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 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:
H 2 O ( l ) + [ hv ] + 2 h + ⟶ 2 H + ( aq ) + 1 2 O 2 ( g ) {\displaystyle {\ce {H2O(l) + [hv] + 2h+ -> 2H+ (aq) + 1/2O2(g)}}}
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:
2 H + + 2 e − ⟶ H 2 ( g ) {\displaystyle {\ce {2H+ + 2e- -> H2(g)}}}
A photosynthetic cell is another form of photoelectrolytic cell, with the output in that case being carbohydrates instead of molecular hydrogen.
Photoelectrolytic cell
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. 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. 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. Photoelectrolytic cells have passed the 10 percent economic efficiency barrier. Corrosion of the semiconductors remains an issue, given their direct contact with water. Research is now ongoing to reach a service life of 10000 hours, a requirement established by the United States Department of Energy.
Other photoelectrochemical cells 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. 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-TiO2) to produce electrical energy.
Materials for photoelectrolytic cells 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:
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