Photocatalysis

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Environmental Pollution
Atmosphere pollution
Green house effect (CO
2
)
Acid rain
Water pollution
Soil pollution

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Air Pollution
Smog
Acid rain
Burning of fossil fuels
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Water Pollution
Waste water from textile industry
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Soil Pollution
Contaminated soil
Pesticides buried with strong odor
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Advanced Oxidation Technology
O
3
/H
2
O
2
O
3
/UV
O
3
/CATALYSTS
Fenton reaction (H
2
O
2
/Fe
2+
)
Photo-Fenton reaction (H
2
O
2
/Fe
2+
/UV)
H
2
O
2
/UV
O
3
/H
2
O
2
/UV
UV/TiO
2
(Photocatalysis)
OH
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Natures CleanerOH
In Atmosphere:
1) O
3
+ h( < 320 nm) O
2
(1g) + O (1D)O
(1D) + H
2
O 2OH
2) HONO + h( < 400 nm) NO + OH
[OH]
avg
10
6
radicals cm
-3
(< 0.1 ppt!!)
In Water:
1) Fe
III
(OH)
2+
(aq) + h(< 400 nm) Fe
2+
(aq) + OH
2) NO
3
-
(aq) + h NO
2
+ O
-
O
-
+ H
2
O OH
-
+ OH
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Oxidation Potentials of Common Chemical
Oxidants
Oxidation Potentials (V vs NHE)
HO 2.80
O
3
2.07
H
2
O
2
1.78
HO
2
1.70
ClO
2
1.57
HOCl 1.49
Cl
2
1.36

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TiO
2
Photocatalysis-the environmental super
hero!
The recent years has seen the development of a relatively new
process called the Photocatalysis (photocatalyst) .
In the year 1972, Fujishima and Honda discovered titanium
dioxide (TiO
2
) has been the primary photocatalysis.
When photocatalyst are exposed to UV lights, REDOX reaction
will then occur at the surface of the catalyst and generates

OH,
Hydroxyl Radicals and O
-
2
, Superoxide Ions. These 2 powerful
oxidizing agents will then disintegrate and rearrange the structure of
the VOCs (Volatile Organic Compounds) and convert them into CO
2

and H
2
O.
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What is Photocatalyst ?
A catalyst that accelerates photoreaction does not change in itself or
being consumed in the chemical reaction.
It has strong oxidation and decomposition strength.
Photocatalytic activity (PCA) is the ability of a material to create an
electron hole pair as a result of exposure to ultraviolet radiation
Chlorophyll of plants is a typical natural photocatalyst. The difference
between chlorophyll photocatalyst to man-made nano photocatalyst,
usually chlorophyll captures sunlight to turn water and carbon dioxide into
oxygen and glucose, but on the contrary photocatalyst creates strong
oxidation agent and electronic holes to breakdown the organic matter to
carbon dioxide and water in the presence of photocatalyst, light and water.
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Photosynthesis vs Photocatalysis
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How Does Photocatalyst Work?
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Principle of TiO
2
Photocatalyst

OH

OH
CB
VB
-0.5V
+2.7V
TiO
2
e
-
/
H
+

H
2
O
2

O
2

OH
-
OH
.
/OH
-

O
2
-
UV light (< 387.5nm)
3.2eV
O
2
-
/O
2

e
-

h
+

H
+
(hi nc)
ng nt t Th oxi ha kh ca O
2
-
v OH
-

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Important Reactions during Photocatalyst
TiO
2
UV
h
+
+ e
-
e- + O
2

O
2
-
O
2
-
+ 2H
+
+ e
-
H
2
O
2

H
2
O
2
+ O
2
-

OH + OH
-
+ O
2
h
+
+ H
2
O
OH + H
+
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Photocatalysts & their band gap energy

Semiconductor
Valence
band
Conductance
band
Band gap
(eV)
Band gap
wavelength
(nm)
SnO
2
+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
TiO
2
+3.1 -0.1 3.0 380
GaP +1.3 -1.0 2.3 540
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Common Semiconductor Photocatalyst
TiO
2
Why TiO
2
?
Strong oxidizing power of valance band hole
Excellent chemical and photochemical stability
Availability: One of top 50 chemicals
Band gap: 3.2 eV
Only active under UV light (4% of the incoming solar
energy)
Low cost, low toxicity, high turnover rate and wide substrate
activity make TiO
2
a useful catalyst.

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Three Parameters Affecting Photocatalytic Activity
Light absorption Property
Light absorption spectrum and coefficient
Rate of reduction and oxidation of reaction substrate
by e
-
and h
+
, respectively
Rate of e
-
and h
+
recombination
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Enhancement of Photocatalytic Activity
Enhancing interfacial charge-transfer
Improving charge separation
Inhibiting charge carrier recombination

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Approaches to Improve the Activity of TiO
2
To enlarge band gap by reducing crystal sizes
(quantum size effect)
To increase surface area (mesoporous structure)
To reduce crystal defects ( high crystallinity )
To dope metal ions
To deposit noble metal nanoparticles
To couple two kinds of semiconductors

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Hot Research Topics of Photocatalysis
How to enhance the efficiency
Preparation of nanostructured photocatalysts
Extension of absorption of TiO
2
to the visible region
Design of novel non-titania based visible Light
photocatalysts
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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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Preparation Methods of Nanostructured TiO
2
Thermal decomposition method
Sol-gel method
Microemulsion method
Hydrothermal (or solvothermal) method
Combustion method
Other methods
microwave
nonhydrolytic
sonochemical
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Advantages of Using Photocatalyst
Degradation of pollutants at ambient air
and temperature
Adapted for a large range of pollutant
Build with easily available materials and
by mean of well-known techniques
Economical, cheap and low energy
consumption
Excellent transparent and strength,
possible for coating

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Cc Phng Php Ch To Mng Mng
Function of Photocatalyst
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Applications of photocatalyst air purification
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Applications of Photocatalyst
Photocatalytic superhydrophilicity technology, e.g.. anti-fogging
and self-cleaning properties

Oil on the super-hydrophilic surface is easily removed by
soaking the material in water

Hydroxyl radicals kills bacteria and breaks down odor-causing
organic compounds
Sollar cell


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Super-hydrophilic
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Suggested applications of super-hydrophilic technology

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Division Function Application
Materials for a road
Cleaning easiness
Tunnel lighting, Tunnel wall,
Clear soundproof wall
Self Cleaning by a rainfall
Traffic sign, Lightning,
Soundproofed wall, Guardrail,
Decorative laminated panel and
Reflector on a read
Anti-fogging property Road mirror
Materials for a house
Cleaning easiness
Parts of a Kitchen, a Bathroom and
Interior furnishings
Self Cleaning by a rainfall
Exterior tiles, Siding boards,
Window, Sash, Screen door, Gate
door, Roof, Sun parlor, Handrail of
a verandah
Anti-fogging property
Mirror of a Bathroom and a
Dresser
Accelerated drying Toilet, Window, Bathroom
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Materials for a tall
building
Self Cleaning by a rainfal
Window, Sash, Curtain wall,
Painted steel plate, Aluminum
panel, Tile, Building stone,
Crystallized glass, Glass film
Materials for a store
Cleaning easiness Showcase
Self Cleaning by a rainfall
Signboard, Fingerpost, Show
window, The exterior of a store
Anti-fogging property Refrigerated showcase
Materials for
agriculture
Self Cleaning by a rainfall,
Preventing dewdrops forming
Plastic and Glass greenhouse
Materials for an
electric and
electronic instrument
Cleaning easiness Computer display
Self Cleaning by a rainfall
Upper glass of a solar cell,
Insulator
Preventing dewdrops forming
Heat exchanger of an air
conditioner, High-voltage cable
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Materials for vehicles
Self Cleaning by a rainfall
Painting and Coating of vehicles,
The outside of windows,
Headlights
Anti-fogging property
The inside of windows, Glass film,
Helmet visor
Preventing dewdrops forming
Side view mirror, Rearview mirror
and Windshield of a motorcycle,
Side mirror film
Materials for optical
instrument
Anti-fogging property Optical lens
Materials for medical
instruments and
supplies
Bio-compatibility Contact lens, Catheter
Daily necessities and
Consumer products
Cleaning easiness Tableware, Kitchenware
Self Cleaning by a rainfall Spray of anti-fouling coat
Anti-fogging property
Spray of anti-fogging coat, Anti-
fogging film
Paint All properties mentioned above Paint, Coat
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Self-cleaning glass
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Self-Cleaning Glass
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Bacterial Endospores
Complex shell structure
Core
Cellular components, DNA
UV resistance, SASP
Cortex
Heat Resistance,
Peptidoglycan, ~200nm
Inner spore coat
Acid resistant proteins,
20-40nm
Outer spore coat
Alkali resistant proteins,
40-90nm
Destruction of inner, outer spores coats and cortex required
for inactivation of spores
Exosporium
Outer Spore Coat
Inner Spore Coat
Cortex
Core
DNA
SASP
Germ Cell-wall
Exosporium
Outer Spore Coat
Inner Spore Coat
Cortex
Core
DNA
SASP
Germ Cell-wall
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Gram Negative Bacteria
E. coli has fimbriae
Fimbriae are long filamentous structure located on the surface of Gram
negative bacteria
Fimbriae may reduce the adsorption of TiO
2
coated multi-wall carbon
nanotubes due to steric hindrance
E. coli
Spores
Exosporium
Outer Spore Coat
Inner Spore Coat
Cortex
Core
DNA
SASP
Germ Cell-wall
Exosporium
Outer Spore Coat
Inner Spore Coat
Cortex
Core
DNA
SASP
Germ Cell-wall
35 VP04VL
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Mechanism of Microbial Inactivation by Photocatalysis
Photocatalyst should be in contact with the cell surface for
membrane damage to occur
TiO
2

TiO
2

TiO
2

OH OH
TiO
2

Leakage of
intracellular
constituents
Cytoplasm
Cell Wall
Cell Lysis
Possible reasons
Electrostatic interactions
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Systems Heat Radiation Chemical agents
(Mild) (Strong)
Photocatalysis
Water
Air
Surfaces
Food
Disadv. Cannot
kill all
microbes
Has less
penentration
power, High
intensity
reqd.
Toxic by
products
Toxic by
products
General Overview of Disinfection Techniques
Slow, less
efficient
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Anti- bacterial
1 hours later
3 months later
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