Photoelectrochemical Cells
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A photoelectrochemical cell (PEC) uses light energy for the conversion of chemical energy or electricity. Light activates a semiconductor or photosensitizer component within the cell and either generates electrical energy (similar to how dye-sensitized solar cells work) or drives chemical reactions that store energy by forming chemical bonds, such as producing hydrogen through water splitting.
The key difference between standard electrochemical cells and photoelectrochemical cells is the integration of an optical window for convenient and directed light transmission onto the working electrode, while maintaining a sealed electrochemical environment.
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Different Types
Photoelectrochemical cells come in a variety of body designs tailored for specific research and application needs. Common types include:
- Glass PECs are known for their clarity and chemical resistance, making them ideal for standard light-driven experiments.
- PTFE PECs offer superior chemical inertness and thermal stability, making them suitable for more demanding or corrosive environments.
- H-type PECs are ideal for gas-phase studies and advanced photoelectrochemical measurements where light access and separation of reaction products are critical.
- PECs with a water bath provide precise temperature control during experiments, making them valuable for studies that require consistent thermal conditions.
In the scaling of steady-state processes and high-throughput or continuous operation studies, flow PECs move solution through the cell, ensuring a constant supply of fresh electrolyte during operation, improving mass transport within the system. This also helps remove the reaction products, reducing concentration gradients near the electrode surface and supporting more stable operating conditions. Flow cells are especially useful experiments where mass transport limitations can influence performance, such as CO2 reduction.
Comparing PECs
Single Photoelectrochemical Cells
 Glass PEC |
 Glass PEC with Water Bath |
 PTFE PEC |
|
|---|---|---|---|
| Advantages | Simple, single cell. Good for basic photocurrent measurements, preliminary screening and evaluation. | Good for long-term stability tests that require temperature control. Increases accuracy and repeatability of experiments. | Superior chemical inertness and thermal stability compared to glass. |
| Example Uses | Screening of new semiconductor thin films for photocurrent response under chopped illumination. | Temperature control where light exposure may heat the apparatus altering the kinetics of the electrochemical reaction. | For corrosive experiments. |
H-type Photoelectrochemical Cells
 Glass H-Cell |
 Glass H-Cell with Water Bath |
 Double Window Glass H-Cell |
|
|---|---|---|---|
| Advantages | Independent cell control with limited roduct crossover for gas evolution, reaction selectivity and long-term stability. | Individual temperature control over each cell, as well as less cross contamination. | Double window allows illumination of both cells, enabling two photoelectrodes to operate simultaneously. |
| Example Uses | Photo-driven or photo-assisted water splitting studies, CO2 reduction, any other experiments requiring product collection or gas seperation. | Temperature control where light exposure may heat the apparatus altering the kinetics of the electrochemical reaction. | Testing tandem photochemical systems, independent studies of anodic and cathodic photoresponses under identical conditions. |
How Does a Photoelectrochemical Cell Work?
Components
Photoelectrochemical cells are composed of a working electrode, counter electrode, electrolyte and optionally a reference electrode. The working electrode is photoactive and can absorb light to generate charge carriers.
The working electrode, also referred to as a photoanode, is normally an n- or p-type semiconductor, i.e. a polymer semiconductor on an ITO/FTO substrate, held by a platinum plate electrode holder. The counter electrode can be platinum or platinum free, i.e. multi-walled carbon nanotubes (MWCNT).
The critical component of the photoelectrochemical cell is the photosensitizer (semiconductor) on the working electrode. Electron-hole pairs are generated by the irradiation of photons with an energy level that is equal to or greater than the bandgap (Eg) of the semiconductor. When light illuminates the photoanode, electrons in the valence band (VB) get excited to the conduction band (CB), and leave a hole behind.
Production of electricity
For the production of electricity, photogenerated electrons are swept toward the conducting back contact. They then diffuse through the bulk semiconductor to the external circuit. The electrical energy produced and stored in this process is similar to the a photovoltaic dye-sensitized solar cell (DSSC). The holes are driven to the semiconductor surface and get scavanged by the reduced redox species to become oxidized. The separated electrons which have traveled to the counter electrode then reduce the oxidized species and so on. The regenerative cycle allows for continued electrical current generation.
Chemical reactions
Both the excited electrons and the holes left behind in the photoelectrodes will be involved in some form of chemical reactions, i.e. water splitting. At the counter electrode, the electrons reduce protons (H+) to form hydrogen (H2) while the photogenerated holes at the photoanode oxidize water (or OH-) to form oxygen (O2).
Key Applications
Photoelectrochemical cells are light or solar energy driven and they offer a promising potential applications in clean energy capture, energy production and storage and light-emitting devices.
- Water splitting for hydrogen fuel production
- To reduce CO2 into desirable products such as methane and methanol that can be directly used as fuel
- Photoelectrochemical dye-sensitized solar cells (DSSCs) by incorporating dyes such as N719 which absorb light and oxidize within the system
- Photoelectrochemical perovskite solar cells
Related Collections
Resources
Photoelectrochemistry
Photoelectrochemistry combines electrochemistry, photochemistry, and semiconductor physics to study electrochemical reactions influenced or driven by light. It is a fast-growing research area due to the many potential applications of accessing endothermic electrochemical reactions using solar energy.
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Photoelectrochemical Cell Setup
Learn how to set up your photoelectrochemical cells correctly by following this step-by-step video guide.
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What is a Redox Reaction?
A redox reaction, also referred to as an oxidation-reduction reaction, involves the loss or gain of electrons. The loss of electrons is called oxidation and the gain of the electrons reduction.
Read more...References
- Hodes, G. et al. (2012).Photoelectrochemical Cell Measurements: Getting the Basics Right. J. Phys. Chem. Lett., 9. doi:10.1021/jz300220b
- Hsu, CY. et al. (2024). Improvement of the photoelectric dye sensitized solar cell performance using Fe/S–TiO2 nanoparticles as photoanode electrode. Sci Rep, 14. doi:10.1038/s41598-024-54895-z
- Fehr, A.M.K. et al. (2023). Integrated halide perovskite photoelectrochemical cells with solar-driven water-splitting efficiency of 20.8%. Nat Commun, 14. doi:10.1038/s41467-023-39290-y
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