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Introduction

Environmental contamination, which is growing around the world or in our daily home life, is a serious
social problem not to be neglected.
Examples of such contamination can be endlessly listed as follows:
— Water pollution caused by industrial and household wastes
— Respiratory diseases caused by air pollutants such as SOx or NOx
— Room air contamination caused by organic compounds emerging from newly developed
building materials
— Dioxin emerging from resin materials during incineration

The fact that using energy to eliminate such environmental contamination increases emission of CO2
resulting in more global warming, however, leads us to a dilemma not to use energy to achieve our
anti-pollution goal.
Under such circumstances, we have come to the conclusion that we need a new material that
can gently harmonize the contaminated environment to restore original conditions by using natural
energy which is a part of the environment and low-cost energy supplied to our daily home life.
One solution to that problem is our proposal, Photo-catalyst.

What is Photo-catalyst?
Photo-catalyst produces surface oxidation to
eliminate harmful substances such as organic
compounds or nearby bacteria, when it is exposed
to the sun or fluorescent lamp.
By applying this principle to water treatment,
dissolving NOx in the air, or room air purification,
photo-catalyst can be used for various steps in
purifying a contaminated environment.
The function of the photo-catalyst can be
divided into five major categories as follows:

1. Purifying water
2. Preventing contamination
3. Anti-bacteria
4. Deodorizing
5. Purifying the air (dissolving NOx)

It might be well understood that the functions listed above are those which amplify or accelerate the
functions of the sun, or ultra-violet radiation. In this sense, it is not strange to regard titanium dioxide as a
photo-catalyst from the viewpoint that it works as the catalyst in accelerating the functions of the light.

What kind of light is necessary for the photo-catalyst?


As we explained, the photo-catalyst can be activated by light, so what kind of light is necessary for the
photo-catalyst? There are various sources of light such as the sun, incandescent lamps, fluorescent
lamps, light traps, disinfectant light, and so on. Those sources emit lights with different wavelengths
necessary for their specific purposes.
TiO2 is a semiconductor which turns to a high-energy state by receiving light energy, and
releases electrons from its illuminated surface. If the energy received at this stage is high enough,
electrons that were initially located in the so-called ‘valence band’ all jump up to the ‘conduction
band’.
Thus, the energy that makes electrons jump up is provided
by light, and this light energy is believed to be the energy of the
light’s wavelengths. Therefore, calculating from the height that
the electrons have to jump up, this light should have the same
wavelength as ultraviolet light.

E = hv E : energy h : Plank’s constant v : frequency


ν = c / λ c : light speed λ : wavelength
Therefore, E = hc /λ

Here, E is titanium dioxide 3.2 eV (3.2 eV = 3.2 × 1.6 × 10-19J), and if you substitute the determinate
values (c: 3.0 × 108m/s, h: 6.63 × 10-34J・s), you will find out that the necessary wavelength is approx.
380 nm, which tells us that the light needed to activate Photocatalyst is ultraviolet light.

Thin-film Photocatalyst
Titanium dioxide (TiO2) is a harmless substance widely applied in various fields such as cosmetics,
toothpaste, extenders for medicines, and coating. For these uses, TiO2 is usually supplied in the form of
powder. But in order to use TiO2 as an effective photo-catalyst for the 5 functions, powder is not an
appropriate form, for it may be blown off by wind or washed out by water, and when used to purify water,
it has to be separated from the water. Thus, a method to fix the powder has long been considered.
It is easy to fix powdery TiO2 with a binder, but if an organic binder
is used, the photo-catalytic reaction will destroy the binder itself.
Inorganic binder is not influenced by photo-catalytic reaction, but
only the powder exposed on the surface can work effectively despite
the total amount of powder contained in the binder.

In collaboration with National Industrial Research Institute of


Nagoya, we succeeded in developing the coating technology of
photo-catalytic thin-film that can cover all surface only with TiO2,
instead of using powderyTiO2.

This method, called the Sol-Gel method, uses titanium


alkoxide as a starting material. It is hydrolyzed to obtain sol,
and the sol is applied to coat substrate through such coating
methods as the dip-coating method, to form a film.
At this stage, the film is not the film of TiO2. So, the sol is
sintered along with the substrate to be crystallized, and thus
the film of titanium dioxide is formed.
Supercritical Technology
The Sol-Gel method, however has some weaknesses.
It is not effective for granular carriers or carriers with minute cracks because parts of sol fluid get
caught due to the capillary phenomenon.
The fluid left in minute pores or cracks turns into
powder after being sintered, which cannot form a film.
To overcome this weakness, the supercritical
sol-gel method was developed.
When a fluid reaches a certain level of
temperature and pressure, the boundary between
liquid phase and vapor phase is lost. This point is
called the critical point, and the area that exceeds this
point is called the supercritical region.
In the supercritical region, a fluid holds qualities of
both liquid and gas, which enables the fluid to move
freely in any minute spaces.
In this region, even a viscous fluid like
sol can be crystallized as thin-film in any
minute spaces, without causing the
capillary phenomenon.
When discharged from a nozzle into
atmosphere pressure, titanium dioxide
dissolved in supercritical fluid bursts into
deposition. The resulting deposited
substance is usually ultra-fine TiO2
particles. By providing them with
Sol-Gel method Supercritical sol-gel method
appropriate dissolution and deposition
Titania is caught in Fiber surface is coated with
conditions to escape through minute
minute cracks titania film and nothing remains
spaces, we succeeded in coating fibrous
between fibers. in spaces between fibers.
and microscopic substances with
thin-films.

Dye Sensitizing Titanium Dioxide Solar Battery


Supercritical fluid technology has been considered for application to the instantaneous decomposition of
persistent substances, as demonstrated with supercritical water. But because a great amount of energy
is consumed in this application, how this technology can be
applied to new materials is being considered today.
Under these conditions, we have worked on the
development of both titanium dioxide thin-film and
supercritical fluid in association with various national and
public research institutions, and succeeded in producing
unprecedented hybrid thin-film by combining the most
advanced features of the two technologies. As an
example of application of this technology, we are now
considering applying it to the production of dye sensitizing
titanium dioxide solar batteries.
The dye sensitizing titanium dioxide solar battery, which can
be priced low considering its conversion efficiency, is now
being developed as a new-generation solar battery, aiming
to be applied to exterior glass or house windows.