The Process of Water-Splitting at the Anode of a

Photoelectrochemical Cell
A water-splitting photoelectrochemical (WS-PEC) cell is a device designed to capture the nearly
unlimited power of the sun. While a traditional solar panel converts solar energy directly into
electricity, a WS-PEC cell uses solar energy to convert water into hydrogen and oxygen gas. The
hydrogen gas can be stored for long periods of time and burned as a clean, renewable fuel.

A basic WS-PEC cell is composed of an anode and a cathode which respectively form oxygen
and hydrogen gas when immersed in water and exposed to sunlight (Figure 1).

Semiconductor

Catalyst

Figure 1. Diagram of WS-PEC cell’s components (constructed by author)

The function of the anode of a WS-PEC is to facilitate water-splitting: the chemical process that
converts liquid water into oxygen gas and protons. The chemical reaction for water-splitting is
shown in Equation 1.
2𝐻2 𝑂 → 𝑂2 + 4𝐻 + + 4𝑒 − (1)
At the left of the arrow, two water molecules (H2O) are the sole reactants. After water-splitting
occurs, the water is converted to oxygen gas (O2) and four protons (H+). The water molecules
lose four total electrons (e-) which enter the anode of the WS-PEC cell.

The anode is composed of two distinct parts: the semiconductor and the catalyst. The
semiconductor captures solar energy—using it to drive the water-splitting process forward—and
the catalyst increases the rate of water-splitting. The water-splitting process can be separated into
three steps. First, sunlight destabilizes the semiconductor by promoting its electrons. Second, the
catalyst donates electrons to stabilize the semiconductor. Finally, the splitting of water generates
the electrons needed to stabilize the catalyst.
Electron Promotion at the Semiconductor
The first step in the water-splitting process involves a
semiconductor using the sun’s energy to create an electron
vacancy in its valence band. In materials, electrons orbit
atoms in regions called bands—each of a specified energy.
Electrons populate these bands starting closest to the
nucleus (at low energy) and fill bands of successively
higher energy until all electrons have been placed.

In the ground—or lowest energy—atomic state, the highest

energy band populated by electrons is known as the
valence band. In a semiconductor, an unoccupied band—
known as the conduction band—exists above the valence
band. The energy difference between the valence and
conduction band is known as the band gap. The band gaps
for three different semiconductors are shown in Figure 2.
The size of the band gap is unique to a material and is
measured in electron volts (eV), a unit of energy.
Figure 2. Band gaps of
A semiconductor can used be in a WS-PEC cell if solar semiconductors used in WS-PEC
energy can sufficiently promote an electron across its band cells (Reference 1, edited by author)
gap. For this promotion to occur, an electron in the valence
band must gain from sunlight an amount of energy greater than or equal to the band gap.

A successful promotion creates a vacancy, known as a hole, in the valence band. This hole is
highly reactive and strongly desires to be filled by an electron so the semiconductor can return to
a stable state.

Electron Donation from the Catalyst

to the Semiconductor
Once a hole is formed in the semiconductor’s
valence band, the catalyst quickly donates an
electron to fill it. The catalyst is necessary to
increase the rate of water-splitting—which is
related to the efficiency of a WS-PEC cell (see
Catalytic Improvement of WS-PEC Cell
Efficiency). The general reaction that occurs
between the semiconductor and the catalyst is Figure 3. The catalyst donates electrons to stabilize
shown in Equation 2. the semiconductor after an electron promotion event
occurs (constructed by author)
𝑆𝐶 ∗ + 𝐶𝑎𝑡 → 𝑆𝐶 + 𝐶𝑎𝑡1+ (2)
In the reaction, an electron is transferred from the catalyst (Cat) to the hole-bearing
semiconductor (SC*). The reaction results in the semiconductor returning to a ground state (SC)
and the catalyst losing one electron (Cat1+). Once an electron transfer occurs, the promoted
electron in the conduction band cannot return to the valence band and must travel to the cathode
(see Promoted Electron Movement to the Cathode). The electron promotion process and
electron donation from the catalyst to the valence band is diagramed in Figure 3.

A second electron in the semiconductor’s valence band can be promoted by sunlight to form
another hole, and the catalyst can then donate another electron as shown in Equation 3.
𝑆𝐶 ∗ + 𝐶𝑎𝑡1+ → 𝑆𝐶 + 𝐶𝑎𝑡 2+ (3)
n+
As long as the hole-bearing semiconductor SC* is more unstable than Cat (the catalyst minus
n electrons), the process is favorable and can be continually repeated. Once the catalyst loses
four electrons and reaches the Cat 4+ state, it is capable of splitting water.

Catalytic Improvement of WS-PEC Cell Efficiency

Without a catalyst, WS-PEC cells are extremely inefficient and produce very low yields
of oxygen and hydrogen. Since a hole-bearing semiconductor is very unstable, the
promoted electron is likely to leave the conduction band and recombine with the hole—
returning to its place in the valence band. This recombination is a source of inefficiency
in WS-PEC cells since an electron promotion event is not used for water-splitting.

A hole is unlikely to be filled directly by an electron from the water-splitting process

since it takes a much longer time for an electron to be transferred to the valence band
from a water molecule than through the recombination process. However, electron
transfer from a catalyst occurs at a very similar rate as recombination. Once an electron is
promoted, the catalyst is likely to donate an electron to fill the hole before recombination
can occur—greatly increasing the overall efficiency of the water-splitting process.

Promoted Electron Movement to the Cathode

Once the catalyst donates an electron to the semiconductor, the promoted electron cannot
return to the valence band. It is unfavorable for an electron to remain in the high energy
conduction band for a long period of time, so the promoted electron must enter the wire
that connects the electrodes and travel to the cathode. At the cathode, electrons can be
transferred to protons in solution to produce to hydrogen gas.

Water-Splitting to Stabilize the Catalyst

To regain the electrons lost to the semiconductor, the catalyst facilitates the water-splitting
process. While the catalyst can exist briefly as Cat 4+, it now strongly desires electrons so it can
return to a more stable state. The catalyst receives these electrons from the splitting of water. The
catalyst can be incorporated into the previously discussed water-splitting equation (Equation 1)
from the introduction to provide Equation 4.
𝐶𝑎𝑡 4+ + 2𝐻2 𝑂 → 𝐶𝑎𝑡 + 𝑂2 + 4𝐻 + (4)
From an energetic point of view, the main result of the reaction is that the four electrons
generated from water-splitting are transferred to the catalyst. The production of oxygen gas and
four protons is largely a secondary product of the catalyst stabilization. Once water-splitting has
occurred, both the semiconductor and catalyst are in their most stable states and one cycle of the
water-splitting process has been completed.
Conclusion
At the anode of a WS-PEC cell, four electrons are
transferred from two water molecules to the 4 e-
semiconductor through a catalyst. A diagram of
the process is shown in Figure 4. First, sunlight
CB Semiconductor
promotes an electron from the semiconductor’s
valence band (VB) to its conduction band (CB).
Once this promotion event occurs, the catalyst Sunlight (x4)
donates an electron to fill the hole formed at the
valence band, forcing the now displaced electron
to travel to the cathode. This process can occur 4 e- Catalyst
four times to convert the catalyst to Cat 4+, then
two water molecules will be split to transfer their
electrons to the catalyst.

The semiconductor and the catalyst are now able

VB
to repeat the water-splitting process.
Theoretically, the process will occur indefinitely
to produce hydrogen gas as long as sunlight can
Figure 4. Electron motion in WS-PEC cell
reach the semiconductor and water can reach both
(constructed by author)
electrodes in the WS-PEC cell. In this way, a
WS-PEC cell can use the sun to generate a clean, renewable source of energy.
References:

1. Sivula, K. & R. van de Krol. “Semiconducting materials for photoelectrochemical energy

conversion.” Nature Rev. Mater., 1, 15010 (2016).