This feature article highlights work from the authors' laboratories on the synthesis, assembly, reactivity, and optical applications of metallic nanoparticles of nonspherical shape, especially nanorods. The synthesis is a seed-mediated growth procedure, in which metal salts are reduced initially with a strong reducing agent, in water, to produce approximately 4 nm seed particles. Subsequent reduction of more metal salt with a weak reducing agent, in the presence of structure-directing additives, leads to the controlled formation of nanorods of specified aspect ratio and can also yield other shapes of nanoparticles (stars, tetrapods, blocks, cubes, etc.). Variations in reaction conditions and crystallographic analysis of gold nanorods have led to insight into the growth mechanism of these materials. Assembly of nanorods can be driven by simple evaporation from solution or by rational design with molecular-scale connectors. Short nanorods appear to be more chemically reactive than long nanorods. Finally, optical applications in sensing and imaging, which take advantage of the visible light absorption and scattering properties of the nanorods, are discussed.
Gold nanorods prepared by a seed-mediated growth approach use ∼4-nm gold nanospheres as the seeds and subsequent reduction of metal salt with a weak reducing agent (ascorbic acid) in the presence of a directing surfactant to produce nanorods. If insufficient ascorbic acid is added in the growth step, then metal salt remains. Additional input of ascorbic acid preferentially deposits more metal at the ends of the nanorods, to yield “dogbone”-like structures. Surprisingly, heat treatment of the unpurified gold nanorods (prepared with an insufficient amount of ascorbic acid) yielded fatter gold nanorods; the oxidation product of ascorbic acid appears to act as a reductant at higher temperature. These modified shapes of the gold nanorods directly influence their optical properties.
We report here the solution-phase synthesis of highly uniform and monodisperse cubic Cu 2 O nano-and microcubes. Copper(II) salts in water are reduced with sodium ascorbate in air, in the presence of a surfactant. The average edge length of the cubes varies from 200 to 450 nm, as a function of surfactant concentration. Transmission electronic microscopy suggests that these cubes are composed of small nanoparticles and appear to be hollow.
The rapid, microwave-assisted aerobic synthesis of silver nanowires based on the polyol method is described. Benchtop dissolution of NaCl and AgNO3 (ratio 1:6 to 1:3) in ethylene glycol and subsequent heating using microwave irradiation (300 W) in the presence of polyvinylpyrrolidone generates Ag nanowires in ∼80% yield in 3.5 min. Upon purification, microscopy (TEM, SEM) and powder X-ray diffraction reveal a uniform set of crystalline Ag nanowires with dimensions of 45 nm × 4−12 μm. Wire formation is highly dependent upon the microwave heating power, time, and NaCl:AgNO3 ratio because of the rapid heating process and the presence of O2 as an etching coreagent. Extended microwave heating causes the wires to fuse if in proximity or degrade to shorter wires presumably via the etching reaction. In the absence of O2/Cl-, the wires melt upon extended microwave heating (>4 min), suggesting that nanowire melting may contribute to the observed morphology under etching conditions. Compared to existing wet-chemical methods using traditional heating techniques, microwave irradiation not only rapidly heats, but dielectric heating of the growing wires also occurs, resulting in accelerated deposition of Ag0 at the wire ends. Furthermore, this high yielding preparation does not require any external seed crystals, precursors, or mechanical stirring and is conducted under ambient O2 conditions, leading to significant potential for the large-scale fabrication of Ag nanowires using this simple approach.
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