Surface photocatalytic processes semiconductor particles

Abstract A convenient method to synthesize metal nanoparticles with unique properties is highly desirable for many applications. The sonochemical reduction of metal ions has been found to be useful for synthesizing nanoparticles of desired size range. In addition, bimetallic alloys or particles with core-shell morphology can also be synthesized depending upon the experimental conditions used during the sonochemical preparation process. The photocatalytic efficiency of semiconductor particles can be improved by simultaneous reduction and loading of metal nanoparticles on the surface of semiconductor particles. The current review focuses on the recent developments in the sonochemical synthesis of monometallic and bimetallic metal nanoparticles and metal-loaded semiconductor nanoparticles. 

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. 

Similar redox-combined processes have been reported. For example, it has been clarified by control experiments using a photoirradiated semiconductor electrode that the photocatalytic production of indazoles from substituted azobenzenes is based on the condensation of two intermediates formed through oxidation and reduction.38 40) In the case of oxidation of substituted olefins a similar redox combined mechanism is assumed cation and anion radicals are formed by the reaction of olefin with positive hole and of 02 with excited electron, respectively, and they react to produce a 4-membered ring intermediate, a dioxethane, to undergo bond cleavages into the desired products.4l) In the photocatalytic reactions, a positive hole and excited electron must react at the neighboring surface sites of a small semiconductor particle, enabling the combination of reduction and oxidation without the addition of an electrolyte, which is an indispensable component in electrolysis. However, in the particulate system the recombination of positive hole and electron is also likely, as well as... 

As stated previously, another distinction usually made is between slurry and supported catalyst reactors. In slurry photocatalytic reactors the catalyst is present in the form of small particles suspended in the water being treated. These reactors generally tend to be more efficient than supported catalyst reactors, because the semiconductor particles provide a larger contact surface area per unit mass. In fact, the state of the photocatalyst is important both to increase contaminant adsorption and to improve the distribution of absorbed radiation. In a slurry unit the photocatalyst has a better contact with the dissolved molecules and is allowed to absorb radiation in a more homogeneous manner over the reaction volume. Using suspended catalyst has been the usual practice in PTC, CPC, and other types of tubular reactors. The drawback of this reactor design is the requirement for separation and recovery of the very small particles at the end of the water treatment process. This may eventually complicate and slow down the water throughput. 

Colloids of semiconductors are also quite interesting for the transmembrane PET, as they possess both the properties of photosensitizers and electron conductors. Fendler and co-workers [246-250] have shown that it is possible to fix the cadmium sulfide colloid particles onto the membranes of surfactant vesicles and have investigated the photochemical and photocatalytic reactions of the fixed CdS in the presence of various electron donors and acceptors. Note, that there is no vectorial transmembrane PET in these systems. The vesicle serves only as the carrier of CdS particles which are selectively fixed either on the inner or on the outer vesicle surface and are partly embedded into the membrane. However, the size of the CdS particle is 20-50 A, i.e. this particle can perhaps span across the notable part of the membrane wall. Therefore it seems attractive to use the photoconductivity of CdS for the transmembrane PET. Recently Tricot and Manassen [86] have reported the observation of PET across CdS-containing membranes (see System 32 of Table 1), but the mechanism of this process has not been elucidated. Note, that metal sulfide semiconductor photosensitizers can be deposited also onto planar BLMs [251],... 

Investigations of metals (Ag [28-30], Au [31, 33], Pt [18, 22, 30], Pd [11], Cu, Fig [41] etc.) photoreduction at surfaces of porous samples and colloidal particles of Ti02 shows, that in such systems metal is deposited on the semiconductor surface as separate particles of subnanometric - nanometric size. Such metal particles have ohmic contact with semiconductor surface [11, 24, 32] and developed electronic structure [24, 28-32], So, we concluded that photocatalytic nickel(II) reduction takes place at irradiation of suspensions, containing mesoporous Ti02, Ni2+ and ethanol, this process resulting in the... 

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