.

Introduction to Photoelectrochemical Hydrogen

Production:

In its simplest form, a photoelectrochemical (PEC)

hydrogen production cell consists of a semiconductor
electrode and a metal counter electrode immersed in
an aqueous electrolyte. When light is incident on the
semiconductor electrode, it absorbs part of the light
and generated electricity. This electricity is then used
for the electrolysis of water.

Fujishima and Honda first demonstrated the lyses of

water using solar energy in a PEC cell about 30 years
ago. A schematic of their cell is shown in the figure
below:
Schematic showing the structure of a PEC cell
(Fujishima and Honda)

As seen from the diagram, the cell consists of a

semiconductor photo anode which is irradiated with
the electromagnetic radiation. The counter electrode
is a metal. Following processes take place in the cell
when light is incident on the semiconductor
electrode:

1. Photo generation of charge carriers (electron and

hole pairs)
2. Charge separation and migration of the holes to the
interface between the semiconductor and the
electrolyte and of electrons to the counter electrode
through the external circuit. Now, holes are simply
vacancies created in the valence band due to
promotion of electrons from the valence band to the
conduction band. However, in the study of electronic
behavior of materials, "holes" are considered to be
independent entities, with their own mass.

3. Electrode processes: oxidation of water to H+ and

H2O by the holes at the photo anode and reduction of
H+ ions to H2 by electrons at the cathode.

The representation of the same process in band

energy terms is shown in the following diagram:
A schematic illustrating the operating principles photoelectrochemical

cell producing hydrogen. The cell depicted in the figure is

a single photoelectrode type cell, with the anode being the active photoelectrode

The lower yellow band is the valence band of the n-

type semiconductor, while the upper yellow band is
the conduction band. The energy difference between
the top of valence band and the bottom of conduction
band is termed as the band gap of semiconductor, Eg.
Photons having energy greater than Eg are absorbed
by the semiconductor and free electrons are generated
in the conduction band and free holes in the valence
band.

2hν = 2e- + 2h+

The electrons and holes are separated due to the

potential generated at the interface of the
semiconductor-electrolyte due to band bending. The
holes move to the interface and react with water
producing oxygen:

2h+ + H2O = 1/2 O2(gas) + 2H+(aq)

The electrons travel in the external circuit and arrive

at the interface between the counter electrode and
electrolyte. There, they reduce the H+ ions to H2:

2e- + 2H+(aq) = H2(gas)

The complete reaction is absorption of photon and
splitting of water into hydrogen and oxygen.

Some other configurations of the PEC cell are also

possible:

1. The semiconducting material may be a p-type

material. In this case, it will act as photo cathode, and
reduction of H+ ions to H2 will take place at this
electrode. The counter electrode may me a metal in
this case.

2. Both electrodes, the cathode and anode, are photo

active semiconducting materials. In this case, the n-
type electrode will act as anode and oxidation of
water to oxygen and H+ will take place at this
electrode. The p-type electrode will act as cathode,
where H+ ions will be reduced to H2.

PHOTOELECTROCHEMICAL HYDROGEN
PRODUCTION
Developing high-efficiency, potentially low-cost,
photoelectrochemical (PEC) systems to produce
hydrogen directly from water using sunlight as the
energy source. The main thrust of the work has been
the development of integrated multijunction
photoelectrodes, comprising semiconductor, catalytic,
and protective thin-films deposited on low-cost
substrates (such as stainless steel), for solar hydrogen
production (Rocheleau et al. 1998). In the illustration
of a generic hydrogen photoelectrode shown in
Figure 1, sunlight shining on photoactive regions of
the electrode produces electric current to drive the
hydrogen and oxygen evolution reactions (HER,
OER) at opposite surfaces.

Photoelectrochemical hydrogen production

goals, a PEC system must be low-cost, operate at
solar-to-chemical conversion efficiencies greater than
10%, and have long operating lifetimes. research, our
approach has been to develop photoelectrodes
incorporating multijunction thin-film photoconvertors
(for high voltage) and thin-film catalyst and
protective layers (for stability).Specifically, our work
has provided strong evidence that direct solar-to-
hydrogen conversion efficiency of up to 10% can be
expected using photoelectrodes fabricated from low-
cost, multijunction amorphous silicon (a-Si)
(Rocheleau and Miller 1997), while conversion
efficiencies approaching 15% are possible using
advanced photoelectrode designs based on
multijunction copper-indium-gallium-diselenide
(CIGS) cells stacked in a side-by-side
Configuration (Miller and Rocheleau 2000). Both the
a-Si and CIGS photoelectrode systems
have the potential for low cost based on the very thin
semiconductor layers involved of photo electrolysis
of water directly into oxygen at a TiO2 electrode and
hydrogen at a Pt electrode by the
illumination of light greater than the band gap of
TiO2 [3.1 eV]

In the photo electrochemical cell, the photoelectro

process involves the generation of charge carriers in
the semi conducting electrodes and the transfer of
these charge carriers across the electrode/electrolyte
interface. For the direct photo electrochemical
decomposition of water to occur, several key criteria
have to be met with. These can be stated at the first
level as follows:
1. The band edges of the electrode must overlap with
the acceptor and donor states of water decomposition
reaction, thus necessitating that the electrodes should
at least have a band gap of 1.23 V, the reversible
thermodynamic decomposition potential of water.
This situation necessarily means that appropriate
semiconductors alone are acceptable as electrode
materials for water decomposition. The situation is
shown pictorially in Fig.1.
2. The charge transfer from the surface of the
semiconductor must be fast enough
to prevent photo corrosion and shift of the band edges
resulting in loss of photon energy.
Employing these two essential criteria and
considering the physics of semiconductor
solution interface, various materials have been
examined as anodes for direct photo
electrochemical decomposition of water. The
efficiency of this process is still a
point of contention, even though double digit
efficiencies up to 18.3% has been
reported using complex electrodes in an electrolytic
cell. However, realizing this
level of efficiency routinely and cheaply and
sustaining it appear to be still eluding.
In the last three decades, a large number of
semiconductor materials have been investigated for
photo electrochemical applications. The
semiconductor electrode system in efficient solar
energy converters should have optimized band gap so
as to be able to make maximum utilization of solar
radiation, and should also have sufficient chemical
stability against photo or other corrosion processes.
Unfortunately most of the materials that satisfy the
first criterion, namely semiconductor materials with
band gap around 1.4 eV are susceptible for photo
corrosion, while stable materials with a wider band
gap absorb light only in the UV region. In order to
match these two opposing factors, various conceptual
principles have been incorporated into typical TiO2
system so as to make this system responsive to longer
wavelength radiations. These efforts can be classified
as follows:
• Dye sensitization
• Surface modification of the semiconductor to
improve the stability
• Multi layer systems (coupled semiconductors)
• Doping of wide band gap semiconductors like
TiO2 by nitrogen, carbon and
Sulphur
• New semiconductors with metal 3d valence band
instead of Oxide 2p contribution
• Sensitization by doping.
All these attempts can be understood in terms of
some kind sensitization and hence the route of charge
transfer has been extended and hence the efficiency
could not be increased considerably. In spite of these
options being elucidated, success appears to be
eluding the researchers.
PRASHANT MISHRA
B.TECH (AUTOMOTIVE DESIGN ENGG.)
UNIVERSITY OF PETROLEUN AND ENERGY
STUDIES