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TiO2 particles - Fundamentals

and Applications as photocatalyst

Most information taken from TiO2 photocatalysis


– Fundamentals and Applications by Akira
Fujishima, Dr. Kazuhito Hashimoto, and Dr.
Toshiya Watanabe

TiO2 particles
• Used in paints and cosmetics
• Consumption exceeds 3 million tons
• a semiconductor – can be chemically
activated by light energy
• Paint chalking – stabilisers or/and additives
are added to solve the problems

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17.5 cm
Synthesis and Functionalisation

Nanomagnetite
WO3

TiO2
WO3 Pt/WO3

Linkers

Protective
Environment
Layer
Magnetic
Energy
Fluorescent
Core
Health Care
Signaling

Antigen
Detection
Biocompatibility
Shape
Recognition TiO2

Fresh Air
Clean Water

Self cleaning
super - surface
Harnessing Solar Energy through
Photocatalysis
Renewable
Energy

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Photocatalyst
sun
light

Decomposition by
powerful oxidising Self cleaning
action
Self sterilising

TiO2

Solar Induced Photocatalysis


• Need for ecologically clean chemical
processes and technology - solar induced
photocatalysis
• Low quantum efficiency- less than 1% of
the input electrical energy is effectively
utilised by UV-photocatalytic systems
.

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• Two requirements:
Substance to be degraded need to be brought
into contact with TiO2

Light needs to reach the surface

TiO2 Semiconductor
Photocatalyst
Electron
e- + O2 → O2-•
O2-• ⇒ OH•
CB
Organic matter oxidation
UV
Org + h+ → Intermediates → CO2 + H2O
VB
Org + OH• → Intermediates → CO2 + H2O
Light less than
380nm
Hole
h+ + H2O → H+ + OH•
h+ + OH- → OH•

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• Electrons and holes are generated
• For metals, these two are immediately
recombined
• On semiconductors, they survive for longer
periods of time
• Holes have greater oxidising power than the
reducing power of the excited electrons.

• Destructive power is stronger than chlorine,


ozone, hydrogen peroxide – so in theory it
can decompose almost all hydrocarbon
organic compounds to C, H, O
• Energy has been quantised - it means
regardless of the intensity level – energy of
each photon is the same
• Energy of photons of light – equivalent to
greater than 30,000 oC in thermal energy

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Germ Killer
• E.Coli
• Methicilin-resistant Staphylococcus aureus
(MRSA) – resistant to most commonly used
antibiotics
• Pseudomonas aeruginosa
• 1 hour illumination at 1000 lux – 99% of
the three bacteria are killed

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Antimicrobial Tiles
• TiO2 was applied onto the tiles by spray
coating – The tile is then heated at 800oC.

• For tiles where the light is harder to reach –


could deposit metal such as Ag
(antimicrobial metal particles) onto the tiles
. Ag metals could be deposited onto the
TiO2 by illumination.

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• After installing photocatalytic tiles –
numbers of bacteria on the wall surfaces
and number of airborne bacteria dropped.
• Could be used to reduce the unpleasant
odour from public toilet facilities – (pets
and rats)
• In addition to its antibacterial properties, it
has the ability to combat viruses, molds and
algae.

• Decomposing Endotoxin as well as killing


the bacteria
• Endotoxin – toxin released when E.coli
cells die – can cause more problems than
E.coli itself

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100
Dark (P25)
80 UV
E.Coli Survival (%)

P25
60 HPC
MPC
40

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0
0 10 20 30 40 50 60
Time (min)

Self cleaning transparent glass


Development:
• Coating a transparent TiO2 thin film on
glass
• When coated onto a common sheet glass
(soda-lime glass) – activity drops
• WHY?????

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The one that works…………

TiO2

Na+
SiO2
Na+ Na+ Na+ Na+
Na+ Na+ Na+ Na+

Sodium
lime glass

Other examples
• Ventilation fan - 0.1mg/cm2/day – the use
of black-light UV could decompose the
grease to CO2.
• Tunnel light
• Exterior materials

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Antifogging
Typical contact angle between water and inorganic
materials, such as glass (20o to 30o)
• On a plastic – 70o to 90o
• On silicone resin and fluororesins – angle is higher
than 90o
• Some water absorbing surfaces or activated with
surfactants or detergents could show contact angle
lower than 10o

• Superhydrophilicity – completely non water


repellent
• A thin film of titanium dioxide combined with
suitable additives – initial contact angle of water
several tens of degrees
• UV illumination – water droplet spread out flat –
giving contact angle approaching zero –
superhydrophilicity
• When light is off, still retain contact angle of a few
degrees for water for a few days – and eventually
contact angle increases – hydrophobic again
• Superhydrophilicity properties can be recovered by
exposing it with UV light.

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Bare Glass

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TiO2 coated glass

Anti Fogging

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• How does it work? - Postulation – not exact
answer

When TiO2 is illuminated with light – have


“oxygen defects” on the surface of TiO2

Enabling water molecules to be attached on to


the Ti structure

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Superhydrophilicity vs
Photocatalytic technology
• Photocatalytic technology – decompose the
dirt, odourous compounds by oxiding the
compounds
• Superhydrophilicity – altering the properties
of the surface by photocatalytic action
• Both need “light”

Air purification
• Decomposition of malodorous pollutant (of
low concentration – ppm levels)
• Indoor air cleaners
• Oxidation of SOx and NOx
• Limited to 0.01 ppm to 10 ppm levels
• Can be integrated with other process such as
adsorption

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Water Purification
• Treating recalcitrant organic matters in low
concentrations
• Not suitable to treat high concentration of
organic matters
• Suitable as a polishing method
• Application is still limited due to recovery
of the photocatalyst

Magnetic TiO2 Photocatalyst


P

P
P

MAGNET

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Magnetic Photocatalyst Synthesis

Magnetite Sodium
in TMAOH Silicate
80°C

Silica Coated
Titanium
Magnetite
Tetrachloride
(SM)
6 h hydrothermal at 90°C
1 h calcination at 450°C

Magnetic
Photocatalyst (TSM)

Transmission Electron
Microscopy
Magnetite Titania

Silica
SiO2 coated Fe3O4 40 mM TiCl4

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Water splitting
• Electrolysis – (High School Chemistry
experiments)
– two electrodes (cathodes and anodes)
– A little salt, acid
– Apply a direct current
– What did you see?

• Honda and Fujishima – did experiments


which water splitting can be carried out
without the need of electricity
• Problems :
– low H2 generation
– requires artificial light to be effective – ie extra
energy

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• Another application of TiO2 is
Dye sensitised solar cells (DSC)

• More applications out there perhaps you


will be the engineer to put them into reality

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