Self cleaning glass

The term “self-cleaning” means that the process of cleaning the glass is carried out or at
least greatly assisted by natural elements. “Self-cleaning” does not mean “maintenance
free” especially in heavily polluted environments. Self-cleaning glass is a specific type of
glass with a surface that keeps itself free of dirt and grime through photocatalytic
decomposition.

The first self-cleaning glass is based on a thin film titanium dioxide coating. The glass
cleans itself in two stages. The "photocatalytic" stage of the process breaks down the
organic dirt on the glass using ultraviolet light and makes the glass hydrophilic (normally
glass is hydrophobic). During the following "hydrophilic" stage, rain washes away the
dirt, leaving almost no streaks, because hydrophilic glass spreads the water evenly over
its surface. Titanium dioxide, particularly in the anatase form, is a photocatalyst under
ultraviolet light. Recently it has been found that titanium dioxide, when spiked with
nitrogen ions or doped with metal oxide like tungsten trioxide, is also a photocatalyst
under visible and UV light. The strong oxidative potential of the positive holes oxidizes
water to create hydroxyl radicals. It can also oxidize oxygen or organic materials directly.
1
It is generally believed that the photo-catalytic process occurs because light of sufficient
energy (e.g., greater than the optical band gap of Ti-oxides, 3–3.2 eV, i.e., 388–413 nm)
excites electrons in semiconductors from the valence band to the conduction band that
can either recombine and release great amounts of energy, or migrate to the surface
where they are available for reduction and oxidation reactions by charge transfer to
species adsorbed onto the semiconductor surface. The mechanism of TiO2 photo-
catalyzed reactions, shown in Figure 1, is that superoxide, O2•−, and specifically, hydroxyl
radicals, •OH, act as active reagents for the mineralization of the organic compounds.
2
The energy level at the bottom of conduction band determines the reduction ability of
photoelectrons and the energy level at the top of valence band determines the oxidizing
ability of photo-holes. If the adsorbed couples are considered to be water and dissolved
oxygen (H2O/O2), then water gets oxidized by positive holes and it splits into •OH and
H+. Since oxygen is an easily reducible substance, reduction of oxygen by the
photoelectron of the conduction band results in generation of superoxide radical anions
(·O2–), which in turn reacts with H+ to generate hydrogen dioxide radical (·HO2,
hydroperoxyl). On subsequent collisions with an electron to produce a hydrogen dioxide
anion, and then with hydrogen ion, a molecule of H2O2 is eventually produced. The above
chain of reactions and other reactions involved in producing reactive oxygen species
(ROS) such as H2O2, ·O2–, etc. and hydroxyl radical ·OH are described below:
1
H. Xu et al., 2006. Photo-catalytic oxidation of a volatile organic component of
acetaldehyde using titanium oxide nano-tubes, Journal of Nanomaterials, Vol. 2006,
Article ID 78902, pp 1–8.
2
S. Banerjee et al, 2006. Physics and chemistry of photo-catalytic titanium dioxide:
Visualization of bactericidal activity using atomic force microscopy, Current Science,
Vol. 90, No. 10, pp 1378-1383.
The photo-catalytic process begins with absorption of photon (hυ):
T iO2 + hυ → T iO2 (e − cb + h + b v )
Reactions involving the conduction band e-
•−
O2 + T iO2 (e − c b ) → T iO2 + O2
•−
T iO2 (e − c b ) + O2 + 2 H + → T iO2 + H 2 O2
T iO2 (e − cb ) + H 2 O2 → T iO2 + • O H + O H−
• −
O2 + H 2 O2 → • OH + OH − + O2
• −
O2 + H + → • HO2
( )
TiO2 e − cb + • HO2 → TiO2 + HO2
−

−
HO2 + H + → H 2 O2
2 • HO2 → O2 + H 2 O2
Reactions involving the valence band h+
O H− + h + b v → • O H
H 2 Oads + T iO2 (h + bv ) → T iO2 + • O Hads + H +
( )
TiO2 h + bv + 2 H 2 Oads → T iO2 + 2 H + + H 2 O2
TiO ( h ) + O H
2
+
bv
−
ads → T iO2 + • O Hads

Figure 1: Scheme of photo-catalytic process over TiO2

Insertion of •OH radicals into C−H bonds leads ultimately to the complete oxidation of
the organic substrate.
•
OH + O2 + C n Om H ( 2 n −2 m +2 ) →→→ n CO 2 + ( n − m + 1) H 2 O
Thus, illuminated TiO2 can decompose and mineralize organic compounds by
participating in a series of oxidation reactions leading to carbon dioxide and water.

Indeed, complete mineralization of a variety of organic compounds, such as phenols,

hydrocarbons, carboxylic acids, and chlorinated aliphatic and olefinic compounds, has
been realized. The heteroatoms contained in molecules are also completely oxidized,
nitrogen atoms in nitrate anions, sulphur atoms in sulphite anions, phosphate atoms in
phosphate anions.
2
The kinetics of the photo-catalytic reactions is governed by the following physical
parameters:
1. mass of photo-catalyst
2. wavelength of the irradiation photons
3. temperature
4. radiant flux
5. reactant concentration.

The direct proportionality of the initial reaction rate to the mass of catalyst indicates a
true heterogeneous catalytic regime. However, above a certain mass value, the reaction
rate levels off and becomes independent of the mass. This limit corresponds to the
maximum amount of TiO2 totally illuminated. The variations of the reaction rate as a
function of the wavelength, shown in Figure 3, follows the absorption spectrum of the
catalyst, with a threshold corresponding to its band gap energy. In the case of TiO2, this
threshold corresponds to 400 nm, i.e. near-UV wavelength. This fact is important for
outdoor self-cleaning materials. Indeed, about 4% of sunlight reaching the earth surface is
in this wavelength range corresponding to an irradiance of about 40W/m2, which is
enough to activate TiO2. Then, as a function of the temperature, the activity for photo-
catalytic reaction reaches a maximum level for a range of temperature. It corresponds to
room temperature (between 20ºC and 80ºC). This is due to the photonic activation of the
photo-catalytic system not requiring heating.
 Figure 3: Influence of the different physical parameters that govern the initial reaction
rate of a photo-catalytic reaction
3
Anatase TiO2 has a band gap of 3.2 eV. When excited by UV radiations, electron hole
pair is generated. Holes defuse to the surface and react with adsorbed oxygen, creating a
defect site namely Ti3+. It is known that such sites are favorable for dissociative
adsorption of water. A clean glass surface coated with TiO2, has -OH groups sticking out
of it which readily attach to water molecules through hydrogen bonding [The H2O
molecule is electrically neutral, but the positive and negative charges are not distributed
uniformly. The electronic (negative) charge is concentrated at the oxygen end of the
molecule, owing partly to the nonbonding electrons, and to oxygen's high nuclear charge
which exerts stronger attractions on the electrons. This charge displacement constitutes
an electric dipole. Since opposite charges attract, the partially positive hydrogen atom on
one water molecule is electro-statically attracted to the partially negative oxygen on a
neighboring molecule. This process is called hydrogen bonding]. 4The formation of
hydrogen bonds with hydroxyl ions on the surface of the TiO2 coating reduces the
hydrogen bonding between water molecules thereby reducing the surface tension of the
water molecules and decreases the contact angle between the water molecules and the

3
R. Wang et al,1999. Studies of Surface Wettability Conversion on TiO2 Single-
Crystal Surfaces, Journal of Physical Chemistry B, Vol. 103, pp 2188-2194.
4
M. Takeuchi et al, 2005. Mechanism of photoinduced superhydrophilicity on the
TiO2 photocatalyst surface, Journal of Physical Chemistry B, Vol. 109, No. 32, pp
15422-15428.
glass surface coated with TiO2. This causes the water to spread out evenly over the
surface, or to wet it.Oxygen adsorbed site is hydrophobic while dissociatively adsorbed
water makes the site hydrophilic, thus UV radiations change hydrophobic site to
hydrophilic one. However it is noted that oxygen adsorption is more stable state and
therefore when the exciting source namely UV radiations are removed and the material is
stored in dark, oxygen gets readsorbed so that the material recovers to its original state. If
water contact angle is an index of hydrophilicity, then it is reasonable that on UV
irradiation, the contact angle is lowered. In the dark, the material regains its normal state,
showing high contact angle.
5
At present, TiO2 thin films are prepared by a number of different methods, including
CVD, the sol–gel process, thermal methods and sputtering. Two physical constraints have
to be respected, the optical transparency of the glasses and the mechanical resistance of
the TiO2 layer. The first one is principally guaranteed by the very thin thickness of the
layer (less than 100nm and mainly around 10 nm). The second one could be reached by
using binder such as SiO2. Unfortunately, it has been demonstrated that the use of a
binder reduces the photo-catalytic activity of the layer. Consequently, the commercial
products, Activ from Pilkington Glass, Bioclean from St-Gobain and Sun-Clean from
PPG are only based on a very thin TiO2 layer on glass. The formation of by-products by
photo-catalytic oxidation of real stains is another concern.

It has been established that the composition of contaminant layers on outdoor glass
applications contains inorganic materials such as cations (Ca+, Na+, NH4+) and anions
(NO3− , SO42- ) which are not affected by photo-catalytic oxidation and organic materials
such as elemental carbon and particulate organic matter which are concerned by
oxidation. Many works were focused on the mechanisms of the photo-catalytic
degradation of thin layers of organic contaminants such as fatty acids, aldehydes or poly
aromatic hydrocarbons (PAH) that can be found in glass stains. These different works
identify many by-products during the photo-catalytic oxidation such as alkanes,
aldehydes and carboxylic acid compounds, all with a shorter carbon chains than the initial
pollutants and at very low concentration levels. However, in all cases, because of the
experimental set-up consisted in a batch reactor, the total mineralization of the pollutant
is reached. However, in an open space as the atmosphere, the behaviour may be different.

5
E. Puzenat, 2009. Photo-catalytic self-cleaning materials: Principles and impact on
atmosphere, The European Physical Journal Conferences, Vol. 1, pp 69-74.
References:
1. E. Puzenat, 2009. Photo-catalytic self-cleaning materials: Principles and impact
on atmosphere, The European Physical Journal Conferences, Vol. 1, pp 69-74.
2. H. Xu et al., 2006. Photo-catalytic oxidation of a volatile organic component of
acetaldehyde using titanium oxide nano-tubes, Journal of Nanomaterials, Vol.
2006, Article ID 78902, pp 1–8.
3. M. Takeuchi et al, 2005. Mechanism of photoinduced superhydrophilicity on the
TiO2 photocatalyst surface, Journal of Physical Chemistry B, Vol. 109, No. 32, pp
15422-15428.
4. R. Wang et al,1999. Studies of Surface Wettability Conversion on TiO2 Single-
Crystal Surfaces, Journal of Physical Chemistry B, Vol. 103, pp 2188-2194.
5. S. Banerjee et al, 2006. Physics and chemistry of photo-catalytic titanium dioxide:
Visualization of bactericidal activity using atomic force microscopy, Current
Science, Vol. 90, No. 10, pp 1378-1383.
6. Stephen Lower, January 2010. A gentle introduction to water and its structure.
http://www.chem1.com/acad/sci/aboutwater.html
7. http://www.selfcleaningglass.com/self-cleaning-glass.asp