Photochemistry 289

conversion is done by either photovoltaic or photoelectrochemical

(PEC) cells. The former is an all solid state device which has been
developed to an advanced level with about 15-18 per cent efficiency.
The cost of silicon-based photovoltaic devices has been brought
down by innovations in silicon production technology. PEC cell
is a combination of a semi-conductor with an electrolyte containing
a redox system and is said to be a regenerative called liquid
junction photocell. The PEC was introduced by Gerischer in 1960
and has been the subject of intensive research since then. Many
semi-conductors have been studied in a variety of solvents.
The solar energy conversion efficiency is (a maximum of 10
per cent
these over
cells hasshort periods)
greatly is stillour
enhanced poor. However, research
understanding on
of semi-
conductor-electron interphases, the chemistry and physics of semi-
conductors, charge transfer at modified surfaces, semi-conductors
as electrocatalys and photoassisted electrolysis of water towards
production of hydrogen. Another kind of solar energy conversion
occurs in the so called photogalvanic (PG) cell in which the incident
light brings about changes in redox states in solution, leading to
the development of a galvanic cell. The efficiencies reported for
such cells is less than 0.1 per cent.
It may be pointed out that metals are totally unsuitable for
light energy conversion because their excited electronic states
light energy conversion because their excited electronic states
have extremely short lifetime and the energy is rapidly dissipated
as heat. Only semi-conducting materials can store the energy
obtained from incident light and allow the stored energy to be
converted to other forms. The basic properties of these semi-
conductors have to be clearly understood in order to gain further
insight into the electrochemical kinetics of charge transfer at semi-
conductor-solution interface.
While attempting any developments in solar energy
conversion, the following points must be kept in mind.
1. Solar energy is diffuse.
2. The light flux is of relatively low power.
3. There are daily and seasonal fluctuations in solar energy
incidences.
4. The energy conversion devices should preferably be storage
devices, for use when light incidence is absent (i.e., at night).

290 Physical Chemistry

The following table gives an outline of some semi-conductor

conversion devices:
Table:
Table: Features of some Semi-conductor Conversion Devices

Device Material Efficiency Remarks

Solid State Si, Ga, As 1222% Single crystal, highcost,
p-n junction n-Cds/p-CdS
well established.
Schottky barrier
Au/nGa As 912%
M/Scor MO/SC
2+ 3+
Fe Fe All other PG system have
Photogalvanic cells Pt + Pt < 0.2%
TH TH very low efficiency.

Higher efficiency reported

Fe (CN)6314 5-6%
PEC(liquid junction) n-Cds pH =13 Pt by coating semiconductor
with a sensitizer dyes.

It may be observed that in the conversion of solar energy to

electricity directly, PEC devices have to compete with highly
efficient photovoltaic devices. PEC cells, like other conventional
batteries, involve electrochemical oxidation and reduction
processes with necessary charge transfer made to occur at low
electrodes (semi-conductor and metal)-solution interfaces, making
the flow of electrons unidirectional. The redox specie may be
generated in situ by the incidence of light (as in PG cells).
Alternatively, the potential gradient necessary for charge transfer
is produced by the incidence of light on the semi-conductor
electrode.
effect of theThe
lightPG cell isis essentially
energy a concentration
felt within solution. cell where
For the production
of electricity from solar energy in the PEC cells semi-conductor
electrodes are chosen that the effect of incident light energy is felt
directly on the semi-conductor material. This makes available
electrons for reduction or holes for oxidation of the species in
solution. The semi-conductor electrode can be combined with a
counter electrode made of a metal or another semi-conductor so
that both oxidation and reduction process occur at the appropriate
electrodes and electrons flow in the external circuit. Semi-conductor
material must be stable in medium.
A typical PG cell is depicted as

Pt Fe2+ Fe3+ Pt
+
Illuminated TH TH dark
Acid

Photochemistry 291

one The
halftwo
canhalf
be cells are separated
illuminated by an half
and other opaque
keptmaterial
in dark.so TH
that+
stands for thioninea thiazine dye which can be photochemically
converted to TH2+. The major reactions which can occur in the cell
leading to production of electric energy
h
Thionine (TH+) dark

semithionine (TH2+)
The max in water for TH+ is 597 nm and those for TH2+ are
390 and 770 nm. The TH2+ can be reduced to leucothionine (TH3+)
in the dark
dark
2 TH2+ dark

TH+ + TH3+
3+
and leucothionine can be oxidised
dark by Fe according to
TH3+ + Fe3+ TH2+ + Fe2+ + H+
Several other systems have been investigated in this context.
An important condition that has to be satisfied while choosing
system, is that the free energy of photochemical steady state under
sun light illumination should be greater than that when it is dark.
Methylene blue and Fe2+, Co-EDTA complex and thionine, and
excited tri-bipyridyl complex of Ru2+ and Fe2+ are a few systems
that satisfy this condition. The equilibrium in dark with the
bipyridyl system is
Ru byp23 Fe3 Ru byp33 Fe2
The E of the bipyridyl system is 1.2 V and that of the Fe 2+/
Fe system 0.7. The equilibrium is shifted to the left. When the
3+
 Fe3+ system 0.7. The equilibrium is shifted to the left. When the
system is illuminated the excitation reaction occurs as
2+
Ru byp 23 Fe
*Ru byp 33
hv
Ru byp 23 +Fe 3+
There is a change in the ratio of the concentration Fe2+/Fe3+
and Ru2+/Ru3+ with consequent alteration in the redox potentials
and hence a small change in the emf of cell. If the oxidation of
Ru2+ to Ru3+ and reduction of Fe3+ to Fe2+ are made to occur at two
electrodes current will flow in the external circuit.

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