Photodegradation of Methylene Blue
Photodegradation of Methylene Blue
Photodegradation of Methylene Blue
Theory of Semiconductors
Electronic conduction in a solid can be explained with
the help of the Molecular Orbital (MO) Theory. In isolated
atoms, the energy of electrons are defined by the energy of
the atomic orbitals (AO). In a solid, however, considering
the possibility of overlap among n atomic orbitals, elec-
trons will be distributed among the same number of MO
formed as a linear combination of AO. These molecular or-
bitals have such a small difference in energy levels that Figure 1. Schematic representation of the semiconductor palticle
they can be treated as bands instead of discrete levels of showing the pair electron/hole formed in the conduction band (CB)
energy. and valence band (VB), respectively. Band gap energy is repre-
In solid semiconductors such as TiOz, electrons occupy sented by Eg.
these energy bands according to their energy. The occupied
bands are called valence band (VB), and the next band
above, or the conduction band (CB) is totally empty. Be- vided in the solution and allowed to reach the semiconduc-
tween these two bands there is a region with no orbitals, or tor surface, the particle behaves as in a short circuit, and
a band gap. The size of this band gap is used to character- the reaction goes on until one of the compounds or ion is
ize materials as semiconductors or insulators, because it consumed totally.
can act a s a barrier to eletronic mobility. Many mechanisms involved in these redox reactions still
I n the valence band, the highest occupied orbital a t abso- are obscure. Adsorption of the substrate onto the semicon-
lute zero is called the Fermi level and lies near the center ductor surface seems to be the first step in most cases (6).
of the band. As the temperature increases, or upon optical Total oxidation to COz and HzO is rarely achieved with
excitation by photons with energy exceeding the band gap, 100%efficiency, and intermediate products oRen are found
electrons can be promoted to the conduction band, and the in the reactional medium. According to Pruden and Ollis
resulting vacancy in the valence band is called a hole (or (7) and Hsiao et al. (8), chloroform can be mineralized to-
positive charge). The mechanism is shown schematically tally to COz and HC1 according to the reaction:
in Figure 1.For TiOz, this band gap corresponds to a radi- CHC1, + HzO + 4202+C02 + 3Ht + 3CT (1)
ation of 388 n m (3.23 eV), e.p. in the near-UV range.
It is interesting to emphasize that optical ab3orption in Organochlorides are not the only class of PTOC that can
colloidal semiconductors mav differ from that observed for be destructed using light and semiconductors. T i 0 2 has
b u k material. As particles become smaller (-100 A), the been investigated extensively by many workers in the pho-
adsorption edge becomes diffuse, with a blue shift and ad- todegradation of organic contaminants such as phenols,
sorption peaks that correspond to eletronic transitions be- aromatics, and alcohols (6, 7). The oxidation of alcohols
tween discrete levels of energy. More detailed aspects con- shows more complex pathways, depending mainly on the
cerning physicochemical aspects of semiconductors are nature of the electron scavenger (usually dissolved oxy-
discussed in reference (5). gen).
Perhaps one of the most interesting ways of evaluating
Photodegradation of Organic Compounds the photocatalytic activity of metal oxides is in the degra-
dation of organic dyes. Most of these compounds show a
Because electrons and holes are present in the semicon- high molar absorptivity (1allowing the rate of bleaching
ductor surface, the particle shows both reducing and oxi- to be computed easily by colorimetric measurements.
dizing sites (Fig. 1).Once a suitable redox couple is pro- In this paper, we present a simple experiment in which
Methylene Blue (MB)is photodegraded using solar light in
'Author to whom correspondence should be addressed conjunction with TiOz. The extent of degradation is moni-