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 are 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:
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:
A photosynthetic cell is another form of photoelectrolytic cell, with the output in that case being carbohydrates instead of molecular hydrogen.
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.
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-TiO 2) 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:
photo-anode made of a n-type semiconductor and a metal cathode
photo-anode made of a n-type semiconductor and a photo-cathode made of a p-type semiconductor
photo-cathode made of a p-type semiconductor and a metal anode
There are several requirements for photoelectrode materials in PEC production:
light absorbance: determined by band gap and appropriate for solar irradiation spectrum
charge transport: photoelectrodes must be conductive (or semi-conductive) to minimize resistive losses
suitable band structure: large enough band gap to split water (1.23V) and appropriate positions relative to redox potentials for and
catalytic activity: high catalytic activity increases efficiency of the water-splitting reaction
stability: materials must be stable to prevent decomposition and loss of function
In addition to these requirements, materials must be low-cost and earth abundant for the widespread adoption of PEC water splitting to be feasible.
While the listed requirements can be applied generally, photoanodes and photocathodes have slightly different needs. A good photocathode will have early onset of the oxygen evolution reaction (low overpotential), a large photocurrent at saturation, and rapid growth of photocurrent upon onset. Good photoanodes, on the other hand, will have early onset of the hydrogen evolution reaction in addition to high current and rapid photocurrent growth. To maximize current, anode and cathode materials need to be matched together; the best anode for one cathode material may not be the best for another.
TiO 2 and other metal oxides are still most prominent catalysts for efficiency reasons. Including SrTiO 3 and BaTiO 3, this kind of semiconducting titanates, the conduction band has mainly titanium 3d character and the valence band oxygen 2p character. The bands are separated by a wide band gap of at least 3 eV, so that these materials absorb only UV radiation. Change of the TiO 2 microstructure has also been investigated to further improve the performance, such as TiO 2 nanowire arrays or porous nanocrystalline TiO 2 photoelectrochemical cells.
GaN is another option, because metal nitrides usually have a narrow band gap that could encompass almost the entire solar spectrum. GaN has a narrower band gap than TiO 2 but is still large enough to allow water splitting to occur at the surface. GaN nanowires exhibited better performance than GaN thin films, because they have a larger surface area and have a high single crystallinity which allows longer electron-hole pair lifetimes. Meanwhile, other non-oxide semiconductors such as GaAs, MoS 2, WSe 2 and MoSe 2 are used as n-type electrode, due to their stability in chemical and electrochemical steps in the photocorrosion reactions.
In 2013 a cell with 2 nanometers of nickel on a silicon electrode, paired with a stainless steel electrode, immersed in an aqueous electrolyte of potassium borate and lithium borate operated for 80 hours without noticeable corrosion, versus 8 hours for titanium dioxide. In the process, about 150 ml of hydrogen gas was generated, representing the storage of about 2 kilojoules of energy.
Structuring of absorbing materials has both positive and negative affects on cell performance. Structuring allows for light absorption and carrier collection to occur in different places, which loosens the requirements for pure materials and helps with catalysis. This allows for the use of non-precious and oxide catalysts that may be stable in more oxidizing conditions. However, these devices have lower open-circuit potentials which may contribute to lower performance.
Researchers have extensively investigated the use of hematite (α-Fe2O3) in PEC water-splitting devices due to its low cost, ability to be n-type doped, and band gap (2.2eV). However, performance is plagued by poor conductivity and crystal anisotropy. Some researchers have enhanced catalytic activity by forming a layer of co-catalysts on the surface. Co-catalysts include cobalt-phosphate and iridium oxide, which is known to be a highly active catalyst for the oxygen evolution reaction.
Tungsten(VI) Oxide (WO3) , which exhibits several different polymorphs at various temperatures, is of interest due to its high conductivity but has a relatively wide, indirect band gap (~2.7 eV) which means it cannot absorb most of the solar spectrum. Though many attempts have been made to increase absorption, they result in poor conductivity and thus WO3 does not appear to be a viable material for PEC water splitting.
With a narrower, direct band gap (2.4 eV) and proper band alignment with water oxidation potential, the monoclinic form of BiVO4 has garnered interest from researchers. Over time, it has been shown that V-rich and compact films are associated with higher photocurrent, or higher performance. Bismuth Vanadate has also been studied for solar generation from seawater, which is much more difficult due to the presence of contaminating ions and a more harsh corrosive environment.
^Berinstein, Paula (2001-06-30). Alternative energy: facts, statistics, and issues. Greenwood Publishing Group. ISBN1-57356-248-3. Another photoelectrochemical method involves using dissolved metal complexes as a catalyst, which absorbs energy and creates an electric charge separation that drives the water-splitting reaction.
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