrogen
dioxide were obtained using a chemiluminescence NO
x
analyzer (Yanako;
ELC-88AO). Nitrogen and nitrous oxide were analyzed by GC/TCD (helium
containing 20% of O
2
and 10 ppm of NO).
33
The addition of zeolite improves
the adsorption of NO and thus photocatalytic oxidation. The adsorption of
NO initiates rapidly and adsorption equilibrium is reached quickly. In Figure
9, the efciency of NO
x
oxidation is dened by the integration of the dif-
ference between the inlet concentration of NO and outlet concentration of
NO
x
.
33
The solid line shows the outlet concentration of NO
x
and the open
circle shows the outlet concentration of NO, with the difference between
the two indicating the outlet concentration of NO
2
. The results show almost
100% oxidation efciency. However, because an oxidation product (HNO
3
)
was absorbed on the photocatalyst surface area and NO was desorbed until
FIGURE 9. Photocatalytic oxidation of NO and NO
2
over nano-TiO
2
(11 nm) photocatalyst as
time variation: (A) Hycom TiO
2
; (B) TiO
2
-AZ composite (1:1); (C) TiO
2
-YZ composite (1:1);
solid line: outlet concentration of NO
x
(NO
x
= NO + NO
2
); open circle: outlet concentration
of NO; mass of nano-TiO
2
120 mg; inlet NO concentration: 10 ppm balanced with air; pressure
1 atm; ow rate 110 ml/min; and T 300

C.
33
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Photocatalytic Applications of Micro- and Nano-TiO
2
211
the point of equilibrium, oxidation efciency decreased gradually with the
increase in illumination time. As shown in Figure 9, b and c, because the des-
orbed concomitants were absorbed on the zeolite, recovery in the NO con-
centration over nano-TiO
2
with AZ and YZ was lower than over nano-TiO
2
alone after reaching equilibrium.
33
In addition, for oxidation over nano-TiO
2
alone (Figure 9a), the outlet concentration of NO
2
as an oxidation product
increased gradually when illumination time increased. By contrast, due to
the absorption of NO
2
on the zeolite surface area, smaller concentrations
of NO
2
resulted from the oxidation over nano-TiO
2
with AZ (Figure 9b)
and YZ (Figure 9c). Therefore, these results suggest that the addition of ze-
olite to titanium oxide enhances the photocatalytic oxidation of NO using
nano-TiO
2
.
6. REMOVAL OF HG WITH TiO
2
Toxic metal ions such as Hg(II), Ag(II), and Cd(II) are recognized as non-
degradable compounds having long life spans, concentrations of which may
reach toxic levels in the food chain.
85
Yet increasing recognition of the toxi-
city of these metal ions has done little to slow demand for them in the face
of accelerating global industrialization. Mercury, for example, is widely used
in batteries, relays, metallurgy, catalysts, paints, and pesticides, among other
applications.
85
However, because of its cumulative toxic effects, mercury in
water and wastewater signicantly imperils water-based ecosystems.
50
Vari-
ous physical and chemical removal methods have therefore been developed
to degrade this toxic metal in water and wastewater, including precipitation,
activated carbon adsorption, ion exchange, reverse osmosis, and membrane
separation.
50,85
However, these processes themselves produce by-products
in the forms of hazardous and/or toxic compounds that are themselves in
need of disposal.
Among other methods, TiO
2
has been used as a photocatalyst to re-
move mercury from aqueous solutions.
47,5052,85
In particular, Skubal et
al.
50
investigated the photocatalytic degradation of mercury(II) ions in water
over arginine-modied TiO
2
nanoparticles, both with and without UV light.
Anatase TiO
2
colloids (4060

A in diameter) were formed from the hydrolysis
of titanium tetrachloride (TiCl
4
).
50
Analysis of the synthesized colloids was
conducted using the method of Thompson,
110
which is a spectrophotometric
method that measures peroxotitanium(IV) from the dissolution of the colloid
in sulfuric acid. Either the colloid remained unmodied or its surface was
modied with l -arginine (ARG, C
6
H
14
N
4
O
2
). Arginine was used as a modier
because it effectively binds to both the TiO
2
surface, through the carboxyl
functional group, and to mercury ions in solution, through the amino func-
tional groups.
50
Solutions of arginine-modied TiO
2
[ARG (1.67 10
3
M),
TiO
2
(5.00 10
3
M)] were allowed to reach equilibrium condition for 1 d
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under an anoxic atmosphere (argon-purged, AGA 99.995%). Mercuric chlo-
ride was injected under anoxic condition into the modied TiO
2
solution and
diluted to 500 ml in a quartz ask with continuous mixing. After a 10-min
equilibration period, the sample either remained in darkness or was illumi-
nated by an eight-light Rayonet photochemical chamber reactor (RMR model
600) ( max = 253.7 nm).
50
Four milliliters of samples were withdrawn and
ltered anoxically using pressure lters with Amicon YM100 membranes.
50
Precipitate on the lter was examined for the presence of nonsoluble elemen-
tal mercury using a saturated solution of potassium iodide per the method
of Tennakone et al.
111
Filtered sample was analyzed using cold vapor atomic
absorption spectroscopy (Buck Scientic 200 A).
50
In this study, the efciency of mercury(II) degradation over non-
modied nano-TiO
2
was less than 10%. However, because of the effective
binding capacity between mercury ions in solution through the amino func-
tional group and the TiO2 surface through the carboxyl functional group,
degradation was nearly 100% (99.98%) in the UV light reaction for mercury
over TiO
2
nanoparticles modied with arginine.
50,112
Figure 10 indicates that
the dark reaction continued to absorb mercury for about 1 h until the sys-
tem reached equilibrium. This equilibrium point initially represented 60%
of mercury removal. By contrast, removal efciency was almost 95% within
1 h in the UV light reaction, and removal from the solution was virtually
complete (99.98%) within 2 h. These results indicate that the modier, argi-
nine, signicantly improved the removal efciency of mercury, facilitated
charge transfer from the TiO
2
surface to the sorbed mercury, and prevented
charge recombination.
50
Skubal et al.
50
have also studied the effects of adding
methanol to enhance the removal rate of mercury over a shorter length of
UV illumination, achieving total degradation within 32 min.
FIGURE 10. Photocatalytic removal of mercury by of arginine-modied nano-TiO
2
(45 nm);
[TiO2] = 5.0 10
3
M, [ARG] = 1.67 10
3
M, [Hg] = 7.5 10
4
M (150 ppm). Error
bars are derived from the standard deviation of duplicate reactions.
50
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Photocatalytic Applications of Micro- and Nano-TiO
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213
7. DEGRADATION OF OIL SPILLS OVER TiO
2
Due to its high efciency and low costs, photocatalytic degradation over
nano-TiO
2
has attracted the attention of scientists as an emerging technology
to deal with the accidental discharge of crude oil into waterways. Ziolli et al.
70
have investigated the ability of photocatalytic detoxication under nano-TiO
2
with UV illumination to destroy seawater-soluble crude oil hydrocarbons.
Brazilian crude oil samples were obtained from the Campos Basin on the
continental shelf of Rio de Janeiro State, Brazil. Seawater (salinity 33, and
pH 8.4) used in all experiments was collected at S ao Sebasti ao. The experi-
ment was conducted in an aqueous suspension of nano-TiO
2
photocatalyst
(30 nm) at a concentration of 0.1% w/v irradiated with UV by high-pressure
mercury lamp (HPL-N, 125W,
max
= 366 nm) in a Pyrex batch reactor (80
mm 210 mm) over 7 d of exposure.
70
The suspension was stirred and kept
homogeneous in the reactor; cooling water was circulated via a quartz inner
sleeve to avoid a temperature increase.
The toxicity of the water-soluble fraction (WSF) was examined us-
ing a Microtox kit with marine luminescent bacteria (V. scheri) as a test
organism.
70,113
The results are expressed as toxicity units (TU), where TU >
1 means that the compound shows acute toxicity.
Figure 11 shows that photocatalytic degradation of crude oil using nano-
TiO
2
and UV irradiation increased gradually and approached a nearly 90% re-
moval efciency, whereas there was no signicant removal using only either
FIGURE 11. Photocatalytic decomposition of seawater crude oil by 30 nm nano-TiO
2
pho-
tocatalyst; WSF of Brazilian type A crude oil in seawater () WSF-A only (control); WSF-A
with TiO
2
in the dark; () WSF-A during exposure to UVvisible irradiation without TiO
2
; (

)
WSF-A with TiO
2
and irradiation.
70
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214 S. Kwon et al.
FIGURE 12. Toxicity results of photocatalytic decomposition of A and B type seawater crude-
oil with heterogeneous photocatalysis (, 30-nm nano-TiO
2
with UV irradiation) and photol-
ysis (

, UV irradiation).
70
nano-TiO
2
or UV illumination. The degradation of oil over nano-TiO
2
with
UV irradiation was greatest between the rst and second days of UV ex-
posure, suggesting that it takes more than 1 d of UV illumination in the
suspension to substantially degrade spilled oil by photocatalysis.
However, transient toxic compounds have been detected during pho-
tocatalytic degradation. Jardim et al.
93
demonstrated that the decomposition
of four aromatic chlorinated compounds over TiO
2
photocatalyst with UV
irradiation could generate intermediates more highly toxic than the original
compound. In the case of removal using only either nano-TiO
2
or UV sources,
the degradation ratio (C/C
0
) in Figure 11 shows intermediate concentrations
of oil higher than initial concentrations due to the generation of toxic com-
pounds. Figure 12 shows toxicity, indicating the degree of toxicity, results
after up to 5 d of irradiation both with and without the nano-photocatalyst.
The toxicity value was 1.8 TUthe same as before irradiation. For photo-
catalysis with nano-TiO
2
, however, acute toxicity increased signicantly (3.5
TU) after 1 d of irradiation, then decreased to a value of zero after 3 d. This
suggests that both toxic compounds and intermediates were either totally
degraded or converted to non-toxic compounds during photocatalysis. Be-
cause of this intermediate behavior, then, special attention is needed when
applying this technique to the degradation of spilled oil.
8. COD DETERMINATION BY NANO-TiO
2
Chemical oxygen demand (COD) and total organic carbon (TOC) are
major indices in environmental monitoring.
114
COD has been frequently
used as a benchmark to reveal the degree of contamination of or-
ganic compounds.
97,114
Recently, Ai et al. demonstrated COD monitoring
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Photocatalytic Applications of Micro- and Nano-TiO
2
215
by photocatalytic oxidation using a nano-TiO
2
/K
2
Cr
2
O
7
system. K
2
Cr
2
O
7
can facilitate the acceptance of photo-excited conduction band electrons
and improve the efciency of the photocatalytic degradation of organic
compounds.
72,91
The monitoring principle of COD lies in determining
changes in Cr(III) concentrations after the photocatalytic oxidation of or-
ganic matter,
72
then correlating the COD values obtained with those realized
using conventional methods (e.g., dichromate).
The photocatalytic experiments were performed in a water-jacketed,
mixed batch reactor using aqueous suspensions of TiO
2
powder. UV irradia-
tion was provided by an 11-W lamp (Shanghai Jinguang Lamps Factory) with
a maximum wavelength,
max
, of 253.7 nm in the center of the reactor.
72
After
10 min of UV irradiation, samples were centrifuged and ltered to remove
TiO
2
particles and the absorbance of Cr(III) was examined calorimetrically at
610 nm with a UNICO 2100 spectrophotometer.
72
Wastewater samples were
obtained from Shanghai.
The experiment was carried out in order to optimize operating condi-
tions such as pH, catalyst dosage, temperature, and oxygen concentration.
In optimizing pH values, it was found that the absorbance of Cr(III) was
reduced considerably within pH 2, but, due to the effects of pH on the dis-
tribution of Cr(VI) species in aqueous solution, declined only minimally with
an increase in pH at a xed COD value of 100 mg/ml.
72
Therefore, pH 0.5
was determined to be the optimum pH condition for COD determination.
The effects of nano-TiO
2
dosage are shown in Figure 13, and indicate
that the oxidation rate of organic compounds increases signicantly with an
increase in nano-TiO
2
dosages up to 4 g/L, with no considerable increase
FIGURE 13. Effect of nano-TiO
2
photocatalyst (30 nm) dosage on the absorbance of Cr(III).
Conditions: C
Cr(VI)
0.01 mg/L; pH 0.5; C
6
H
12
O
6
100 mg/L;and T 80

C.
72
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216 S. Kwon et al.
at higher dosages of nano-TiO
2
. This is because higher nano-TiO
2
dosages
lower the adsorption of UV light into the catalyst, preventing photocatalytic
oxidation over nano-TiO
2
with UV sources.
72
Therefore, 4 g/L of nano-TiO
2
dosage was selected as the optimum catalyst dosage.
All indications are that the absorbance of Cr(III) generally improves with
increased temperature, which, because it enhances the collision frequency
between nano-TiO
2
and the substrates, also increases the oxidation rate ,
but, due to the evaporation, the absorbance of Cr(III) lessened at relatively
higher temperatures.
72
Hence, for this study 80

C was selected as the opti-

mum temperature.
The effects of oxygen were studied by streaming air balanced with N
2
into the COD solution at pH 0.5. It was determined that oxygen concentration
had no effect on the absorbance of Cr(III).
To summarize, optimum conditions in this experiment were 4 g/L of
nano-TiO
2
at 80

C and a pH of 0.5. In addition, a comparison of COD values

derived using this method with values taken from actual wastewater samples
using a conventional method (dichromate) showed little difference (10%)
between the two.
9. TOC REMOVAL USING NANO-TiO
2
Total organic carbon (TOC) is used to determine the degree of organic con-
tamination in wastewater. Li et al.
19
have investigated photocatalytic oxida-
tion and ozonation of TOC over carbon-black-modied nano-TiO
2
(CB-nano-
TiO
2
) supported by an aluminum sheet.
19
The experiment was carried out
using the same methods described for catechol degradation in section 4.3.
The photocatalytic oxidation of TOC over CB-nano-TiO
2
shows 1.5 times
more activity than that over TiO
2
thin lms.
19
Compared to other oxida-
tion methods, Figure 14 shows that the highest TOC decomposition rate
was obtained using TiO
2
/UV/O
3
. The degradation (C/C
0
) rate of TOC in-
creased gradually compared to that of catechol, which increased sharply
(Figure 8). TOC was almost completely degraded (i.e., 95%) after 1 h using
the TiO
2
/UV/O
3
process. However, without ozone, the efciency of TOC re-
moval in a TiO
2
/UV process was only 20% after 1 h. Accordingly, the rate of
TOC removal increased with increases in ozone concentration. These results
indicate that ozonation enhances the photocatalytic degradation of TOC. As
shown in Figure 15, TOC was degraded by more than 55% at an ozone
ow rate of 12.5 mg/h, and was totally mineralized after 30 min at 50 mg/h,
indicating that more hydroxyl radicals were generated by the TiO
2
/UV/O
3
process.
19
Therefore, the photocatalytic activity of CB-TiO
2
/UV/O
3
is sig-
nicant in the degradation of TOC compared with ozonation alone and
UV/O
3
.
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Photocatalytic Applications of Micro- and Nano-TiO
2
217
TABLE 1. TOC Removal Kinetics of the UV/O
3
and TiO
2
/UV/O
3
Processes With Various Flow
Rates of Ozone
21
UV/O
3
TiO
2
/UV/O
3
O
3
(mg/h) Equations of kinetics R
2
Equations of kinetics R
2
12.5 dTOC/dt = 0.0099 .9949 dTOC/dt = 0.0164 .9914
25.0 dTOC/dt = 0.0159 .9951 dTOC/dt = 0.0287 .9948
37.5 dTOC/dt = 0.0225 .9877 dTOC/dt = 0.0330 .9896
50.0 dTOC/dt = 0.0260 .9910 dTOC/dt = 0.0343 .9867
FIGURE 14. Comparison of TOC degradation by different oxidation methods; TiO
2
methods
employed 18-nm nano-TiO
2
photocatalyst.
19
FIGURE 15. Effect of ozone concentration on degradation of TOC removal by 18-nm nano-
TiO
2
photocatalyst in the UV/O
3
process.
19
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218 S. Kwon et al.
Table 1 provides the kinetic study of semi-batch experiments with vari-
ous ozone ow rate ozone.
19
It revealed that catechol concentrations did not
have a signicant effect on the kinetics of UV/O
3
and TiO
2
/UV/O
3
processes;
these results demonstrated that the zero-order kinetics of TOC removal pro-
cess by UV/O
3
or TiO
2
/UV/O
3
as well as the reaction process of ozone may
play a key role for the complete TOC removal.
10. CONCLUSION
This review focuses on the application of nanoparticulated TiO
2
for air pu-
rication, water degradation, and hazardous waste remediation.
Generally, various types of catalysts in water treatment and air pollu-
tion control show high removal efciency of only certain contaminants. By
contrast, compared to regular TiO
2
and other catalysts, the photocatalytic
activities of nanoparticle TiO
2
, either alone or modied with other chemi-
cals, provide signicant efciency and are environmentally benign during the
degradation or reduction of various pollutants (both organic and inorganic
compounds) in water and air treatment systems, indicating a promising ma-
terial for use in environmental engineering applications. As indicated earlier,
heterogeneous photocatalytic degradation over nano-TiO
2
with UV irradi-
ation provides high efciency, due to its special properties, i.e., (1) small
particle size with high surface area, (2) ease of contact with pollutants, and
(3) small absorbent particles that prevent the agglomeration of gas-phase
contaminants. Thus, TiO
2
should be treated as an emerging technology at-
tractive in terms of photoreaction efciency, ease of usage, and the potential
for economically efcient contaminant degradation. In addition, for the re-
moval of chemical compounds such as mercury, phenol, and catechol, the
photocatalytic activity of nano-TiO
2
modied with other chemicals reveals
much better performance than that of nano-TiO
2
alone.
For the degradation of some components such as crude oil, the pho-
tocatalytic removal efciency of some pollutants by nano-TiO
2
alone was
still not high, and the concentration of contaminant was even returned to
initial concentration due to its desorption. Because of the slow reaction of
electron transfer from TiO
2
to O
2
, which is broadly used as an oxidant, other
stronger oxidants are needed to react with compounds. Moreover, the reac-
tion process of TiO
2
can also produces a waste that is in need of disposal; the
method of by-product treatment should also be considered at the same time
[i.e., during ethanol degradation, acetaldehyde (CH
3
CHO), which is toxic,
an irritant, and a probable carcinogen,
115
can be produced]. Therefore, fur-
ther research is needed to explore the effectiveness of this promising pho-
tocatalyst, either by itself or modied with other chemicals, or the develop-
ment of a reactor system to overcome its disadvantages in the degradation of
contaminants.
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Photocatalytic Applications of Micro- and Nano-TiO
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219
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