Metal Loaded Oxide Semiconductors

As seen in reaction (6.5.3) photogenerated holes are consumed, making electron-hole separation more effective as needed for efficient water splitting. The evolution of CO2 and O2 from reaction (6.5.6) can promote desorption of oxygen from the photocatalyst surface, inhibiting the formation of H2O through the backward reaction of H2 and O2. The desorbed CO2 dissolves in aqueous suspension, and is then converted to HCOs to complete a cycle. The mechanism is still not fully understood, with the addition of the same amount of different carbonates, see Table 6.2, showing very different results [99]. Moreover, the amount of metal deposited in the host semiconductor is also a critical factor that determines the catalytic efficiency, see Fig. 6.7. 

Catalyst. (0.3 wt% Pt/Ti02), 0.3 g yf catalyst suspended in 350 ml of water placed in an inner irradiator quartz cell Irradiated with high-pressure mercnry lamp (400 W) 

With reference to Fig. 6.7, note there is no photocatalytic activity without Ft loading [99] the rate of gas evolution increases with increasing Ft content reaching a maximum at 0.3 wt%. Other metals have shown similar trends in photocatalytic activity. Therefore, it is suggested that metal loading is one of the essential requirements for photocatalytic decomposition of liquid water. However the back reaction of evolved gas on the Ft particles increases with Ft loading. To suppress the backward reaction of H2 

Catalyst Rate of Hi evolution (iimol/h) Pt-catalyst Rate of Hi evolution (pmol/h) Light abs-( nm) 

Catalyst, 1.0 g Water 350 inL Pt 0 1 wt%. Light source 400 W high-pressure Hg lamp, iniiei iiiadiaiion type quatz cell 

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Various pairs of inorganic ions such as lOsVr, Fe /Fe, and Ce /Ce have been used as redox mediators to facilitate electron-hole separation in metal loaded oxide semiconductor photocatalysts [105-107], Two different photocatalysts, Pt-Ti02 (anatase) and Ti02 (rutile), suspended in an aqueous solution of Nal were employed to produce H2 and O2 under, respectively, the mediation of 1 (electron donor) and IOs (electron acceptor) [105]. The following steps are involved in a one-cell reaction in the presence of UV light. 

In addition, the rate of Oz reduction, forming 02 by electron, is of importance in preventing carrier recombination during photocatalytic processes utilizing semiconductor particles. 02 formation may be the slowest step in the reaction sequence for the oxidation of organic molecules by OH radicals or directly by positive holes. Cluster deposition of noble metals such as Pt, Pd, and Ag on semiconductor surfaces has been demonstrated to accelerate their formation because the noble metal clusters of appropriate loading or size can effectively trap the photoinduced electrons [200]. Therefore, the addition of a noble metal to a semiconductor is considered as an effective method of semiconductor surface modification to improve the separation efficiency of photoinduced electron and hole pairs. 

In the past several years noble metal loading, ion doping, composite metal-oxide semiconductors, and multi-component semiconductors have been meticulously designed, fabricated, and then investigated... 

Platinum-loaded Ti02 systems can be considered as a short-circuited photo-electrochemical cell where the Ti02 semiconductor electrode and metal Pt counterelectrode are brought into contact [159]. Light irradiation can induce electron-hole (e -h +) pair formation and surface oxidation and also reduction reactions on each Pt/Ti02 particle (Figure 4.11). These powder-based systems lack the advantage of... 

The addition of a second species can cause a decrease in charge recombination and an increase in the TiOz photocatalytic efficiency. Such behavior was examined by loading a series of species on the surface or into the crystal lattice of photocatalysts inorganic ions [148-152], noble metals [153,154], and other semiconductor metal oxides [155], It was thus proven that modifications produced by these species can change semiconductor surface properties by altering interfacial electron-transfer events and thus the photocatalytic efficiency. 

Figure 4.11 explains how the loaded metal can act as catalyst for both the reductive and oxidative reactions. The essential point is that the barrier height at the metal/semiconductor interface is changeable by the principle of Fig. 4 10 or other mechanisms. Thus, when the band bending is weak, photoexcited electrons mostly enter the metal and the metal acts as a catalyst for a reductive reaction (Fig. 4.11(A)). On the other hand, when the band bending is strong, the holes in the valence band mostly enter the metal and the metal acts as a catalyst for an oxidative reaction (Fig. 4.11(B)). The prevalence of one over the other depends on the magnitude of the band bending, i.e., on the relative rates of reaction of the electrons and holes at the metal-free semiconductor surface.

The details of the operating principles of the dye-sensitized solar cell are given in Fig. 2. The photo excitation of the metal-to-ligand charge transfer (MLCT) of the adsorbed sensitizer (Eq. 1) leads to injection of electrons into the conduction band of the oxide (Eq. 2). The oxidized dye is subsequently reduced by electron donation from an electrolyte containing the iodide/triiodide redox system (Eq. 3). The injected electron flows through the semiconductor network to arrive at the back contact and then through the external load to the counter... 

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