Effect of method of synthesis and different

metal doping on the photocatalytic activity of

titania

P. Vijayan

Department of Chemistry
Anna University
Chennai
 Photocatalysis

 In the year 1972, Fujishima and Honda discovered the photocatalytic

splitting of water on titania semiconductor electrode. Later on Sato and
White decomposed water on platinum loaded TiO2 powder.

 After that researchers concentrated towards the usage of semiconductor

photocatalysis for environmental protection.

 Photocatalysis has been exploited for various environmental process

such as deodorization, water purification, air purification, sterilization
and soil proof.

 Many researchers have put their effort on degradation and

mineralization of variety of toxic substances by photocatalytic
oxidation. Carbon dioxide has been reduced efficiently with water by
photocatalysis.

 Different types of semiconductors were used as photocatalyst. Among

these titania is the widely used photocatalyst due to its strong oxidizing
power, stable at different pH and favorable band gap energy.
 Photocatalysts and their band gap energy

Valence Conductance Band gap Band gap

Semiconductor band band (eV) wavelength
(nm)
SnO2 +4.1 +0.3 3.8 318
ZnO +3.0 -0.2 3.2 390
ZnS +1.4 -2.3 3.7 336
CdS +2.1 -0.4 2.5 497
CdSe +1.6 -0.1 1.7 730
TiO2 +3.1 -0.1 3.0 380
GaP +1.3 -1.0 2.3 540

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 Even though titania is the widely used semiconductor, it has some disadvantage like
low surface area, fast recombination and wavelength maximum lies in UV region.

 Commercial titania P-25 has average particle size of 40-50nm. Since larger particles
increases the specific surface area of the catalyst, reduction of particle size become
essential.

 Recombination are of two types (i) surface recombination (ii) volume recombination.

 Surface recombination can be avoided by doping some foreign material like metal,
non-metals and coupling titania with another semiconductor. Volume recombination
can be reduced by preparing titania in nanoscale. Wavelength of maximum can also
increased to higher wavelength by doping metals or non-metals.

 It is well known that wavelength and surface area are mainly depend on particle size.
Altering the size of the particle alters the degree of confinement of the electrons, and
affects the electronic structure of the solid, in particular ‘band edges’, which are
tunable with particle size.

 From the above fact that the synthesis of titania with controlled nanometer dimension
and doped with altervalent ion is essential.

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 Size Dependence of Light Absorption
 Ismat shah etal studied the effect of
particle size for the degradation of
300 400 500 600 700 2-chlorophenol using titania
synthesized by metallo organic
4 (a) chemical vapour deposition method
with different particle size.
a1 (12nm)
Absorbance

3
a2 (17nm)  Particle size decrease from 29 to 17
a2 a3 (23nm) nm showed red shift and further
2 a1 decrease i.e less than 17nm leads to
a3 blue shift.
1
 Titania with 17nm have shown
0 remarkable catalytic activity towards
300 400 500 600 700 the degradation of 2-chlorophenol
Wavelength than the catalysts having 23nm and
12nm.

Appl.Catal.B:Environ, Vol. 68, 2006,  Comparison of band gaps

Pages. 1-11 B17nm < B12nm < B23nm
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 Methods used

 Sol-gel

 Liquid phase deposition

 Pulse laser deposition

 Chemical vapour deposition

 Magnetic sputtering

 Direct hydrothermal method

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 Sol-gel
 Generation of a dispersion of colloidal particles suspended in Brownian
motion within a fluid matrix.

 Colloids are suspension of particles of linear dimensions between 1nm

and 1 m. The colloidal suspensions can subsequently convert to viscous
gels and then to solid materials

 Sol-gel preparation leads to the greatest possible homogeneous

distribution of the dopant ion in the host matrix.

 Products have high purity and homogeneity, ease of processing and

composition control

Sol-gel synthesis involving following steps

 Ageing
 Gelation
 Drying
 Densification
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 Hydrothermal treatment

 The hydrothermal process including aqueous solvents as reaction medium is

eco-friendly since it is carried out in a closed system and the contents can be
recovered and reused after cooling down to room temperature.

 The equipment and processing required are simpler and reaction is low energy
consumption,

 By controlling hydrothermal temperature and duration of the treatment, various

crystalline products with different composition, structure and morphology could
be obtained.

 Fine particle size can be obtained with more uniform distribution and high
dispersion either in polar and nonpolar solvents

 In this way the energy band structure becomes discrete and titania nanoparticles
exhibit improved optical and photocatalytic properties.

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 Sol-gel +hydrothermal

 Materials can be obtained with high purity

 Particle size can be reduced and controlled

 Highly crystalline material can be obtained

 Material with higher light harvesting character

 Phase formation can be decided before the heat treatment i.e, calcination

 Eco-friendly

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 2,4,6-Trichlorophenol
 Chlorophenols are deadly toxic compounds, present in wastewater which
mainly arise from chemical intermediates or by-products in petrochemical,
paper making, plastic, pesticidal and water disinfection

 PCDD/PCDF are the most toxic chlorinated substances which are 1000 times
poisonous than arsenic. Due to handling problem of these chemicals in the
laboratory, the model pollutant such as chlorophenol and chlorobenzene
which are having structural similarities with them are taken

 19 different chlorophenols have been listed by the US-EPA as priority

pollutants

 Among these 2,4,6-trichlorophenol is one of the most vulnerable water

pollutants, which causes serious damage to the vital organs of human beings .
Thus, the removal of the chlorophenols from the waste water is highly
imperative.

 In this work, we have used a modified sol-gel followed by hydrothermal

treatment to synthesize metals (Fe, Cr, Co and Zr ) doped titania and used
them for the oxidative degradation of 2,4,6-TCP.
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 Experimental
 Pure titania was synthesized by sol-gel, hydrothermal and combination of
these two methods

 Parameters affecting synthesis such as Water : Ethanol ratio, hydrothermal

temperature and duration were optimized for effective synthesis.

 Doped titania were synthesized by sol-gel + hydrothermal method with

various weight percentage of loading (0.3, 0.5, 0.7 and 1wt%).

Reactor

 Slurry photoreactor

 8x8w lamp

 Emits 365nm wave length

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Procedure adopted------Sol-gel

12
Procedure adopted----hydrothermal

13
Procedure adopted----sol-gel + hydrothermal

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Effect of synthesis parameters

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 XRD pattern of (a) sol-gel (b) hydrothermal and (c )
sol-gel + hydrothermal synthesized titania
 In sol-gel, hydrothermal and
combination of sol-gel and
hydrothermal methods, only
sol-gel
Hydrothermal
anatase phase is formed.
sol-gel + hydrothermal
 Particle size and Crystallinity of
titania with different method of
Intensity (a.u)

synthesis follows the order sol-

gel< sol-gel + hydrothermal <
hydrothermal.
 Most of the particle are in same
size in both the hydrothermal
and sol-gel + hydrothermal
20 30 40 50 60 70 80 methods
2 Theta (degree)  In sol-gel restriction of particle
size within a range is not
possible. Particles are in wide
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Histogram of (a) sol-gel (b) hydrothermal and (c)
sol-gel + hydrothermal

(a) (b)

(c)

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 UV-Vis DRS spectra of (a) sol-gel (b) hydrothermal and
(c )sol-gel + hydrothermal synthesized titania
2  Titania synthesized by sol-gel (11nm),
sol-gel + hydrothermal hydrothermal (24 nm) and
1.6
sol-gel
hydrothermal
combination of these two methods
(17nm) show different electrical and
1.2 optical properties
Absorbance

0.8
 Titania synthesized by combination of
sol-gel followed by hydrothermal
0.4 show red shift while titania
synthesized by sol-gel and
0 hydrothermal separately show blue
200 300 400 500 600 700 800
shift
Wavelength (nm)

 From the above observation it can be

concluded that the particle size greatly
influenced on the electrical and optical
properties of the catalysts
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 XRD pattern of metals (Fe, Cr, Co and Zr) doped
titania

Co/TiO2 Cr/TiO2
Fe/TiO2 Zr/TiO2  Metals doping does not alter the
phase formation
 Metal doping reduces the crystallite
Intensity (a.u)

growth
 There is no peak observed for the
formation of metal oxide
 Particle size was calculated using
scherrer equation. Among the
20 30 40 50 60 70 80 metals doped, cobalt doped titania
having the smaller size.
2 Theta (degree)

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 UV-Visible DRS of metals doped titania

1.8  Cr, Fe and Co doping shifted the

1.6 Cr/TiO2 Co/TiO2 wavelength maximum towards
1.4 visible region. Whereas
Fe/TiO2 Zr/TiO2
1.2
zirconium showed blue shift
when compared with bare
Absorbance

1
titania.
0.8
0.6
 The band gap energies of Co, Cr,
Fe and Zr are 2.85, 2.92, 2.95
0.4
and 3.18 eV respectively.
0.2
0
 Among the different metal
200 300 400 500 600 700 800 doping, cobalt doped titania
shows an extra absorption at
Wavelength (nm)
500-700nm.

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 EPR spectral analysis of metals doped titania

(A) (B)  Spectra shows the EPR signal of

(A) Fe/TiO2 (B) Co/TiO2 and
(C) Cr/TiO2 catalyst respectively

 All the spectra show only one signal

(C) corresponding to (A) Fe3+, (B) Co2+
and (C) Cr3+ in anatase matrix
respectively.

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Transmission Electron Microscopy

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 Extent of degradation

 Among the different metal ion doped,

100 cobalt doped titania which is having
Co/TiO2 Fe/TiO2 smaller particle size and increased
80 Zr/TiO2 Cr/TiO2
wavelength absorption showed higher
activity
60  Iron and chromium doped titania are
%of Concentration

almost same in catalytic activity.

40 Among these two, iron doped titania
shows better activity.
20  Zirconium doped titania showed poor
catalytic activity when compared with
0 others. Wavelength maximum shifts to
0 30 60 90 120 150 180 blue line of the spectrum as zirconium
Time in minutes concentration is increased may be the
reason for this.
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 Extent of mineralization
1.2
Co/TiO2 Fe/TiO2
1
Cr/TiO2 Zr/TiO2
0.8
C/Co

0.6

0.4

0.2

0
0 30 60 90 120 150 180

Time in minutes

 Mineralization profile follows the same order with degradation profile

 Rate of Mineralization follows the order: Cobalt > Iron > Chromium >
Zirconium

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 Conclusion
 Sol-gel method can be used for the preparation of nanosized titania with
high purity but size restriction is not possible anywhere in the preparation
procedure. Sol-gel method does not produce phase purity

 Titania synthesized by hydrothermal method have more uniform

distribution in particle size. High purity and reduced particle size is not
possible in hydrothermal methods.

 Titania synthesized by combination of these two methods have the

advantages of sol-gel and hydrothermal methods and overcame the
disadvantages.

 Catalysts synthesized by combination methods have lower band gap

energy and controlled particle size ( 15-20 nm) than sol-gel and
hydrothermal methods.

 These observations conclude that titania synthesized by the combination

method is the opt one for photocatalytic activity.

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 Iron, cobalt and chromium doping shifts the wavelength absorption
maximum in to visible region whereas zirconium doping shifts towards UV
region.

 From the XRD patterns of metal doped titania, metal doping doesn’t affect
the phase formation of core species i.e titania. But restricted the crystallite
growth and thereby reduced the particle size.

 From the EPR spectra, all the dopant ion present in anatase matrix and not
in the surface is confirmed.

 From the TEM histogram, the uniform distribution of particle size acquired
by combination methods is confirmed. From the TEM picture, particle size
of all the doped catalyst is ranging between 15-20nm is observed.

 Cobalt doped titania have smaller particle size and higher wavelength of
absorption than the other doped titania.

 Above synthesized catalysts was tested for the photocatalytic oxidative

degradation of 2, 4, 6- Trichlorophenol in aqueous suspension.
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 From the degradation and mineralization profiles, cobalt shows higher
catalytic activity than other doped catalysts.

 Iron and chromium doped titania shows almost similar activity profile, but
iron doping shows higher catalytic activity.

 Zirconium doped titania which showed blue shift as the metal content
increased shows poor catalytic activity.

 On comparison with other dopant ion, cobalt shows higher catalytic activity
even at higher concentration (1 wt%).

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