Small metal clusters exhibit physical and chemical properties that differ substantially from those of corresponding bulk metals. Furthermore, the properties of clusters vary greatly depending on the number of constituent atoms. Metal clusters with these characteristics currently attract great attention in a wide range of fields as new nanoscale functional materials. In recent years, the techniques to precisely synthesize metal clusters protected with organic ligands and polymers with atomic precision have advanced dramatically. In addition, substantial knowledge of the size-specific physical/chemical properties exhibited by these metal clusters has been accumulated. In this chapter, we describe the precise synthesis methods of the most studied thiolate (SR)-protected gold clusters Aun(SR)m and their heteroatom-substituted clusters (alloy clusters).
Part of the book: Descriptive Inorganic Chemistry Researches of Metal Compounds
Small gold clusters with diameters less than or equal to 2 nm (below approximately 200 atoms) possess geometric and electronic structures different from bulk gold. When these gold clusters are protected by ligands, these clusters can be treated as chemical compounds. This review focuses on gold clusters protected by chalcogenate (thiolate, selenolate, or tellurolate) ligands and describes the methods by which these clusters are synthesized as well as their geometric/electronic structures and physical and chemical properties. Recent findings regarding ligand exchange reactions, which may be used to impart functionality to these compounds, are also described.
Part of the book: Ligand
Methane exists abundantly around Japan as methane hydrate. As the effective use of such methane, the conversion of methane into methanol has recently attracted much attention. Photocatalytic reaction is one of the methods which convert methane into methanol without using much energy. However, it is indispensable to improve the photocatalytic activity for their practical use. Our group has attempted to improve the activity of mesoporous tungsten trioxide and titanium dioxide (m-WO3 and m-TiO2) photocatalysts, which convert methane into methanol, by loading the ultrafine metal clusters as cocatalyst on the photocatalysts. As a result, we have succeeded in loading ultrafine metal-cluster cocatalysts onto m-WO3 and m-TiO2 and thereby improving their photocatalytic activity. Our study also demonstrated that the kind of metal element suitable for each photocatalyst depends on the kind of the photocatalysts, and thereby it is important to select the metal clusters suitable for each photocatalyst for improving its photocatalytic activity.
Part of the book: Concepts of Semiconductor Photocatalysis