Photoelectrolysis of water. Photoelectrolysis of water, also known as photoelectrochemical water splitting, occurs in a photoelectrochemical cell when light is used as the energy source for the electrolysis of water, producing dihydrogen which can be used as a fuel. This process is one route to a "hydrogen economy", in which hydrogen fuel is produced efficiently and inexpensively from natural sources without using fossil fuels. In contrast, steam reforming usually or always uses a fossil fuel to obtain hydrogen. Photoelectrolysis is sometimes known colloquially as the hydrogen holy grail for its potential to yield a viable alternative to petroleum as a source of energy; such an energy source would supposedly come without the sociopolitically undesirable effects of extracting and using petroleum.

Mechanism

The PEC cell primarily consists of three components: the photoelectrode the electrolyte and a counter electrode. The semiconductor crucial to this process, absorbs sunlight, initiating electron excitation and subsequent water molecule splitting into hydrogen and oxygen.

Photoanode Reaction (Oxygen Evolution):
H2O              →     2H++1     2O2+    2e−
 
Photocathode Reaction (Hydrogen Evolution):
2H++    2e−   →     H2	

These half-reactions show the fundamental chemistry involved in photoelectrolysis, where the photoanode facilitates oxygen evolution and the photocathode supports hydrogen evolution.

Current Research and Technological Advances

Recent advancements have focused on enhancing the semiconductor materials and cell design to improve the solar-to-hydrogen (STH) conversion efficiency, currently between 8%-14%, with a theoretical maximum around 42%. Innovations include:

Semiconductor Materials: Research emphasizes the importance of semiconductors with smaller band gaps (under 2.1 eV) which are more effective at utilizing broader light spectra, thus improving efficiency.

Cocatalysts: The use of transition metal-based cocatalysts has been pivotal in enhancing charge separation and reducing overpotential, thereby improving the overall efficiency of the water-splitting reaction.

Nanoporous Materials: These materials have been utilized to increase the surface area for electron transport, significantly boosting the efficiency of photoelectrochemical systems.

Advantages: Utilizing sunlight, photoelectrolysis serves as a renewable method for hydrogen production, offering scalability and adaptability across different geographical conditions.

Challenges: The primary hurdles include the still-developing efficiency of the process and the intermittent nature of solar energy, which can affect consistent hydrogen production. Additionally, finding durable and efficient materials for long-term operation remains a challenge.

Role in the Hydrogen Economy

As part of a sustainable hydrogen economy, photoelectrolysis presents a promising avenue for clean hydrogen production. Although currently more expensive than traditional methods like steam methane reforming, the potential for technological advancements could make it more economically viable.

Conclusion and Future Prospects

The ongoing development in materials science and cell design is likely to enhance the viability of photoelectrolysis, making it a key player in the future landscape of renewable energy technologies. Continued research and investment in overcoming existing challenges will be crucial to harness the full potential of this technology.

Devices based on hydrogenase have also been investigated.

See also 

 Artificial photosynthesis
 Electrochemiluminescence
 Photoelectrochemical reduction of CO2
 Photoelectrochemistry
 Electrolysis of water
 Photocatalytic water splitting

References 

Hydrogen production
Photoelectrochemistry

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