Application of nanotitania in water treatment

Dr. Radwa A. Elsalamony

Egyptian Petroleum Research Institute
EPRI

Titanium dioxide, TiO2

Titanium dioxide, also known as titanium(IV) oxide or titania,
is the naturally occurring oxide of titanium, chemical formula
TiO2.
When used as a pigment, it is called titanium white, Pigment
White 6 (PW6), or CI 77891.
Generally it is sourced from Ilmenite ore, Titanium dioxide occurs
in nature as well-known minerals rutile, anatase and brookite.
It has a wide range of applications, from paint, sunscreen to
food coloring. Photocatalyst, Electronic data storage
medium, It can be employed for solar energy conversion
based on dye polymer.
Synthetic single crystals and films of TiO2 are used as a
semiconductor,
Dr. Radwa A. Elsalamony
and also in dielectricEPRI
mirrors due to the high
refractive1index of TiO2 (2.52.9).

Photocatalyt
ic activity of
TiO2

Dr. Radwa A. Elsalamony

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2

Photocatalysis refers to the acceleration of the rate

of chemical reactions (oxidation/reduction) brought about by the
activation of a catalyst, usually a semiconductor oxide, by
ultraviolet (UV) or visible radiation.
History dates backs to 1972, when Fujishima and Honda
discovered that water can be split, i.e., simultaneously oxidized
to oxygen and reduced to hydrogen, when a bias potential is
applied to an illuminated TiO2 single crystal electrode. This
remarkable discovery marked the onset of photo induced redox
reactions on semiconductor surfaces. It was soon realized that
such redox processes could be utilized for environmental
cleanup applications, when Frank and Bard, in 1977,
showed the photocatalytic oxidation of CNand SO-3 using
different semiconductor materials like TiO2, ZnO, CdS, Fe2O3
and WO3.
Thus, a brilliant start in TiO2 photocatalysis was followed by
Dr.
Radwa
A. Elsalamony
EPRI metal ion doped TiO2
some
notable
developments including,
(1994), 3super-hydrophilic TiO2films (1997), anion doped

Mechanism of UV
Photocatalysis

Dr. Radwa A. Elsalamony

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TiO2 + hv h+ + eThe photo-induced hole can oxidize a donor molecule

(D) adsorbed on the TiO2 surface.
D + h+ D +
The electron in the conduction band can reduce an
acceptor molecule (A).
A + e- AThe strong oxidation power of the hole enables a
one-electron oxidation step with water to produce a
hydroxyl radical (OH).
H2O + h+ OH + H+
Oxygen can act as an electron acceptor, and be
reduced by the promoted electron in the conduction
band to form a superoxide ion (O2-). The
superoxide
ion is a highly reactive
particle, able to
Dr. Radwa A. Elsalamony
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oxidize5 organic materials.

Super-hydrophilicity
The superhydrophilic effect is also caused to the
production of holes because the electrons tend to
reduce the Ti(IV)-cations to Ti(III)-ions
e- + Ti+4 Ti+3
and the holes oxidize the O2- anions.
4h+ + 4O2 - 2O2
This process leads to ejection of oxygen atoms
and creation of oxygen vacancies at the TiO2
surface.
These vacancies are covered by water molecules
that
are
forming OH-groups that
Dr.
Radwa
A. Elsalamony
EPRIcreate the
6
superhydrophilic
effect.

Why Nanosized TiO2??

The two most important properties of a nano material, which

makes it superior to other microscopic or macroscopic particles
for applications in catalysis, are
(i) the high surface to volume ratio, and
(ii) the quantum confinement at the nano scale.
The first property results in catalysts with high surface area and
high porosity, which ensures enhanced reaction rates due to the
high level of interaction of the reactants with the active sites.
The second property governs the transport of electrons and
holes from the bulk to the surface of the material, whose length
scale is also of the order of a few nanometers (called as electron
Bohr radius).
Moreover, for photo-applications, the catalyst should absorb,
and not block or scatter, incident radiation, and generate
charge carriers by band gap excitation.
This is possible only with nano-sized semiconductor materials
with suitable band gap energy. Therefore, owing to the enhanced
molecular transport properties at the surface, it is evident that

Nano-TiO2photocatalysts have been synthesized in

different shapes and morphologies, which include,
nanoparticles,. nanorods, nanotubes, nanopillars and
nanowire arrays, nanobowls, nanowhiskers, aerogels,
nanosheets, opal and inversed opals

Dr. Radwa A. Elsalamony

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Solutio
n
phase

Gas
phase
Synthes
is of
TiO2

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sol method
(nonhydrolytic
sol-gel)

Hydrotherm
al synthesis

sol-gel
method
Solution
phase

Precipitati
on method

Solvothermal
synthesis

Combustion
synthesis

Micelle and
inverse
micelle
method

Microwave
synthesis
methodologi
es

Electrochem
ical
synthesis
Solution
phase

Sonochemical
synthesis

Chemical
vapor
depositio
n (CVD)

Gas
phase

Physical
vapor
depositio
n

Spray
pyrolysis
depositio
n

The final properties of the TiO2 nanoparticles like

the phase composition (anatase : rutile), particle
size, porosity, surface area, band gap and
surface hydroxyl content can be tailored by
varying the reaction conditions like:
the precursor compound (TiCl4, titanium(IV)
isopropoxide, etc.),
hydrolyzing agent (in the case of sol-gel synthesis),
fuel (in the case of solution combustion synthesis),
molar composition of the reactants,
reaction temperature,
reaction time (ageing time),
calcination temperature and
presence of gas atmosphere (air, Ar, NH3)
Dr. Radwa A. Elsalamony
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Preparation of
TiO2

Precipitation
Method

*Effect of
precursor
*Effect of
calcinations
temperature,
*Degradation
of Black-b dye

By gamma ray
irradiation

*Effect of
preparation
method,
*Degradation
of
p-nitrophenol

Preparation of
Ru/TiO2

*Effect of
metal loading,
*Degradation
of 2chlorophenol

Photo-catalytic Apparatus

Dr. Radwa A. Elsalamony

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Preparation of TiO2 by
Precipitation Method
Titanium tetrachloride (TiCl4, 15%) was used as a precursor
for preparing nanosized TiO2 powder by precipitation method
using ammonia solution as precipitating agent and ethanol
as dispersing agent.
25 ml TiCl4 was dissolved in 20 ml distilled water in an icewater bath. The titanium solution was then slowly mixed with 30
ml distilled water and 20ml ethanol under vigorous stirring,
then ammonia solution was added dropwise until pH 9. During
the ammonic addition, an intensive precipitation occurred.
After the solvent was evaporated at 80C for 24h, the
precipitates were dried at 300C for 2h to remove NH4Cl, then
Dr. Radwa A. Elsalamony
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calcined
in an air stream for 4h.
18

Preparation of TiO2 by
"Sol-gel Method
A second method for TiO2 nanoparticles
preparation "sol-gel method. Ti(OH)4 sol was
prepared by mixing 5ml titanium
tetraisopropoxide (Ti(OCH(CH3)2)4, 99.5%, Aldrich)
with 50 ml isopropanol (Adwic, A.R.) under vigorous
stirring.
The mixture was then allowed to undergo partial
hydrolysis at room temperature by drop-wise
addition of 5ml isopropanol and 2ml HCl (pH 3-4)
with constant stirring.
Ti(OH)4 gel was dried at 100 oC overnight then
Dr.
Radwa A. Elsalamony
calcined
in an air stream for 4hEPRI
each.
27

Textural and structural properties of

TiO2 samples
Phase ratio Crystal size
a
(nm)
Sampl
es

A 500

10
0

A 600

95

A 700

83 17

B 500

64

19

17

B 600

52

48

DA

28.
5
16.
6
37.
8
17.
1
25.
8

DR

DB

17.
3
46.
4
34.
9.7
3
32.
1

Specific
surface
areab
(m2/g)

Pore
Total
Radiu
pore
s
Volume
c
Dv (r)c
(nm)
(cc/g)

69.5

4.1

0.271

54.3

6.9

0.325

46.6

6.9

0.19

61.3

3.1

0.135

21.7

3.9

0.061

Hazardous
Effect of
Dyes
The effluent water of many industries, such as textiles,
leather, paper, printing, cosmetics, etc., contains
large amount of hazardous dyes.
These compounds can cause changes in biological
cycles, particularly in the photosynthesis process. These
dyes can block both sunlight penetration and
oxygen dissolution, which are essential for aquatic life.
Moreover,
some
of
these
compounds
can
be
carcinogenic Presence of color and color-causing
compounds has always been undesirable in water for any
use. Thus there is a considerable need to treat these
colored effluents before discharging them to various water
bodies.
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Black-b Dye

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TiO2 Anatase nano-powder Prepared

by
a Gamma
Ray
Irradiation
Ti(OH)
gel was obtained
at room
temperature by the addition of
4

concentrated ammonia solution (35% NH3) dropwise to a

vigorously stirred dilute solution of TiCl4 (Fluka 15%) until a pH 9
was attained. The ammonia solution was added dropwise to
prevent particle adhesion and sudden grain growth of particles.
The white hydrous Ti (OH)4 solution was irradiated under a
60
Co source (NCRRT) with 30 kGy and at a dose rate of
3.3476 kGy/h. The reactant solution was stirred mildly while
irradiating it, so as not to become agglomerated with each other.
The particles were then washed rigorously and repeatedly with
bidistilled water to remove any remaining impurities. After the
solvent was evaporated at 100C for 24 h, the precipitates
were dried at 300C for 2 h to remove NH4Cl, and then
Dr. Radwa A.
calcined
atElsalamony
500C for 4 h to get titaniaEPRI
TiO2.
25

Preparation of Cu-doped TiO2

Cu-doped TiO2 nanoparticles containing 0.5wt% Cu (II) ion
dopant were synthesized via a co-preceptation.
Briefly, 6 mL ethanol solution of 0.5 M of Cu(NO3).6H2O was
added dropwise to TiCl4 solution under stirrering. The pH value
of the reaction solution was adjusted to ca. 9 by ammonia.
Then the blue and dense colloid was formed. The colloid was
stirred gently for 3h, and then washed rigorously and repeatedly
with bidistilled water to remove any remaining impurities.
After the solvent was evaporated at 100C for 24 h, the
precipitates were dried at 300C for 2 h to remove NH4Cl, and
then calcined in an air stream of 400C for 4 h.
Dr. Radwa A. Elsalamony
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Dr. Radwa A. Elsalamony

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Textural and structural properties

of TiO2 Catalysts
Total
pore
Acidity
Volum
mol/g
e
m
(cc/g)

Samples

Crystal
size of
TiO2
(nm)

Specific
surface
area
(m2/g)

Pore
Radius
Dv (r)
(nm)

-TiO2

22.35

127.1

1.24

0.334

6055

Cu/-TiO2

16.91

115.8

1.13

0.324

6334

Cu-TiO2

18.62

60.8

1.01

0.476

13343

Dr. Radwa A. Elsalamony

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P-Nitrophenol
Phenolic compounds are among the most
refractory pollutants present in industrial
wastewater.
Their high stability and solubility in water
represent the main obstacles to complete
removal.
Purification of wastewater contaminated with
these pollutants is very difficult since they
are resistant to conventional treatment
techniques.
The p-nitro phenol which are used in various
industries like textiles, pulp, paper, leather,
wool, silk etc. ultimately enter into aquatic
system as effluent and create various
environmental problems.
Dr. Radwa
A. Elsalamony
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The
p-nitro
phenols exert various biochemical
30
and morphological effects on plants and

4-NP concentration vs. irradiation time

using different photocatalysts under UV
irradiation

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The apparent first-order kinetics

for the photocatalysts

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Preparation of mesoporous TiO2

For mesoporous TiO2materials, 3.6 g of tetrabutyl
titanate was dissolved in absolute ethanol with a
weight ratio of 1/7 under stirring. The resulting
suspension was stirred for 3 h at room temperature,
and then 5 ml of deionized water was added
dropwise.
The solution was stirred for an additional 2 h,
followed by evaporation at 150 oC. The obtained solid
product was exhaustively washed with deionized
water and ethanol, dried at 80 oC overnight, and then
calcined at 500 oC for 3 h.
Dr. Radwa A. Elsalamony
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Preparation of Ru/TiO2 samples

Ru/TiO2 samples with Ru loading ranging from 0.2 to
0.8 % (w/w) using TiO2was prepared by incipient wet
impregnation method with an aqueous solution of
ruthenium trichloride trihydrate. An appropriate
amount of the precursor, so as to obtain the desired
Ru concentration in TiO2, was mixed with TiO2in
distilled water.
The resulting slurry was subjected to continuous
stirring at ambient temperature, and subsequently
dried in an oven at
110 oC for 10 h. The solid
residue was then crushed and calcined in air for 5 h.
Dr. Radwa A. Elsalamony
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Textural and structural

properties of TiO2 and Ru/TiO2
samples
Crystal
size
Samples

Anatase:
Rutile

TiO2

70 : 30

0.2 Ru/ TiO2

66 : 33

0.4 Ru/ TiO2

57 : 43

0.6 Ru/ TiO2

0.8 Ru/ TiO2

DA

DR

33.5 50.6

Specific
surface
area
(cm2/g)

Pore
Total pore
Radius Dv
volume
(r)
(cc/g)
(nm)

27.8

6.2

0.123

27

28.5

6.6

0.125

50.
6

23.4

7.9

0.107

66 : 34

19.4 23.7

24.7

6.6

0.12

63 : 37

33.6 67.5

22.9

6.1

0.094

23.
7
28.
8

2-Clorophenol
They can be found in ground waters, waste waters
and even low pollution levels. They might produce
disagreeable taste and odor to drinking water at
concentrations below 0.1 g-1 and adverse effects
on the environment.
Chlorophenols are thus found on both the U.S.
Environmental Protection Agency list and the
European community red list of priority.
Cps are into the environment as a result of several
man-made activities. Because of their broad
spectrum antimicrobial properties, Cps has been
used as preservative agents for wood, paints,
vegetable
fibers
and
leather
and
as
disinfectants. In addition, they have been widely
employed in many industrial processes as synthesis
intermediates or as raw materials in the
manufacturing of herbicides, fungicides, pesticides,
insecticides, pharmaceuticals, dyes, and in the
manufacture
of paper Cps may be also generated
Dr. Radwa A. Elsalamony
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as by-products
during waste incineration, the

Effect of Ru doping concentrations on the 2CP

photodegradation using UV irradiation

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Formation of chloride ions during the

photodegradation of 2CP using UV light

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Formation of acetate ions during the

photodegradation of 2CP using UV light

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THANK
S

Dr. Radwa A.
Elsalamony
EPRI