Chemical Engineering Journal 195–196 (2012) 233–240

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Chemical Engineering Journal

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Photocatalytic decomposition of gaseous 1,2-dichlorobenzene on TiO2 films: Effect

of ozone addition
Sheng-yong Lu ⇑, Qiu-lin Wang, Alfons G. Buekens, Jian-hua Yan, Xiao-dong Li, Ke-fa Cen
State Key Laboratory of Clean Energy Utilization, Institute for Thermal Power Engineering, Zhejiang University, Hangzhou 310027, China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

" Real destruction is the main reason

for removal compared to residual on
catalyst.
" There is an optimum dosage in
ozone addition.
" Ozone addition is an effective
method to reduce required
activation energy.
" Pathways based on the nature of
intermediate products identified are
discussed.
" CO rather than CO2 is the main
product of aromatic ring cleavage.

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

Article history: Gaseous 1,2-dichlorobenzene (1,2-DCBz) was photocatalytically decomposed on a powdered TiO2 layer
Received 27 December 2011 using UV-light, or the latter combined with ozone addition. The effect of various experimental parame-
Received in revised form 27 April 2012 ters was studied, including inlet concentrations of ozone, UV irradiation or not, carrier gas (dry air or
Accepted 28 April 2012
nitrogen) and treatment time period. A temperature of 150 °C is selected, to replicate flue gas conditions
Available online 7 May 2012
after bag house filter. An optimum ozone addition of ca. 165 ppm was established, higher concentrations
barely improving photocatalytic removal. Possible pathways and mechanisms are discussed on the basis
Keywords:
of the intermediate products identified, the chloride ions distribution in the effluent and catalyst surface,
Gaseous 1,2-DCBz
Ozone-assisted photocatalysis
and a carbon conversion balance.
Intermediate products Ó 2012 Elsevier B.V. All rights reserved.
Degradation pathways

1. Introduction
Waste incineration reduces solid waste volume and allows
energy recovery. These two features explain its rapid expansion in
China for the last 20 years [1]. However, poor combustion and inad-
equate flue gas treatment lead to the emission of polychlorinated
dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans
(PCDFs), in brief, dioxins. The concentration of dioxins in raw flue
⇑ Corresponding author. Tel.: +86 571 87952629; fax: +86 571 87952438.
E-mail address: lushengyong@zju.edu.cn (S.-y. Lu).
gas varies in wide ranges, i.e. 5–30 ng TEQ/Nm3 [2,3] and exceeds
the stringent emission limit of the European Union (0.1 ng TEQ/
Nm3). These semi-volatiles distribute between waste gas and fly
ash [4]. Their adsorption on activated carbon [5] transfers dioxins
from gas to solid residues. Additional treatment is still needed to
decontaminate ash and spent activated carbon.
Photocatalysis has been proposed to destroy dioxins (along with
almost all other organic compounds) using TiO2 or other inorganic
catalysts [6–9]. TiO2-derived catalysts are widely applied because
of their high efficiency, chemical stability and low cost [10].
The basis of photocatalysis has been widely documented [11].
Several free radicals (OH, OOH, O
2 ) generated during photocatal-

1385-8947/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2012.04.094
234 S.-y. Lu et al. / Chemical Engineering Journal 195–196 (2012) 233–240
Nomenclature
A pre-exponential factor (s1)
Cinlet inlet concentration of 1,2-DCBz (mmol/Nm3)
Coutlet outlet concentration of 1,2-DCBz (mmol/Nm3)
Cr residual concentration of 1,2-DCBz on the catalyst
surface
CCOþCH4 CO + CH4 carbon concentration after photocatalysis
(mmol/Nm3)
CCl chloride ion concentration (mmol/Nm3)
DRE Destruction and Removal Efficiency (%)
Ea activation energy (kJ mol1)
k rate constant (s1)
PDE Photocatalytic Degradation Efficiency (%)
PCDD/Fs polychlorinated dibenzo-p-dioxins and dibenzofurans
Qr flow rate of reactant gas at room temperature (ml/min)
ysis in the presence of H2O are active oxidants, strong enough to
oxidize organics to CO2, H2O or other oxidation products. The
superoxide ion radical O 2 not only intervenes in photocatalytic
reaction, but also generates reactive hydroxyl radicals OH respon-
sible for photo-oxidation in the atmosphere.
Both pure and doped TiO2 are applied to photocatalytic degra-
dation of organic pollutants. Recently, much work has focused on
aqueous media [12] and suspensions [13]. Dioxin surrogates, such
as monochlorobenzene and 1,4-dichlorobenzene are also de-
graded in suspension [14,15]. The strong toxicity of dioxins as
well as the difficulty of developing stable generation systems
has restricted direct application of dioxins in lab-scale tests. Only
few photocatalytic degradation experimental studies focus diox-
ins directly [16–20]. Hence, in most cases model compounds,
e.g. chlorophenols, chlorobenzenes, or polychlorobiphenyls, are
used as substitutes for dioxins. Okumura et al. investigated
PCDD-conversion over an innovative multicomponent catalyst
[21] and compared this with o-chlorophenol conversion over
the same catalyst; the results showed great similarity. In this pa-
per, gaseous 1,2-dichlorobenzene (1,2-DCBz) was selected as
model compound for dioxins and comparable chlorinated
refractory compounds.
Furthermore, ozone addition was reported to enhance catalytic
decomposition of organic compounds [22–24], due to catalyst
activation and/or creation of additional activated species. Thus,
the present paper reports on synergetic effects of UV-irradiation,
photocatalysis, and oxidation by ozone in the decomposition of
1,2-DCBz. Moreover, various experimental parameters, including
carrier gas composition, and exposure time per unit catalyst
surface to the gas stream are evaluated. Possible pathways are
discussed, based on identification of intermediate products and
inorganic chloride ions, and on establishing the carbon balance.
This study provides experimental stepping-stones for further re-
search on catalytic photolysis of PCDD/Fs in flue gas from actual
incinerator plant. Therefore, the reactor is heated to 150 °C to sim-
ulate such conditions.
2. Experimental
2.1. Materials
All reagents, including 1,2-DCBz, hexane, sodium bicarbonate
and potassium iodide are analytical grade. High purity nitrogen
(>99.999%) and air are used as dry carrier gas. All are used without
further purification. A commercial catalyst is selected, i.e. P-25 (De-
Qg volumetric flow rate of reactant gas at reaction
temperature (ml/min)
Q inlet molar flow rate of 1,2-DCBz (mmol/min)
R gas constant (8.314 J/K, mol)
RE Residual Efficiency (%)
r reaction rate (mmol/Nm3 s1)
S reactor bottom area (cm2)
Tr room temperature (K)
Tg reaction temperature (K)
tg residence time of reactant gas in the reactor (s)
te exposure time per unit catalyst surface exposed to
reactant gas (s/cm2)
t photocatalytic reaction time (s)
V internal volume of the photochemical reactor (cm3)
gussa) TiO2, particle size of 20–50 nm, composed of 80% anatase,
20% rutile, and with a B.E.T. specific surface SBET = 50 ± 15 m2/g.
2.2. Film preparation and photocatalysis procedure
The deposition method described in [25] is used for coating the
TiO2 particles, exposed onto the UV-irradiated bottom of the
quartz reactor, a rectangular parallelepiped with dimen-
sions: length  width  height = 200 mm  50 mm  10 mm. The
required TiO2 coating density (2 mg/cm2) is obtained by repeating
the same coating procedure a number of times. Scanning electron
microscopy (SEM) images show the surface morphology of the TiO2
film, constituted by discrete particles (Fig. 1a) and forming a uni-
form film on the bottom of the reactor. Higher magnification
(Fig. 1b) shows the catalyst surface as an association of
nanoparticles and its porous structure. Particle size (20–50 nm)
stays unchanged after coating; inter-particle pore sizes vary be-
tween 50 and 125 nm. The porous structure enlarges gas to particle
contact, enhancing photocatalysis, as far as light penetration into
this structure is not entirely obstructed.
A thermostatic bubbler is used to generate gaseous suitable 1,2-
DCBz concentrations in the carrier gas stream selected (air or nitro-
gen). The resulting stream is led to the photocatalytic reactor, after
dilution by a second carrier gas stream and (possibly) ozone, and
mixing by static gas mixers. Mass flow meters are employed to reg-
ulate the flow rates of the carrier gas streams and thus establish
the inlet concentration of 1,2-DCBz. A 500 W mercury lamp (dom-
inant wavelength 365 nm) is positioned above the reactor as ultra-
violet light source. The surface temperature of the lamp could
reach about 300 °C, so it remains fixed outside the reactor and dur-
ing operation it is cooled by an air fan. The quartz photocatalytic
reactor is designed as a shallow rectangular parallelepiped, with
its entire bottom (area 100 cm2) irradiated, exposing the catalyst
film to the UV-light source. The reactor is heated to 150 °C, its tem-
perature maintained by heating tape, wrapping sides and bottom
of the reactor. The vertical distance between lamp and reactor bot-
tom (with TiO2 film coating) is 5 cm; the light intensity reaching
the catalyst upper surface, as measured by a UV-irradiatometer,
is 14.8 mW/cm2.
Experiments start by connecting the 1,2-DCBz generator with
reactor and subsequent tail gas absorbers and turning on the
light source about 30 min after the thermo-regulated bubbler
and the flow rate of carrier gas have attained the desired reaction
conditions, including the selected inlet concentration of 1,2-DCBz.
The flow rate of carrier gas through the bubbler is fixed at 50 ml/
 S.-y. Lu et al. / Chemical Engineering Journal 195–196 (2012) 233–240
Fig. 1. Scanning Electron Microscope (SEM) images of TiO2 film. (a) Magnification of 104 and (b) magnification of 105.
min. The different inlet concentrations of 1,2-DCBz are obtained
by varying the temperature of the bubbler between 40 and
50 °C. Unconverted 1,2-DCBz is sampled at the outlet, after pho-
tocatalytic (or other) reaction, and analyzed at regular intervals.
Two absorption bottles in ice-bath each with 150 ml hexane are
connected in series to absorb any 1,2-DCBz remaining in the tail
gas.
2.3. Analysis
Quantitative analysis of 1,2-DCBz concentrations proceeds by
gas chromatography using an Agilent 6890N GC, equipped with
electron capture detector (ECD) and a 30 m DB-5 column. Oven
temperature initially is maintained for 4 min at 80 °C, then in-
creases to 106 °C at 5 °C/min and to 250 °C at 8 °C/min; then, the
final temperature is held for 4 min.

The chloride ion (Cl) concentrations in both tail gas (Cltg ) and

rinse liquid (Clad ) are analyzed by means of Ion Chromatography
(Basic 792). The samples arise either from absorbing Cl from tail
gas, or from rinsing the catalyst surface with 1  104 mmol/Nm3
NaHCO3 and KI aqueous solution. Potassium iodide (KI) allows

detecting whether Cl2 or ClOx is generated during photocatalysis:

if the samples remain colorless, no Cl2 or ClOx is present. The
chloride ion distribution (in tail gas or as residual chloride ex-
tracted from the catalyst) is closely linked with photocatalytic re-
moval efficiency; it throws some light on the pathways of
photocatalytic reactions. Intermediates (chlorobenzene, methyl-
benzene, and organic acids) are analyzed by Gas Chromatogra-
phy–Mass Spectrometry (GC–MS, Trace DSQ II, Thermo
scientific). The GC–MS is equipped with a DB-WAX capillary col-
umn (column length 30 m); the NIST Mass Spectral Search Program
is used for identification. A Fourier transform infrared gas ana-
lyzer GASMET – FTIR (Dx 4000) equipped with infrared source
(Sic, 1550 K), sample cell (temperature: 180 °C) and a ‘‘Calcmet
Library search program’’ ensures the on-line analysis of inorganic
products (e.g. carbon monoxide, hydrogen chloride, methane) in
the tail gas stream.
3. Results and discussions
3.1. Photocatalytic destruction and removal efficiency DRE
Eqs. (1)–(3) define the terms (largely Photocatalytic) Destruc-
tion and Removal Efficiency (DRE) as composed from two contribu-
tions: Photocatalytic Degradation Efficiency PDE and Residual
Efficiency RE:
DRE ¼ ðCinlet  Coutlet Þ=Cinlet  100%
235
PDE ¼ ðCinlet  Coutlet  Cr Þ=Cinlet  100% ð2Þ
RE ¼ Cr =Cinlet  100% ð3Þ
where Cinlet (mmol/Nm3) is the inlet concentration of 1,2-DCBz;
Coutlet (mmol/Nm3) the concentration of 1,2-DCBz in tail gas and,
Cr (mmol/Nm3) the concentration of residual 1,2-DCBz on the cata-
lyst surface as established by extraction after finishing the
experiment.
From the volumetric flow rate of reactant gas Qg and the
internal volume of the photochemical reactor V, the residence time
tg of reactant gas inside the reactor at 150 °C can be derived as
Eq. (5).
Tg 423 K
Qg ¼ Qr  ¼ 100 ml= min  ¼ 141 ml= min ð4Þ
Tr 300 K
1
tg ¼ V=Q g ¼ ð200 mm  50 mm  10 mmÞ=141 ml min
¼ 42:6 s ð5Þ
Bearing in mind that the reactor bottom (area S) is uniformly cov-
ered with catalyst, an additional measure of catalytic contact time
can now be defined by:
te ¼ t g =S ¼ 42:6 s=100 cm2 ¼ 0:426 s=cm2 ð6Þ
yielding the exposure time te per unit catalyst surface exposed to
reactant gas.
In MSWI flue gas the PCBz concentration value is quite low
(<0.045 mmol/Nm3). However, it is difficult to generate 1,2-DCBz
concentrations reliably at such low levels suitable for lab-scale
experiments (e.g., due to wall adsorption). Baseline values of Cinlet
and te of respectively 3.9 mmol/Nm3 and 0.426 s/cm2 are adopted
in this comparative testing. Photocatalytic removal of 1,2-DCBz is
suitably efficient during the full 120 min test, since DRE attains al-
most 100%, in particular during the first 30 min (Fig. 2). Thus the te
value of 0.426 s/cm2 set during this test is sufficiently high.
This DRE-value consists of PDE proper and of RE, residual 1,2-
DCBz remaining on the catalyst. The RE-value after photocatalytic
reaction, however, at most represents less than 5%. Therefore deg-
radation dominates DRE, and the contribution from RE becomes
virtually nil after only 30 min.
According to this study 1,2-DCBz is almost totally decomposed
while it is still adsorbed onto the catalyst surface. However, both
DRE and PDE gradually decline during operation, at a time scale
of only 2 h (Fig. 2). Deactivation becomes stronger at higher
1,2-DCBz concentrations. The reduction in PDE may be linked to
a waning adsorption ability of the catalyst, possibly related to
the accumulation on the catalyst of intermediates, occupying ac-
ð1Þ tive sites and restricting additional adsorption of 1,2-DCBz.
236 S.-y. Lu et al. / Chemical Engineering Journal 195–196 (2012) 233–240

Fig. 2. The proportion of PDE and RE in DRE during 2 h reaction (Cinlet = 3.9 mmol/Nm3, te = 0.426 s/cm2, air as carrier gas).

Fig. 3. Adsorption properties of fresh catalyst and used catalyst towards 1,2-DCBz compared to DRE when light is on (Cinlet = 3.9 mmol/Nm3, te = 0.426 s/cm2, air as carrier
gas).

This trend is confirmed in Fig. 3, comparing the adsorption

capacity of fresh and of used catalyst, i.e. before and after a photo-
catalytic test. Fresh catalyst at the start (when the light is still off)
adsorbs about 58% of the Cinlet. Once the UV lamp is turned on,
the DRE far exceeds the efficiency related to adsorption alone (with-
out light). Conversely, photocatalytic decomposition ends at once
as soon as illumination stops and then the catalyst shows much
lower RE than that at the start with fresh catalyst. Also, the DRE-va-
lue obviously drops for catalyst that was used once before in an
adsorption test (Fig. 3 vs. Fig. 2): compounds adsorbed onto the cat-
alyst surface and thus occupying active sites reduce PDE. Hager
et al. [26] established the maximum adsorption capability of the
photocatalyst (cfr. Fig. 3): given enough time, adsorption tends to
saturate the catalyst film in the absence of UV light.

3.2. Oxidants assisted photocatalysis

3.2.1. Oxygen-rich and oxygen-free photocatalysis
The presence of oxygen stimulates DRE (Fig. 4). Oxygen has the
ability of capturing photo-generated electrons, thus successfully
restraining recombination of electron–hole pairs (reaction (8)). It
is also the source of superoxide ion radicals O 2 that accelerate
reaction [11]. Valuable, yet little OH and OOH are formed in the
case of completely dry air as carrier gas. The effect of water has
been studied in Ref. [27].
hv þ
TiO2 ! h þ e
Fig. 4. Effect of reaction atmosphere on DRE and inorganic carbon conversion
efficiency. (Cinlet = 28.6 mmol/Nm3; te = 0.426 s/cm2, reaction time = 3.5 h).
O2 þ e ! O2 ð8Þ
According to the tail gas composition established by GASMET,
carbon monoxide CO, hydrogen chloride HCl and trace methane
CH4 are the three main products under oxygen-rich conditions;
this implies cleavage of aromatic rings, as well as dechlorination.
ð7Þ Carbon monoxide CO rather than carbon dioxide CO2 is the main
 S.-y. Lu et al. / Chemical Engineering Journal 195–196 (2012) 233–240
product. Einaga et al. [28] photocatalytically decomposed gas-
phase benzene over both TiO2 modified with Pt (Pt/TiO2) and pure
TiO2 catalysts, with CO2 and CO as main products, yet stressing that
conversion of CO to CO2 does not occur over pure TiO2 catalyst.
Hence, CO is not an intermediate of CO2, consistent with the results
from GASMET analysis results in this study. Eq. (9) states that in air
around 30% of organic carbon in the aromatic ring is converted into
inorganic carbon after 3.5 h of photocatalytic decomposition. How-
ever, only HCl but no CO or CO2 is detected in the tail gas, as for an
oxygen-free environment, suggesting that O2 and O 2 facilitate the
mineralization of organic compounds; moreover, de-chlorination
instead of benzene ring cleavage is the main reason for 1,2-DCBz
degradation in absence of oxygen.
Inorganic chlorine may either remain adsorbed onto the cata-
lyst surface, or report to tail gas. Both rinse liquid and tail gas
absorption liquid were collected and analyzed through ion chro-
matography to investigate dechlorination efficiency calculated by
Eq. (10). The results shown in Fig. 5 affirm that dechlorination is
more complete with oxygen in carrier gas and again substantiate
that the photocatalytic removal efficiency is due to degradation,
not to adsorption. Furthermore, in the absence of oxygen the
inorganic chloride, generated by photocatalysis, tends to remain
on the catalyst rather than to report to tail gas as hydrogen chlo-
ride, which may be a major reason for catalyst deactivation.
Inorganic carbon conversion efficiency
¼ CCOþCH4 =Cinlet6  100% ð9Þ
Dechlorination efficiency ¼ CCl =Cinlet2  100% ð10Þ
3.2.2. Ozone assisted photocatalysis
The contact time parameter te is drastically reduced from
0.426 s/cm2 to 0.036 s/cm2 by increasing the flow rate Qr from
100 ml/min to 1200 ml/min. For simulating photocatalytic clean-
up conditions more realistically, the physical residence time is re-
duced from 42.6 to 3.6 s. Thus, the average DRE obtained during
the 3.5 h period of irradiation through TiO2/UV significantly drops
from 90% (Fig. 4) to around 5% (Fig. 6). Further work will look at
this important parameter in more detail.
Fortunately, this dramatic loss in DRE can still be corrected by
addition of ozone, which accelerates reaction rates dramatically
(Fig. 6): the DRE (77%) is markedly higher at an ozone dosage of
110 ppm in TiO2/UV (i.e. Ozone/TiO2/UV), than that without ozone
Fig. 5. Dechlorination efficiency under oxygen-rich or oxygen-free conditions
(Cinlet = 28.6 mmol/Nm3, te = 0.426 s/cm2, reaction time = 3.5 h).
237
Fig. 6. Comparison of removal efficiencies of 1,2-DCBz by TiO2/UV/oxygen, ozone,
Ozone/UV and Ozone/TiO2/UV respectively (Cinlet = 27.8 mmol/Nm3, te = 0.036 s
/cm2, ozone concentration = 110 ppm, reaction time = 3.5 h).
(only 5%). In an Ozone/TiO2/UV process gaseous 1,2-DCBz may be
destroyed through one of the following pathways:
(1) Direct photolysis of 1,2-DCBz by UV. Even without catalyst
1,2-DCBz can be still photo-decomposed: 1,2-DCBz has its
proper UV light absorption ability, thus subjecting 1,2-DCBz
to direct photolysis (the same process is responsible for
atmospheric photodecomposition, restricting the atmo-
spheric lifetime of most organic compounds):
1; 2  DCBz þ hv ! oxidation products ð11Þ
(2) Direct oxidation of 1,2-DCBz by ozone. Ozone is a strong oxi-
dant, widely used in the treatment of potable water and
wastewater because of its oxidation and disinfection capa-
bilities [29–31]. In this case, ozonation of gaseous 1,2-DCBz
in air removes on average less than 3% of 1,2-DCBz (Fig. 6).
Hence, only little 1,2-DCBz is oxidized directly by ozone
alone according to:
1; 2  DCBz þ O3 ! oxidation products ð12Þ
(3) Indirect oxidation of 1,2-DCBz by radicals generated via TiO2
photocatalysis (TiO2/UV) or by ozone photolysis (Ozone/UV).
Simultaneous application of ozone with UV (i.e. Ozone/UV),
greatly increases the DRE, when compared to direct ozona-
tion alone (Fig. 6), because of the generation of supplemental
oxygen atom O through ozone photolysis:
O3 þ hv ! O þ O2 ð13Þ
Ozone/UV realizes an obviously more attractive DRE compared to
TiO2/UV, because the generation of O 2 relies on absorption of O2
onto the catalyst as a first step in TiO2/UV process, which is much
slower than ozone photolysis. Secondly, there is also the contribu-
tion of homogeneous gas-phase reactions in the Ozone/UV system.
The heterogeneous reaction in the TiO2/UV process is held-up by
mass transfer from the gas to the catalyst surface [32].
In the Ozone/TiO2/UV process, the DRE rises sharply to 77%,
much more than the individual contributions of TiO2/UV (5%)
and Ozone/UV (25%). This implies that synergetic effects occur in
the Ozone/TiO2/UV process. Ozone substitutes oxygen as photo-
generated electron acceptor and forms OH free radicals by
238 S.-y. Lu et al. / Chemical Engineering Journal 195–196 (2012) 233–240
reactions (14)–(16). The H+ derives from the C–H bond broken dur-
ing the photocatalytic decomposition of 1,2-DCBz.
O3 þ e ! O3
O3 þ 
þ H ! O3 H

O3 H ! O2 þ  OH
Ozone, however, not only promotes photocatalytic reactions, but
also competes with the photocatalyst for UV rays [33], as shown
in reaction (14). Moreover, excess ozone eliminates hydroxyl radi-
cals by reaction (17) [34,35], which blocks the photocatalytic
reaction:
O3 þ  OH !  O2 H þ O2
Thus high ozone concentrations actually attenuate photocata-
lytic removal (Fig. 7).
The DRE-value in Ozone/TiO2/UV treatment increases almost
linearly with ozone concentrations ranging from 0 to 165 ppm.
Further ozone addition (e.g. 220 ppm) brings a slight drop, ascribed
to UV-absorption by ozone, as well as scavenging of hydroxyl rad-
icals by ozone. Consequently, some 165 ppm is regarded as opti-
mum dosage of ozone under these experimental conditions.
3.3. Kinetics study of photocatalysis reaction
Photocatlytic decomposition of organic compounds was re-
ported according to the first order reaction kinetics equation
[36,37]:
dCoulet
r¼ ¼ kCoutlet
dt
The above equation can be integrated to
lnð1  DRE=100Þ ¼ kt
The reaction rate constant k is thus calculated as:
k ¼ Q =CinletV  106  lnð1  DRE=100Þ
Moreover, the relationship between activation energy Ea and rate
constant k is expressed by the Arrhenius equation [38]:
Fig. 7. Impact of ozone concentration on DRE in Ozone/TiO2/UV process
(Cinlet = 27.8 mmol/Nm3, te = 0.036 s/cm2, reaction time = 3.5 h).
Table 1
The reaction rate constants k of different reaction conditions.
Reaction atmosphere te (s cm3) k (s1)
ð14Þ
TiO2/UV/N2 0.426 0.030
TiO2/UV/O2-21% 0.062
ð15Þ TiO2/UV/O2-21% 0.036 0.013
TiO2/UV/O3-55 ppm 0.289
ð16Þ TiO2/UV/O3-110 ppm 0.410
TiO2/UV/O3-165 ppm 0.593
TiO2/UV/O3-220 ppm 0.558
k ¼ A expðEa =RT g Þ ð21Þ
From Table 1 it follows that different reaction conditions result
ð17Þ in different rate constant values k. Both te extension and oxidant
addition lead to higher rate constant values k, possibly indicating
a reduction in activation energies (as Tg fixed at 150 °C) according
to Eq. (21).
Ozone addition benefits the photocatalysis reaction most: as
shown in Table 1, k-value for photocatalytic decomposition of
1,2-DCBz with 55 ppm O3 (TiO2/UV/O3-55 ppm) is 0.289, which is
respectively about 22 times or five times higher than that for
TiO2/UV/O2-21% with te = 0.036 s/cm2 or 0.426 s/cm2. Nevertheless,
further O3 concentration increases cannot further enhance k once
the ozone dosage reaches 220 ppm, which is consistent with the
results in Fig. 7.
3.4. Reaction mechanism
As explored above, any intermediate products adsorbed on the
ð18Þ photocatalyst may restrict or even suppress further decomposition
of 1,2-DCBz. Moreover, various intermediates, derived from photo-
catalytic decomposition of 1,2-DCBz, are identified in the rinse li-
quid by GC–MS analysis. These intermediates indicate possible
ð19Þ pathways of photocatalytic decomposition, when analyzed jointly
with the tail gas compositions established by means of GASMET.
Based on the above findings, two different pathways for photocat-
alytic decomposition reaction with or without oxygen are
ð20Þ suggested.
In the case of dry air as carrier gas, DRE of 1,2-DCBz (above 90%)
is obviously higher than the conversion efficiency of organic car-
bon to inorganic carbon; the difference probably corresponds to
dechlorination and decomposition of 1,2-DCBz to other organic
compounds. Photo-generated electrons (e) are preferentially cap-
tured by oxygen as reaction (23) generating O 2 . Considering the
ortho-para directing effect of Cl atom in the aromatic ring, the po-
sitive photo-generated hole (h+) tends to attack its ortho (shown in
reaction (22)) or para position. The further cleavage of aromatic
rings is induced by the super oxide ion radicals O 2 (rather than

OH and OOH due to the absence of water). CH3CHO and
CH2(CH)3COOH are detected by GC–MS as the reaction intermedi-
ates further verifies the occurring of ring cleavage, consistent with
the findings from Sobczyński et al. [39], reporting the presence of –
CHO and –COOH intermediates during the photocatalytic decom-
position of phenol. Toluene and o-xylene are also detected as inter-
mediates, which may be due to the reaction between methyl
groups and benzene, produced during aromatic ring cleavage and
dechlorination, respectively.
Under anaerobic condition (nitrogen as carrier gas) dechlorina-
tion proceeds easier (following the reaction (25)), now that no oxy-
gen competes with 1,2-DCBz for photo-generated electrons (e).
Cleavage of an aromatic ring is not usual under anaerobic condi-
tions. As a result, PDE depends mainly on dechlorination. The
vaporization of HCl from catalyst surface postpones the deactiva-
tion of the catalyst and helps to carry on photocatalytic decompo-
 S.-y. Lu et al. / Chemical Engineering Journal 195–196 (2012) 233–240
sition. In anaerobic conditions, however, chloride ions separated
from 1,2-DCBz tends to accumulate onto the catalyst surface (as
shown in Fig. 5) as no water present to provide H+ or OH; there
they contaminate the active sites, obstructing further photocata-
lytic reactions and resulting in relatively lower DRE. Excess
electrons not captured by O2 may also attack the carbon-chlorine
bonds of the aromatic ring even in oxygen-rich environment, as
follows from the detection of monochlorobenzene in both
oxygen-rich and oxygen-free environments.
ð22Þ
ð23Þ
ð24Þ
ð25Þ
4. Conclusions
The Decomposition and Removal Efficiency (DRE) of gaseous
1,2-DCBz is studied on nano-TiO2 catalyst film under UV irradiation,
in the absence or presence of oxygen. The 1,2-DCBz concentrations
studied are much higher than those occurring under real operating
conditions, which means that the results represent a worst-case ap-
proach. The DRE of 1,2-DCBz relies on photocatalytic decomposi-
tion, as well as on adsorption, mainly at initial conditions.
The presence of oxygen enhances the photocatalytic elimina-
tion of 1,2-DCBz not only by capturing electrons (which restricts
the recombination of photo-generated electron–hole pairs), but
also by forming active oxidants, i.e. super oxide ion radicals O
2.
Fortunately, ozone addition can make up the DRE loss caused by
residence time reduction. As expected, the DRE of 1,2-DCBz in an
O3/UV/TiO2 process is comparatively attractive and larger than
the sum of those obtained from TiO2/UV and O3/UV individually.
The DRE increases almost linearly with ozone concentrations rang-
ing from 0 to 165 ppm. Further increase of ozone again slows down
the conversion due to UV intensity attenuation as well as hydroxyl
radical elimination by excess ozone. According to the kinetic anal-
ysis, ozone assistance is indeed one of the most effective methods
to enhance the rate.
Inorganic carbon conversion efficiency, dechlorination effi-
ciency, as well as the nature of the intermediate products, suggests
that the dominant photocatalysis pathways in oxygen-rich and
oxygen-free environments are cleavage of aromatic rings and
dechlorination processes. In the presence of oxygen, HCl preferen-
tially evolves, which is beneficial for continuity of the reaction.
Conversely, chlorine ions are likely to remain onto the catalyst sur-
face under nitrogen, aggravating catalyst deactivation.
239
Acknowledgements
This work was supported by the National State Basic Research
Program of China (973 Program, 2011CB201500), National Project
of Scientific and Technical Supporting Program (2007BAC27B04),
Zhejiang University Y.C. Tang Disciplinary Development Fund,
and Program of Introducing Talents of Discipline to University
(No. B08026).
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