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?

https://pureadmin.qub.ac.uk/ws/files/126683921/Edited_sudagar_R1.pdf

Electroless nickel, alloy, composite and nano coatings – A critical review

Publisher Summary Metals constitute a wide class of catalysts, and because catalysis occurs on the surface, there is an economic incentive, especially for precious metals, to obtain catalysts in the form of small metal particles. This, however, raises two main problems. One is fundamental in nature and addresses the question as to below which particle size the metallic properties are lost. The other is more practical and concerns the preparation and characterization of very small particles and their catalytic activity. The other problem concerns the practical ways of producing metals with particle sizes around the critical value calculated above. The easiest and most practical way to achieve this goal is to deposit the metal in low concentration on a high-surface-area support. The main purpose of using a carrier is, of course, to achieve a high dispersion of the metal and to stabilize it against sintering. In a number of reactions, however, the metal support is not inert and the overall process is actually a combination of two functions: that of the metal and that of the catalytically active support.

The Influence of Particle Size on the Catalytic Properties of Supported Metals

Nanoclusters open fascinating opportunities for quantum engineering because quantum-size effects become dominant in determining catalytic,1-3 optical,4 electronic,5 and magnetic6 properties. We succeeded in the controlled production of low-energy and high-flux monodispersed cluster beams, which allow for a systematic study of their reactivity after deposition onto a chemically inert substrate. We investigated the catalytic reaction that is the oxidation of CO on platinum and observed a distinct atom by atom size dependency for monodispersed platinum clusters on thin MgO(100) films. These results clearly show that the efficiency of a heterogeneous catalytic reaction can be tuned by the judicious choice of particle size.

Catalytic oxidation of carbon monoxide on monodispersed platinum clusters: Each atom counts

We studied the cyclotrimerization of acetylene on size-selected Pdn clusters (1 ≤ n ≤ 30) supported on thin MgO(100) films by thermal desorption and Fourier transform infrared spectroscopy. Surprisingly, the production of benzene is already observed on a single palladium atom at low temperature (300 K). Using density functional theory (DFT) calculations we show that free inert Pd atoms are activated by charge transfer from defect sites of the MgO substrate upon deposition. For larger clusters (7 ≤ n ≤ 30) benzene is additionally produced at a temperature of 430 K and our results suggest the existence of a critical ensemble of seven palladium atoms for this high-temperature reaction mechanism.

Acetylene cyclotrimerization on supported size-selected Pd-n clusters (1 <= n <= 30): one atom is enough!

Silver cluster ions (${\mathrm{Ag}}_{1}$${\mathrm{}}^{+}$, ${\mathrm{Ag}}_{3}$${\mathrm{}}^{+}$, ${\mathrm{Ag}}_{4}$${\mathrm{}}^{+}$, ${\mathrm{Ag}}_{5}$${\mathrm{}}^{+}$, ${\mathrm{Ag}}_{7}$${\mathrm{}}^{+}$, and ${\mathrm{Ag}}_{9}$${\mathrm{}}^{+}$) generated in a sputtering arrangement were filtered in energy selected by size, and deposited onto specimens containing binder-free AgBr microcrystals prepared from a photographic emulsion Development was observed after exposure to beams containing ${\mathrm{Ag}}_{4}$${\mathrm{}}^{+}$ or larger aggregates No development occurred after exposure to beams of smaller cluster sizes These experiments prove directly the existence of a ``critical'' size required for catalyzing development This size may depend on the development conditions (eg, the redox potential), as suggested by theories

Latent-image generation by deposition of monodisperse silver clusters.

Size-selected silver cluster ions have been produced in a mass spectrometer arrangement and have been deposited onto binder-free AgBr microcrystals. Clusters containing less than four silver atoms did not catalyze development (reduction) of the microcrystals. However, application of clusters containing four or more silver atoms rendered the crystals immediately developable in a conventional photographic developer. This for the first time proves directly, that a so-called latent image speck under these conditions of development requires a minimum number of four silver atoms.

The Role of Small Silver Clusters in Photography

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Latent-image generation by deposition of monodisperse silver clusters.

The Role of Small Silver Clusters in Photography