Although gold is the subject of one of the most ancient themes of investigation in science, its renaissance now leads to an exponentially increasing number of publications, especially in the context of emerging nanoscience and nanotechnology with nanoparticles and self-assembled monolayers (SAMs). We will limit the present review to gold nanoparticles (AuNPs), also called gold colloids. AuNPs are the most stable metal nanoparticles, and they present fascinating aspects such as their assembly of multiple types involving materials science, the behavior of the individual particles, size-related electronic, magnetic and optical properties (quantum size effect), and their applications to catalysis and biology. Their promises are in these fields as well as in the bottom-up approach of nanotechnology, and they will be key materials and building block in the 21st century. Whereas the extraction of gold started in the 5th millennium B.C. near Varna (Bulgaria) and reached 10 tons per year in Egypt around 1200-1300 B.C. when the marvelous statue of Touthankamon was constructed, it is probable that “soluble” gold appeared around the 5th or 4th century B.C. in Egypt and China. In antiquity, materials were used in an ecological sense for both aesthetic and curative purposes. Colloidal gold was used to make ruby glass 293 Chem. Rev. 2004, 104, 293−346

Gold nanoparticles: assembly, supramolecular chemistry, quantum-size-related properties, and applications toward biology, catalysis, and nanotechnology.

The interest in nanoscale materials stems from the fact that new properties are acquired at this length scale and, equally important, that these properties * To whom correspondence should be addressed. Phone, 404-8940292; fax, 404-894-0294; e-mail, mostafa.el-sayed@ chemistry.gatech.edu. † Case Western Reserve UniversitysMillis 2258. ‡ Phone, 216-368-5918; fax, 216-368-3006; e-mail, burda@case.edu. § Georgia Institute of Technology. 1025 Chem. Rev. 2005, 105, 1025−1102

Chemistry and properties of nanocrystals of different shapes.

Nanocrystals are fundamental to modern science and technology. Mastery over the shape of a nanocrystal enables control of its properties and enhancement of its usefulness for a given application. Our aim is to present a comprehensive review of current research activities that center on the shape-controlled synthesis of metal nanocrystals. We begin with a brief introduction to nucleation and growth within the context of metal nanocrystal synthesis, followed by a discussion of the possible shapes that a metal nanocrystal might take under different conditions. We then focus on a variety of experimental parameters that have been explored to manipulate the nucleation and growth of metal nanocrystals in solution-phase syntheses in an effort to generate specific shapes. We then elaborate on these approaches by selecting examples in which there is already reasonable understanding for the observed shape control or at least the protocols have proven to be reproducible and controllable. Finally, we highlight a number of applications that have been enabled and/or enhanced by the shape-controlled synthesis of metal nanocrystals. We conclude this article with personal perspectives on the directions toward which future research in this field might take.

Shape‐Controlled Synthesis of Metal Nanocrystals: Simple Chemistry Meets Complex Physics?

While the nanocatalysis field has undergone an explosive growth during the past decade, there have been very few studies in the area of shape-dependent catalysis and the effect of the catalytic process on the shape and size of transition metal nanoparticles as well as their recycling potential. Metal nanoparticles of different shapes have different crystallographic facets and have different fraction of surface atoms on their corners and edges, which makes it interesting to study the effect of metal nanoparticle shape on the catalytic activity of various organic and inorganic reactions. Transition metal nanoparticles are attractive to use as catalysts due to their high surface-to-volume ratio compared to bulk catalytic materials, but their surface atoms could be so active that changes in the size and shape of the nanoparticles could occur during the course of their catalytic function, which could also affect their recycling potential. In this Feature Article, we review our work on the effect of the shape of the colloidal nanocatalyst on the catalytic activity as well as the effect of the catalytic process on the shape and size of the colloidal transition metal nanocatalysts and their recycling potential. These studies provide important clues on the mechanism of the reactions we studied and also can be very useful in the process of designing better catalysts in the future.

Catalysis with transition metal nanoparticles in colloidal solution: nanoparticle shape dependence and stability.

The activation energies and the average rate constants are determined in the 298 K−318 K temperature range for the early stages of the nanocatalytic reaction between hexacyanoferrate (III) and thiosulfate ions using 4.8 ± 0.1 nm tetrahedral, 7.1 ± 0.2 nm cubic, and 4.9 ± 0.1 nm “near spherical” nanocrystals. These kinetic parameters are found to correlate with the calculated fraction of surface atoms located on the corners and edges in each size and shape.

Shape-Dependent Catalytic Activity of Platinum Nanoparticles in Colloidal Solution

Using oxalate as a stabilizing agent, stable colloidal solutions of platinum nanoparticles of different shape distributions were prepared by reducing K2[Pt(C2O4)2], K2PtCl6, or K2PtCl4 with hydrogen. The mean diameters of the Pt nanoparticles prepared from these precursors are 6.5, 3.5, and 7.9 nm, respectively. UV−vis absorption spectroscopy and transmission electron microscopy studies on the preparation processes and the products indicate that not only the rate of reduction and particle size but also the shape distributions of the prepared Pt nanoparticles depend on the used precursors. The reduction of K2[Pt(C2O4)2] in water at room temperature is quite slow, while adding suitable amounts of CaCl2 or increasing temperature can accelerate the reduction process. Pt nanoparticles prepared from K2[Pt(C2O4)2] have quite narrow size and shape distributions, and the selectivity of cubic nanoparticles is greater than 90%. Adding CaCl2 in the reaction system does not obviously affect the size and shape distribu...

Shape-Selective Preparation and Properties of Oxalate-Stabilized Pt Colloid

Assembling colloidal Au nanoparticles with functionalized self-assembled monolayers

Colloidal Au nanoparticles were assembled on a gold substrate via a p-aminothiophenol coupling layer. The surface coverage of Au nanoparticles was found to be closely related to the pH value of gol...

pH-Dependent adsorption of gold nanoparticles on p-aminothiophenol-modified gold substrates

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Shape-Selective Preparation and Properties of Oxalate-Stabilized Pt Colloid

Assembling colloidal Au nanoparticles with functionalized self-assembled monolayers

pH-Dependent adsorption of gold nanoparticles on p-aminothiophenol-modified gold substrates