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Mikaeili, F.;  Gilmore, T.;  Gouma, P. Photocatalysis for Water Splitting Capabilities. Encyclopedia. Available online: (accessed on 11 December 2023).
Mikaeili F,  Gilmore T,  Gouma P. Photocatalysis for Water Splitting Capabilities. Encyclopedia. Available at: Accessed December 11, 2023.
Mikaeili, Fateh, Tessa Gilmore, Pelagia-Irene Gouma. "Photocatalysis for Water Splitting Capabilities" Encyclopedia, (accessed December 11, 2023).
Mikaeili, F.,  Gilmore, T., & Gouma, P.(2022, November 03). Photocatalysis for Water Splitting Capabilities. In Encyclopedia.
Mikaeili, Fateh, et al. "Photocatalysis for Water Splitting Capabilities." Encyclopedia. Web. 03 November, 2022.
Photocatalysis for Water Splitting Capabilities

Water could be used as the main source of hydrogen production. By definition, the dissociation of the water molecules into their constituents (hydrogen and oxygen) is known as water splitting. Rapid population growth and ever-increasing energy consumption have resulted in increased environmental pollution and energy demands. Accordingly, studies and research on innovative and efficient ways of wastewater clean-up and exploiting eco-friendly and renewable energy sources such as sunlight have become a necessity. 

photochemical hydrogen water

1. Photocatalytic Water Splitting

Photocatalytic water splitting uses sunlight, water, and a semiconducting photocatalyst to dissociate water molecules through the two redox reactions mentioned above. The breakthrough study was started in 1972 by Fujishima and Honda [1] in a photoelectrochemical cell using TiO2 as their photocatalyst. Afterwards, photocatalytic water splitting received an enormous amount of attention due to its potential. During the past 40 years, various photocatalyst materials and systems were used to split water under ultraviolet light or visible light. Photocatalytic water splitting could be categorized into either photochemical water splitting or photoelectrochemical (PEC) water splitting [2].
Both types include three basic steps: a semiconductor photocatalyst absorbs more photon energy than the band gap energy of the photocatalyst and excites the electron–hole pairs; the photogenerated charge carriers are then separated out and move toward different sites of the photocatalyst’s surface; finally, at these sites water reacts with the charge carriers in two separate redox reactions and therefore is reduced by electrons to produce H2 in the same time its oxidized by holes to produce O2 [3].
Even though the general concept of photochemical and PEC systems is the same, the setup is different. In photochemical reactions, the water-splitting reaction takes place at the semiconductor–electrolyte junction, whereas in a PEC setup the reaction takes place at two different sites. In this method, illuminating the cathode or anode would provide the required potential [2].
In order to understand the difference between these two setups, an important characteristic of the semiconductor should be taken into consideration. This characteristic is the band edge position of the semiconductor [4]. A suitable semiconductor for water splitting has a valance band position that is more positive than the O2/H2O energy level (1.23–0.059 pH, V versus NHE) and a conduction band position that is more negative than the H+/H2 energy level (0–0.059 pH, V versus NHE). In other words, in the ideal case, a single semiconductor material should have a band gap that is large enough to split water, so the conduction band energy and valance band energy should straddle the electrochemical potentials E0 (H+/H2) and E0 (O2/H2O) [5]. However, in the case of a single semiconducting material, the second requirement is not satisfied in most of the material systems (as will be discussed in depth in further sections). Scaife [6] mentioned in 1980 that it is exceptionally difficult to find a single semiconductor photocatalyst with both characteristics. This difficulty is why many studies focus on two semiconductor photocatalytic systems (PEC water splitting). By using two different materials, each one will act as either a photoanode or photocathode, which when used in tandem, satisfies the band gab requirement.
A two-step PEC system involves water splitting in two parts: one for the hydrogen evolution using a semiconductor that satisfies the conduction band position for that reaction, and the other for the O2 evolution. In this method, a semiconductor that only partially satisfies the band edge position for the redox reaction could still be used in conjunction with another semiconductor to facilitate a water-splitting reaction [7]. However, there are many drawbacks to and critics of this method.
First, it requires the number of photons to be double that for the one-step system to achieve overall water splitting. The number of photons required in two-step photocatalytic water splitting is eight, whereas in one-step overall water splitting it is four. This difference causes the amount of hydrogen and oxygen produced in a two-step process to be half that of the one-step process at light absorption values and apparent quantum yield of unity [8].
Second, there are still some drawbacks that involve promoting electron transfer between two semiconductors and opposing and suppressing the possible backward reactions that involve shuttle redox mediators [9]. Therefore, since the number of backward electron-transfer routes increases, which is the result of an increase in the number of elementary steps, this route is kinetically unfavorable. Overall, two different studies summarized the techno-economic analyses which determined that a high capital cost prevents PEC devices from being implemented into solar hydrogen production. For these reasons, authors will focus on one-step photochemical water-splitting systems.

2. Photochemical Water Splitting

In order to understand the photocatalytic process in photochemical water splitting, which is a quite complicated process, a simple step-by-step description of the process will be discussed in this section. Overall, the following steps occur:
  • Photon absorption: Photocatalysts absorb photons and generate electrons and holes at the surface. When the material absorbs the photons with an energy that is equal to or more than the band gap energy of the semiconductor, an electron jumps from the valance band to the conduction band, leaving a hole in the valance band. Electrons and holes release energy (heat) and move the conduction and valance bands to the minimum and the maximum positions, respectively [10].
  • Charge transport: After the charge carriers have been excited, there are different scenarios that could occur. The first scenario, which is highly unfavorable, is that excited-state conduction band electrons and valance band holes recombine. In the case where there is not a suitable force to separate these charged carriers, the energy stored in them will dissipate in a very short time (typically a couple of nanoseconds) in the form of heat. In the event that there is a defect state, a trap on the surface of the material, or a suitable scavenger, the recombination is potentially avoided. Another scenario is that the excited electrons and holes will move to the respective reaction sites [11]. In bulk, if the carriers do not recombine, it is only possible for either an electron or hole to be accumulated at the anode or cathode, whereas in a nanostructured semiconductor both of the photogenerated charge carriers could be present at the same surface. Low dimensionality, few numbers of defects, and a high surface area in nanostructured materials result in key differences in electron transport compared to their bulk counterparts [12][13].
  • After the charges have moved to the reaction sites in the material/water interface, they can participate in the surface chemical reactions between these carriers and the compounds (e.g., water) [2].


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