474 Chem. Eng. Technol. 2007, 30, No.

4, 474–480

Kayzad J. Vajifdar1 Research Article

Daniel H. Chen1
John L. Gossage1 Photocatalytic Oxidation of PCE and
Kuyen Li1
Xuejun Ye1 Butyraldehyde over Titania Modified with
Govind Gadiyar1 Perovskite Optical Crystal BaTiO3
Bonnie Ardoin1

1 Photocatalysis utilizes near-UV or visible light to break down organic pollutants

Lamar University, Department
of Chemical Engineering,
Beaumont, USA.
into innocuous compounds at room temperatures. This paper introduces the use
of semiconducting optical crystals as an additive to a photocatalyst. The perovs-
kite optical material BaTiO3 (band gap of 3.7–3.8 eV) is found to increase VOC
destruction when black light is used. The best composition found is 0.1 wt %
BaTiO3 with the balance being TiO2. This photocatalyst increases tetrachloro-
ethylene (PCE) conversion by 12 % to 32 % for space times between 1.4 and 17.2
seconds and inlet concentrations of 40 to 130 ppm with a 4 W black light. The
average enhancement is approximately 25 %. For butyraldehyde conversion the
maximum enhancement is 20 % at 130 ppm in 3.6 seconds. The UV/VIS spectro-
scopy data indicate a lower absorbance with the additive. The reaction parameters
studied are space velocity, inlet concentration and light source. Oxidation by-pro-
ducts are identified using a GCMS.

Keywords: Organic pollution, Oxidation, Photocatalysis

Received: June 20, 2006; revised: December 18, 2006; accepted: December 21, 2006
DOI: 10.1002/ceat.200600194

1 Introduction concentrates on TiO2, which exists in two crystalline forms:

Volatile organic compounds (VOCs) along with nitrogen ox-
ides (NOx) are the precursors to tropospheric ozone, smog
and fine particulate matter [1, 2]. As a result, VOCs pose major
threats to the air quality of many metropolitan areas world-
wide and their control is crucial. The Clean Air Act Amend-
ments of 1990, various state implementation plans, and the
recent EPA regulations to tighten ozone and particulate matter
standards make VOC emission control even more crucial [2].
The most common VOC emission control methods [3, 4] in-
clude carbon adsorption, incineration, catalytic oxidation, bio-
filtration and photocatalytic oxidation (PCO) using titanium
dioxide (TiO2), which has gained much attention in the treat-
ment of air and water pollutants, especially in low-concentra-
tion, low-flow-rate, and room-temperature applications. Ex-
amples of such applications are process vent treatment, soil
vapor extraction, air stripping, indoor air purification, patho-
gen inactivation, and ground water decontamination [5–9].
PCO employs semiconductors such as SrTiO3, TiO2, ZnO,
ZnS, CdS and InTaO4 as a photocatalyst [1, 10, 11]. This paper
– BaTiO3 (bandgap 3.7–3.8 eV) [17] may enhance photocatalysis
Correspondence: D. H. Chen (chendh@hal.lamar.edu), Lamar Uni-
versity, Department of Chemical Engineering, P.O. Box 10053,
Beaumont, TX 77710, USA.
anatase and rutile. Anatase TiO2 with a band gap of 3.2 eV is
used here. The oxidant used in PCO is the oxygen present in the
air, so it is not necessary to employ additional chemicals such as
O3 or H2O2. The chemical activation is provided by the photo-
excitation of the catalyst by UVA or visible light to generate elec-
tron-hole pairs (e– – h+). Holes are trapped by the OH– group
present on the surface yielding highly oxidative hydroxyl (OH·),
superoxide (O2–·), and hydroperoxide (HO2·) radicals, which
are responsible for the oxidative attacks on VOCs [5, 13].
Many recent works in PCO have concentrated on modifying
the photocatalyst by mixing it with other metal oxides and ad-
sorbents, as well as by plasma or ion implantation treatment
[1, 8, 14–16]. In this paper, the TiO2 semiconductor is modified
by the addition of commercially available perovskite optical
crystals to improve the utilization of UV/visible light. The origi-
nal idea was that perovskite optical crystals such as BaTiO3 are
nonlinear opticals (NLO) that have an anionic group structure
capable of emitting light with double or triple the frequency of
the incident light. Consequently, BaTiO3 was used with the in-
tention that it might help to convert some visible light to near
UV light by a nonlinear optical process, but this does not appear
to be the case. However, the results shown below indicate that
through other mechanisms such as refracting and transmitting
through the crystal (internal waveguide) or prolonging the life
of electron-hole pairs by the ferroelectric effect.

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Chem. Eng. Technol. 2007, 30, No. 4, 474–480
BaTiO3 is a perovskite that exhibits a ferroelectric effect. The
most common perovskite structure is an FCC structure, as
shown in Fig. 1. Due to the special arrangement of the largest
atoms at the corners of the cube and the smaller atoms on the
faces of the cube, the significantly smaller central atom can
shift slightly. This shift can be effected through two means,
either by applying an electric field, or by applying pressure to
Figure 1. Single perovskite crystal.
the crystal and essentially bending the bonds to the point
where the small central atom is displaced, thus creating an
overall electric field. Many ferroelectrics are chemically ex-
pressed as ABO3 (BaTiO3), with an octahedron constructed by
six oxygen atoms with a smaller metallic element at its center
[18]. ABO3 type ferroelectric crystals are divided into the per-
ovskite, ilmenite, and tungsten-bronze types.
The tetragonal perovskite structure is a cubic lattice with
one face of the lattice with a (001) orientation extended, and
the other two orientations shrinking. In the extended orienta-
tion, when the central atom shifts, the displacement of positive
ions (Ba+2 and Ti+4) and negative ions (O–2) separates the cen-
ter of gravity of the positive charges from that of the negative
charges, which allows an electrical polarization moment to oc-
cur. The stability of the structure depends on the relative ionic
radii. If the cations are too small for close packing with the
oxygens, they can be displaced slightly. Since these ions carry
electrical charges, such displacements can result in a net elec-
tric dipole moment (opposite charges separated by a small dis-
tance). The material is said to be ferroelectric by analogy with
a ferromagnet, which contains magnetic dipoles. The structur-
al stability of oxides consisting of octahedra such as shown in
Fig. 1 can be estimated by calculating the tolerance factor
[16, 19] defined as:
p
t = (rA + rO) / (( 2)(rB + rO))
where rA, rB and rO are the radii of the respective ions. A toler-
ance factor between 0.79 and 1.1 gives an ideal cubic perov-
skite structure. The value of tBaTiO3 = 0.93 (ionic radii of Ba+2
= 1.35
, Ti+4 = 0.68
and O–2 = 1.40
[20]).
2 Experimental
As shown in Fig. 2, the experimental apparatus consists of the
air/chemical mixing system, the photocatalytic reactor, the

2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Photocatalysis 475
F
F
M F
I
X
E VOC A
R I
R
Fiber-Optic
Photoreactor System
(EIFOPR / IIFOPR)
Vent Auto-Sampling
System
GC/FID GC/MS
Figure 2. Flowchart of experimental setup.
automatic on-line sampling valves, the Varian Star 3400 GC-
FID and the HP G1800A GCMS. Air supplied with an instru-
ment air cylinder is divided into two streams. One air stream
is bubbled through a gas wash bottle containing the pollutant
reagent (PCE or butyraldehyde). This stream is combined with
the second air stream to give the desired pollutant concentra-
tion to the inlet stream of the reactor.
The on-line Varian Star 3400 gas chromatograph has two
sampling valves and is equipped with a flame ionization detec-
tor (FID). The separation column is a 30 m  0.53 mm ID
fused silica capillary column coated with Bentone (Supelco #
752802B). Gases at the reactor inlet and outlet are sampled
through two automatic sampling valves with a sampling loop
volume of 250 microliters.
A GC/MS (HP G1800A GCD) is used to detect the inter-
mediates during the oxidation of the pollutants [6, 13, 14]. The
on-line GC/MS blank test (i.e., without photocatalytic reac-
tion) indicates that the standard error of the on-line chemical
analysis of this experimental apparatus is less than 3 %. A por-
table CEA GD-444 CO2 analyzer (not shown in Fig. 2) is used
to measure carbon dioxide during PCO of butyraldehyde. The
instrument is calibrated with standard CO2 gases (Scotty Ana-
lyzed Gases, Alltech Corporation).
In this study, the gas phase PCO of PCE is carried out in a
packed-bed reactor where the catalyst is supported on fiber-
optic packing. The reactor is covered with aluminum foil,
which reflects most of the light produced by the light source.
Two types of photoreactors are used here: internally illumi-
nated fiber-optic photoreactor (IIFOPR) and externally illumi-
nated fiber-optic photoreactor (EIFOPR). These are described
below. Fibers coated via the dip-coating method [21] with
TiO2 and a variable proportion of BaTiO3 are randomly placed
around the lamp (i.e., between the lamp and reactor). The
concentration of the inlet and the outlet streams is measured
using a GC/FID and the conversion is calculated. By-product
identification is conducted by effluent analysis with the
GC/MS.
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476 K. J. Vajifdar et al.
2.1 Photoreactor
As mentioned above under Experimental, two types of optical
fiber reactors, externally illuminated fiber-optic photoreactor
(EIFOPR) and internally illuminated fiber-optic photoreactor
(IIFOPR), have been used in this study. In either setup the cat-
alyst is coated on stripped (i.e., cladding removed) fiber optics
packed inside the reactor.
The catalyst used is P25 TiO2 (Degussa) with a primary par-
ticle diameter of 21 nm, a surface area of 50 – 8 m2/g, and a
crystal structure primarily of anatase. For experiments involv-
ing the NLO material BaTiO3, the required amount of BaTiO3
(here from 0.05 wt-% to 2.0 wt %) is mixed with the TiO2
before coating. The tapped density (T.D.) [22] of TiO2 is ap-
proximately 100 g/L. This powdered semiconductor catalyst is
coated on the surface of optical fibers (Ceramoptec Inc.) to a
length of 10–15 cm. The effects of coating thickness and ap-
propriate lengths have been previously determined [23].
2.1.1 Externally Illuminated Fiber-Optic Photoreactor
(EIFOPR) System
From an optical standpoint the two key elements of an optical
fiber are its core and cladding [24], as illustrated in Fig. 3,
which shows an untreated single optical fiber. The refractive
index of the core is higher than that of the cladding, so light in
the core that strikes the boundary with the cladding at an angle
less than the angle of acceptance is confined in the core by total
internal reflections. Another way to look at light guiding in a
fiber is to measure the fiber’s acceptance angle defined as the
angle over which light rays entering the fiber will be guided
along its core. A ray that bounces several times back and forth
within the core will travel a slightly greater distance than one
that goes straight through it.
The fused silica optical fibers (Ceramoptec Inc., 600 lm
OD, part # PUV 600/750/1010 T) are used as a means of light
transmission to the catalyst substrate. Eighty-eight fibers with
a numerical aperture of 0.4 are preheated before they are
placed into the EIFOPR, as shown in Fig. 3. Light energy is
transmitted to the catalyst particles, which are coated onto
fused silica fiber cores via radial refraction of light out of the
fiber. A 30 mm diameter, 250 mm long tubular fused silica
glass reactor is used as the photoreactor. The reactor is packed
Figure 3. Sketch of complete setup of EIFOPR.

2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eng. Technol. 2007, 30, No. 4, 474–480
with fused silica fibers. These fibers are 25 cm in length. The
15 cm portion inside the reactor is stripped of cladding and
coated with catalyst; the 10 cm portion outside the reactor re-
tains its cladding. The ends of these fibers pointing towards
the lamp are polished. The reactor is wrapped with aluminum
foil to retain the photons and thereby enhance photon efficien-
cy. The reactor also has two openings for the gas inlet and out-
let. To distribute the light effectively from the reactor end, light
needs to propagate through the optical fiber in an attenuated
total reflection mode. A 450 W Oriel Instruments Xe-Hg arc
lamp with model 66984 lamp housing is used to test the opti-
cal fibers as a waveguide. The photoreactor is designed to keep
the clad part of the fibers outside the reactor so that all the
photons enter the reactor through the optic fibers [25].
2.1.2 Internally Illuminated Fiber-Optic Photoreactor
(IIFOPR) System
A cylindrical glass chamber 35 mm in diameter and
135 mm in length is used as the photoreactor. A schematic
sketch is shown in Fig. 4. The lamp is put in the center and
each end is sealed with a viton septum. Inlet and outlet open-
ings are provided to allow the reactant stream to pass through
the reactor. The reactor is wrapped with aluminum foil. The
stripped optical fibers (Ceramoptec Inc., 200 lm OD) are dip-
coated with photocatalyst before being packed into the reactor.
The photocatalyst-coated optical fibers are packed between the
lamp and the reactor wall. Thus, the photons from the lamp
strike the catalyst surface without passing through the optical
fiber itself.
Figure 4. Sketch of IIFOPR.
3 Results and Discussion
The results are reported in three sections. The first section fo-
cuses on the effect of NLO concentration, residence time, PCE
concentration and light source on PCE conversion using the
IIFOPR system. The second section shows the effect of NLO
concentration and butyraldehyde concentration on butyralde-
hyde conversion in the IIFOPR system. The last part concen-
trates on the EIFOPR setup where the effect of the pure TiO2
catalyst loading on an optical fiber and the effect of NLO con-
centration (at the best value of catalyst loading obtained) on
PCE conversion are studied.
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Chem. Eng. Technol. 2007, 30, No. 4, 474–480 Photocatalysis 477

3.1 Results of IIFOPR for PCE Residence Time and Inlet Concentration Effect on PCE
Conversion
Effect of NLO Concentration on PCE Conversion
Fig. 6 shows the residence time effect on conversion over the
To observe the effect of NLO (BaTiO3) concentration on con-
range of the residence times from 1.4 seconds to 17.2 seconds.
version of PCE in the IIFOPR (using black light), seven sets of
Three sets of experiments are shown: two using pure TiO2 cata-
catalyst-coated optical fibers with varying weight percent of
lyst with differing inlet PCE concentration (40 ppm and
BaTiO3 (balance TiO2) are used: 0 %, 0.075 %, 0.1 %, 0.25 %,
130 ppm) and one with 0.1 wt % BaTiO3 in TiO2. These reac-
0.5 %, 1.0 % and 2.0 %. The best composition shown in Fig. 5
is 0.1 wt % BaTiO3, which gives a PCE conversion of 63.2 %.
The 0 wt % data point represents the conversion using pure 100
TiO2. As shown, the conversion initially increases above the
pure TiO2 value with increasing concentration of BaTiO3, up 90
to a maximum conversion of 63.2 % at a concentration of 80
0.1 wt %. Fig. 6 also shows the effect of adding 0.1 wt %

PCE Conversion (%)

BaTiO3 to PCE conversion at different residence times. This 70
increase may be due to the ferroelectric behavior of the perov- 60
skite structure of the BaTiO3, as described above in the Intro-
duction. As the concentration of BaTiO3 increases beyond 50
0.1 wt %, the conversion falls, eventually dropping below the
40
pure TiO2 value (at a concentration between 1.0 wt % and
2.0 wt %). Additional results (not shown in Fig. 5) show that 30
the conversion falls even more at higher BaTiO3 concentra-
20
tions (5 wt % gives 34.2 % conversion).
0 5 10 15 20
R es id en ce T im e (se c o n ds)
70
63.2% Figure 6. Residence time and PCE concentration effect on PCE
59.8%
60 conversion; (s)TiO2 modified with 0.1 wt % BaTiO3 at 40 ppm
PCE Conversion (%)

inlet PCE concentration; (~) TiO2 modified with 0.1 wt %

51.1% 49.2%
50 BaTiO3 at 130 ppm inlet PCE concentration; (&) pure TiO2 at
42.7% 130 ppm inlet PCE concentration.
40 39.2%

30 Black-Light tion conditions are maintained the same: catalyst loading

Fluorescent-Light 0.846 mg/cm2, fiber area 148 cm2, 4 W black light source. All
20 three sets show the PCE conversion increases with increasing res-
idence time, since higher residence times mean the reactants stay
10 longer inside the reactor and so have more opportunity to react.
4.7% 3.8% 2.9%
A comparison of the triangles (~) to the rectangles (&)
0 shows that the average increase in conversion for the BaTiO3-
0 0.2 0.4 0.6 0.8 1
Weight percent of BaTiO (NLO) in TiO added catalyst over the pure TiO2 catalyst is 25 %. In particu-
3 2
lar, the advantage of perovskite optical additive is seen to de-
Figure 5. PCE conversion as a function of BaTiO3 weight % (resi- crease at higher residence times: at low residence times the in-
dence time 3.6 sec., inlet PCE 130 ppm, catalyst loading crease in conversion is more than 25 %, at high residence times
0.846 mg/cm2, fiber area 148 cm2) using black light (r) and the increase in conversion is less than 25 %. Fig. 6 also shows
fluorescent light (&). PCE conversions at two different inlet PCE concentrations of
130 ppm and 40 ppm. At every residence time shown, PCE
conversion is higher at the lower inlet concentration of
The decrease in conversion at high perovskite concentra- 40 ppm rather than at 130 ppm. This may be due to the PCE
tions may be due to the BaTiO3 particles blocking the active at the higher concentration filling the active sites of the TiO2
sites on the TiO2 particles (the size differential 700 nm for surface and thereby hindering the adsorption of the oxygen
BaTiO3 and 20 nm for TiO2) as shown below under Discus- molecules.
sion. Thus, the use of small amounts of BaTiO3 gives increased
PCE conversion (adding 0.1 wt % BaTiO3 increases the PCE Effect of Light Source on PCE Conversion
conversion from 39.2 % to 63.2 %), but larger amounts are
Fig. 5 shows the effect of two different light sources on PCE
detrimental.
conversion: a 4 W black light (these are the same data as dis-
cussed under section 4.1.1) and a 4 W fluorescent light. The
space time is 3.6 seconds, PCE inlet concentration is 130 ppm,
the catalyst loading is 0.846 mg/cm2 and the BaTiO3 concen-

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478 K. J. Vajifdar et al. Chem. Eng. Technol. 2007, 30, No. 4, 474–480

tration in TiO2 varies from 0 wt % to 1 wt %. The effect of the 3.3 Results of EIFOPR for PCE
BaTiO3 additive is much different under reaction with a black
light than under reaction with a fluorescent light. PCE conver- Optimum Catalyst Loading
sion using the fluorescent light is significantly lower than that In the EIFOPR the light traveling through the fiber has to be
obtained by utilizing the black light. This is because photocata- refracted through the walls of the fiber and then the catalyst
lytic oxidation of PCE requires photons having a wavelength coating, to reach the surface of the catalyst to initiate the pho-
of 387 nm, while the spectrum of fluorescent light mainly lies tocatalytic oxidation reaction. If the coating thickness is more
between 400 nm and 700 nm. Furthermore, fluorescent light than required then it may prevent the light from reaching the
actually seems to decrease conversion of PCE with additional surface of the catalyst and thereby hinder the reaction; con-
BaTiO3 in the catalyst. versely, if the coating thickness is less than required, the reac-
tion will not be efficient. Further, a thick TiO2 coating also
hinders the diffusion of VOC to reach the illuminated layers.
3.2 Results of IIFOPR for Butyraldehyde Hence, it is desirable to find the optimum thickness of the
coating on the fibers. The fibers with 15 cm stripped length
Effect of NLO Weight Percent on Butyraldehyde Conversion
are coated with different weights of TiO2 catalyst and the PCE
To observe the effect of BaTiO3 weight percent on conversion conversion at different catalyst loading is tabulated in Tab. 1.
of butyraldehyde in the IIFOPR, seven sets of catalyst-coated As shown in Fig. 8, the catalyst loading of 80 mg on 88 fibers
optical fibers with varying weight percent of BaTiO3 are used: (i.e., 0.32 mg/cm2) gives the highest conversion.
0 %, 0.1 %, 0.25 %, 0.36 %, 0.5 %, 0.75 % and 1.0 %. As shown
in Fig. 7, the best composition is 0.36 wt % BaTiO3, which
Table 1. Effect of Degussa P-25 TiO2 loading on PCE conversion.
gives a butyraldehyde conversion of 44.7 %. The 0 wt % data
point represents the conversion using pure TiO2. Thus, the Weight Catalyst Coating PCE
beneficial effect of BaTiO3 is not restricted to PCE alone but of coating loading thickness conversion
also applies to butyraldehyde. As shown previously for PCE, (mg) (mg/cm2) (cm) (%)
low BaTiO3 weight percent is good for high butyraldehyde W t/n p D L Loading/T.D.
conversion whereas high BaTiO3 weight percent is bad proba-
30 0.12 0.0012 14.3
bly due to the same reasons as for PCE.
The conversion of butyraldehyde at two BaTiO3 concentra- 40 0.16 0.0016 16.8
tions, 0.36 % and 0.5 %, at varying butyraldehyde concentra- 50 0.20 0.0020 24.8
tions but constant residence time is shown in Fig. 7. As ex-
pected, for a given BaTiO3 weight percent, the conversion falls 70 0.28 0.0028 27.2
as the concentration of butyraldehyde increases. This may be 75 0.30 0.0030 32.8
due to the butyraldehyde at the higher concentration filling
80 0.32 0.0032 33.8
the active sites of the TiO2 surface and thereby hindering the
adsorption of the oxygen molecules. 90 0.36 0.0036 31.9
100 0.40 0.0040 24.1

B utyra ldeh yde C on cen tratio n (p p m ) 110 0.44 0.0044 11.7

1 00 2 00 30 0 40 0 50 0 6 00 70 0 80 0
45
Butyraldehyde Conversion (%)

40 W e ig h t o f ca talyst o n o p tica l fib ers ( m g )

20 40 60 80 1 00 1 20
35 40
30
35
PCE Conversion (%)

25
30
20

15 25

10
20
5
0 0 .2 0.4 0 .6 0 .8 1 15
W e igh t Percen t o f B a T iO in T iO
3 2
10
Figure 7. (r) Effect of BaTiO3 concentration on butyraldehyde 0 0.2 0 .4 0 .6 0.8 1
conversion at 130 ppm inlet concentration; (h) butyraldehyde W e ig h t P e rc en t o f B a T iO in T iO
3 2
conversion using TiO2 modified with 0.36 wt % BaTiO3 at var-
ious butyraldehyde concentrations; (s) butyraldehyde conver- Figure 8. (&) Effect of weight of catalyst (mg) coated on PCE
sion using TiO2 modified with 0.5 wt % BaTiO3 at various butyr- conversion; (~) BaTiO3 concentration effect on PCE conversion;
aldehyde concentrations; (residence time 3.6 sec., fiber area (EIFOPR, residence time 6.3 sec., inlet PCE concentration
148 cm2, 4 W black light source 315–400 nm). 130 ppm, 400 W UV light source 280–400 nm).

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Chem. Eng. Technol. 2007, 30, No. 4, 474–480
Effect of BaTiO3 Concentration in EIFOPR
For the experimental results shown in Fig. 8, the PCE inlet
concentration is kept constant at 130 ppm. The BaTiO3 weight
percent in TiO2 is varied from 0.0 % (pure TiO2) to 1 % while
maintaining the optimum catalyst loading of 0.32 mg/cm2.
The PCE conversions for different BaTiO3 weight percents in
TiO2 are shown in Fig. 8. As in IIFOPR experiments, there is
an optimum weight percent at 0.5 %. The explanation given
earlier in IIFOPR is believed to be valid here, i.e., too much
BaTiO3 blocks the TiO2 from light harvesting due to the size
differences (TiO2 21 nm vs. BaTiO3 700 nm).
4 Further Discussion
Fig. 9 shows the absorption spectrum for the catalyst samples:
(a) unmodified TiO2 before reaction, (b) unmodified TiO2
after use as a catalyst, (c) TiO2 modified with BaTiO3 before
reaction and (d) TiO2 modified with BaTiO3 after use as a cat-
alyst. Furthermore, the absorption by modified TiO2 is less
than that of Degussa P-25 TiO2 across the UVA spectrum
Figure 9. TiO2 and BaTiO3 absorption spectrum.
range (300–350 nm). In other words, the modified TiO2 is
more transparent than the unmodified TiO2, which is consis-
tent with the property of pure BaTiO3 in this spectrum range.
Thus, the transparent BaTiO3 crystals pave the way for the UV
light penetrating to the deeper layers of the catalyst, as illus-
trated in Fig. 10. Refraction would contribute to PCO by con-
taining the light energy instead of letting it escape out of the
system. If BaTiO3 prevents electron-hole pair recombination
better than TiO2 does, this would improve PCO by enabling
more electrons and holes to trigger the oxidation-reduction
reaction.
The electrons and holes thus produced by photons can be
conducted to all surfaces by semiconducting TiO2. Further, the
light reflected by internal TiO2 could activate other TiO2 parti-
cles, thereby enhancing the light utilization efficiency. In this
process, BaTiO3 plays the role of a light-conducting medium.
The photocatalytic oxidation reactions are still carried out on

2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Photocatalysis 479
BaTiO3 TiO2
(700 nm) (20 nm)
Figure 10. BaTiO3 optical crystals serve as a refraction internal
waveguide in TiO2 photocatalyst.
the TiO2 surfaces. The decrease of conversion with BaTiO3
after optimum weight could be due to the large-sized BaTiO3
(700 nm) occupying the outer surface area, which leads to less
TiO2 crystals exposed directly to light, O2 and VOCs. The UV/
VIS spectrum, however, only represents the optical properties
of the top layers of the catalyst.
Initially, BaTiO3 was used with the intention that it might
help to convert some visible light to near-UV light by a non-
linear optical process. However, barium titanate does not help
the photocatalytic oxidation of PCE by fluorescent light, as
shown above in Fig. 5. Further, the identical by-products from
GC/MS identification indicate BaTiO3 does not alter the reac-
tion pathways. These results appear to disprove the theory that
BaTiO3 increases the conversion of PCE by the nonlinear opti-
cal process. Two possible reasons for BaTiO3 showing extraor-
dinary efficiency when used with black light are as follows:
– The perovskite or ferroelectric behavior that impedes elec-
tron-hole recombination, and
– Enhanced transmission into the inner layers of the photoca-
talyst.
BaTiO3 is an excellent perovskite refractive material. The
stability of the BaTiO3 structure depends on the relative ionic
radii. The cation (octahedron titania), being too small for close
packing with the oxygens, can be displaced slightly. Since these
ions carry electrical charges, such displacement results in a net
electric dipole moment (opposite charges separated by a small
distance). Also, by possessing a high dielectric constant (20–25
at 10 kHz) [17] BaTiO3 can retain the charge separation for a
long period of time.
5 Conclusion
Two types of reactors, IIFOPR and EIFOPR, have been used to
demonstrate the effect of BaTiO3 added catalyst over the pure
TiO2 catalyst. In an IIFOPR, 0.1 wt % of the perovskite optical
crystal BaTiO3 in TiO2 increases PCE destruction by 12 % to
32 % for space times between 1.4 and 17.2 seconds, respective-
ly, using a 4 W black light. The average increase in PCE con-
version for the BaTiO3 added catalyst over the pure TiO2 cata-
lyst in an IIFOPR is 25 %. For PCE conversion the maximum
enhancements are 28 % (130 ppm) and 34 % (40 ppm) at 3.6
seconds. In an IIFOPR, 0.36 wt % of the perovskite optical
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480 K. J. Vajifdar et al.
crystal BaTiO3 in TiO2 increases butyraldehyde conversion
using black light by 20 % in 3.6 seconds and for a given BaTiO3
weight percent, the conversion falls as the concentration of
butyraldehyde increases. BaTiO3 is responsible for the en-
hancement of PCO of perchloroethylene and butyraldehyde by
serving as an electron-hole reservoir by virtue of a high dielec-
tric constant and ferroelectric property. It also serves as an
internal-refraction waveguide.
Acknowledgements
Financial supports from Gulf Coast Hazardous Substance
Center (Grant # 051LUB3744) and Texas Higher Education
Coordinating Board Advanced Technology Program (Grant #
003581-0019-1999) are gratefully acknowledged.
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