The Role of Metal Nanoparticles in Promoting Photocatalysis by TiO2

In this review, we highlight the role played by metal nanoparticles (NPs) in photocatalytic oxidation with titania as a support. This is presented in two parts, namely, partial photo-oxidation in which an organic sacrificial agent is oxidised in anaerobic conditions to produce hydrogen (photo-reforming), and photo-oxidative mineralisation of organics in aerobic conditions. We present some rules for such reactions that dictate which organic molecules can react readily, and which metals are likely to be useful for such reactions. Generally, the presence of metal NPs enhances enormously the ability of titania to yield hydrogen from photo-reforming, and a wide range of molecules can be used, including biomass. The metal NPs most used are those that are easily reduced, that is, the precious metals. The large enhancement in rate seen with metal for hydrogen production is not so extreme for the oxidation reactions, but is still significant. An important factor in all of this catalysis is the nature of the interaction between the metal NPs, which can play a multiplicity of chemical and electronic roles, and the photoactive support. A sharp dependency of rate on loading of metal is found, with maximum rates at similar to 0.5-2 wt% loading, depending on the metal used. The source of this dependency is the bifunctional nature of the system, in which the intimacy of both materials is crucial to performance. This rate variation is linked to the interface between the two, which is then linked to the size of the metal NPs. In fact, the rate is proportional to an area adjacent to the metal particles that we call the expanding photocatalytic area and overlap (EPAO) kinetic model. This model describes the dependence well. Rising rates with increasing coverage of particles is associated with increase in this total area but, at the maximum, these areas overlap and at higher loadings the available active area diminishes, reproducing the observed behaviour well.