Вы находитесь на странице: 1из 8

Chemosphere 48 (2002) 437444

www.elsevier.com/locate/chemosphere

Photocatalytic degradation of volatile organic compounds


at the gassolid interface of a TiO2 photocatalyst
Sang Bum Kim
a

a,*

, Hyun Tae Hwang a, Sung Chang Hong

Department of Chemical Engineering, Korea University, 1, 5-ka, Anam-dong, Sungbuk-ku, Seoul 136-701, South Korea
b
Department of Environmental Engineering, Kyonggi University, 94 San, Iui-dong, Paldal-ku, Suwon-si,
Konggi-do 442-760, South Korea
Received 25 February 2001; received in revised form 19 February 2002; accepted 19 February 2002

Abstract
In the present work, photocatalytic degradation of volatile organic compounds including gas-phase trichloroethylene (TCE), acetone, methanol and toluene over illuminated TiO2 was closely examined in a batch photoreactor as a
function of water vapor, molecular oxygen and reaction temperature. Water vapor enhanced the photocatalytic degradation rate of toluene, but was inhibitive for acetone, and, there was an optimum water vapor concentration in the
TCE and methanol removal. In a nitrogen atmosphere, it showed lower photocatalytic degradation rate than in air and
pure oxygen. Thus, it could be concluded that oxygen is an essential component in photocatalytic reactions by trapping
photogenerated electrons on the semiconductor surface and by decreasing the recombination of electrons and holes. As
for the inuence of reaction temperature, it was found that photocatalytic degradation was more eective at a moderate
temperature than at an elevated temperature for each compound. 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Photocatalytic degradation; TiO2 lm; Gas phase; Volatile organic compound; Batch photoreactor

1. Introduction
Volatile organic compounds (VOCs) are widely used
in industrial processes and domestic activities, leading
to water and air pollution, even indoor work-place air
pollution (EPA, 1987). Many VOCs are known to be
toxic and considered to be carcinogenic. The most signicant problem related to the emission of VOCs is
centered on the potential production of photochemical
oxides: for example, ozone and peroxyacetyl nitrate.
The TiO2 -sensitized photodegradation of organic
compounds has been proposed as an alternative advanced oxidation process (AOP) for the decontamination of water and air. The AOP is initiated from the

Corresponding author. Tel.: +82-2-924-8362; fax: +82-2926-6102.


E-mail address: sbkim@prosys.korea.ac.kr (S.B. Kim).

generation of holeelectron pairs on the semiconductor,


absorbing the ultra-violet (UV) light with energy equal
to or higher than the band gap energy (Eg ) of semiconductor. Electrons and holes are photogenerated in the
bulk of the semiconductor, and move to the particle
surface; electrons reduce an electron acceptor such as
molecular oxygen, and holes can oxidize electron donors
including adsorbed water or hydroxide anion to yield
hydroxyl radicals.
The common VOCs such as halogenated hydrocarbons, ketones, alcohols and aromatic compounds have
been widely used in many industries, and are often
found in the emission ow (Shen et al., 1993). Some
workers have recently examined the photocatalytic degradation of TCE in gas phase. To determine the kinetics of conversion of TCE (up to 100 ppm), Dibble
and Raupp (1992) systematically investigated the photooxidation in air using both a xed-bed reactor and a
uidized bed reactor. They showed that trace water

0045-6535/02/$ - see front matter 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 4 5 - 6 5 3 5 ( 0 2 ) 0 0 1 0 1 - 7

438

S.B. Kim et al. / Chemosphere 48 (2002) 437444

vapor was essential to maintain the photocatalytic catalyst activity for an extended period, but higher water
vapor levels were strongly inhibitory. Anderson et al.
(1993) studied the dependency of the TCE photocatalytic degradation rate on the light intensity, feed composition (TCE, O2 , H2 O) and temperature in a bed
reactor packed with TiO2 pellets. They showed that the
reaction rate was rst order with respect to the light
intensity, independent of the concentration in the range
of 37450 ppm, oxygen mole fraction 0.010.2 and
water vapor mole fraction 0.0010.028, and the temperature did not aect the reaction rate in the range of
2362 C.
Peral and Ollis (1992) reported that the water vapor
inhibited oxidation of acetone. On the contrary, some
researchers showed that water vapor could enhance the
photocatalytic oxidation of hydrocarbons such as formic acid (Muggli and Falconer, 1999). Ibusuki and
Takeuchi (1986) investigated the photooxidation with
toluene (80 ppm) in air over UV irradiated TiO2 at an
ambient temperature. They observed that the CO2 concentration with 10 min residence time in reactor increased linearly with the increase of relative humidity
over 060%. Obee and Brown (1995) studied the photooxidation of toluene and other organic pollutants by
using polycrystalline TiO2 photocatalyst. They focused
on the inuence of the competitive adsorption between
water and toluene vapors.
The purpose of this paper is to nd the optimum
condition for the removal of the hazardous and nondegradable VOCs including TCE, acetone, methanol
and toluene as a function of water vapor, oxygen, and
reaction temperature. A batch photoreactor was applied
prior to the acquisition of fundamental data for a scaledup photoreactor design and the application of continuous
process for the gassolid heterogeneous photocatalytic
reaction.

Deionized and doubly distilled water was used for the


generation of water vapor and the preparation of the
photocatalyst.
2.2. Photoreactor and light source
The photocatalytic degradation processes at the gas
solid interface were carried out in a batch reactor made
of Pyrex glass and depicted schematically in Fig. 1. The
batch reactor was 100 mm of inside diameter, 210 mm of
height and about 1600 cm3 of total volume. The reactor
was shielded by the jacket of Pyrex glass. The upper part
of the reactor was sealed with a Teon lid. A vertical UV
lamp (outside diameter of 20 mm, length of 210.5 mm)
was vertically inserted in the center of the reactor. Pyrex
glass tube (inside diameter of 26 mm, height of 165 mm)
coated by a TiO2 photocatalyst suspension in the internal surface was xed to the exterior of the UV lamp.
The distance between the surface of the UV lamp and
the TiO2 thin lm photocatalyst was 3 mm. A magnetic
stirrer at the bottom of the reactor was rotated during
the operation. It ensured eective dispersion of the
gaseous molecules. A thermoregulated bathcirculator
(Model TB-85, Shimazu) unit was connected to the reactor jacket for controlling temperature of the reactor.
To ush and ll the dry air of the reactor, an air cylinder
was connected to the reactor. The concentration of VOCs
was measured by a gas chromatograph (Model HP 6890,
HewlettPackard).
The light source was the germicidal lamp (Model
G6T5, 6 W, Sankyo Denki Co., LTD). The wavelength
of the germicidal lamp ranged from 200 to 300 nm with
the maximum light intensity at 254 nm.

2. Experimental methods
2.1. Materials
All of the chemicals used in the work were reagentgrade. The liquid phase VOCs were purchased from
Aldrich (TCEanhydrous, 99%, acetoneACS reagent,
99.5%, methanolanhydrous, 99.8%, toluene anhydrous, 99%).
The photocatalyst was prepared with TiO2 suspension (STS-01, anatase, 7 nm in diameter, 300 m2 /g of
specic surface area, Ishihara Sangyo Co.), tetraethyl
orthosilicate (TEOS, 98%, Aldrich), dimethoxy dimethyl
silane (DMDMS, 95%, Aldrich), isopropyl alcohol
(IPA, anhydrous, 99.5%, Aldrich) and nitric acid (65
wt% solution in water, Aldrich).

Fig. 1. Schematic representation of the experimental apparatus.

S.B. Kim et al. / Chemosphere 48 (2002) 437444

439

2.3. Preparation of photocatalyst


Photocatalyst suspension was prepared through a
three-step process as follows: tetraethyl orthosilicate (2
g) and dimethoxy dimethyl silane (1 g) were added to
isopropyl alcohol (10 g) on a vessel connected to a
condenser at room temperature (rst step). A solution
combined with isopropyl alcohol (10 g), deionized water
(0.5 g) and nitric acid (0.03 g) was dropped in the solution prepared in the rst step at a temperature of
about 5 C for 60 min, and stirred for 2 h (second step).
STS-01 anatase (35 g) was dropped in the solution
combined with isopropyl alcohol (15 g), deionized water
(15 g) and the solution (22.5 g) prepared in the second
step at a temperature of about 5 C for 60 min, and
stirred for 3 h (third step).
A TiO2 thin lm photocatalyst was formed by the
dip-coating method. After lling a Pyrex glass tube with
the TiO2 photocatalyst suspension, it was removed from
the Pyrex glass tube at a constant rate of 5 mm/min.
Then, the Pyrex glass tube coated with TiO2 was dried at
120 C for 1 h.
2.4. Characterization of catalyst
A uniform and transparent TiO2 thin lm with a
thickness of about 65 nm was prepared onto an internal
surface of a Pyrex glass tube. Scanning electron microscopy (SEM, Philip SEM-535M) images are shown in
Fig. 2(a) and (b), which show top and cross-sectional
views, respectively. The lm consists of small crystalline
particles with an average diameter of about 40 nm. Since
the average particle size in the TiO2 suspension was
about 7 nm, it is assumed that the particles aggregated
during heat treatment. The used TiO2 was found to be
anatase by means of X-ray diraction (Rigaku D/MAXIII (3 kW) diractometer). As shown in Fig. 3, there
were four remarkable peaks at the angles of 2h: 25.38,
38.14, 48.04 and 55.02 (Sanjines et al., 1994). The specic surface area of the particles was determined by the
BET (Micrometritics ASAP 2100) method. The BET

Fig. 3. X-ray diraction patterns of TiO2 lm.

surface area of the prepared TiO2 particles was 277


m2 g1 , which represents decrease in the surface area of
STS-01 anatase due to heat treatment.
2.5. Procedures
The batch reactor was ushed and lled with dry gas
(air, pure nitrogen, or pure oxygen) prior to the injection
of the liquid VOCs and/or water. The desired amount of
water, then, was injected and allowed to evaporate, mix,
and reach the adsorption equilibrium with the Pyrex
glass tube coated TiO2 . The desired amounts of VOCs
were then injected in liquid phase and allowed to evaporate, mix, and also reach the gassolid adsorption
equilibrium, and the concentrations of VOCs were
monitored with time. Once the concentrations of VOCs
stabilized, the UV lamp was turned on and the degradation of VOCs with the reaction time was recorded.
2.6. Analysis
VOCs concentration in the gas phase was monitored
using an automated sampling system. All gas transportation tubes were made of 1/800 o.d. stainless steel. The
lines were wrapped with heating tape to maintain a

Fig. 2. SEM photographs of (a) top and (b) cross-sectional views of the TiO2 lm on the Pyrex glass tube.

440

S.B. Kim et al. / Chemosphere 48 (2002) 437444

temperature between 75 and 85 C. The lines were


connected to the photoreactor by means of a 1/400 1/800
zero dead volume Swagelok stainless steel ttings. The
sample transfer lines from the reactor to the sampling
port were inserted into the reactor in some distance to
ensure the collection of a representative sample. Sampled VOCs were circulated by a diaphragm pump
(Model SP 600 EC-LC, SP J. Schwarzer GmbH u. Co.)
and injected through a six-port external injection GC
valve (6890 Valve system, Agilent Technologies) with a
200 ll automatic sample loop. The sample was then
transferred to a gas chromatograph with pure helium as
a carrier gas. The gas chromatograph was equipped with
a HP-5 capillary column (Agilent Technologies) of 30 m
length, 0.25 lm lm thickness and 0.32 mm internal
diameter. Temperatures of the injector and column were
120 and 200 C, respectively. The ame ionization detector was maintained at 250 C.

3. Results and discussion


When the kinetic data of photocatalytic degradation
is interpreted by the dierential method, owing to the
complex mechanism of reactions, it is dicult to develop
a model for the dependence of the photocatalytic degradation rate on the experimental parameters for the entire
treatment time. Thus, kinetic modeling of the photocatalytic process is usually restricted to analysis of the initial rate (i.e., dC=dtt0 ) of photocatalytic degradation
(Levenspiel, 1972). This can be obtained from the initial
slope of curves in which the variation of the VOCs concentration is measured as a function of time. The extrapolation of the photocatalytic degradation rate to time,
t 0 avoids the possible interference from by-products.
3.1. The eect of water
Numerous studies have revealed a dual function of
water vapor. The inuence of water vapor in gas phase

photocatalytic degradation reaction depends on the


species of contaminant. It has been known that water
vapor strongly inhibits the oxidation of isopropanol,
TCE and acetone; enhances oxidation of toluene and
formic acid; and has no signicant eect on 1-butanol
oxidation (Luo and Ollis, 1996; Alberici and Jardim,
1997; dHennezel et al., 1998; Wang et al., 1998; Augugliaro et al., 1999).
In order to examine the eect of water vapor, different volume percentages of water vapor were applied
to a xed concentration of VOCs. Table 1 summarizes
the photocatalytic degradation rate of each VOC. The
photocatalytic degradation rate of TCE was enhanced
by water vapor with concentrations up to 0.383 mol m3
(1.0 vol%), and more or less inhibited above 0.383
mol m3 . In the presence of water vapor, the hydroxyl
radicals formed on the illuminated TiO2 cannot only
directly attack VOC molecules but also suppress the
electronhole recombination (Fox and Dulay, 1993;
Mark et al., 1993). Hydroxyl group or water molecules
behave as a hole trap, forming surface adsorbed hydroxyl radicals. However, under higher concentrations
of water vapor, the water molecules might compete with
the TCE molecules on the catalyst surface sites during
adsorption (Luo and Ollis, 1996; dHennezel et al., 1998;
Wang et al., 1998). Therefore, the photocatalytic degradation rate of TCE decreased with increasing water
vapor.
Acetone was also examined with various concentrations of water vapor. As shown in Table 1, the addition
of water vapor decreases the photocatalytic degradation
rate of acetone. Although water molecules could form
hydroxyl radicals behaving as a simultaneous hole
trapper, water vapor eventually seemed to hinder the
adsorption of acetone molecules on the catalyst surface
(Sauer and Ollis, 1994; Vorontsov et al., 1999). In addition, a gradual accumulation of water vapor molecules
on the surface of TiO2 can block acetone adsorption
sites. Furthermore, before photocatalytic reaction of
acetone, it requires desorption of water vapor molecules,

Table 1
The photocatalytic degradation rate of each VOC according to water vapor contents
Water vapor contents
(mol m3 (vol%))
None
0.191 (0.5)
0.383 (1.0)
0.766 (2.0)
1.149 (3.0)
1.532 (4.0)
1.914 (5.0)

Photocatalytic degradation rate of VOCs (103 mol m3 min1 )


TCE

Acetone

Methanol

Toluene

1.22  0.01

1.88  0.02

7.13  0.10
4.14  0.02
3.92  0.02
1.86  0.02

1.08  0.02
0.561  0.008

1.57  0.02
1.72  0.01
1.81  0.01
1.20  0.02
0.963  0.008

0.154  0.005
0.254  0.005
0.325  0.007
0.456  0.004

Initial concentration of each compound: TCE 1:206  102 mol m3 , acetone 1:208  102 mol m3 , methanol 1:151  102
mol m3 , and toluene 3:835  103 mol m3 UV source: germicidal (254 nm) lamp, light intensity 2:1  103 W cm2 , temperature:
45 C.

S.B. Kim et al. / Chemosphere 48 (2002) 437444

which can form hydroxyl radicals through combination


with holes. Simultaneously, oxygen molecules combine
with electrons to form O
2 (Munuera et al., 1979).
However, during photocatalytic reaction, the continuous consumption of hydroxyl radicals requires replenishment to maintain catalyst activity. Under low water
vapor content, there exists suitable equilibrium between
consumption and adsorption to keep stable photocatalytic degradation rate. Upon raising water vapor content
in photocatalytic reaction mixture, such equilibrium can
be destroyed with more adsorption of water vapor
molecules on the surface of catalyst to lower the photocatalytic degradation rate.
On the other hand, the photocatalytic degradation
rate of methanol was relatively high in lower water vapor
concentrations. Above 0.383 mol m3 (1.0 vol%) of water
vapor, the photocatalytic degradation rate of methanol
decreased with increasing water vapor. Since methanol
has a hydroxyl group itself, it may produce hydroxyl
radicals even in the absence of water. Thus, the eect of
hydroxyl radicals generated from the water molecules
might be insignicant. On the contrary, when excess
water vapor was admitted, the photocatalytic degradation rate decreased. As previously stated, it seems that
the water molecules could compete with the methanol
molecules on the catalyst surfaces during the adsorption.
In the case of toluene, a toxic compound resistant to
oxidation, the phenomenon of catalyst deactivation was
observed. The photocatalytic degradation reaction of
toluene with low water vapor concentration (below
0.383 mol m3 (1.0 vol%)) deactivated the catalyst being
implicated by the change of color to brown. In this experiment, the examination of photocatalytic degradation
of toluene is thus fullled with a low concentration of
3:835  103 mol m3 (100 ppm). As can be seen in
Table 1, the photocatalytic degradation rate of toluene
increased with increasing water vapor. Carboxylate
formation and carboxylic acid accumulation postulated
by previous investigators could be a major cause of
catalyst deactivation (dHennezel et al., 1998; Rafael
and Nelson, 1998; Augugliaro et al., 1999; Chen and
Ray, 1999). An important role of water vapor is regeneration of catalysts. That is, the increase of toluene
reaction rate in the presence of water vapor could lead
to desorption or degradation of carboxylate molecules
which were accumulated on the catalyst surface. It was
also observed that the deactivated catalyst was restored
to its inherent transparent appearance as well as activity
observed prior to deactivation after UV illumination for
3 h with enough water vapor concentration (above 0.766
mol m3 (2.0 vol%)) and pure air.
3.2. The eect of oxygen
When the TiO2 particles are illuminated by photons
with appropriate energy, the valence band electrons of

441

TiO2 can be excited to the conduction band, creating

highly reactive electron (e


cb ) and hole (hvb ) pairs (Eq.
(1)). Those migrate to the TiO2 solid surface and are
trapped at dierent sites. Those electrons and holes play
a part in the reduction and oxidation of photocatalytic
reaction, respectively. The photogenerated holes may be
trapped by hydroxyl ions on the surface forming, hydroxyl radicals (Eq. (2)) (Munuera et al., 1979; Miller
and Fox, 1993), and the electrons may be trapped by an
electron acceptor of oxygen forming oxygen species

(O
2 ; super-oxide radical) on the surface (Eq. (3)).

TiO2 hm ! TiO2 e
cb hvb



h
vb OH ! OH

O2

e
cb


O
2

If water vapor takes part in the gassolid photocatalysis, the super-oxide radical can react with water
molecules, eventually forming the hydroxyl radicals as
shown in Eq. (4). Thus, the photocatalytic degradation
of VOCs can be increased due to the formation of hydroxyl radicals (Fox et al., 1990).



2O
2 2H2 O ! 2OH OH O2

In order to examine the eect of oxygen on the


photocatalytic conversion of VOCs, the photocatalytic
degradation tests were carried out at an atmosphere of
synthetic air (20.9 vol% O2 ), pure nitrogen, and pure
oxygen. Fig. 4 shows the oxygen dependency on the
photocatalytic degradation rate of VOCs. From these
gures, it can be seen that oxygen facilitates the photocatalytic degradation rate of VOCs. As previously
stated, while oxygen as an electron acceptor forms hydroxyl radicals, nitrogen cannot form hydroxyl radicals.
In the case of TCE, however, the existence of oxygen has
less eect than other VOCs on the photocatalytic degradation rate as shown in Fig. 4(a). Several researchers
reported that TCE degradation was predominantly
through a chain reaction by chlorine radicals (Luo and
Ollis, 1996). In this study, it seems that chlorine radicals
as well as hydroxyl radicals are formed through the
photocatalytic reaction of TCE. Thus, the existence of
oxygen may have less eect than other VOCs on the
photocatalytic degradation rate of TCE.
3.3. The eect of temperature
As a whole, temperature is one of the most important
factors in gassolid heterogeneous reactions. However,
photocatalytic reactions are not sensitive to minor
variations in temperature (Fox and Dulay, 1993). From
Pichat and Hermanns (1989) study for dehydrogenation
of alcohol over Pt/TiO2 , it was found that the desorption
step of hydrogen was rate determining at lower temperatures. On the contrary, the photocatalytic reaction

442

S.B. Kim et al. / Chemosphere 48 (2002) 437444

Fig. 4. The eect of molecular oxygen on the photocatalytic degradation rate of each VOC. (a) TCE (CO 1:206  102 mol m3 ,
CH2 O 0:383 mol m3 ), (b) Acetone (CO 1:208  102 mol m3 , CH2 O 0:0 mol m3 ), (c) Methanol (CO 1:151  102 mol m3 ,
CH2 O 0:383 mol m3 ), (d) Toluene (CO 3:835  103 mol m3 , CH2 O 0:766 mol m3 ); UV source: germicidal (254 nm) lamp, light
intensity: 2:1  103 W cm2 ; temperature: 45 C.

rate decreased over 70 C. In this case, adsorption would


be the rate determining step. That is, at low temperature,
desorption of the products from the photocatalyst surface is the rate determining step, whereas at higher
temperatures adsorption of the reactants become the
rate determining step (Pichat and Hermann, 1989).
Fig. 5 shows the lamp output of a 254 nm UV lamp
at various temperatures. It showed the light intensity
had a maximum output at 42.5 C. The eect of tem-

perature on the photocatalytic degradation rate of


VOCs was investigated at three dierent temperatures
(25, 45 and 75 C).
Fig. 6 demonstrates the temperature dependency on
the photocatalytic degradation rate. The most ecient
temperature was at 45 C for all compounds except
toluene. In the case of toluene, however, it was most
ecient at 25 C. This phenomenon might be caused by
the diculty of VOC adsorption on a catalyst at a
higher temperature range (75 C).

4. Conclusions

Fig. 5. Relative output of germicidal UV lamp according to


various bulb wall temperatures at 254 nm (presented by Atlantic Ultraviolet Corporation).

The photocatalytic degradation of VOCs including


gaseous TCE, acetone, methanol and toluene as a
function of water vapor, oxygen, and reaction temperature was investigated using a batch photoreactor. A
batch photoreactor was applied in this work prior to the
application of continuous process for the gassolid
heterogeneous photocatalytic reaction.
For the inuence of water vapor on the photocatalytic degradation of VOCs, there was an optimum water
vapor concentration in TCE and methanol, and, water
vapor enhanced the photocatalytic degradation rate of
toluene, but was inhibitive for acetone.

S.B. Kim et al. / Chemosphere 48 (2002) 437444

443

Fig. 6. The eect of temperature on the photocatalytic degradation rate of each VOC. (a) TCE (CO 1:206  102 mol m3 ,
CH2 O 0:383 mol m3 ), (b) Acetone (CO 1:208  102 mol m3 , CH2 O 0:0 mol m3 ), (c) Methanol (CO 1:151  102 mol m3 ,
CH2 O 0:383 mol m3 ), (d) Toluene (CO 3:835  103 mol m3 , CH2 O 0:766 mol m3 ); UV source: germicidal (254 nm) lamp, light
intensity: 2:1  103 W cm2 .

For the eect of oxygen on the photocatalytic degradation of VOCs, molecular oxygen is an essential
component in photocatalytic reactions because it traps
photogenerated electrons on the semiconductor surfaces
and decreases the recombination of electrons and holes.
As for the eect of reaction temperature on the
photocatalytic degradation of VOCs, it can be seen that
the photocatalytic degradation was more eective at a
moderate temperature than at an elevated temperature
for each compound because the adsorption of reactants
from the photocatalyst surface was dicult at a higher
temperature range (75 C).
Acknowledgements
The authors thank the Korea Institute of Industrial
TechnologyNational Center for Cleaner Production
and MAGREEN INC. for support of this work.
References
Alberici, R.M., Jardim, W.F., 1997. Photocatalytic destruction
of VOCs in the gas-phase using titanium dioxide. Appl.
Catal. B: Environ. 14, 5568.
Anderson, M.A., Yamazakinishida, S., Salvador, C.M., 1993.
Photodegradation of TCE in the gas phase using TiO2

porous ceramic membranes. In: Photocatalytic Purication


and Treatment of Water and Air. Elsevier Science Publisher,
Amsterdam, pp. 405418.
Augugliaro, V., Coluccia, S., Loddo, V., Marchese, L., Martra,
G., Palmisano, L., Schiavello, M., 1999. Photocatalytic
oxidation of gaseous toluene on anatase TiO2 catalyst:
mechanistic aspects and FT-IR investigation. Appl. Catal.
B: Environ. 20, 1527.
Chen, D., Ray, A.K., 1999. Photocatalytic kinetics of phenol
and its derivatives over UV irradiated TiO2 . Appl. Catal. B:
Environ. 23, 143157.
dHennezel, O., Pichat, P., Ollis, D.F., 1998. Benzene and
toluene gas-phase photocatalytic degradation over H2 O
and HCl pretreated TiO2 : by-products and mechanisms.
J. Photochem. Photobiol. A: Chem. 118, 197204.
Dibble, L.A., Raupp, G.B., 1992. Fluidized bed photocatalytic
oxidation of trichloroethylene in contaminated air streams.
Environ. Sci. Technol. 26, 492495.
EPA, 1987. Total exposure assessment methodology (TEAM)
study. Report 600/6-87/002a. Environmental Protection
Agency, Washington, DC.
Fox, M.A., Dulay, M.T., 1993. Heterogeneous photocatalysis.
Chem. Rev. 93 (1), 341357.
Fox, M.A., Aldel-Wahab, A.A., Kim, Y.S., Dulay, M.J.,
1990. Photocatalytic oxidation of Multifunctional organic
molecules: The eect of an intramolecular aryl thioether
group on the semiconductor-mediated oxidation/dehydrogenation of a primary aliphatic alcohol. J. Catal. 126,
693696.

444

S.B. Kim et al. / Chemosphere 48 (2002) 437444

Ibusuki, T., Takeuchi, K., 1986. Toluene oxidation on UVirradiated titanium dioxide with and without O2 , NO2 ,
or H2 O at ambient temperature. Atmos. Environ. 20 (9),
17111715.
Levenspiel, O., 1972. In: Chemical Reaction Engineering, second ed. John Wiley & Sons Inc., New York, pp. 6971.
Luo, Y., Ollis, D.F., 1996. Heterogeneous photocatalytic oxidation of trichloroethylene and toluene mixtures in air:
Kinetic promotion and inhibition, time-dependent catalyst
activity. J. Catal. 163, 111.
Mark, R.N., William, A.J., Danial, M.B., Thomas, A.M., 1993.
Detection of intermediates from the gas phase photocatalytic oxidation of TCE. In: Photocatalytic purication and
treatment of water and air. Elsevier Science Publisher,
Amsterdam, pp. 387391.
Miller, R., Fox, R., 1993. In: The rst international conference
on TiO2 photocatalytic purication and treatment of water
and air. Elsevier, London, Ontario, Amsterdam, New York,
p. 573.
Muggli, D.S., Falconer, J.L., 1999. Parallel pathways for
photocatalytic decomposition of acetic acid on TiO2 . J.
Catal. 187, 230237.
Munuera, G., Rives-Arnau, V., Saucedo, A., 1979. Photoadsorption and photo-desorption of oxygen on highly
hydroxylated TiO2 surface: Part 1role of hydroxyl groups
in photo-adsorption. J. Chem. Soc., Faraday Trans. 175,
736.
Obee, T.N., Brown, R.T., 1995. TiO2 photocatalysis for indoor
air applications: Eect of humidity and trace contaminant

levels on the oxidation rate of formaldehyde, toluene, and


1,3-butadiene. Environ. Sci. Technol. 29 (5), 12231231.
Peral, J., Ollis, D.F., 1992. Heterogeneous photocatalytic
oxidation of gas-phase organics for air purication: acetone,
1-butanol, butyraldehyde, formaldehyde and m-xylene oxidation. J. Catal. 136, 554565.
Pichat, P., Hermann, J.M., 1989. Adsorptiondesorption,
related mobility and reactivity in photocatalysis. In: Serpone, N., Pelizzetti, E. (Eds.), Photocatalysis: Fundamentals
and Applications. John Wiley & Sons, NTC, pp. 217250.
Rafael, M.R., Nelson, C.M., 1998. Relationship between the
formation of surface species and catalyst deactivation
during the gas-phase photocatalytic oxidation of toluene.
Catal. Today 40, 353365.
Sanjines, R., Tang, H., Berger, H., Gozzo, F., Margaritondo,
G., Levy, F., 1994. Electronic structure of anatase TiO2
oxide. J. Appl. Phys. 75 (6), 29452951.
Sauer, M.L., Ollis, D.F., 1994. Acetone oxidation in a photocatalytic monolith reactor. J. Catal. 149, 8191.
Shen, T.T., Schmidt, C.E., Card, T.R., 1993. Assessment and
control of VOC emission from waste water treatment and
disposal facilities. Van Nostrand Reinhold, New York.
Vorontsov, A.V., Kurkin, E.N., Savinov, E.N., 1999. Study of
TiO2 deactivation during gaseous acetone photocatalytic
oxidation. J. Catal. 186, 318324.
Wang, K.H., Tsai, H.H., Hseieh, Y.H., 1998. The kinetics of
photocatalytic degradation of trichloroethylene in gas phase
over TiO2 supported on glass bead. Appl. Catal. B: Environ.
17, 313320.

Вам также может понравиться