Pt Nanoparticles Surfactant-Directed Assembled into Colloidal Spheres and usedas Substrates in Forming Pt Nanorods andNanowires**
Jingyi Chen, Yujie Xiong, Yadong Yin, andYounan Xia*
One-dimensional (1D) nanostructures have been extensivelystudied in recent years because of their extraordinary prop-erties arising from reduction in both dimensionality andsize, as well as their potential applications in fabricatingnanoscale devices.
In spite of many successful demonstra-tions, it remains a grand challenge to produce large quanti-ties of 1D nanostructures from various noble metals, togeth-er with well-controlled dimensions and morphologies. Here,we demonstrate that Pt nanoparticles formed via polyol re-duction could be assembled into spherical aggregates underthe direction of sodium dodecyl sulfate (SDS) and thenserve as substrates to generate Pt nanorods and nanowires.Platinum has found widespread use in a range of appli-cations due to its unique physical and chemical properties.
For instance, it prevails as a major catalyst in many industri-al processes such as the synthesis of nitric acid, reduction of pollutant gases emitted from automobiles, oil cracking, andproton-membrane-exchange (PME) fuel cells.
A greatdeal of effort has been devoted to the preparation of Ptnanostructures via chemical protocols.
However, most of these previous studies have been limited to nanoparticles;only polycrystalline nanorods and nanotubes have recentlybeen prepared by templating against channels within porousmaterials,
Ag or Se nanowires,
and assemblies of organicsurfactants.
Although template-directed syntheses haveproven straightforward and versatile, they are restricted bya number of drawbacks that may include, for example, therequirement of template removal in order to generate pureproduct, the limited scope of morphological variation, andthe polycrystallinity usually associated with the product.In a recent study,
we discovered that the addition of asmall amount of an iron species (Fe
) to the polyolprocess could significantly alter the reduction kinetics of aPt precursor and thus induce the formation of Pt nanorodscharacterized by uniform diameters and relatively highaspect ratios. We demonstrate here that the synthesis couldbe further modified to program the growth of such nanorodsinto nanowires with lengths
500 nm. Based on our previ-ous scanning electron microscopy (SEM) and transmissionelectron microscopy (TEM) studies of the reaction mecha-nism, Pt nanoparticles tended to aggregate into large colloi-dal spheres before the concentration of Pt atoms was re-duced to a certain level to facilitate highly anisotropicgrowth. When SDS was added as the directing agent, thespherical aggregates could be synthesized with much smallersizes. These spherical aggregates were sufficiently stable insolvents such as acetone, alcohol, and water, even under theapplication of sonication for up to 30 min. As a result, thesespherical aggregates could serve as substrates to grow Ptnanorods and nanowires through polyol reduction in thepresence of a trace amount of iron species. As a major ad-vantage over previous protocols, one might be able to usematerials less precious than Pt to form the substrates forgrowing Pt nanowires with controllable lengths.
Figure 1 illustrates the two-step protocol that was de-signed to achieve a tight control over the formation of Ptnanorods and nanowires. In the first step, Pt nanoparticleswere formed and then assembled into spherical aggregateswhen H
was reduced by ethylene glycol (EG) at110
C in the presence of SDS. Depending on the molarratio of H
to SDS, the Pt nanoparticles were found toexist in different forms. When the molar ratio of H
toSDS was lower than 1:1, the Pt nanoparticles were well-dis-persed as individual entities (product A in Figure 1). As themolar ratio was increased to 1:5, the Pt nanoparticles weredirected by SDS to further assemble into submicrometer-sized spheres (product B in Figure 1). These spherical aggre-gates could be separated from the reaction solution andwashed several times with ethanol and water. In the nextstep, these spherical aggregates were added to 4 mL of EGwith a trace amount of iron species. After heating at 110
Cin air for one hour to activate the surface layer of the aggre-gates, certain amounts of H
/EG and PVP/EG (PVP:poly(vinyl pyrrolidone)) were then added dropwise to thereaction. Similar to our previous observations,
species were reduced at an extremely slow rate, and the re-sultant Pt atoms started to nucleate and grow into uniform1D nanostructures on the surface of each aggregate (pro-duct C in Figure 1).Figure 2 shows TEM and SEM images of Pt nanostruc-tures corresponding to the products illustrated in Figure 1.Consistent with the schematic drawing, uniform sphericalaggregates of Pt nanoparticles could be synthesized underthe direction of SDS and further used as substrates to formPt nanorods and nanowires. Figure 2A shows a TEM imageof the Pt nanoparticles when the reduction of the Pt
[*] J. Chen, Dr.Y. Xiong, Prof.Y. XiaDepartment of Chemistry, University of WashingtonSeattle, WA 98195-1700 (USA)Fax: (
1)206-685-8665E-mail: email@example.comDr. Y. YinThe Molecular FoundryLawrence Berkeley National LaboratoryBerkeley, CA 94720 (USA)[**] This work was supported in part by the NSF (DMR-0451788) anda fellowship from the David and Lucile Packard Foundation. Y.X.is a Camille Dreyfus Teacher Scholar. This work used the Nano-tech User Facility (NTUF) at the University of Washington, amember of the National Nanotechnology Infrastructure Network(NNIN) funded by the NSF. We also thank the Molecular Foundryat the Lawrence Berkeley National Laboratory for the HRTEManalysis.Supporting information for this article is available on the WWWunder http://www.small-journal.com or from the author.
2006 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim
, No.11, 1340–1343
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