Chemical

Engineering
Journal
181182 (2012) 4555
Contents
lists
available
at
ScienceDirect
Chemical Engineering Journal
journal
homepage:
www.elsevier.com/locate/cej
Nanocomposite
TiO2SiO2
gel
for
UV
absorption
Angkhana
Jaroenworaluck
a,*,
Nuchanaporn
Pijarn
a,
Nudthakarn
Kosachan
a,
Ron
Stevensb
a
National
Metal
and
Materials
Technology
Center,
114
Thailand
Science
Park,
Paholyothin
Rd.,
Klong
1,
Klong
Luang,
Pathumthani
12120,
Thailand
b
Mechanical
Engineering
Department,
University
of
Bath,
BA2
7AY
Bath,
UK
article
info
abstract
Article
history:
Received
5
April
2011
Received
in
revised
form
8
August
2011
Accepted
9
August
2011
Keywords:
TiO2SiO2
gel
TiO2fumed
SiO2
Mesoporous
SiO2
gel
UV
absorption
Energy
band
gap
Rice
husk
Nano-sized
particle
TiO2-doped
SiO2
gels
have
been
synthesized
for
use
as
composites
in
which
the
UV
absorption
efficiency,
the
major
factor
for
UV
protection,
can
be
enhanced.
SiO2
gels
having
a
mesoporous
morphology
have
been
synthesized
via
a
solgel
processing
route
using
rice
husk
as
the
starting
material
and
further
treated
using
additions
of
TiO2
from
two
sources.
The
chemical
purity
of
the
SiO2
was
measured
by
X-ray
fluorescence
analysis
(XRF).
Typical
samples
of
pure
TiO2,
SiO2
and
their
composites
were
tested
for
surface
characteristics
using
N2-sorption
(BET
surface
area).
All
the
different
compositions
processed
have
been
characterized
by
X-ray
diffraction
(XRD),
Fourier
Transform
Infrared
Spectroscopy
(FT-IR),
and
imaged
using
Scanning
and
Transmission
Electron
Microscopy
(SEM,
TEM).
The
UV
absorption
values
which
determine
the
degree
of
UV-protection,
were
measured
and
the
results
discussed.
The
concentration
of
TiO2
loading,
the
particle
size,
and
the
surface
characteristics
are
shown
to
relate
to
the
degree
of
UV
absorption
and
the
measured
energy
band
gap
of
the
composites.
2011 Elsevier B.V. All rights reserved.
1.
Introduction
Rice
husk
(RH)
has
been
long
recognized
as
one
of
the
prime
natural
sources
for
silicon
(Si).
Many
studies
describe
how
to
recycle
RH
to
produce
useful
ceramic
materials
such
as
silica
(SiO2),
silicon
carbide
(SiC),
silicon
nitride
(Si3N4),
zeolites
(alumino-silicate),
etc.
[1].
However,
when
sophisticated
technology
methods
are
used,
the
economics
of
such
processing
needs
to
be
considered
when
the
product
is
intended
for
practical
uses
in
various
industries.
Among
these
reformed
materials,
SiO2
is
considered
to
be
a
viable
material
because
of
its
cheaper
and
easier
processing.
Previous
studies
have
revealed
not
only
amorphous
SiO2
particles
having
a
size
in
the
nanoscale
range,
but
also
the
typical
characteristics
of
the
particles,
specifically
that
a
high
surface
area,
could
be
generated
by
the
final
process
of
heat
treatment
[24].
These
characteristics
are
considered
to
be
useful
for
further
processing
in
that
intimate
mixing
with
other
oxides
is
possible,
generating
higher
value
end-products
for
more
effective
applications.
Titania
(TiO2),
because
of
its
attractive
properties,
has
found
wide
ranging
applications;
it
is
non-toxic,
inexpensive,
has
good
stability,
demonstrates
superior
photocatalytic
property,
etc.
[5].
In
practice
it
can
be
used
for
anti-bacterial
applications,
water
and
air
purification,
self-cleaning
surfaces,
UV-screening
of
agriculture
films,
as
an
opacifying
agent
in
paint,
and
for
UV-absorption
in
the
form
of
sunscreen
cosmetic
products.
*
Corresponding
author.
Tel.:
+66
2
564
6500;
fax:
+66
2
564
6447.
E-mail
address:
angkhanj@mtec.or.th
(A.
Jaroenworaluck).
Modification
of
the
TiO2
involving
doping
or
coating
with
various
metal
oxides
to
enhance
properties
has
been
carried
out
in
order
to:
(i)
increase
its
efficiency,
(ii)
extend
usage
range
from
the
UV
to
the
visible
light
region,
(iii)
reduce
the
energy
band
gap
for
energy
conversion
applications,
(iv)
retard
or
accelerate
phase
transformation,
and
finally,
(v)
modify
its
surface
characteristics.
For
UV
protection,
TiO2,
as
a
fine
powder
has
been
mixed
with
organic
oils
or
suspended
in
water
in
sunscreen
cosmetics,
and
large
quantities
are
used
in
household
paints
to
enhance
brightness,
whiteness
and
preserve
stability
in
sunlight.
TiO2,
has
been
preferred
to
ZnO,
for
addition
to
sunscreens
because
it
can
absorb
a
broad-spectrum
of
both
the
UVB
(290320
nm)
and
UVA
(320400
nm,
UVA1:
320340
nm,
UVA2:
340400
nm),
whereas
ZnO
can
absorb
well
only
in
a
wide
range
of
UVA
[6].
However,
in
UV
protective
sunscreen
products,
the
absorption
characteristics
need
to
be
optimized
usually
by
employing
a
combination
of
organic
and
inorganic
UV
absorbers
to
provide
a
board-spectrum
formula
for
the
range
of
natural
UV
[69].
The
maximum
amount
of
TiO2
that
can
be
added
is
restricted
since
high
levels
of
TiO2
can
cause
irritation
of
the
skin,
it
becomes
difficult
to
remove
and
the
viscosity
becomes
excessive.
During
exposure
to
light,
the
visible
light
is
scattered,
providing
opacity
while
the
UV
components
are
absorbed
by
the
TiO2
crystal.
Here,
rutile
is
preferred
to
anatase
[5]
since
the
UV
is
absorbed
more
efficiently
and
it
is
the
more
stable
phase.
The
latest
cosmetics
use
nanosized-TiO2
in
place
of
1385-8947/$

see
front
matter
2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2011.08.028
A.
Jaroenworaluck
et
al.
/
Chemical
Engineering
Journal
181182 (2012) 4555
Fig.
1.
N2
adsorptiondesorption
isotherms
of
samples:
(a)
the
synthesized
SiO2
gel
and
the
fumed
SiO2,
(b)
TiO2
(TIP)
and
TiO2
(P25),
(c)
TiO2
(TIP)SiO2
(gel)
and
(d)
TiO2
(P25)SiO2
(gel).
micron-sized
particles
in
the
sunscreen
formulations
together
with
various
other
metal
oxides
additives
such
as
CeO2,
Fe2O3,
Al2O3,
ZrO2
and
SiO2,
to
optimize
the
combined
properties
of
reflection,
absorption
and
transparency.
In
this
study,
TiO2-doped
SiO2
gels
in
the
form
of
nanocomposite
particles
have
been
prepared.
TiO2
was
doped
into
the
SiO2
gel
particles
with
the
intention
that
nanosized
TiO2
particles
would
coat
or
deposit
on
the
gel
particle
surfaces.
This
typical
microstructure
would
be
expected
to
relate
to
enhancement
of
UV
absorption.
The
SiO2
gel
used
has
been
synthesized
via
a
solgel
route
using
rice
husks
as
the
starting
material
selecting
a
process
route
designed
to
give
a
mesoporous
structure,
unlike
previous
studies
of
TiO2SiO2
or
SiO2TiO2
nanocomposites
where
commercial
chemicals
were
used
[1020].
The
energy
band
gaps
of
TiO2-doped
SiO2
gel
for
various
TiO2
loadings
in
the
SiO2
gel
has
been
measured,
and
the
use
of
different
TiO2
sources
is
reported.
UV
absorption
properties
of
the
synthesized
nanocomposites,
intended
for
use
as
the
active
ingredient
for
sunscreen,
have
been
determined.
The
experimental
results
are
discussed
in
terms
of
the
phases
present,
the
energy
band
gaps
and
the
microstructural
changes.
2.
Experimental
2.1.
Materials
Rice
husk
without
any
prior
chemical
treatment
or
washing
process
was
used
as
the
starting
source
of
the
SiO2.
The
reflux
solvent
was
sodium
hydroxide,
with
the
pH
adjusted
by
addition
of
sulfuric
acid.
Titanium
(IV)
isopropoxide
(TIP)
and
TiO2
powder
(AEROXIDE TiO2
P25,
Degussa,
Germany)
were
used
as
the
source
of
TiO2.
The
TiO2
(TIP)
was
dissolved
in
isopropyl
alcohol
whereas
ethyl
alcohol
was
used
to
dissolve
the
commercial
TiO2
(P25)
powder.
Fumed
silica
(SiO2),
AEROSIL 200,
Degussa,
Germany,
was
used
for
comparison
with
the
laboratory
produced
SiO2
gel.
2.2.
Preparation
of
SiO2
gel
The
rice
husk
was
calcined
at
650
.C
for
6
h.
A
mixture
of
rice
husk
ash
(10
g)
and
1
M
NaOH
(320
mL)
was
heated
under
a
reflux
for
5
h.
The
reaction
mixture
was
then
filtered
using
No.
5
Whatman
filter
paper,
and
the
carbon
residue
washed
with
400
mL
of
heated
DI
water,
and
then
cooled
to
room
temperature.
The
solution
was
titrated
with
1
M
H2SO4
to
pH
7.
The
solgel
aged
for
18
h
was
gently
fragmented
and
centrifuged
for
5
min
at
6000
rpm.
To
wash
out
the
impurities,
distilled
water
(400
mL)
was
added,
gently
swirled
and
the
suspension
again
centrifuged.
The
washing
process
was
repeated
6
times
to
clean
the
gel,
which
was
then
spread
on
a
glass
dish
and
dried
in
a
vacuum
oven
at
80
.C
for
24
h.
The
dried
gel
was
dry-milled
using
ZrO2
ball
media
in
a
HDPE
plastic
container
2.3.
Preparation
of
TiO2-doped
SiO2
gels
SiO2
gel
powder
prepared
as
described
in
Section
2.2
was
added
to
titanium
(IV)
isopropoxide
(TIP)
and
dissolved
in
isopropyl
alcohol
under
constant
stirring
at
room
temperature.
Water
was
then
added
to
obtain
a
molar
ratio
of
H2O:TIP
=
4:1.
The
sol
was
allowed
A.
Jaroenworaluck
et
al.
/
Chemical
Engineering
Journal
181182 (2012) 4555
Table
1
Nomenclature
for
the
powders
and
their
composites.
Samples
No.
Powders
and
its
composites
Sample
names
TiO2
SiO2
TiO2SiO2
1

Silica
gel
SiO2
(gel)
2

Fumed
silica
SiO2
(fume)
3
TIP
TiO2
(TIP)
4
TIP
Silica
gel
TiO2
(TIP)SiO2
(gel)
5
TIP
Fumed
silica
TiO2
(TIP)SiO2
(fume)
6
P25

TiO2
(P25)
7
P25
Silica
gel
TiO2
(P25)SiO2
(gel)
8
P25
Fumed
silica
TiO2
(P25)SiO2
(fume)
to
age
for
1
h
at
room
temperature.
The
samples
were
then
placed
in
an
oven
and
heated
from
30
to
110
.C
for
0.5
h
at
20
.C
intervals.
Using
a
similar
processing
route,
a
second
composite
was
made
when
SiO2
gel
was
added
to
TiO2
(P25)
and
suspended
in
ethyl
alcohol
at
room
temperature
with
constant
stirring,
followed
by
heating.
The
TiO2
loading
was
2.5,
6.5,
10.0
and
25.0
wt%,
respectively.
2.4.
Characterization
The
chemical
purity
of
SiO2
produced
from
the
synthesized
SiO2
gel
was
evaluated
by
X-ray
fluorescence
analysis
(XRF,
a
Phillips,
PW-2404,
The
Netherlands).
The
sample
for
the
XRF
analysis
was
prepared
by
pressing
5.0g
powder
with
1.0g
of
boric
acid
(H3BO3)
binder.
An
X-ray
diffractometer
(XRD,
JDX-3530,
JEOL,
Japan)
employing
Cu
K.
radiation
(
=
1.5418
A)
at
a
scanning
rate
of
0.04
2
s-1

was
used
to
measure
crystallinity
and
determine
the
phases
present
in
the
composites.
The
accelerating
voltage
and
the
applied
current
used
was
30
kV
and
40
mA,
respectively.
The
X-ray
diffraction
traces
were
acquired
in
the
2
range
1080..
The
diffraction
peaks
were
identified
with
JCPDS
data
using
Jade
7.5
software.
The
crystallite
size
of
the
powders
was
calculated
using
the
software
and
standard
formulae
based
on
the
Scherrer
equation
[21]:
K
t
=
B
cos
B
where
t
is
crystallite
size,
K
is
the
Scherrer
constant
(0.94),
is
the
wavelength
of
X-radiation
(1.5418

A),
B
is
peak
width
(FWHM),
and
B
is
the
diffraction
angle
at
which
the
half
width
is
measured.
The
surface
area,
pore
size
and
pore
volume
of
the
SiO2
gel
and
fumed
SiO2,
were
measured
using
nitrogen
(N2)
adsorption
(Quantachrome
Autosorp-1,
USA).
The
samples
were
degassed
at
250
.C
for
660
min
before
testing.
Surface
area,
pore
size
and
pore
volume
of
as-received
TiO2
(P25),
calcined
TiO2
(TIP),
TiO2
(TIP)SiO2
gel
TiO2
(P25)fumed
SiO2
including
typical
TiO2SiO2
compos-
Fig.
2.
X-ray
diffraction
patterns:
(a)
uncalcined
pure
SiO2
and
TiO2,
(b)
calcined
pure
SiO2
and
TiO2,
(c)
calcined
TiO2
(TIP)SiO2
(gel)
composites,
and
(d)
calcined
TiO2
(TIP)SiO2
(fume)
composites.
A.
Jaroenworaluck
et
al.
/
Chemical
Engineering
Journal
181182 (2012) 4555
Table
2
Surface
characteristics
of
samples
determined
by
the
N2
adsorptiondesorption
method.
Samples
BET
surface
Total
pore
Average
pore
area
(m2
g-1
)
volume
diameter
(nm)
(cm3
g-1)
SiO2
(gel)
353.04
0.6743
7.64
SiO2
(fume)
170.14
0.8685
20.42
TiO2
(TIP)
57.09
0.1664
11.66
TiO2
(P25)
55.42
0.8335
60.16
2.5
wt%
TiO2
(TIP)SiO2
(gel)
301.75
0.6394
8.48
6.5
wt%
TiO2
(TIP)SiO2
(gel)
385.52
0.6003
6.23
10.0
wt%
TiO2
(TIP)SiO2
(gel)
378.56
0.5436
5.74
25.0
wt%
TiO2
(TIP)SiO2
(gel)
349.77
0.5287
6.05
2.5
wt%
TiO2
(P25)SiO2
(gel)
211.55
0.6432
12.16
6.5
wt%
TiO2
(P25)SiO2
(gel)
230.68
0.6546
11.35
10.0
wt%
TiO2
(P25)SiO2
(gel)
154.10
0.6239
16.20
25.0
wt%
TiO2
(P25)SiO2
(gel)
238.13
0.8055
13.53
25.0
wt%
TiO2
(TIP)SiO2
(fume)
132.34
1.3090
39.57
25.0
wt%
TiO2
(P25)SiO2
(fume)
97.56
1.5080
61.83
ites
were
measured
using
the
same
methods
as
used
for
analysing
surface
characteristics
of
the
SiO2
gel
and
fumed
SiO2.
Infrared
spectra
were
collected
on
a
FT-IR
spectrometer
(System
2000,
Perkin-Elmer,
England)
at
20
.C
using
the
standard
KBr
method.
Sample
spectra
were
recorded
for
the
chemically
functional
groups
at
wavelengths
in
the
region
4000400
cm-1.
The
UV
absorption
properties
of
the
composites
were
measured
using
a
diffused
UVvis
spectrophotometer
(UV-2550,
Shimadzu,
Japan),
at
wavelengths
in
the
range
200800
nm,
at
0.1
step
scan
speed,
0.1
sampling
interval
and
1.0
slit
width.
A
scanning
electron
microscope
(SEM,
JSM-6310F,
JEOL,
Japan)
operated
at
20
kV
and
a
transmission
electron
microscope
(TEM,
JSM
2010,
JEOL,
Japan)
operated
at
200
kV
were
used
to
examine
the
morphology
and
microstructure
of
each
of
the
TiO2SiO2
composites.
Samples
for
SEM
investigation
were
dispersed
in
ethanol,
sonicated
in
an
utrasonic
bath
for
10
min,
dropped
onto
brass
stubs,
dried
in
a
vacuum
chamber
at
room
temperature
and
coated
with
sputtered
gold
prior
to
examination.
Samples
for
TEM
examination
were
dispersed
in
ethanol
and
sonicated
in
an
ultrasonic
bath
for
10
min,
and
then
fished
out
onto
carbon
films
supported
on
200
mesh
Cu
grids.
The
grids
were
dried
and
placed
in
the
microscope
for
microstructural
observation.
3.
Results
and
discussion
3.1.
Composite
characteristics
and
phases
present
A
list
of
samples
prepared
using
the
present
synthesis
route
is
shown
in
Table
1.
The
TiO2SiO2
gels
were
made
using
TiO2
from
two
sources;
TIP
and
P25.
Fumed
SiO2
was
used
as
a
standard
for
comparison
with
the
synthesized
SiO2
gel.
The
laboratory
processed
SiO2
gel
and
TiO2SiO2
gels
are
all
in
the
form
of
white
powders.
High
purity
SiO2
gel
(98.79%
SiO2
from
XRF
analysis).
Fig.
1(a)
shows
the
N2
adsorptiondesorption
isotherms
of
the
fumed
SiO2
and
SiO2
gel.
A
characteristic
hysteresis
loop
of
mesopores
of
the
SiO2
gel
isotherm
is
seen
and
considered
to
be
the
so-called
type
IV
which
has
been
attributed
to
ink-bottle
pores
[22]
while
the
isotherm
of
the
fumed
SiO2
appears
somewhat
different.
The
SiO2
gel
isotherm
may
relate
to
localization
of
agglomerated
particles.
Unlike
pure
fumed
SiO2,
the
gel
can
adsorb
moisture
because
of
its
highly
porous
structure,
defined
by
a
BET
specific
surface
area
of
353.04
m2
g-1,
a
pore
diameter
of
7.64
nm,
and
a
mesoporous
structure.
Fumed
SiO2
has
a
lower
BET
specific
surface
area
of
170.14
m2
g-1,
with
a
larger
pore
diameter
of
20.42
nm
(see
the
inset
table
in
Fig.
1).
It
is
noted
that
the
pore
volume
of
the
synthesized
SiO2
gel
is
lower
than
that
of
the
fumed
SiO2,
which
may
be
related
to
its
agglomerated
morphology.
Fig.
3.
(a)
FT-IR
spectrograms
of
the
composites:
TiO2
(TIP)SiO2
(gel),
TiO2
(TIP)SiO2
(fume),
TiO2
(P25)SiO2
(gel)
and
TiO2
(P25)SiO2
(fume)
at
10
wt%
TiO2
loading
(a)
before
and
(b)
after
calcination
at
400
.C
for
10
h.
Pure,
white
TiO2
can
be
obtained
from
TIP,
a
colorless
liquid
that
rapidly
hydrolyses,
readily
evaporates
and
easily
forms
a
solid
(powder)
residue.
Fig.
1(b)
shows
the
N2
adsorptiondesorption
isotherms
of
the
calcined
TiO2
(TIP)
and
as-received
TiO2
(P25).
A.
Jaroenworaluck
et
al.
/
Chemical
Engineering
Journal
181182 (2012) 4555 49
Table
3
Crystal
size
of
uncalcined
and
calcined
sample
powders
based
on
XRD
analysis.
Samples
TiO2
SiO2
Anatase
Rutile
Before
After
Before
After
Before
After
SiO2
(gel)




18.10
21.60
SiO2
(fume)




18.70
19.30
TiO2
(TIP)
10.87
19.60




TiO2
(P25)
23.20
24.40
35.40
38.10


2.5
wt%
TiO2
(TIP)SiO2
(gel)
ND
ND


ND
ND
6.5
wt%
TiO2
(TIP)SiO2
(gel)
ND
ND


ND
ND
10.0
wt%
TiO2
(TIP)SiO2
(gel)
ND
11.10


ND
ND
25.0
wt%
TiO2
(TIP)SiO2
(gel)
ND
13.10


ND
ND
2.5
wt%
TiO2
(P25)SiO2
(gel)
16.00
15.80
ND
ND
ND
ND
6.5
wt%
TiO2
(P25)SiO2
(gel)
18.43
18.50
ND
ND
ND
ND
10.0
wt%
TiO2
(P25)SiO2
(gel)
19.50
19.40
22.90
22.90
ND
ND
25.0
wt%
TiO2
(P25)SiO2
(gel)
20.20
21.30
29.10
31.90
ND
ND
2.5
wt%
TiO2
(TIP)SiO2
(fume)
ND
ND


ND
ND
6.5
wt%
TiO2
(TIP)SiO2
(fume)
ND
ND


ND
ND
10.0
wt%
TiO2
(TIP)SiO2
(fume)
ND
ND


ND
ND
25.0
wt%
TiO2
(TIP)SiO2
(fume)
ND
11.20


ND
ND
2.5
wt%
TiO2
(P25)SiO2
(fume)
ND
ND
ND
ND
ND
ND
6.5
wt%
TiO2
(P25)SiO2
(fume)
ND
ND
ND
ND
ND
ND
10.0
wt%
TiO2
(P25)SiO2
(fume)
18.40
19.50
23.80
25.20
ND
ND
25.0
wt%
TiO2
(P25)SiO2
(fume)
19.70
19.90
28.20
31.10
ND
ND
Note:
:
none,
ND:
not
detectable
because
of
the
analyzed
limitation.
Fig.
4.
UVvisreflectancespectraof(a)pureSiO2
andTiO2,(b)TiO2
(TIP)SiO2
(gel),(c)TiO2
(TIP)SiO2
(fume),and(d)allcompositesdopedwith10wt%TiO2.
A.
Jaroenworaluck
et
al.
/
Chemical
Engineering
Journal
181182 (2012) 4555
Fig.
5.
The
energy
band
gap
(Eg)
of
TiO2
(TIP)SiO2
gel,
TiO2
(TIP)fumed
SiO2,
TiO2
(P25)SiO2
gel
and
TiO2
(P25)fumed
SiO2
versus
wt%
TiO2
present.
Different
profiles
can
be
observed
which
suggest
that
the
TiO2
(P25)
is
not
agglomerated
and
there
is
no
mesoporous
characteristic,
as
is
present
in
the
TiO2
(TIP)
formed
by
agglomeration
of
individual
small
particles.
Fig.
1(c)
and
(d)
show
for
comparison
profiles
of
the
N2
adsorptiondesorption
isotherms
of
the
TiO2
(TIP)SiO2
gel
and
TiO2
(P25)SiO2
gel,
respectively.
The
mesoporous
characteristics
can
be
obvious
for
each
composition.
The
isotherm
characteristics
of
the
TiO2
(TIP)SiO2
gel
is
similar
to
the
TiO2
(P25)SiO2
gel
although
the
BET
surface
area
of
both
types
composites
show
significant
differences.
The
BET
surface
area
of
TiO2
(P25)SiO2
gel
has
a
lower
value
than
the
TiO2
(TIP)SiO2
gel
composites,
as
summarized
in
Table
2,
while
the
different
values
for
BET
surface
area
of
TiO2
(P25)
and
TiO2
(TIP)
are
not
significant.
This
indicates
a
different
characteristic
which
can
imply
that
the
TiO2
(P25)
particles
covering
the
SiO2
gel
surfaces
decrease
the
overall
composites
surface
area
whereas
this
has
not
occurred
in
TiO2
(TIP)SiO2
gel.
It
is
possible
that
the
TiO2
(P25)
particles
are
not
agglomerated
and
can
distribute
readily
on
the
gel
particle
surfaces
which
could
well
reduce
the
surface
area
of
the
gel.
However,
the
TiO2
(TIP)
particles
which
are
agglomerated
can
be
distributed
locally
on
the
gel
surfaces.
It
is
possible
that
the
gel
surfaces
can
be
exposed
without
the
TiO2
being
totally
covered
by
particles.
It
is
also
interesting
that
the
TiO2SiO2
gel
composites
have
higher
BET
values
than
the
TiO2fumed
SiO2.
This
should
be
related
to
the
surface
area
of
the
SiO2
gel
which
is
higher
than
that
of
the
fumed
SiO2
itself.
The
number
of
TiO2
particles
attaching
onto
the
substrate
surfaces
is
possible
to
be
higher.
Fig.
2(a)
and
(b)
shows
a
comparison
of
phase
present
in
the
uncalcined
and
calcined
samples
from
pure
TiO2
and
the
synthesized
and
commercial
SiO2,
respectively.
The
calcined
temperature
and
holding
time
in
this
study
was
fixed
to
control
the
phase
present
in
the
TiO2SiO2
composites.
XRD
profiles
show
clearly
that
both
the
SiO2
gel
and
fumed
SiO2
have
an
amorphous
structure
with
a
diffuse
intensity
peak
at
2
~
22.
.
For
analysis
of
the
XRD
profiles
of
pure
TiO2
(P25),
JCPDS
no.
211272
and
21-1276
were
used,
the
highest
peak
intensity
of
(1
0
1)
and
for
(1
1
0)
were
measured
to
calculate
the
phases
present
and
to
determine
the
crystallite
size
of
anatase
and
rutile,
respectively.
The
XRD
results
indicate
the
presence
of
the
crystalline
phases
of
anatase
and
rutile
for
the
as-received
and
calcined
TiO2
(P25).
However
the
ratio
of
anatase:rutile
phases
changed
from
approximately
90:10
to
80:20
after
the
TiO2
(P25)
had
been
calcined.
This
is
a
clear
Fig.
6.
SEM
micrographs
of
the
pure
oxides,
(a)
SiO2
gel,
(b)
fumed
SiO2,
(c)
TiO2
(TIP),
and
(d)
TiO2
(P25).
A.
Jaroenworaluck
et
al.
/
Chemical
Engineering
Journal
181182 (2012) 4555
Fig.
7.
SEM
micrographs
of
the
calcined
composites
doped
with
10wt%
TiO2:
(a)
TiO2
(TIP)SiO2
(gel),
(b)
TiO2
(TIP)SiO2
(fume),
(c)
TiO2
(P25)SiO2
(gel),
and
(d)
TiO2
(P25)SiO2
(fume).
indication
that
the
calcination
condition
used
in
this
study
had
an
effect
on
the
phase
transformation
process.
For
the
synthesized
TiO2
(TIP),
for
both
the
uncalcined
and
calcined
powder,
characteristic
peaks
of
anatase
were
found.
In
addition
a
high
intensity
peak
at
2
~
30.8.,
the
characteristic
peak
of
the
(1
2
1)
plane
of
brookite
was
clearly
apparent.
Based
on
the
JCPDS
file
no.
29-1360,
this
peak
is
the
second
highest
intensity
peak
of
brookite.
The
first
and
the
third
are
at
2
~
25.3.
and
2
~
25.7.
,
respectively,
which
overlap
the
major
characteristic
peak
of
anatase
(2
~
25.3
of
(1
0
1)
plane).
For
the
uncalcined
powder,
this
characteristic
peak
of
anatase
appears
to
be
split
at
its
top,
all
of
which
suggests
that
a
brookite
phase
is
present
with
the
anatase.
These
particular
characteristic
peaks
could
also
be
found
in
the
calcined
powder
but
the
peaks
of
the
calcined
powder
are
noticeably
sharper.
It
may
well
be
that
the
brookite
formation
takes
place
by
a
phase
transformation
from
anatase
during
the
calcination
process.
It
is
clear
that
the
majority
of
the
crystalline
phase
in
the
TiO2
(TIP)
powder
is
anatase
and
that
for
the
calcination
condition
used,
the
rutile
phase
could
not
be
identified
in
any
of
the
samples
of
TiO2
(TIP).
Fig.
2(c)
shows
XRD
profiles
of
the
calcined
TiO2
(TIP)SiO2
gel
composites.
With
less
than
10.0
wt%
TiO2,
the
crystalline
phase
of
anatase
cannot
be
clearly
identified.
The
base
line
of
all
the
XRD
traces
includes
a
signal
due
to
the
amorphous
phase.
For
TiO2
(TIP)fumed
SiO2
composites,
the
trend
of
the
XRD
profiles
is
similar
to
that
of
the
calcined
TiO2
(TIP)SiO2
gel
composites,
as
shown
in
Fig.
2(d).
However
the
brookite
phase
could
be
seen
in
the
XRD
traces
of
the
25
wt%
TiO2
(TIP)fumed
SiO2
composites.
For
all
the
TiO2
(P25)SiO2
composites,
their
XRD
profiles
indicate
the
presence
of
crystalline
phases
of
anatase
and
rutile
before
and
after
calcination.
Table
3
summarises
the
calculated
crystal
size
of
pure
SiO2,
TiO2
and
their
composites.
The
amorphous
nature
of
SiO2
had
a
marked
effect
on
the
base
lines
of
the
XRD
profiles
which
limited
the
process
of
identifying
the
crystalline
size
by
this
technique.
However,
the
crystallite
size
of
the
calcined
SiO2
gel
and
TiO2
(TIP)
is
in
the
same
size
range
as
the
commercial
fumed
SiO2
and
TiO2
(P25).
The
estimated
size
of
the
TiO2
in
the
TiO2
(TIP)SiO2
composites
is
smaller
than
that
measured
for
the
pure
TiO2
(TIP)
or
for
the
composites
of
TiO2
(P25)SiO2.
3.2.
Chemical
functional
groups
FT-IR
spectra
of
the
composites,
10.0
wt%
TiO2
(TIP)
and
TiO2
(P25)
for
both
fumed
SiO2
and
SiO2
gel
before
and
after
calcination,
have
been
determined
and
are
compared
in
Fig.
3(a)
and
(b),
respectively.
The
spectral
peaks
near
3500
and
1640
cm-1
present
in
all
samples
are
attributed
to
the
stretching
mode
of
water
hydroxyl
bonds
[12,14,23].
There
are
strong
bands
at
470,
800
and
1100
cm-1
ascribed
to
the
bending
modes
of
SiOSi,
to
symmetric
vibration
of
SiOSi
and
to
asymmetric
stretching
of
SiOSi,
respectively
[10,12,19,20].
A
weak
band
at
~900950
cm-1
is
attributed
to
SiOH
stretching
frequency
for
the
silanol
groups
[24,25].
The
samples
exhibit
a
slightly
more
intense
broad
band
at
3500
cm-1
prior
to
calcination.
The
FT-IR
results
in
the
region
of
the
peaks
at
~3500
cm-1
demonstrate
that
the
SiO2
gel
shows
a
higher
adsorbed
water
content
than
fumed
SiO2.
The
composites
of
the
SiO2
gel
have
a
higher
intensity
peak
than
that
of
the
fumed
SiO2
around
3500
cm-1.
This
large
broad
band
is
attributed
to
the
presence
of
the
OH
stretching
frequency
of
the
silanol
groups
and
also
to
any
of
the
remaining
adsorbed
water
[26].
Thus
it
would
appear
that
the
composites
based
on
the
SiO2
gel
can
adsorb
water
rather
more
effectively
than
those
of
fumed
SiO2.
Furthermore,
the
A.
Jaroenworaluck
et
al.
/
Chemical
Engineering
Journal
181182 (2012) 4555
Fig.
8.
TEM
bright
field
images
of
pure
oxides,
(a)
SiO2
gel,
(b)
fumed
SiO2,
(c)
TiO2
(TIP),
and
(d)
TiO2
(P25).
TiO2
(TIP)SiO2
gel
shows
higher
adsorbed
water
content
than
the
calcined
sample
and
has
a
higher
adsorbed
water
content
than
the
TiO2
(P25)SiO2
gel
or
the
uncalcined
sample.
From
the
FT-IR
spectra
at
450750
cm-1,
only
one
absorption
peak
for
anatase
is
present
at
~500
cm-1
whereas
the
rutile
gives
two
peaks
at
510
cm-1
and
640
cm-1.
The
spectral
peaks
are
ascribed
to
the
stretching
vibrations
of
the
TiO
bond
[10,23].
As
the
calcined
temperature
reaches
400
.C,
a
broad
absorption
band
appears
at
500650
cm-1,
which
indicates
the
formation
of
the
rutile
phase,
probably
on
or
near
the
surface
of
anatase
crystals.
Thus
the
phase
transformation
from
anatase
to
rutile
can
be
monitored
by
the
relative
intensity
of
these
characteristic
peaks.
3.3.
UV
absorption
properties
Fig.
4(a)
shows
the
UV
absorption
spectra
of
pure
samples.
The
absorption
edge
is
absent
in
the
two
lowest
curves
corresponding
to
the
pure
fumed
SiO2
and
pure
SiO2
gel,
respectively.
It
is
clear
that
SiO2
itself
does
not
have
good
absorption
properties,
however,
the
SiO2
having
the
high
porosity
may
be
used
as
a
support
medium
for
the
TiO2
particles.
The
results
indicate
that
the
absorption
spectrum
for
pure
calcined
TiO2
(TIP)
shows
the
largest
shift
to
a
longer
wavelength
and
higher
absorption
than
TiO2
(P25).
Fig.
4(b)
and
(c)
show
for
comparison
the
absorption
spectra
of
pure
SiO2
gel,
fumed
SiO2
and
their
composites
formed
with
2.5,
6.5,
10.0
and
25.0
wt%
TiO2
(TIP)
The
degree
of
absorption
appears
to
be
increased
with
the
increase
in
wt%
TiO2
and
shift
to
longer
wavelength.
For
the
TiO2
(TIP)SiO2
(gel)
composites,
the
highest
absorption
is
found
at
6
wt%
TiO2
(TIP).
The
higher
additions
of
TiO2
may
show
a
reduced
absorption
as
a
result
of
particle
agglomeration.
It
is
apparent
that
the
absorption
edges
shift
to
a
higher
wavelength
(red
shift)
as
the
wt%
TiO2
(TIP)
increases.
The
results
indicate
a
trend
in
that
the
increasing
absorption
value
depends
on
the
wt%
TiO2
(TIP)
added.
In
Fig.
4(d),
the
TiO2
(TIP)SiO2
composites
are
seen
to
have
higher
absorption
values
when
compared
to
the
commercial
TiO2
(P25).
The
shift
of
the
absorption
edge
towards
longer
wavelength,
the
so
called
red
shift,
could
be
observed.
The
observed
red
shift
of
the
absorption
edge
for
the
TiO2fumed
SiO2
and
TiO2SiO2
gel
compared
to
pure
TiO2
(P25)
and
TiO2
(TIP)
is
suggested
to
be
due
to
size
effects
typical
of
small
particles.
UV
absorption
of
TiO2SiO2
gel
is
higher
than
for
the
TiO2fumed
SiO2
for
both
the
TiO2
from
P25
and
TIP.
This
may
well
relate
to
the
A.
Jaroenworaluck
et
al.
/
Chemical
Engineering
Journal
181182 (2012) 4555 53
Table
4
Absorption
edge
and
Eg
values
of
pure
and
composite
samples.
Sample
Absorption
edge
(nm)
Eg
(kV)
wt%
TiO2
wt%
TiO2
2.5
6.5
10.0
25.0
100.0
2.5
6.5
10.0
25.0
100.0
TiO2
(TIP)




385




3.22
TiO2
(P25)




390




3.18
TiO2
(TIP)SiO2
(gel)
350
370
370
385

3.54
3.35
3.35
3.22

TiO2
(P25)SiO2
(gel)
390
395
400
400

3.18
3.14
3.10
3.10

TiO2
(TIP)SiO2
(fume)
358
367
367
386

3.47
3.38
3.38
3.21

TiO2
(P25)SiO2
(fume)
380
385
390
402

3.26
3.22
3.18
3.09

Fig.
9.
TEM
bright
field
images
of
the
calcined
10
wt%
TiO2
composites:
(a)
TiO2
(TIP)SiO2
(gel),
(b)
TiO2
(TIP)SiO2
(fume),
(c)
TiO2
(P25)SiO2
(gel),
and
(d)
TiO2
(P25)SiO2
(fume).
mesoporous
structure
of
SiO2
gel
allowing
the
TiO2
to
deposit
on
where
E
is
the
Energy
gap,
h
is
Plancks
constant
(6.625

10-34
Js),
the
gel
surfaces
and
particularly
to
the
smaller
pore
size
of
the
gel.
c
is
the
velocity
of
light
(3.0

108
ms-1)
and
is
the
wavelength
(nm),
respectively.
The
wavelengths
were
determined
from
the
3.4.
Energy
band
gap
absorbance
curves
at
the
point
of
contact
with
the
x-axis
of
the
absorbance-wavelength
plots.
This
method
was
used
to
evaluate
The
energy
band
gap
can
be
calculated
by
substituting
the
energy
band
gaps
(Eg)
after
a
trial
and
error
calculation
for
the
appropriate
wavelength
value
()
into
the
equation
[27]:
energy
band
gap
of
TiO2
(P25).
The
energy
band
gap
of
TiO2
(P25)
obtained
using
this
method
is
closer
to
the
theoretical
value
when
hc
E
=
compared
to
the
two
methods:

A.
Jaroenworaluck
et
al.
/
Chemical
Engineering
Journal
181182 (2012) 4555
(i)
the
(F(R)

h)1/2
versus
h
plot,
in
term
of
the
KubelkaMunk
function,
where
F(R)
=
(1
-
R)2/(2R)
and
R
is
reflectance
(%)
[13]
and
(ii)
differential
reflectance
(dR/d)
versus
plot
[28].
The
relationship
between
Eg
and
wt%
TiO2
doped
in
SiO2
is
summarized
and
plotted
in
Table
4
and
Fig.
6,
respectively.
For
crystalline
TiO2,
the
theoretical
band
gap
between
the
valence
band
and
the
conduction
band
is
3.2
eV
for
anatase
[7,10,18,23]
and
3.0
eV
for
rutile
[7,8,10,18,23].
From
this
study,
the
energy
band
gap
was
determined
~3.18
eV
for
the
TiO2
(P25)
consisting
of
mixed
anatase
and
rutile
phases.
The
trend
in
values
of
Eg
for
mixed
TiO2
nano-crystals
of
both
rutile
and
anatase
phases
decreases
continuously
with
the
increase
in
rutile
content.
The
energy
gap
in
the
TiO2
(P25)SiO2
gel
and
TiO2
(TIP)SiO2
gel
is
higher
than
that
for
TiO2
(P25)fumed
SiO2
and
TiO2
(TIP)fumed
SiO2
for
all
the
different
TiO2
additions.
The
results
in
Fig.
5
show
that
the
highest
value
for
Eg
is
given
for
the
2.5
wt%
TiO2
(TIP)SiO2
gel.
The
band
gap
decreases
for
all
the
samples
with
increase
in
the
TiO2
content.
Again,
the
crystalline
form
of
the
samples
affects
the
change
in
band
gap
with
the
TiO2
(P25)SiO2
gel
giving
the
lowest
value
and
the
TiO2
(TIP)SiO2
gel
giving
the
highest
value.
The
lack
of
sensitivity
of
the
energy
band
gap
to
small
additions
of
dopant
(TiO2)
strongly
suggests
that
the
energy
change
is
due
to
small
bond
length
changes
induced
by
nearest
neighbor
crystal
chemistry.
However
for
additions
>10.0
wt%,
the
energy
band
gap
decreases.
Consequently,
it
would
appear
that
10.0
wt%
TiO2
(P25)
addition
is
the
optimum
composition
for
the
TiO2
(P25)SiO2
gel.
The
energy
band
gap
decreases
with
the
amount
of
TiO2
(TIP)
added.
At
25.0
wt%
TiO2
addition,
the
highest
absorption
and
the
lowest
value
for
the
energy
band
gap
was
found.
The
absorption
increases
with
the
wt%
TiO2
(TIP)
increase
up
to
10.0
wt%,
but
above
this
value
the
absorption
decreases,
the
10
wt%
TiO2
(TIP)SiO2
gel
having
the
highest
absorption.
Conversely,
the
energy
band
gap
increases
when
the
wt%
TiO2
(TIP)
decreases.
The
energy
band
gap
values
for
6.5
and
10.0
wt%
TiO2
(TIP)SiO2
gel
are
not
significantly
different
from
that
of
the
25.0
wt%
addition
which
has
the
lowest
energy
band
gap
in
the
series.
However
for
ease
of
preparation
of
the
TiO2
(TIP)SiO2
gels,
the
most
suitable
concentration
is
considered
to
be
~10.0
wt%
of
TiO2
(TIP).
3.5.
Microstructure
investigations
3.5.1.
SEM
observation
Fig.
6(a)(d)
are
SEM
images
showing
the
microstructures
of
Fig.
10.
HR-TEM
images
of
(a)
10
wt%
TiO2
(TIP)SiO2
gel
and
(b)
10
wt%
TiO2
calcined
SiO2
gel,
fumed
SiO2,
as-received
TiO2
(P25),
and
calcined
(TIP)fumed
SiO2
after
calcination
at
400
.C
for
10
h.
TiO2
(TIP),
respectively.
It
is
clear
that
particles
of
TiO2
(TIP)
and
SiO2
gel
have
agglomerated
while
particles
of
TiO2
(P25)
and
fumed
SiO2
are
randomly
dispersed.
The
image
revealed
that
pure
SiO2
3.5.2.
TEM
observation
gel
consists
of
both
large
and
small
agglomerated
particles.
The
Bright
field
images
of
the
pure
SiO2
and
TiO2
samples
are
shown
agglomerated
mass
has
broken
up
into
small
pieces
revealing
the
in
Fig.
8(a)(d).
The
SiO2
gel
particles
are
agglomerated
whereas
fine
individual
gel
particles
on
the
fractured
surfaces.
the
grains
of
the
fumed
SiO2
are
well
dispersed
and
have
a
fairly
The
microstructure
of
all
the
composites
observed
differs
some-narrow
size
distribution.
The
TiO2
(TIP)
particles
are
smaller
than
what.
Fig.
7(a)(d)
are
selected
as
being
representative
of
the
TiO2
(P25)
but
these
smaller
particles
tend
to
have
agglomerated.
microstructures
of
the
10.0
wt%
TiO2SiO2
composites.
The
images
The
particle
characteristics
of
the
TiO2
(P25)
and
the
fumed
SiO2
of
the
10.0
wt%
TiO2
(TIP)SiO2
gel
show
a
structure
consisting
are
similar,
as
shown
in
Fig.
8(b)
and
(d).
of
agglomerations
of
both
large
and
small
particles
which
may
Fig.
9(a)(d)
shows
the
microstructures
of
the
composites,
themselves
be
formed
of
even
smaller
agglomerates
covering
their
which
can
be
readily
compared.
For
the
composite
made
up
of
TiO2
surfaces.
However
the
images
of
the
10.0
wt%
TiO2
(TIP)fumed
(TIP)SiO2
(gel),
the
crystalline
TiO2
grains
are
agglomerated
and
SiO2
show
well
dispersed
nanoparticles
having
a
narrow
size
distri-attached
onto
the
SiO2
gel
surface
as
is
shown
in
Fig.
9(a).
However
bution.
From
examination
of
the
TiO2
(P25)fumed
SiO2,
particles
with
the
sample
of
TiO2
(TIP)fumed
SiO2,
individual
TiO2
(TIP)
of
TiO2
and
SiO2
are
observed
to
be
dispersed
uniformly
(see
particles
could
be
observed
on
the
surfaces
of
the
fumed
SiO2
(the
Fig.
7(c)).
In
the
course
of
the
SEM
observations,
it
was
not
pos-dark
spots
in
Fig.
9(b)).
In
the
TiO2
(P25)SiO2
gel
composite
it
can
sible
to
distinguish
between
the
TiO2
and
SiO2
particles
which
are
be
seen
that
the
TiO2
(P25)
particles
have
attached
to
each
other
of
a
similar
size
and
shape
and
have
similar
brightness
and
contrast.
and
some
are
completely
surrounded
on
the
gel
surface.
The
TiO2
A. Jaroenworaluck et al. / Chemical Engineering Journal 181 182 (2012) 45 55 55
(P25)fumed SiO2 composite shows different behavior in that both
types of particles are intimately mixed. Grains of the TiO2 (P25)
and the SiO2 gel particles have different structural forms, being
crystalline and amorphous respectively.
HRTEM images, Fig. 10(a) and (b) reveal agglomeration of crystalline
TiO2 (TIP) on SiO2 gel and fume SiO2. It is noted that the size
of the individual particles in the composite is smaller when measured
from calibrated micrographs than the values obtained from
XRD data and the Scherrer equation,
~7 nm (see Table 3 and the figures).
It is suggested that the TiO2 particles in the composites are
limited in their ability to grow easily since they become occluded
by the SiO2 grains and pores. A detailed investigation reveals that
individual TiO2 (TIP) particles having a crystalline structure are
attached onto the fumed SiO2 surfaces, a feature which may be
related to the larger pore diameters compared to those present in
the SiO2 gel.
The TEM images allow conclusions to be made particularly
regarding the influence of the nanostructure in that the UV absorption
properties of the TiO2SiO2 gel or TiO2fumed SiO2 depend on
the particle size of the active TiO2 phase in the composites and the
surface properties of the supporting media (SiO2 gel or fumed SiO2),
relating directly to the particle distribution of the components.
4. Conclusions
A mesoporous SiO2 gel was synthesized utilising recycled rice
husk as a precursor. The gel was doped with various amounts of
TiO2 using TIP and P25 and these were characterized and measured
for UV absorption for evaluation of their energy band gap
by comparing with TiO2fumed SiO2 composites. At the temperatures
and conditions used for calcination, the synthesized TiO2
prepared from the TIP forms a well crystallised pure anatase phase.
SiO2 gel particles are preferable to agglomerates and the TiO2 (TIP)
particles are best dispersed on the SiO2 gel with its mesoporous
structure. However, with the TiO2 (P25)SiO2 gel, the TiO2 (P25),
particles are preferable to agglomerates. The UV absorption properties
have been related to the level of TiO2 doping and the phase,
size and surface characteristics of the support media (SiO2 gel or
fumed SiO2).
Acknowledgement
This work is financially supported by the National Metal and
Materials Technology Center (MTEC) under funded no. MT-B-48-
CER-07-190-I and MT-B-51-CER-07-206-I.
References
[1] L. Sun, K. Gone, Silicon-based materials from rice husks and their applicati
ons,
Ind. Eng. Chem. Res. 40 (2001) 58615877.
[2] R. Conradt, P. Pimkhaokham, U. Leela-Adisorn, Nano-structured silica from ri
ce
husk, J. Non-Cryst. Solids 145 (1992) 7579.
[3] T.H. Liou, Preparation and characterization of nano-structured silica from r
ice
husk, Mat. Sci. Eng. A: Struct. A364 (2004) 313323.
[4] M. Estevez, S. Vargas, V.M. Castano, R. Rodriguez, Silica nano-particles prod
uced
by worms through a bio-digestion process of rice husk, J. Non-Cryst. Solids 355
(2009) 844850.
[5] A. Fujishima, X. Zhang, D.A. Tryk, TiO2 photocatalysis and related surface p
henomena,
Surf. Sci. Rep. 63 (2008) 515582.
[6] P. Kullavanijaya, H.W. Lim, Photoprotection, J. Am. Acad. Dermatol. 52 (2005
)
937958.
[7] N. Serpone, D. Dondi, A. Albini, Inorganic and organic UV filters: their rol
e
and efficacy in sunscreens and suncare products, Inorg. Chim. Acta 360 (2007)
794802.
[8] T.A. Egerton, N.J. Everall, J.A. Mattinson, L.M. Kessell, I.R. Tooley, Inter
action of
TiO2 nano-particles with organic UV absorbers, J. Photochem. Photobiol. A 193
(2008) 1017.
[9] S. Yabe, T. Sato, Cerium oxide for sunscreen cosmetics, J. Solid State Chem.
171
(2003) 711.
[10] S.I. Seok, J.H. Kim, TiO2 nanoparticles formed in silica solgel matrix, Mate
r.
Chem. Phys. 86 (2004) 176179.
[11] E. Pabn, J. Retuert, R. Quijada, A. Zarate, TiO2SiO2 mixed oxides prepared by

a combined solgel and polymer inclusion method, Microporous Mesoporous
Mater. 67 (2004) 195203.
[12] Z. Li, B. Hou, Y. Xu, D. Wu, Y. Sun, W. Hu, F. Deng, Comparative study of s
olgel
hydrothermal and solgel synthesis of titaniasilica composite nanoparticles,
J. Solid State Chem. 178 (2005) 13951405.
[13] J. Aguado, R. van Grieken, M.J. Lpez-Munoz, J. Marugn, A comprehensive
study of the synthesis, characterization and activity of TiO2 and mixed
TiO2/SiO2 photocatalysts, Appl. Catal. A: Gen. 312 (2006) 202212.
[14] A.A. Ismail, H. Matsunaga, Influence of vanadia content onto TiO2SiO2 matrix

for photocatalytic oxidation of trichloroethylene, Chem. Phys. Lett. 447 (2007)
7478.
[15] G. Calleja, D.P. Serrano, R. Sanz, P. Pizarro, Mesostructured SiO2-doped Ti
O2
with enhanced thermal stability prepared by a soft-templating solgel route,
Microporous Mesoporous Mater. 111 (2008) 429440.
[16] E. Beyers, E. Biermans, S. Ribbens, K. de Witte, M. Mertens, V. Meynen, S.
Bals,
G. van Tendeloo, E.F. Vansant, P. Cool, Combined TiO2/SiO2 mesoporous photocatal
ysts
with location and phase controllable TiO2 nanoparticles, Appl. Catal.
B: Environ. 88 (2009) 515524.
[17] H.E. Byrne, W.L. Kostedt IV, J.M. Stokke, D.W. Mazyck, Characterization of
HFcatalyzed
silica gels doped with Degussa P25 titanium dioxide, J. Non-Cryst.
Solids 355 (2009) 525530.
[18] B. Llano, G. Restrepo, J.M. Marn, J.A. Navo, M.C. Hidalgo, Characterisation a
nd
photocatalytic properties of titaniasilica mixed oxides doped with Ag and Pt,
Appl. Catal. A: Gen. 387 (2010) 135140.
[19] A. Nilchi, S. Janitabar-Darzi, A.R. Mahjoub, S. Rasouli-Garmarodi, New TiO2
/SiO2
nanocompositesphase transformations and photocatalytic studies, Colloids
Surf. A 361 (2010) 2530.
[20] J. Zou, J. Gao, H2O2-sensitized TiO2/SiO2 composites wit high photocatalyti
c
activity under visible irradiation, J. Hazard. Mater. 185 (2011) 710716.
[21] B.D. Cullity, Element of X-ray Diffraction, second ed., Addison-Wesley Publ
ishing
Company, United States of America, 1978.
[22] T. Allen, Particle Size Measurement, 5th ed., Kluwer Academic Publishers, T
he
Netherlands, 1999.
[23] W. Jun, Z. Gang, Z. Zhaohong, Z. Xiangdong, Z. Guan, M. Teng, J. Yuefeng, Z
.
Peng, L. Ying, Investigation on degradation of azo fuchsine using visible light
in the presence of heat-treated anatase TiO2 powder, Dyes Pigments 75 (2007)
335343.
[24] J.A.A. Sales, C. Airoldi, Calorimetric investigation of metal ion adsorptio
n on
3-glycidoxypropyltrimethylsiloxane + propane-1,3-diamine immobilized on
silica gel, Thermochim. Acta 427 (2005) 7783.
[25] Y.M. Wang, S.W. Liu, Z. Xiu, X.B. Jiao, X.P. Cui, J. Pan, Preparation and p
hotocatalytic
properties of silica gel-supported TiO2, Mater. Lett. 60 (2006) 974978.
[26] J. Estella, J.C. Echeverra, M. Laguna, J.J. Garrido, Effects of aging and dr
ying
conditions on the structural and textural properties of silica gels, Microporous

Mesoporous Mater. 102 (2007) 274282.
[27] V. Balzani, F. Scandola, Supramolecular Photochemistry, Ellis Horwood Limit
ed,
Chichester, 1991.
[28] M. Radecka, A. Trenczek-Zajac, K. Zakrzewska, M. Rekas, Effect of oxygen no
nstoichiometry
on photo-electrochemical properties of TiO2-x, J. Power Sources
173 (2007) 816821.