1.

INTRODUCTION
Recent trend in material science have focused on development of doping or
supported material of metal oxide and mixed metal oxides. The conventional materials
such as metal oxide and mixed metal oxides have wide and important applications in
catalysis, environmental science, ceramic, electronic devices and several other fields of
material science.

It is well known that TiO2 is an excellent catalyst in photodegradation of organic

pollutants because it is a photocatalyst, reusable, inexpensive, non-toxic and easily
available catalyst. The low photocatalytic degradation efficiency on the surface of TiO2
particle is due to the fast recombination rate of photogenerated electron hole pairs.
Lanthanide oxide exhibit unique properties to enhance the photocatalytic performance of
TiO2.Cerium is a particular lanthanide element and it has two stable oxidation statesCe4+
and Ce3+ as a result of an apparent difference in the ionic radius between Ce and Ti ions
.CeO2 and TiO2 phase can coexist in the mixed oxide. Several researchers have reported
the structure and redox properties of the Ce-TiO2 catalyst and thought that this kind of
mixed oxide showed a potential interest in the field of photodegradation of organic
pollutant.

Why graphene is doped

Graphene is a semimetal with high electrical conductivity and charge carrier

mobility .It is the strongest known material and harder than diamond. Extremely good
thermal conductor, thermal conductivity is higher than diamond and nearly 10 times higher
than aluminium and copper, very wide range of application in integrated circuit, electronic
device etc. available in different layers and size with range of properties.

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2. LITERATURE REVIEW

TiO2 and CeO2 are important functional oxide materials. There are a lot of reports
on the preparation structure and property of CeO2-TiO2 mixed oxides [1-20]. Reddy and
co-workers investigated in detail the structure of the CeO2-TiO2 mixed oxide with 1:1
atomic ratio by means of X-ray diffraction, UV-Vis diffuse reflective spectroscopy, X-ray
photoelectron spectroscopy, high-resolution transmission electron microscopy, BET
surface area and thermogravimetry [11-14].

Lopez et al. studied the structure and morphology CeO2-TiO2 mixed oxides (10 wt.
% CeO2-90Wt%TiO2) calcined at different temperatures and found that the presence of
cerium increases the thermal stability of the TiO2 materials by restricting particle sintering
and pore collapse [15]. They suggested that cerium affected the crystallographic and
sintering characteristics of CeO2-TiO2 compounds due to the progressive segregation of
cerianite on the surface of TiO2 globules as the temperature was raised and by possible
substitutions of Ti4+ by Ci4+ species within the TiO2 anatase structure. This can increase
the phase stabilization also.

Fang et al. reported a detailed study of the structures of CeO2-TiO2 mixed oxides
prepared by the sol-gel method by means of X-ray diffraction, high-resolution X-ray
photoelectron spectroscopy, Raman spectroscopy and scanning electron microscopy [20].
They also reported the interfacial and surface structures of CeO2-TiO2 mixed oxides
prepared by the sol-gel method by means of X-ray diffraction (XRD), BET surface area
measurement, X-ray absorption spectroscopy (XAS), high-resolution transmission electron
microscope (HRTEM), and selective chemisorption of methyl orange [21].

Periyat et al., synthesized nanosized ceria-doped Titania by aqueous colloidal SDI-

gel route and found that the synthesized material possesses high surface area and increased
anatase phase stability [22].

Sinha and Suzuki synthesized, novel thermally stable mesoporous ceria-titania

mixed oxides by a neutral templating route and found at these materials showed high
performance for the removal of volatile organic compound (toluene) [23].

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 Silva et al., prepared Ce-doped TiO2 Catalysts by solvothermolysis method, studied
their characteristics by several techniques like DR UV-Vis, XRD etc. and tested their
photocatalytic activity by studying the degradation of 4-chlorophenol[24].

Present work deals with the synthesis of graphene doped CeO2- TiO2 mixed
oxides varying the amount of graphene by different methods like sol-gel, co-precipitation
methods and evaluation of physio-chemical properties including photocatalytic dye
degradation, adsorption of different anions like PO43-, CrO42-, MoO42-, F- etc. and
decomposition of H2O2. Materials will be characterized with XRD, SEM, BET surface
area, FTIR for understanding the surface properties of the materials.

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3. EXPERIMENTAL

3.1. Synthesis of Ce-TiO2 mixed oxide.

450ml of deionised water was taken in a 1000ml beaker and its pH was adjusted
to 2.5 by adding HNO3. 0.06370gm of Ce (NH4)2(NO3)6 was dissolved in 25ml of water in
another beaker. Again, 3.763ml of Titanium isopropoxide was diluted to 30ml by adding
1-propanol in another beaker. Then Ceric ammonium nitrate was kept in burette. Then
Ceric ammonium nitrate from burette and Titanium isopropoxide from beaker were added
drop wise to beaker containing 450ml of water of pH 2.5 with constant stirring for
4hours.Then the resulted Ceria titania mixed hydroxide was calcined at 4000C for 4hours
to obtain Ceria titania mixed oxide.

3.2. Synthesis of graphene

Graphene was synthesized by modified Hummer’s method. In this method, 1gm of

Graphite was taken in a round bottom flask, put in ice bath and 46ml of conc. H2SO4 was
added. It was stirred for 15minutes, 1gm of NaNO3 was added and stirred for 30minutes.
Then 8gm of powder KMNO4 was added, stirred for 2hr and 80ml of water was added
slowly. It is the crucial step because it is an exothermic reaction (acid+water).Then it was
left for stirring for some time. Again 200ml of water was added by stirring. Then H2O2
was added drop wise till the reaction stops. Then it was kept for some time to settle down.
The acid part was drawn and put for centrifugation (200rpm).After centrifugation, the
cube was taken and the liquid part was drawn in waste beaker and 30% HCl was put .It
was stirred with glass rod to distribute uniformly, distilled water was put and put again for
centrifugation. This process was repeated for 4-5 times till all the acid part (mixed ions)
once removed or washed out. After that it was centrifuged with Ethanol for 2-3 times.
Then small amount of alcohol was added to the cube, removed to a 100ml beaker and put
in oven to dry.

3.3. Synthesis of Graphene CeO2-TiO2 composites by chemical reduction

method.

0.025gm of graphene was taken in a 100ml beaker and 20ml of water was added to
it followed by sonication for 15minutes.Then 0.5gm of CeO2-TiO2 sample was added to it
followed by sonication and stirred for 2hours.Then NaBH4 solution was added to it till the
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reaction stops and centrifuged. Then it was dried in an oven and sonicated.After drying,
the resulted Gr-Ce-TiO2 composite was grinded and put in a tube.

3.4. Preparation of Stock Solution

Stock solution of Methylene Blue (1000mg/l) was prepared by adding 0.25 gm of

Methylene Blue to 250 ml of distilled water i.e. of 1000ppm & its absorbance was
calculated at different dye concentration, catalyst concentration variation & PH variation &
its absorbance was calculated from which % of decolourization is calculated.

3.5. Material Characterization

For crystallographic characterization, all the synthesized materials were subjected

to X-ray powder diffraction and the obtained spectra was recorded. Similarly, the
synthesized materials were also subjected to another method, Photoluminescence
spectroscopy, also known as PL to know the electronic structure of material as it is a
contactless, non-destructive method. The obtained PL spectra was recorded.

3.6 Photo Catalytic Activity

Prepared Ce-Ti mixed oxides samples, after calcination at 400 °C temperatures

were used as photo catalyst for the reductive removal of Methylene Blue Stock solutions
of Methylene Blue were prepared by dissolving required amount Methylene Blue in
double distilled water. All the photo catalytic experiments were carried out in a 200 ml
capacity three necked glass reactor of 25 cm length and 4.9 cm internal diameter. Centrally
fitted 125 W high pressure mercury lamps with most intense peak at 546 nm were used as
visible light source. Constant reaction temperature was maintained through water
circulation in the outer jacket of the lamp. All the experiments were performed in presence
of air at atmospheric pressure and constant magnetic stirring condition. For all the
experiments 0.5g /L of photo catalyst was dispersed in 100 ml of solution. After reaction,
solid catalyst was separated by filtration or centrifuge. Methylene Blue concentration was
determined by UV-visible spectrophotometer at 665nm. (Shimadzu-2550).

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4. RESULT AND DISCUSSION

4.1. Characterization of material

From powder XRD pattern of the material Fig.1 (a), it was seen that only anatase
phase was detected. Detection of only Titania phase for the material indicate the
homogeneous distribution of cerium and graphene on the anatase crystal lattice without
forming any separate phase.

Fig.1 (a)

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 PL of spectra of sample A: TiCe-2 and B: Gr-TiCe-2 were shown in the
fig.1(b).The intensity of the PL spectra decreased in the presence of Graphene ,which
indicates suppression of the recombination of the photo induced electron-hole pair .Hence
the electron hole pair lifetime was effectively increased.

Fig.1 (b)

All the N2 adsorption–desorption isotherms are of type II or type IV indicating the

mesosporous nature of the material. It is quite noticeable that addition of graphene
increases the surface area in comparision to that of ceria-titania mixed oxide.

Sample Specific Surface Area(m2/gm)

TiCe-2 82.42
Gr-TiCe-2 87.02
TiCe-5 74.76
TiCe-10 65.22

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4.2. Decolourization of methylene blue

4.2.1. Preliminary observation

The Photocatalytic activity experiment towards decolourization of Methylene Blue

was done for the sample, graphene doped TiCe-2 taking catalyst dose 0.2 g/L, dye
concentration 10mg/L and at fixed pH ~ 3.0. It was found that graphene doped TiCe-2
sample showed maximum percentage of decolourization after 3hrs (Fig.2). So for present
study sample graphene doped TiCe-2 was taken for studying other variations.

Fig.2.Decolourization of methylene blue by graphene doped TiCe-2

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4.2.2. Effect of catalyst dose

The effect of catalyst dose on decolourization of methylene blue by graphene

doped ceria titania mixed oxide sample was studied (Fig.3) by taking methylene blue
concentration 10mg/L at initial pH 3.0 for 3hours reaction. The catalyst dose was varied
from 0.1 to 0.5 gm. /L. By increasing catalyst dose the decolourization percentage
increases with increase in weight of the catalyst due to increase of surface area.

Fig.3.Effect of catalyst dose on decolourization of methylene blue

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4.2.3. Effect of dye concentration

The effect of methylene blue concentration on decolourization by graphene doped

Ce-Ti-2 was studied (Fig.4.) by taking catalyst dose 0.2g/L at initial pH 3.0.The
concentration of methylene blue ranges from 6 to 20mg/L. At the concentration 5mg/L, the
decolourization percentage reached 37% within 3hours.However, the percentage of
decolourization decreases by increasing concentration of methylene blue.

Fig.4.Effect of dye concentration on decolourization of methylene blue

It is well established that oxidative degradation of organic matter by oxide samples

occurs on the surface of the catalyst not in the aqueous phase. The organic compounds
adsorbed on the surface form surface precursor complex and then electron transfer takes
place from organic compound to the surface of the catalyst followed by release of
oxidation product. This indicates that reactive surface sites were saturated and did not
provide active site for further formation of precursor complex at higher concentration of
the dye. Thus percentage of decolourization decreased at higher Methylene Blue
concentration. The experimental findings suggest that surface reactivity and number of
absorption sites are two crucial factors for decolourization of Methylene Blue.

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4.2.4. Effect of pH

The decolourization of Methylene Blue at various pH (pH = 3,5,7,9) as a function

of reaction time was studied at fixed dye concentration 10mg/L, catalyst loading 0.2 gm./L
for graphene doped Ti-Ce-2 sample(Fig.5). The decolourization rate of dye compound
increases up to pH 7.0 and then decreases for further increase in pH of initial solution. At
pH 7.0 the reduction potential of Ce3+/Ce4+couple increases which probably enhances
decolourization of Methylene Blue.

Fig.5.Effect of pH on decolourization of methylene blue

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4.2.5. Effect of competitive ions

The effect of competitive ions on decolourization of methylene blue by Gr-CeTi-2

was studied (Fig.6) by taking dye concentration 10mg/L and wt. of the catalyst 0.2g/L.The
decolourization experiment was conducted in presence of other anions such as chloride
and nitrate. It is found that due to interference of other anions the percentage of
decolourization decreases and percentage of decolourization increases without anions.

Fig.6.Effect of competitive ions on decolourization of methylene blue

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5. CONCLUSION

For Ceria-Titanium mixed oxide samples it was seen that Gr-CeTi-2 shows the best
result than the sample without graphene doped. Best result was shown at initial Methylene
Blue concentration 10mg/L, catalyst dose 0.2g/L and at initial pH 3.0. Presence of
graphene in the composite can stabilize the anatase phase. Synthesized materials show
increasing visible light absorption and surface area in presence of graphene. Highest photo
catalytic activity is observed for graphene TiCe-2 sample. In the presence of Graphene the
recombination of electron and hole is reduced which improves the photocatalytic.

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6. REFERENCE

(1) A Dauscher, P Wehrer,.; L Hilaire,. Catal. Lett. 14(1992)171.

(2) A Preuss,.; R Gruehn,. J. Solid State Chem. 110 (1994)363.

(3) J Lin, J. C Yu, J. Photochem. Photobiol., A 116(1998), 63.

(4) J Rynkowski,.; J Farbotko,.; R Touroude,.; L. Hilaire, Appl. Catal A 203(2000) 335.

(5) M. F Luo, J Chen, L. S Chen, J. Q Lu, Z.C. Feng, C Li, Chem. Mater 13(2001) 197.

(6) M. S. P.Francisco; V. R Mastelaro; P. A. P Nascente.; A. O. Florentino, J. Phys.Chem. B

105(2001) 10515.

(7) M. S. P Francisco; V. R Mastelaro; A. O Florentino; D Bazin,. Topic Catal.18(2002)

105.

(8) J. Purans; A. Azens; C. G Granqvist,. Electrochim. Acta 46(2001) 2055.

(9) A. W. Xu.; Y. Gao.; H. Q. Xu,. J. Catal. 207(2002) 151.

(10) Jing, L. Q.; Sun, X. J.; Cai, W. M.; Li, X. Q.; Fu, H. G.; Hou, H. G.; Fan, N. T. Act
Chim. Sin. 61 (2003) 1241.

(11) B. M Reddy; A. Khan; Y. Yamada; T. Kobayashi; S.Loridant,; , J. C. Volta, J. Phys.

Chem. B107 (2003) 5162.

(12) B. M Reddy; P. Lakshmanan; A. Khan,. J. Phys. Chem. B 108( 2004) 16855.

(13) B. M Reddy; A. Khan; P. Lakshmanan,.; M. Aouine,.; S.Loridant,; , J. C Volta.

J.Phys. Chem. B 109(2005) 3355.

(14) B. M Reddy; A. Khan, Catal. SurV. Asia , 9(2005)155.

(15) T Lo´pez,.; F Rojas.; R Alexander-Katz,.; F Galindo,.; A Balankin,.; A Buljan,. J.

Solid State Chem. 177(2004)1873.

(16) S Pavasupree; Y Suzuki.; S Pivsa-Art,.; S Yoshikawa,. J. Solid State Chem.

178(2005) 128

(17) B. S Liu; X. J Zhao,.; N. Z Zhang,.; Q. W Zhao,.; X He,.; J. Y Fen,. Surf. Sci. 595
(2005) 203.

(18) H. Q Zhu; Z. F Qin,.; W. J Shan,.; W. J Shen,.; J. G. Wang, J. Catal. 333( 2005) 41.

(19) G Dutta,.; U. V Waghmare,.; T Baidya,.; M. S Hegde,.; , K. R Priolkar.; P.

R.Sarode, Chem. Mater. 18 (2006) 3249.

14
(20) J Fang,;X. Z Bi; D. J Si.; Z. Q Jiang,.; W. X Huang,. Appl. Surf. Sci. 253(2007)
8952.

(21) J. Fang, H. Bao, B. He, F. Wang, D. Si, Z. Jiang,Z. Pan, S. Wei and W. Huang, J.
Phys-Chem. C 111(2007) 19078.

( 22) P. Periyat, K. V. Raju, P. Mukundan, P. Krishna Pillai, K.G. K. Warrier, J Sol Sci
Technol 43(2007) 299.

(23) A. K. Sinha, K. Suzuki, J. Phys-Chem. B 109(2005) 1708.

(24) [17. A. M. T. Silva; C. G. Silva; G. Drazic; J. L. Faria, Catalysis today,

144 (2009)13.

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