Photoluminescent and

Photocatalytic Properties of TiO

2

decorated Bismuth doped
Strontium Aluminates
L.A. Daz-Torres
1

Carlos R. Garca
1
, P. Salas
2
, M. Guzmn
1

1.Centro de Investigaciones en ptica A. C. Len Mxico
2. Centro de Fsica Aplicada y Tecnologa Avanzada. Universidad
Nacional Autnoma de Mxico.
June 2014
Introduction
Functional
materials
Optical
Magnetic
Electrical
Catalytic
Chemical

Luminescence
Photocatalysis

Multifunctional
TiO
2
decorated Bi
doped Strontium
aluminates

Phosphorescent materials (PMs)
Emergency signaling.
Compact fluorescet lamps.
Lasting for hours.
1
1) Materials 2010, 3, 2536-2566.
TiO
2
is one of the best photocatalyst.

SrAl
2
O
4
:Eu
2+
,Dy
3+
and Sr
4
Al
14
O
25
:Eu
2+
,Dy
3+

show long persistence time.

PMs improve the photocatalyc of the TiO
2
in composites.
2

Bismuth enhance the photocatalytic
activity of some crystalline lattices.
3

2) J. Mater Chem A, (2013), 1, 1123-1126.
3) M Sc. and Eng. B (2011) 176, 1382 1387.
Introduction
Sr
4
Al
14
O
25
: Eu,Dy can be used without irradiation to assist the Ag
3
PO
4
photocatalyst
in water solutions.
6

Persistent materials (PMs) create free carriers (electron or holes) which promote the
photocatalytic process.

Persistent materials have been proposed to help, with exciting light, the
photocatalyst to degrade some contaminants from water and environment.
5
5) J. Mater Chem A, (2013), 1, 1123-1126.
6) J. Mol. Cat. A, (2012), 363-364, 129-133.
Produce a decorated TiO
2
Bi-doped strontium aluminate with a good
photocatalytic activity under UV irradiation (365 nm).


That the decorated TiO
2
Bi-doped strontium aluminate could degrade
methylene blue (MB) dye in water solutions.


That the Persistence of the strontium aluminates improves with Bismuth
concentration.


Is it possible to ?
Motivation
Dyes in wastewater are the major pollutants.
7
Wastewater from
textile industry.
MB as pollutant in
water.
Methylene blue (MB)
contamination dye in a
lake.
7) Int. J. of Env. Sci. (2012),3,3, 940-955.
Objectives:

1) Synthesize Eu,Dy-strontium aluminate codoped with different Bi molar concentrations
between 0.0% and 15.0% mol.
2) Then decorate it with TiO
2
at low temperature.

2) Study the structural, morphological and optical properties.

3) Evaluate the photocatalytic activity of the TiO
2
decorated samples
in methylene blue degradation in solutions under UV (365 nm) irradiation.


Synthesis
We use the combustion synthesis method with urea as fuel.
1 2 3 4
Stage 1
Stage 2
1. Dissolved nitrates
in 15 ml of deionised
water.






2. Introduce the beaker
at 600C into the preheated
mufle.

3. Combustion ocurred
lasting 20-30 sec.
4. Green phosphorescent
foaming is obtained.
Sr(NO
3
)
2 ,
Al(NO
3
)
3
Eu(NO
3
)
3
Dy (NO
3
)
3
Bi(NO
3
)
3 .
Powders are pressed
with 2.5 t and disks of
1.0 g are produced.
The disks are annealed
at 1150C for 6h in a carbon
reducing atmosphere
5
6
(TiO
2
-SrAlO-Bi)
Stage 3
Grind the disks for
Characterization of obtained
powders
7
SrAlO-Bi
Wet mixing in ethanol

1:1 in weight Mixture

TiO
2
: SrAlO-Bi
Dry for 24 h and anneal
at 450C for 1h.
Grind and use
as a photocatalyst.
8
9 10
Photocatalysis
At the beginning After 190 min
1) 0.5 mM solutions of methylene blue and 30 mg of
TiO
2
-SrAlO-Bi photocatalyst in water strongly
stirred for 1 h in darkness.

2) Then, the UV lamps (365 nm) are turned ON
keeping the stirring. Samples of 0.2 ml are extracted
in regular periods. Samples are centrifuged at 5000 rpm.

3) We measure the absorbance spectrum at regular periods.


Procedure
UV lamps
(365 nm)
Quartz beaker
filled with the solution
magnetic
stirrer plate
Reactor design
Agilent UV-Vis cary 60 spectrophotometer
Utilised to measure the absorbance spectra
Results
20 30 40 50 60 70
SrAl
2
O
4
JCPDS 34-0379
15.0%
10.0%
5.0%
2.0%
1.0%
2tetha ()
0.0%
Bi, mol.%
Structural analysis by X-ray difraction
of the SrAlO-Bi powders.
For low concentrations of Bi
(x=0.0%, 1.0%, 2.0% and
5.0 %) the powders are
composed
Mainly of the phases: SrAl2O4
and
Sr4Al14O25.

For high concentrations of Bi
( x =10.0 % and 15.0%) the
same strontium aluminates
phases appear but Bi
2
O
3
phase
also appear in the
XRD patterns.
Morphology of the SrAlO-Bi powders
0%
2.0%
5.0%
10% 15%
1.0%
Micrograins of irregular shapes
are observe for all samples after
the annealed in carbon reduced
atmosphere.

The sample without Bi codoping
show particles with
larger sizes than the other
samples.



400 450 500 550 600 650


P
L

(
a
.
u
.
)
Wavelength (nm)
0.0%
1.0%
2.0%
5.0%
7.0%
10.0%
15.0%
= 380nm
exc
510 nm
463 nm
Bi mol.%
0.0 2.5 5.0 7.5 10.0 12.5 15.0
P
L

I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
Bi concentration, mol.%
510 nm band:SrAl
2
O
4
:Eu,Dy
0.0 2.5 5.0 7.5 10.0 12.5 15.0
P
L

I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
Bi concentration, mol.%
463 nm band: Sr
4
Al
14
O
25
:Eu,Dy
Photoluminescence of the SrAlO-Bi
powders.
The sample codoping with the 1.0 % of Bi
show the highest luminescence when is
excited with 380 nm UV light.
As Bi concentration increases the
luminescence intensity decreases and
a shift to the blue region is observed.
Tendencies of the 510 nm and 463 nm
luminescence bands as a function of Bi
codoping.
For photocatalysis we select the 0%, 2.0 %, 15.0% and pure TiO
2
in order to
evaluate the methylene blue degradation.
These samples were decorated with TiO
2
and then the photocatalysis experiment
was made for each sample.
TiO
2
- decorated SrAlO-Bi for photocatalysis
20 30 40 50 60 70
0
50
100
150
200
250
300
350
c
o
u
n
t
s
2 )
TiO
2
Anatase phase JCPDS 84-1286
20 30 40 50 60 70
0
20
40
60
80
100
120
140
**
*
*
*
*
*
*
*
*
*
*
*
*
*
c
o
u
n
t
s

2
strontium aluminates phases
TiO
2
anatase phase
*
XRD pattern of the 2.0 % sample after decorated with TiO
2
Pure commercial TiO
2

Decorated TiO
2
-SrAlO-Bi-2.0 %
powder sample
TiO
2
- decorated SrAlO-Bi for photocatalysis
Morphology of the pure TiO
2
and the TiO
2
-decorated SrAlO-Bi 2.0%
Pure TiO
2
TiO2- decorated SrAlO Bi 2.0%

Aparently the TiO
2
nanoparticles are attached to the surface of the
large micro grains of the SrAlO-Bi 2.0 % sample.
This fact is beneficial for the photocatalytic activity because the surface
area is enhance.
0 50 100 150 200
0
25
50
75
100
%

D
e
g
r
a
d
a
t
i
o
n
Exposure time (min)
0.0% Bi
2.0% Bi
15.0% Bi
Reference Only TiO
2
Photocatalytic degradation of of methylene blue
under UV (365 nm) light.
The 2.0 % Bi TiO
2
decorated SrAlO sample reach almost a complete
degradation after 210 min of UV irradiation.
Conclusions
Long persistent green and grenish blue materials were produced by
the combustion synthesis method followed by annealing in a reducing
carbon atmosphere.

The persistent powders were decorated with TiO
2
and the photocatalytic
activity was evaluated for the concentrations of x= 0.0%, 2.0%, 15.0%
and pure TiO
2
.

The decorated TiO
2
SrAlO 2.0 % Bi-codoping sample show good
photocatalytic activity, the degradation was 97 % after 210 min under
UV (365 nm) irradiation.

The 2.0 % sample show the long lasting persistence time and the
Photocatalytic activity probably due to the Bi levels into the strontium
aluminates lattices which creates electron or holes traps.