Metal hybrid nanoparticles for catalytic organic and photochemical transformations.

Abstract

In order to understand heterogeneous catalytic reactions, model catalysts such as a single crystalline surface have been widely studied for many decades. However, catalytic systems that actually advance the reactions are three-dimensional and commonly have multiple components including active metal nanoparticles and metal oxide supports. On the other hand, as nanochemistry has rapidly been developed and been applied to various fields, many researchers have begun to discuss the impact of nanochemistry on heterogeneous catalysis. Metal hybrid nanoparticles bearing multiple components are structurally very close to the actual catalysts, and their uniform and controllable morphology is suitable for investigating the relationship between the structure and the catalytic properties in detail. In this Account, we introduce four typical structures of metal hybrid nanoparticles that can be used to conduct catalytic organic and photochemical reactions. Metal@silica (or metal oxide) yolk-shell nanoparticles, in which metal cores exist in internal voids surrounded by thin silica (or metal oxide) shells, exhibited extremely high thermal and chemical stability due to the geometrical protection of the silica layers against the metal cores. The morphology of the metal cores and the pore density of the hollow shells were precisely adjusted to optimize the reaction activity and diffusion rates of the reactants. Metal@metal oxide core-shell nanoparticles and inverted structures, where the cores supported the shells serving an active surface, exhibited high activity with no diffusion barriers for the reactants and products. These nanostructures were used as effective catalysts for various organic and gas-phase reactions, including hydrogen transfer, Suzuki coupling, and steam methane reforming. In contrast to the yolk- and core-shell structures, an asymmetric arrangement of distinct domains generated acentric dumbbells and tipped rods. A large domain of each component added multiple functions, such as magnetism and light absorption, to the catalytic properties. In particular, metal-semiconductor hybrid nanostructures could behave as effective visible photocatalysts for hydrogen evolution and CO oxidation reactions. Resulting from the large surface area and high local concentration of the reactants, a double-shell hollow structure showed reaction activities higher than those of filled nanoparticles. The introduction of plasmonic Au probes into the Pt-CdS double-shell hollow particles facilitated the monitoring of photocatalytic hydrogen generation that occurred on an individual particle surface by single particle measurements. Further development of catalysis research using well-defined metal hybrid nanocatalysts with various in situ spectroscopic tools provides a means of maximizing catalytic performances until they are comparable to or better than those of homogeneous catalysts, and this would have possibly useful implications for industrial applications.