How do photoelectrodes work?

Understanding Photoelectrodes in Photoelectrochemical Cells

Photoelectrodes are crucial components of photoelectrochemical (PEC) cells, playing an integral role in harnessing solar energy to drive chemical reactions. These specialized electrodes operate by converting light energy into electrical energy, which in turn is used to initiate and sustain a chemical transformation.

Composition and Function

Photoelectrodes are typically made from semiconducting materials such as titanium dioxide (TiO2), silicon (Si), or gallium arsenide (GaAs). When light strikes the surface of the photoelectrode, it excites electrons within the semiconductor material, promoting them from the valence band to the conduction band, thereby creating electron-hole pairs. This process is known as photoexcitation.

Electron-Hole Pair Separation

For a photoelectrode to be effective, it is essential to separate the electron-hole pairs before they recombine. This is achieved by applying an external bias or by the inherent electric field present at the semiconductor/electrolyte interface. The electrons move towards the photoelectrode surface, while the holes move in the opposite direction, creating a flow of electrical current.

Photocatalytic Reaction

At the photoelectrode surface, the photogenerated electrons or holes participate in redox reactions with the electrolyte. Electrons can reduce species in the electrolyte, while holes can oxidize them, leading to a variety of chemical reactions that can include water splitting, carbon dioxide reduction, and organic contaminant degradation.

Types of Photoelectrodes

  • n-Type Photoelectrodes: These electrodes accumulate electrons at their surface, promoting reduction reactions.
  • p-Type Photoelectrodes: In contrast, p-type electrodes accumulate holes, facilitating oxidation reactions.


The practical applications of photoelectrodes extend beyond PEC cells. They are also used in water splitting to produce hydrogen gas, CO2 reduction to produce carbon-neutral fuels, and pollutant degradation in wastewater treatment processes. The development of efficient and durable photoelectrodes is critical for advancing renewable energy technologies and environmental remediation efforts.

Back to blog

Leave a comment