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By Edward William Lane

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Because the electron–hole recombination is particularly sustained, moderate quantum yields for water splitting can very often be achieved only when specific catalyst (generally called cocatalysts in the context of photocatalytic systems) are deposited on the semiconductor particles. In a similar way to sacrificial agents, these materials act as electron and/or hole scavengers and therefore play a fundamental role in achieving effective charge separation. Noble-metal-based materials are known to be among the most active catalysts for water reduction and oxidation and have been traditionally widely used as cocatalysts for photocatalytic water splitting; this class of materials, however, is generally very efficient in catalyzing the reverse reaction (combination of oxygen and hydrogen to yield water) as well.

Although platinum is among the most widely used materials in the literature for oxygen evolution from water, in particular in the context of solar water splitting, its performances as a WOC are actually moderate. In fact, it is believed that only metal oxides are expected to be sufficiently robust to withstand the highly oxidizing conditions necessary for oxygen evolution from water [154]. Until the end of 2000s, the most effective WOCs were considered to be RuO2 and IrO2, which are both based on quite expensive and scarce metals.

In this work, a bio-inspired cubane-like cluster based on molybdenum and sulfur (Mo3S4) was grafted on p-type silicon, showing very efficient water splitting in the absence of external bias or sacrificial agents [149]. 2 Water Oxidation Catalysts Compared to water reduction, the mechanism of water oxidation reaction is much more complex and strongly depends on the pH conditions as well as on the nature of the surface on which it occurs. The general mechanism for water oxidation occurring in alkaline solutions at the surface of metals is believed to be the following [150]: M + OH − →†M − OH ads M − OH ads + OH → M − Oads + H 2O + e − 2M − OH ads †→ M − Oads + H 2O + M 2M − Oads → 2M + O2 (I) − (IIa) (IIb) (III) In acidic solutions, the mechanism is believed to be analogous, with the reactive species in the first step (I) being H2O instead of OH−.

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