Anatase TiO

2
Nanoparticle Coating on BariumFerrite
Using TitaniumBis-AmmoniumLactato Dihydroxide and
Its Use as a Magnetic Photocatalyst
Seung-woo Lee,

Jack Drwi ega,

Chang-Yu Wu,

Davi d Mazyck,

and
Wol fgang M. Si gmund*
,
Departments of Materials Scienceand Engineering and Environmental Engineering Sciences,
University of Florida, Gainesville, Florida 32611
Received November 18, 2003. Revised Manuscript Received J anuary 28, 2004
Photoacti ve anatase Ti O
2
nanoparti cl es wi th a si ze l ess than 10 nm were coated on bari um
ferri te formi ng compl ete coverage by the control l ed hydrol ysi s and condensati on of ti tani um
bi s-ammoni um l actato di hydroxi de i n the presence of pol yethyl enei mi ne at a rel ati vel y l ow
temperature (95 C). The as-prepared composi te parti cl es (hard magneti c bari um ferri te
(core)-anatase Ti O
2
nanoparti cl es (shel l )) can be uti l i zed as a magneti c photocatal yst, whi ch
can be fl ui di zed and recovered by an appl i ed magneti c fi el d enhanci ng both the separati on
and mi xi ng effi ci ency for remedi ati ng fl ui ds. The morphol ogy of composi te parti cl es was
characteri zed wi th scanni ng el ectron mi croscopy and transmi ssi on el ectron mi croscopy. The
crystal l i ne structure of Ti O
2
was characteri zed by X-ray di ffracti on and el ectron di ffracti on.
Energy-di spersi ve spectroscopy was uti l i zed for the el emental anal ysi s of the products. The
as-prepared Ti O
2
-bari um ferri te composi te has hi gher photocatal yti c acti vi ti es than the
Ti O
2
-bari um ferri te composi te heat-treated at 500 C for 1 h. The hi gher photoacti vi ti es of
the unheated composi te are ascri bed to hi gher speci fi c surface area and preservati on of the
surface hydroxyl groups on Ti O
2
.
Introduction
Ti tani um di oxi de (Ti O
2
) photocatal yst has been wi del y
studi ed for water and ai r puri fi cati on.
1-4
I n fact, i t i s
regarded as the best semi conductor photocatal yst for the
destructi on of organi c pol l utants i n water and ai r.
5,6
I n
treati ng pol l utants i n water, Ti O
2
sl urry i s the most
commonl y appl i ed method.
7
Because of i ts hi gh speci fi c
surface area and di spersi on, Ti O
2
sl urry has been
demonstrated to be more effecti ve than i mmobi l i zed
Ti O
2
. However, the use of Ti O
2
sl urry i s sti l l l i mi ted
mai nl y due to the di ffi cul ty to separate Ti O
2
parti cl es
from treated water.
8
Recentl y, i ron oxi de parti cl es have
been coated wi th Ti O
2
to synthesi ze magneti c photo-
catal yti c parti cl es to recover the photocatal yst parti cl es
from the treated water stream by appl yi ng an external
magneti c fi el d.
9-11
Amal et al .
12,13
reported that they
synthesi zed the magneti c photocatal yst, whi ch was
Fe
3
O
4
coated wi th Ti O
2
or Si O
2
and Ti O
2
, wi th vari ous
heat treatments and a coupl e of di fferent Ti O
2
precur-
sors, that i s, ti tani um butoxi de and ti tani um i sopro-
poxi de. They demonstrated that the prepared magneti c
photocatal ysts had comparabl e photocatal yti c acti vi ti es
wi th respect to anatase Ti O
2
that they prepared, whi ch
yet need to be i mproved, compared to Degussa P25
photocatal yst. However, i t has been reported that the
heat treatment, whi ch i s necessary to crystal l i ze the
amorphous Ti O
2
coati ng, l owered the speci fi c surface
area and the amount of surface hydroxyl groups of Ti O
2
,
eventual l y decreasi ng the photoacti vi ty of the magneti c
photocatal ysts.
14
To mi ni mi ze the heat treatment step,
the modi fi ed sol -gel route was adopted to deposi t
crystal l i ne Ti O
2
di rectl y onto the magneti c cores.
14
However, the photoacti ve Ti O
2
l ayer di d not form a
uni form coati ng on the surface of the magneti c cores;
rather, they formed patches on the surface when
crystal l i ne Ti O
2
was di rectl y deposi ted by the modi fi ed
sol -gel route. Gao et al .
9
al so reported that the heat
treatment l ed to converti ng the magneti c cores and Ti O
2
i nto an unfavorabl e Fe
2
Ti O
5
composi te, deteri orati ng
the photocatal yti c acti vi ty and magneti c properti es.
* To whom correspondence shoul d be addressed. Tel ephone: 1 352
846 3343. Fax: 1 352 846 3355. E-mai l : wsi gm@mse.ufl .edu.

Department of Materi al s Sci ence and Engi neeri ng.

Department of Envi ronmental Engi neeri ng Sci ences.

(1) Hoffmann, M. R.; Marti n, S. T.; Choi , W. Y.; Bahnemann, D.
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2002, 180, 193.
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2002, 148, 303.
1160 Chem. Mater. 2004, 16, 1160-1164
10.1021/cm0351902 CCC: $27.50 2004 Ameri can Chemi cal Soci ety
Publ i shed on Web 02/26/2004
I n thi s work, the magneti c photocatal yst was pre-
pared by control l ed hydrol ysi s and condensati on of
ti tani um bi s-ammoni um l actato di hydroxi de (TALH) i n
the presence of pol yethyl enei mi ne (PEI ). TALH has
been used for synthesi zi ng Ti O
2
parti cl es
15
and Ti O
2
coati ngs on vari ous substrates.
16-18
The advantages of
usi ng TALH as a Ti O
2
precursor are that i t i s a water-
sol ubl e precursor, whi ch does not requi re an al cohol -
based sol uti on, and i t i s stabl e at ambi ent temperature
i n ai r, whi ch el i mi nates the need for the use of an i nert
atmosphere duri ng hydrol ysi s and condensati on proce-
dures. TALH al so faci l i tates the control of hydrol ysi s
and condensati on of a Ti O
2
precursor due to i ts stabl e
nature. The present work focused on the synthesi s of
uni form photoacti ve crystal l i ne (anatase) Ti O
2
l ayers on
the magneti c cores (bari um ferri te) usi ng a nonal koxi de
Ti O
2
precursor i n water at rel ati vel y l ow temperature
(95 C). The prepared hard magneti c photocatal ysts can
not onl y be recovered but al so fl ui di zed by appl yi ng an
external magneti c fi el d, enhanci ng both the separati on
and mi xi ng effi ci enci es for oxi di zi ng organi cs i n both
l i qui d and ai r.
Experimental Section
Materials. TALH ([CH3CH(O

)CO2NH4]2Ti (OH)2, 50 wt %
aqueous sol uti on) from Al dri ch Chemi cal s was used as the Ti O2
precursor wi thout any further puri fi cati on. Bari um ferri te
(BaFe
12O19) from Arnol d Engi neeri ng and PEI (Mw ) 1800)
from Al fa Aesar were used i n thi s study. Dei oni zed water (18.2
Mcm, Barnstead E-Pure) was used i n al l the experi ments.
Degussa P25 photocatal yst was suppl i ed by Degussa Corpora-
ti on. HCl (0.1 N) aqueous sol uti on was purchased from Al dri ch.
Preparation of Samples. Two hundred mi l l i grams of
bari um ferri te parti cl es were di spersed i n 150 mL of 1 vol %
PEI aqueous sol uti on and soni cated for 5 mi n i n an ul trasoni c
cl eani ng bath. After soni cati on, the PEI aqueous sol uti on was
decanted, l eavi ng onl y PEI adsorbed on bari um ferri te parti cl es
(PEI -bari um ferri te). PEI -bari um ferri te, 150 mL of dei on-
i zed water, and 2 mL of TALH were pl aced i n a 250-mL fl ask
and the pH of the sol uti on was adjusted to 5.5, empl oyi ng a
0.1 N HCl aqueous sol uti on. The prepared sol uti on was
magneti cal l y sti rred for 30 mi n at room temperature and then
heated to 95 C at a rate of 1 C/mi n where i t stayed for the
next 22 h. The prepared sampl e was recovered from the
sol uti on by magneti c separati on and washed wi th dei oni zed
water and ethanol . The wet sampl e was then dri ed i n an oven
at 60 C for 2 days. Hal f of the dri ed sampl e was taken and
heat-treated i n a furnace at 500 C for 1 h.
Characterization. The sampl e i mages were taken wi th a
transmi ssi on el ectron mi croscope (TEM, JEOL 200CX) and a
hi gh-resol uti on TEM (HRTEM, JEOL 2010F). A HRTEM was
al so used to obtai n the sel ected area di ffracti on patterns. The
el emental anal ysi s was conducted usi ng an energy-di spersi ve
X-ray spectroscope (Oxford). X-ray di ffracti on (XRD) patterns
of the powder sampl es were recorded wi th a Phi l i ps APD 3720
di ffractometer. For the composi ti onal anal ysi s, 50 mg of the
sampl e was di gested i n 100 mL of the sul furi c aci d and the
anal ysi s was carri ed out wi th an i nducti vel y coupl ed pl asma
(I CP) spectroscope (Perki n-El mer Pl asma 3200). The speci fi c
surface area was measured usi ng a BET anal yzer (Quantach-
rome Nova 1200). Zeta potenti al was measured wi th a Zeta
Reader Mark 21.
Photocatalytic Degradation of Procion Red MX-5B.
Photodegradati on of Proci on Red MX-5B (Proci on) was con-
ducted i n a 100-mL Pyrex gl ass vessel wi th magneti c sti rri ng.
The i l l umi nati on sources were four 12-i n. 8-W UV bul bs (UVP
I nc.) wi th a wavel ength of 365 nm. Aqueous sol uti ons of
Proci on (50 mL, 10 mg/L) and photocatal yst parti cl es (30 mg
of the composi te parti cl es, 2.2 mg of Ti O
2 parti cl es or Degussa
P25, the same amount of Ti O2 was used i n al l experi ments)
were pl aced i n a Pyrex vessel . At gi ven i nterval s of UV
i l l umi nati on, a speci men of the suspensi on was col l ected and
anal yzed by UV-vi s spectroscopy usi ng a Perki n-El mer
Lambda 800 spectrophotometer.
Results and Discussion
TiO
2
Coatingon BariumFerrite. I n Fi gure 1, the
measured zeta potenti al of bari um ferri te and PEI -
adsorbed bari um ferri te i n dei oni zed water i s pl otted
as a functi on of pH. PEI adsorpti on on bari um ferri te
l eads to si gni fi cant charge reversal . As the pH i s l owered
from pH 10, the zeta potenti al of PEI -adsorbed bari um
ferri te parti cl es i ncreases and the hi ghest val ue of zeta
potenti al i s measured at pH 5.5, reversi ng the charge
from -38 mV to +92 mV. As the pH i s l owered agai n
from pH 5.5, the zeta potenti al decreases. Thi s behavi or
can be expl ai ned from the adsorpti on and el ectroki neti c
properti es of PEI . As the pH i s l owered from pH 10, the
protonati on degree of PEI i ncreases, enhanci ng zeta
potenti al , whereas the adsorbed amount of PEI de-
creases due to the el ectrostati c repul si on between the
PEI segments, l eadi ng to reducti on i n zeta potenti al .
Adsorpti on and el ectroki neti c properti es of PEI are wel l -
descri bed el sewhere.
19
(15) Mockel , H.; Gi ersi g, M.; Wi l l i g, F. J . Mater. Chem. 1999, 9,
3051.
(16) Caruso, F.; Shi , X. Y.; Caruso, R. A.; Susha, A. Adv. Mater.
2001, 13, 740.
(17) Hanprasopwattana, A.; Ri eker, T.; Saul t, A. G.; Datye, A. K.
Catal. Lett. 1997, 45, 165.
(18) Mayya, K. S.; Gi tti ns, D. I .; Caruso, F. Chem. Mater. 2001,
13, 3833.
Figure 1. Zeta potenti al of (9) bari um ferri te parti cl es and
(b) PEI (Mw ) 1800)-adsorbed bari um ferri te parti cl es i n
dei oni zed water as a functi on of pH.
Figure 2. XRD patterns of (a) free Ti O2 nanoparti cl es, (b)
free Ti O2 nanoparti cl es heat-treated at 500 C for 1 h, (c)
Ti O2-bari um ferri te composi te, (d) Ti O2-bari um ferri te com-
posi te heat-treated at 500 C for 1 h, and (e) uncoated bari um
ferri te parti cl es. A ) anatase. B ) bari um ferri te.
TiO
2
Coating on BariumFerritesMagnetic Photocatalyst Chem. Mater., Vol. 16, No. 6, 2004 1161
I n the Ti O
2
coati ng process, TALH, a doubl y nega-
ti vel y charged Ti O
2
precursor,
20
i s deposi ted onto the
posi ti vel y charged PEI -adsorbed bari um ferri te parti cl es
through the el ectrostati c attracti on at room tempera-
ture. As stated before, unl i ke an al koxi de precursor,
TALH i s rel ati vel y stabl e at ambi ent temperature i n
water. Therefore, i t i s easi er to control i ts hydrol ysi s
and condensati on. Another advantage of usi ng TALH
as a Ti O
2
precursor i s that hydrol yzed TALH can be
converted i nto anatase Ti O
2
nanoparti cl es upon heati ng
around 90-100 C.
16
Wi th control l ed heati ng, TALH
undergoes hydrol ysi s and condensati on i n a sl ow man-
ner onto the surface of the bari um ferri te parti cl es.
Duri ng refl uxi ng at 95 C, hydrol yzed TALH i s con-
verted i nto a Ti O
2
network compri sed of anatase Ti O
2
nanoparti cl es. Ti O
2
l oadi ng wt % of the prepared
composi te i s onl y 7.2% due to the rel ati vel y l arge si ze
of bari um ferri te parti cl es. The speci fi c surface area for
the as-prepared composi te parti cl es (17.9 m
2
/g) i s en-
hanced compared wi th that of uncoated bari um ferri te
parti cl es (4.1 m
2
/g) due to the coati ng of Ti O
2
nanopar-
ti cl es on bari um ferri te. Meanwhi l e, heat treatment
resul ted i n the growth of Ti O
2
parti cl e si ze, as evi denced
by the decrease of speci fi c surface area (11.9 m
2
/g). The
average parti cl e si ze of the coated Ti O
2
, whi ch was
measured usi ng a BETanal yzer, was 7.6 nm for the as-
prepared composi te parti cl es and 13.3 nm for the heat-
treated composi te parti cl es.
XRD patterns of free Ti O
2
nanoparti cl es (free Ti O
2
parti cl es from the supernatant after magneti cal l y sepa-
rati ng the composi te parti cl es), Ti O
2
-bari um ferri te
composi te parti cl es, and uncoated bari um ferri te par-
ti cl es are presented i n Fi gure 2. The peaks from anatase
phase of Ti O
2
are present i n XRD patterns of Ti O
2
nanoparti cl es and Ti O
2
nanoparti cl es heat-treated;
however, peaks are very broad and weak due to thei r
nanocrystal si ze. When the XRD pattern of Ti O
2
-
bari um composi te parti cl es i s compared wi th that of
uncoated bari um ferri te parti cl es, the strongest peak
of anatase Ti O
2
peaks i s present at 25.6; however, the
peak i s weak and broad si nce the amount of Ti O
2
l oadi ng i s l ow and the crystal si ze of Ti O
2
i s much
smal l er than that of bari um ferri te.
The SEM i mages of the as-prepared Ti O
2
-bari um
ferri te composi te parti cl es and the uncoated bari um
ferri te parti cl es are gi ven i n Fi gure 3. Di fferent surface
morphol ogi es due to Ti O
2
coati ng on the bari um ferri te
between the composi te parti cl es and the uncoated
parti cl es are cl ear i n Fi gure 3. The representati ve TEM
mi crographs and sel ected area di ffracti on patterns of
the prepared sampl es are presented i n Fi gure 4. Parts
(a)-(c) of Fi gure 4 are taken from the as-prepared
sampl e and (d)-(f) are from the sampl e heat-treated at
500 C for 1 h. I t i s cl earl y seen that a Ti O
2
coati ng i s
made on the bari um ferri te, formi ng compl ete coverage
i n Fi gure 4a,d. The thi ckness of the Ti O
2
l ayer i s i n the
range of 20-40 nm. (b) and (e) of Fi gure 4 are HRTEM
i mages of the Ti O
2
coati ng regi on. These l atti ce-resol v-
i ng i mages show that coated Ti O
2
nanoparti cl es are
nanocrystal l i ne. The sel ected area di ffracti on patterns
i n (c) and (f) of Fi gure 4 confi rm that the Ti O
2
coati ng
i s composed of anatase nanocrystal l i ne Ti O
2
parti cl es.
The sel ected area di ffracti on pattern i s the ri ng pattern,
whi ch i s characteri sti c of the pattern of nanocrystal s.
EDS spectrum i mages taken from the Ti O
2
-bari um
ferri te composi te i s represented i n Fi gure 5. Fi gure 5a
i s taken from the core of the Ti O
2
-bari um ferri te
composi te, showi ng the presence of Fe, Ba, Ti , and O
atoms, whereas Fi gure 5b i s from the Ti O
2
coati ng
regi on, confi rmi ng the presence of onl y Ti and O atoms.
Photocatalytic Performance. The resul ts of pho-
tocatal yti c performances of the prepared Ti O
2
-bari um
ferri te composi te parti cl es for photodegradati on of Pro-
ci on Red MX-5B under UV i l l umi nati on i s shown i n
Fi gure 6. The photocatal yti c performance of a com-
merci al photocatal yst, Degussa P25, and the free Ti O
2
parti cl es i s al so gi ven i n the fi gure for compari son. Both
of the as-prepared Ti O
2
-bari um ferri te composi te and
the heat-treated Ti O
2
-bari um ferri te composi te par-
ti cl es are photoacti ve, as can be seen i n Fi gure 6;
however, both of them have l ower photocatal yti c acti vi -
ti es than Degussa P25, whi ch i s known as the best
photocatal yst commerci al l y avai l abl e. The hi gher pho-
toacti vi ty of Degussa P25 can be ascri bed to several
factors i ncl udi ng i ts l arger speci fi c surface area, the 70:
30 rati o between anatase and ruti l e, whi ch tends to
promote charge separati on, and the exi stence of surface
oxygen vacanci es, wi th thei r effect on the producti on of
hydroxyl radi cal s. Neverthel ess, i t shoul d be recal l ed
(19) Meszaros, R.; Thompson, L.; Bos, M.; de Groot, P. Langmuir
2002, 18, 6164.
(20) Shi , X. Y.; Cassagneau, T.; Caruso, F. Langmuir 2002, 18, 904.
Figure 3. SEM mi crographs of (a) uncoated bari um ferri te parti cl es and (b) Ti O2-bari um ferri te composi te parti cl es.
1162 Chem. Mater., Vol. 16, No. 6, 2004 Leeet al.
that the magneti c photocatal yst coul d be easi l y recycl ed
whi l e Degussa P25 cannot. Photoacti vi ty of the as-
prepared composi te i s sl i ghtl y hi gher than that of the
heat-treated composi te parti cl es. Thi s i s i nteresti ng
si nce the as-prepared (unheated) composi te parti cl es
have l ess perfect crystal l i ni ty than the heat-treated
composi te parti cl es. A crystal l i te form of Ti O
2
, i n ana-
tase or ruti l e phase, i s necessary for an effi ci ent pho-
Figure4. TEM mi crographs and sel ected area di ffracti on patterns of Ti O2-bari um ferri te composi te. (a, b, and c) As-prepared
sampl e; (d, e, and f) sampl e heat-treated at 500 C for 1 h. (a) TEM i mage of Ti O2 coati ng on bari um ferri te. (b) HRTEM i mage
of Ti O2 coati ng and (c) i ts correspondi ng di ffracti on pattern. (d) Heat-treated Ti O2-bari um ferri te composi te. (e) HRTEM i mage
of Ti O2 coati ng and (g) i ts correspondi ng di ffracti on pattern.
Figure5. EDS spectrum i mages of (a) Ti O2-bari um ferri te composi te parti cl e and (b) Ti O2 coati ng regi on of the composi te. The
unl abel ed peaks are adventi ti ous copper.
TiO
2
Coating on BariumFerritesMagnetic Photocatalyst Chem. Mater., Vol. 16, No. 6, 2004 1163
tocatal yst.
21
However, the effects of smal l er crystal si zes
of Ti O
2
nanoparti cl es i n the unheated composi te par-
ti cl es compensate for and overcome the effects of the
degree of crystal l i ni ty. The smal l er Ti O
2
nanoparti cl es
i n the unheated composi te l ead to hi gher speci fi c surface
area, resul ti ng i n hi gher photocatal yti c acti vi ti es. An-
other i mportant advantage that the unheated composi te
has i s i ts better surface property. Duri ng the heat
treatment of the composi te, there i s l oss of the surface
hydroxyl groups on Ti O
2
, reduci ng the acti ve si tes for
the photocatal yti c reacti on.
22,23
Preservi ng the surface
hydroxyl groups on Ti O
2
by mi ni mi zi ng the heat treat-
ment can be one of the reasons for hi gher photoacti vi ti es
i n the unheated composi te parti cl es. The heat treatment
can al so l ead to oxi dati on of the magneti c core, resul ti ng
i n l oss of magneti c properti es.
Conclusion
I n thi s work, Ti O
2
has been coated on bari um ferri te
by the control l ed hydrol ysi s and condensati on of ti ta-
ni um bi s-ammoni um l actato di hydroxi de, a water-
sol ubl e precursor, from an aqueous system formi ng
compl ete coverage. I t was found that the Ti O
2
coati ng
i s composed of anatase nanoparti cl es wi th a si ze l ess
than 10 nm. The photocatal yti c acti vi ti es of the prepared
Ti O
2
-bari um ferri te composi te parti cl es have been
tested by the photodegradati on of organi c dye under UV
i l l umi nati on. The photoacti vi ty of the as-prepared com-
posi te was hi gher than that of the heat-treated com-
posi te. The synthesi zed hard magneti c composi te par-
ti cl es can be not onl y recovered but al so fl ui di zed by
appl yi ng an external magneti c fi el d, enhanci ng both the
separati on and mi xi ng effi ci enci es for treati ng water
and ai r.
Acknowledgment. Thi s work was fi nanci al l y sup-
ported by the U.S. Envi ronmental Protecti on Agency
(EPA)-Sci ence To Achi eve Resul ts (STAR) program
(Grant R829602).
CM0351902
(21) Ooka, C.; Aki ta, S.; Ohashi , Y.; Hori uchi , T.; Suzuki , K.; Komai ,
S.; Yoshi da, H.; Hattori , T. J . Mater. Chem. 1999, 9, 2943.
(22) Sanchez, E.; Lopezm, T.; Gomez Bokhi mi , R.; Moral es, A. J .
Solid StateChem. 1996, 122, 309.
(23) GunKo, V.; Zarko, V.; Chi bowski , E.; Dudni k, V.; Leboda, R.;
Zaets, V. J . Colloid I nterfaceSci. 1997, 188, 39.
Figure 6. Resul ts of photodegradati on of Proci on Red MX-
5B under UV i rradi ati on wi th (9) no photocatal yst, (b) Ti O2-
bari um ferri te composi te heat-treated at 500 C for 1 h, (2)
Ti O2-bari um ferri te composi te, ([) free Ti O2 parti cl es heat-
treated at 500 C for 1 h, (+) free Ti O2 parti cl es, and (1)
Degussa P25.
1164 Chem. Mater., Vol. 16, No. 6, 2004 Leeet al.