A "photoelectrochemical cell" is one of two distinct classes of

device. The first produces electrical energy similarly to a dye-

sensitized photovoltaic cell, which meets the standard definition
of a photovoltaic cell. The second is a photoelectrolytic cell,
that is, a device which uses light incident on
a photosensitizer, semiconductor, or aqueous metal immersed
in an electrolytic solution to directly cause a chemical reaction,
for example to produce hydrogen via the electrolysis of water.
Both types of device are varieties of solar cell, in that a
photoelectrochemical cell's function is to use the photoelectric
effect (or, very similarly, the photovoltaic effect) to
convert electromagnetic radiation (typically sunlight) either
directly into electrical power, or into something which can itself
be easily used to produce electrical power (hydrogen, for
example, can be burned to create electrical power,
see photohydrogen).
Two principles[edit]
The standard photovoltaic effect, as operating in
standard photovoltaic cells, involves the excitation of negative
charge carriers (electrons) within a semiconductor medium, and
it is negative charge carriers (free electrons) which are
ultimately extracted to produce power. The classification of
photoelectrochemical cells which includes Grätzel cells meets
this narrow definition, albeit the charge carriers are
often excitonic.
The situation within a photoelectrolytic cell, on the other hand,
is quite different. For example, in a water-splitting
photoelectrochemical cell, the excitation, by light, of an electron
in a semiconductor leaves a hole which "draws" an electron
from a neighboring water molecule:

This leaves positive charge carriers (protons, that is, H+

ions) in solution, which must then bond with one other proton
and combine with two electrons in order to form hydrogen
gas, according to:
A photosynthetic cell is another form of photoelectrolytic
cell, with the output in that case being carbohydrates
instead of molecular hydrogen.
Photoelectrolytic cell[edit]

Photoelectrolytic cell band diagram

A (water-splitting) photoelectrolytic cell electrolizes water
into hydrogen and oxygen gas by irradiating
the anode with electromagnetic radiation, that is, with
light. This has been referred to as artificial
photosynthesis and has been suggested as a way of
storing solar energy in hydrogen for use as fuel.[1]
Incoming sunlight excites free electrons near the surface
of the silicon electrode. These electrons flow through
wires to the stainless steel electrode, where four of them
react with four water molecules to form two molecules of
hydrogen and 4 OH groups. The OH groups flow through
the liquid electrolyte to the surface of the silicon electrode.
There they react with the four holes associated with the
four photoelectrons, the result being two water molecules
and an oxygen molecule. Illuminated silicon immediately
begins to corrode under contact with the electrolytes. The
corrosion consumes material and disrupts the properties
of the surfaces and interfaces within the cell. [2]
Two types of photochemical systems operate
via photocatalysis. One uses semiconductor surfaces as
catalysts. In these devices the semiconductor surface
absorbs solar energy and acts as an electrode for water
splitting. The other methodology uses in-solution metal
complexes as catalysts.[3][4]
Photoelectrolytic cells have passed the 10
percent economic efficiency barrier. Corrosion of
the semiconductors remains an issue, given their direct
contact with water.[5] Research is now ongoing to reach
a service life of 10000 hours, a requirement established
by the United States Department of Energy.[6]
Other photoelectrochemical cells[edit]
The first photovoltaic cell ever designed was also the first
photoelectrochemical cell. It was created in 1839,
by Alexandre-Edmond Becquerel, at age 19, in his
father's laboratory.[7]
The mostly commonly researched modern
photoelectrochemical cell in recent decades has been
the Grätzel cell, although much attention has recently
shifted away from this topic to perovskite solar cells, due
to relatively high efficiency of the latter and the similarity in
vapor assisted deposition techniques commonly used in
their creation.
Dye-sensitized solar cells or Grätzel cells use dye-
adsorbed highly porous nanocrystalline titanium
dioxide (nc-TiO
2) to produce electrical energy.
Materials for photoelectrolytic cells[edit]
Water-splitting photoelectrochemical (PEC) cells use light
energy to decompose water into hydrogen and oxygen
within a two-electrode cell. In theory, three arrangements
of photo-electrodes in the assembly of PECs exist: [8]

• photo-anode made of a n-type semiconductor and

a metal cathode
• photo-anode made of a n-type semiconductor and
a photo-cathode made of a p-type semiconductor
• photo-cathode made of a p-type semiconductor
and a metal anode
There are several requirements for photoelectrode
materials in PEC production:[9]

• light absorbance: determined by band gap and

appropriate for solar irradiation spectrum
• charge transport: photoelectrodes must be
conductive (or semi-conductive) to minimize
resistive losses
• suitable band structure: large enough band gap to
split water (1.23V) and appropriate positions
relative to redox potentials for and
• catalytic activity: high catalytic activity increases
efficiency of the water-splitting reaction
• stability: materials must be stable to prevent
decomposition and loss of function
In addition to these requirements, materials must be low-
cost and earth abundant for the widespread adoption of
PEC water splitting to be feasible.
While the listed requirements can be applied generally,
photoanodes and photocathodes have slightly different
needs. A good photocathode will have early onset of the
oxygen evolution reaction (low overpotential), a large
photocurrent at saturation, and rapid growth of
photocurrent upon onset. Good photoanodes, on the other
hand, will have early onset of the hydrogen evolution
reaction in addition to high current and rapid photocurrent
growth. To maximize current, anode and cathode
materials need to be matched together; the best anode for
one cathode material may not be the best for another.
TiO
2[edit]

In 1967, Akira Fujishima discovered the Honda-Fujishima

effect, (the photocatalytic properties of titanium dioxide).
TiO
2 and other metal oxides are still most
prominent[10] catalysts for efficiency reasons.
Including SrTiO
3 and BaTiO
[11]
3, this kind of semiconducting titanates, the conduction
band has mainly titanium 3d character and the valence
band oxygen 2p character. The bands are separated by a
wide band gap of at least 3 eV, so that these materials
absorb only UV radiation.
Change of the TiO
2 microstructure has also been investigated to further
improve the performance. In 2002, Guerra (Nanoptek
Corporation) discovered that high localized strain could be
induced in semiconductor films formed on micro to nano-
structured templates, and that this strain shifted the
bandgap of the semiconductor, in the case of titanium
dioxide, into the visible blue.[12] It was further found (Thulin
and Guerra, 2008) that the strain also favorably shifted
the band-edges to overlay the hydrogen evolution
potential, and further still that the strain improved hole
mobility, for lower charge recombination rate and high
quantum efficiency.[13] Chandekar developed a low-cost
scalable manufacturing process to produce both the nano-
structured template and the strained titanium dioxide
coating.[14] Other morphological investigations include TiO
2 nanowire arrays or porous nanocrystalline TiO
[15]
2 photoelectrochemical cells.
GaN[edit]
GaN is another option, because metal nitrides usually
have a narrow band gap that could encompass almost the
entire solar spectrum.[16] GaN has a narrower band gap
than TiO
2 but is still large enough to allow water splitting to occur
at the surface. GaN nanowires exhibited better
performance than GaN thin films, because they have a
larger surface area and have a high single crystallinity
which allows longer electron-hole pair
lifetimes.[17] Meanwhile, other non-oxide semiconductors
such as GaAs, MoS
2, WSe
2 and MoSe
2 are used as n-type electrode, due to their stability in
chemical and electrochemical steps in the photocorrosion
reactions.[18]
Silicon[edit]
In 2013 a cell with 2 nanometers of nickel on a silicon
electrode, paired with a stainless steel electrode,
immersed in an aqueous electrolyte of potassium
borate and lithium borate operated for 80 hours without
noticeable corrosion, versus 8 hours for titanium dioxide.
In the process, about 150 ml of hydrogen gas was
generated, representing the storage of about 2 kilojoules
of energy.[2][19]
Structured materials[edit]
Structuring of absorbing materials has both positive and
negative affects on cell performance. Structuring allows
for light absorption and carrier collection to occur in
different places, which loosens the requirements for pure
materials and helps with catalysis. This allows for the use
of non-precious and oxide catalysts that may be stable in
more oxidizing conditions. However, these devices have
lower open-circuit potentials which may contribute to
lower performance.[20]
Hematite[edit]

Hematite structure
Researchers have extensively investigated the use of
hematite (α-Fe2O3) in PEC water-splitting devices due to
its low cost, ability to be n-type doped, and band gap
(2.2eV). However, performance is plagued by poor
conductivity and crystal anisotropy. [21] Some researchers
have enhanced catalytic activity by forming a layer of co-
catalysts on the surface. Co-catalysts include cobalt-
phosphate[22] and iridium oxide,[23] which is known to be a
highly active catalyst for the oxygen evolution reaction. [20]
Tungsten oxide[edit]
Tungsten(VI) oxide (WO3), which exhibits several different
polymorphs at various temperatures, is of interest due to
its high conductivity but has a relatively wide, indirect
band gap (~2.7 eV) which means it cannot absorb most of
the solar spectrum. Though many attempts have been
made to increase absorption, they result in poor
conductivity and thus WO3 does not appear to be a viable
material for PEC water splitting. [20]
Bismuth vanadate[edit]
With a narrower, direct band gap (2.4 eV) and proper
band alignment with water oxidation potential, the
monoclinic form of BiVO
[20]
4 has garnered interest from researchers. Over time, it
has been shown that V-rich and compact films[25] are
[24]

associated with higher photocurrent, or higher

performance. Bismuth Vanadate has also been studied for
solar generation from seawater,[26] which is much
more difficult due to the presence of contaminating ions
and a more harsh corrosive environment.
Oxidation form[edit]
Photoelectrochemical oxidation (PECO) is the process by
which light enables a semiconductor to promote
a catalytic oxidation reaction. While a
photoelectrochemical cell typically involves both a
semiconductor (electrode) and a metal (counter-
electrode), at sufficiently small scales, pure
semiconductor particles can behave as microscopic
photoelectrochemical cells.[clarification needed] PECO has
applications in the detoxification of air and
water, hydrogen production, and other applications.
Reaction mechanism[edit]
The process by which a photon initiates a chemical
reaction directly is known as photolysis; if this process is
aided by a catalyst, it is called photocatalysis.[27] If a
photon has more energy than a material's characteristic
band gap, it can free an electron upon absorption by the
material. The remaining, positively charged hole and the
free electron may recombine, generating heat, or they can
take part in photoreactions with nearby species. If the
photoreactions with these species result in regeneration of
the electron-donating material—i.e., if the material acts as
a catalyst for the reactions—then the reactions are
deemed photocatalytic. PECO represents a type of
photocatalysis whereby semiconductor-based
electrochemistry catalyzes an oxidation reaction—for
example, the oxidative degradation of an airborne
contaminant in air purification systems.
The principal objective of photoelectrocatalysis is to
provide low-energy activation pathways for the passage of
electronic charge carriers through the electrode electrolyte
interface and, in particular, for the photoelectrochemical
generation of chemical products.[28] With regard to
photoelectrochemical oxidation, we may consider, for
example, the following system of reactions, which
constitute TiO2-catalyzed oxidation.[29]
TiO2 (hv) → TiO2 (e− + h+)
TiO2(h+) +RX → TiO2 + RX.+
TiO2(h+) + H2O → TiO2 + HO. + H+
TiO2(h+) + OH− → TiO2 + HO.
TiO2(e−) + O2 → TiO2 + O2.−
This system shows a number of pathways
for the production of oxidative species that
facilitate the oxidation of the species, RX, in
addition to its direct oxidation by the excited
TiO2 itself. PECO concerns such a process
where the electronic charge carriers are able
to readily move through the reaction
medium, thereby to some extent mitigating
recombination reactions that would limit the
oxidative process. The
“photoelectrochemical cell” in this case
could be as simple as a very small particle
of the semiconductor catalyst. Here, on the
“light” side a species is oxidized, while on
the “dark” side a separate species is
reduced.[30]
Photochemical oxidation (PCO) versus
PECO[edit]
The classical macroscopic
photoelectrochemical system consists of a
semiconductor in electric contact with a
counter-electrode. For N-type
semiconductor particles of sufficiently small
dimension, the particles polarize into anodic
and cathodic regions, effectively forming
microscopic photoelectrochemical
cells.[28] The illuminated surface of a particle
catalyzes a photooxidation reaction, while
the “dark” side of the particle facilitates a
concomitant reduction.[31]
Photoelectrochemical oxidation may be
thought of as a special case of
photochemical oxidation (PCO).
Photochemical oxidation entails the
generation of radical species that enable
oxidation reactions, with or without the
electrochemical interactions involved in
semiconductor-catalyzed systems, which
occur in photoelectrochemical
oxidation.[clarification needed]
Applications[edit]
PECO may be useful in treating both air and
water, as well as producing hydrogen as a
source of renewable energy.
Water Treatment[edit]
PECO has shown promise for water
treatment of
both stormwater and wastewater. Currently,
water treatment methods like the use
of biofiltration technologies are widely used.
These technologies are effective at filtering
out pollutants like suspended solids,
nutrients, and heavy metals, but struggle to
remove herbicides. Herbicides
like diuron and atrazine are commonly used,
and often end up in stormwater, posing
potential health risks if they are not treated
before reuse.
PECO is a useful solution to treating
stormwater because of its strong oxidation
capacity. Investigating different mechanisms
for herbicide degradation in stormwater, like
PECO, photocatalytic oxidation (PCO), and
electro-catalytic oxidation (ECO),
researchers determined that PECO was the
best option, demonstrating complete
mineralization of diuron in one
hour.[32] Further research into this use for
PECO is needed, as it was only able to
degrade 35% of atrazine in that time,
however it is a promising solution moving
forward.
Air Treatment[edit]
PECO has also shown promise as a means
of air purification. For people with severe
allergies, air purifiers are important to
protect them from allergens within their own
homes.[33] However, some allergens are too
small to be removed by normal purification
methods. Air purifiers using PECO filters are
able to remove particles as small as 0.1 nm.
These filters work as photons excite a
photocatalyst, creating hydroxyl free
radicals, which are extremely reactive and
oxidize organic material and microorganisms
that cause allergy symptoms, forming
harmless products like carbon dioxide and
water. Researchers testing this technology
with patients suffering from allergies drew
promising conclusions from their studies,
observing significant reductions in total
symptom scores (TSS) for both nasal
(TNSS) and ocular (TOSS) allergies after
just 4 weeks of using the PECO filter. [34] This
research demonstrates strong potential for
impactful health improvements who suffer
from severe allergies and asthma.
Hydrogen Production[edit]
Possibly the most exciting potential use for
PECO is producing hydrogen to be used as
a source of renewable energy.
Photoelectrochemical oxidation reactions
that take place within PEC cells are the key
to water splitting for hydrogen production.
While the main concern with this technology
is stability, systems that use PECO
technology to create hydrogen from vapor
rather than liquid water has demonstrated
potential for greater stability. Early
researchers working on vapor fed systems
developed modules with 14% solar to
hydrogen (STH) efficiency, while remaining
stable for 1000+ hours.[35] More recently,
further technological developments have
been made, demonstrated by the direct air
electrolysis (DAE) module developed by
Jining Guo and his team, which produces
99% pure hydrogen from the air and has
demonstrated stability of 8 months thus
far.[36]
Promising research and technological
advancement using PECO for different
applications like water and air treatment and
hydrogen production suggests that it is a
valuable tool that can be utilized in a variety
of ways.
History[edit]
In 1938, Goodeve and Kitchener
demonstrated the “photosensitization” of
TiO2—e.g., as evidenced by the fading of
paints incorporating it as a pigment. [37] In
1969, Kinney and Ivanuski suggested that a
variety of metal oxides, including TiO 2, may
catalyze the oxidation of dissolved organic
materials (phenol, benzoic acid, acetic acid,
sodium stearate, and sucrose) under
illumination by sunlamps.[38] Additional work
by Carey et al. suggested that TiO2 may be
useful for the photodechlorination of
PCBs.[39]