Twin Cell Technology for Hydrogen the electrolyte and upon light absorption and gener-

ation of electron and hole pairs in the semiconductor

Generation photoanode (photocathode), one redox system reacts
with the photogenerated holes (electrons) at the sur-
face of the semiconductor photoanode (photocath-
ode) and the other reacts with the electrons (holes)
1. Introduction entering at the counter electrode. A schematic
diagram of a water splitting device based on this
Since photoelectrochemical water splitting is a vast principle is shown in Fig. 1, where an n-type semi-
area, it is not our objective to cover all its aspects conductor electrode is used as the photoanode to
within this article, but to discuss the twin cell tech- generate oxygen and a suitable counter electrode is
nology based Tandem CellTM for water splitting. It used to generate hydrogen. The overall reaction is the
has long been accepted that world demand for energy cleavage of water by sunlight (Eqn. (5)).
will increase steadily for the foreseeable future, but Light absorption and generation of electron/hole
until the last decade more intensive exploitation of pairs at the photoanode,
conventional sources seemed able to provide an ad-
equate supply. However, today the situation has n  SC þ hn-n  SCðe þ hþ Þ ð2Þ
changed entirely and everyone acknowledges the
threat of depletion of fossil fuel. Therefore, nonre- Light-driven reaction at the photoanode,
newable fuels need to be conserved. Another major
VB -4H þ O2
2H2 O þ 4hþ þ
ð3Þ
concern associated with the use of fossil fuels is the
formation of large amounts of CO2, SO2, and NOx by
combustion that adversely contributes to the world Light-driven reaction at the cathode,
climate. Hence, fossil fuels are becoming ecologically
CB -H2
2Hþ þ 2e ð4Þ
unpopular. Since nuclear power presents social and
political problems, today searching for a carbon-free The overall reaction is
renewable energy source has become more important
than ever before. It is fair to say that renewable en- 4hn þ 2H2 O-O2 þ 2H2 ð5Þ
ergy sources such as wind and tidal power still face
technological challenges. Using a titanium dioxide electrode as the photo-
Hydrogen is a potential fuel with desirable prop- anode in this type of device, Fujishima and Honda
erties. Its energy storage capacity is 120 000 J g–1 as (1972) demonstrated water photolysis for the first
compared to 40 000 for oil and 30 000 for coal
(Gr.atzel 1989). Furthermore, hydrogen has the ad-
vantage over conventional fossil or nuclear energy
sources in that combustion in a thermal engine or fuel
cell does not result in pollution of the environment.
Biological photosynthesis is one of the fascinating
phenomena of nature in which water and carbon
dioxide are converted into oxygen and carbohydrates H2
EC
in the presence of sunlight. In this process a manga-
nese complex, which is in an intricate enzymatic en- EF
H2O
vironment, provides an active site for splitting water.
Designing a process based on this generic concept to
drive a reaction thermodynamically uphill to split water hv
into hydrogen and oxygen (sometimes referred to as O2
artificial photosynthesis) is a highly rewarding task:

H2 O-0:5O2 þ H2 EV
1
DG0298 ¼ 237 kJ mol ð1Þ

2. Historical Background n-Type Aqueous Counter

semiconductor electrolyte electrode
Water splitting has been a goal of photoelectrochem-
istry for nearly a decade. The concept is based on a Figure 1
photosynthetic cell. The photosynthetic cell operates Photolysis of water by using an n-type semiconductor
on the principle that there are two redox systems in electrode.