Semiconductor photocatalysis has been identified as a promising avenue for the conversion of solar energy into environmentally friendly fuels, most notably by the production of hydrogen from water.[1-5] Nanometer-scale materials in particular have attracted considerable scientific attention as the building blocks for light-harvesting applications.[6,7] Their desirable attributes include tunability of the optical properties with size, amenability to relatively inexpensive low-temperature processing, and a high degree of synthetic sophistication leading to increasingly complex and multi-functional architectures. For photocatalysis in particular, the high surface-to-volume ratios in nanoscale materials should lead to an increased availability of carriers for redox reactions on the nanoparticle surface. Recombination of photoexcited carriers directly competes with photocatalytic activity.[3] Charge separation is often achieved with multi-component heterostructures. An early example is the case of TiO2 powders functionalized with Pt and RuO2 particles, where photoexcited electrons are transferred to Pt (the reduction site) and holes to RuO2 (the oxidation site).[8] More recently, many colloidally synthesized nanometer-scale metal-semiconductor heterostructures have been reported.[7,9,10] A majority of these structures are made by thermal methods.[7,10] We have chosen to study photochemical formation of metal-semiconductor heterostructures. The detailed understanding of the mechanisms involved in photodeposition of metals on nanometer-scale semiconductors is necessary to enable a high degree of synthetic control. At the same time, because the results of metal deposition can be directly observed by electron microscopy, it can be used to understand how factors such as nanocrystal composition, shape, carrier dynamics, and surface chemistry influence the photochemical properties of semiconductor nanocrystals. In this communication, we report on the photodeposition of Pt on colloidal CdS and CdSe/CdS core/shell nanocrystals. Among the II-VI semiconductors, CdS is of particular interest because it has the correct band alignment for water photolysis[2] and has been demonstrated to be photocatalytically active.[11-16] We have found that the photoexcitation of CdS and CdSe/CdS in the presence of an organometallic Pt precursor leads to deposition of Pt nanoparticles on the semiconductor surface. Stark differences are observed in the Pt nanoparticle location on the two substrates, and the photodeposition can be completely inhibited by the modification of the semiconductor surface. Our results suggest that tuning of the semiconductor band structure, spatial organization and surface chemistry should be crucial in the design of photocatalytic nanostructures.
