Xianmao Lu

Pd-Pt Bimetallic Nanodendrites with High Activity for Oxygen Reduction

Extending Platinum Catalysts Platinum performs extremely well as a catalyst for the oxygen-reduction reaction that runs under highly acidic conditions in proton-exchange membrane fuel cells, but is expensive. One strategy for reducing costs is to increase the surface area of the platinum. Lim et al. (p. 1302, published online 14 May) describe a simple chemical route, in which Pt ions in solution are reduced onto Pd seed crystals, which creates faceted Pt nanocrystals with a high area owing to their dendritic architecture. On a Pt mass basis, these catalysts are several times more active than conventional Pt catalysts. The catalytic activity of platinum is enhanced through a growth process that creates nanocrystals with high surface area. Controlling the morphology of Pt nanostructures can provide a great opportunity to improve their catalytic properties and increase their activity on a mass basis. We synthesized Pd-Pt bimetallic nanodendrites consisting of a dense array of Pt branches on a Pd core by reducing K2PtCl4 with L-ascorbic acid in the presence of uniform Pd nanocrystal seeds in an aqueous solution. The Pt branches supported on faceted Pd nanocrystals exhibited relatively large surface areas and particularly active facets toward the oxygen reduction reaction (ORR), the rate-determining step in a proton-exchange membrane fuel cell. The Pd-Pt nanodendrites were two and a half times more active on the basis of equivalent Pt mass for the ORR than the state-of-the-art Pt/C catalyst and five times more active than the first-generation supportless Pt-black catalyst.

Gold Nanocages: Synthesis, Properties, and Applications

Noble-metal nanocages comprise a novel class of nanostructures possessing hollow interiors and porous walls. They are prepared using a remarkably simple galvanic replacement reaction between solutions containing metal precursor salts and Ag nanostructures prepared through polyol reduction. The electrochemical potential difference between the two species drives the reaction, with the reduced metal depositing on the surface of the Ag nanostructure. In our most studied example, involving HAuCl(4) as the metal precursor, the resultant Au is deposited epitaxially on the surface of the Ag nanocubes, adopting their underlying cubic form. Concurrent with this deposition, the interior Ag is oxidized and removed, together with alloying and dealloying, to produce hollow and, eventually, porous structures that we commonly refer to as Au nanocages. This approach is versatile, with a wide range of morphologies (e.g., nanorings, prism-shaped nanoboxes, nanotubes, and multiple-walled nanoshells or nanotubes) available upon changing the shape of the initial Ag template. In addition to Au-based structures, switching the metal salt precursors to Na(2)PtCl(4) and Na(2)PdCl(4) allows for the preparation of Pt- and Pd-containing hollow nanostructures, respectively. We have found that changing the amount of metal precursor added to the suspension of Ag nanocubes is a simple means of tuning both the composition and the localized surface plasmon resonance (LSPR) of the metal nanocages. Using this approach, we are developing structures for biomedical and catalytic applications. Because discrete dipole approximations predicted that the Au nanocages would have large absorption cross-sections and because their LSPR can be tuned into the near-infrared (where the attenuation of light by blood and soft tissue is greatly reduced), they are attractive materials for biomedical applications in which the selective absorption of light at great depths is desirable. For example, we have explored their use as contrast enhancement agents for both optical coherence tomography and photoacoustic tomography, with improved performance observed in each case. Because the Au nanocages have large absorption cross-sections, they are also effective photothermal transducers; thus, they might provide a therapeutic effect through selective hyperthermia-induced killing of targeted cancer cells. Our studies in vitro have illustrated the feasibility of applying this technique as a less-invasive form of cancer treatment.

Dimers of silver nanospheres: facile synthesis and their use as hot spots for surface-enhanced Raman scattering.

This paper describes a simple, one-pot method that generates dimers of silver nanospheres in one step without any additional assembly steps. The dimers are consisted of single-crystal silver nanospheres approximately 30 nm in diameter and separated by a gap of 1.8 nm wide. The key to the success of this method lies in the control of colloidal stability and oxidative etching by optimizing the amount of chloride added to a polyol synthesis. The dimers provide a well-defined system for studying the hot spot phenomenon (hot spot: the gap region of a pair of strongly coupled silver or gold nanoparticles), an extremely important but poorly understood subject in surface-enhanced Raman scattering (SERS). Because of the relatively small size of the silver nanospheres, only those molecules trapped in the hot spot region are expected to contribute to the detected SERS signals. By correlating SERS measurements with SEM imaging, we found that the SERS enhancement factor within the hot spot region of such a dimer was on the order of 2 x 10(7).

Chemical Synthesis of Novel Plasmonic Nanoparticles

Under the irradiation of light, the free electrons in a plasmonic nanoparticle are driven by the alternating electric field to collectively oscillate at a resonant frequency in a phenomenon known as surface plasmon resonance. Both calculations and measurements have shown that the frequency and amplitude of the resonance are sensitive to particle shape, which determines how the free electrons are polarized and distributed on the surface. As a result, controlling the shape of a plasmonic nanoparticle represents the most powerful means of tailoring and fine-tuning its optical resonance properties. In a solution-phase synthesis, the shape displayed by a nanoparticle is determined by the crystalline structure of the initial seed produced and the interaction of different seed facets with capping agents. Using polyol synthesis as a typical example, we illustrate how oxidative etching and kinetic control can be employed to manipulate the shapes and optical responses of plasmonic nanoparticles made of either Ag or Pd. We conclude by highlighting a few fundamental studies and applications enabled by plasmonic nanoparticles having well-defined and controllable shapes.

Ultrathin gold nanowires can be obtained by reducing polymeric strands of oleylamine-AuCl complexes formed via aurophilic interaction.

This Communication describes a facile route to the preparation of ultrathin gold nanowires using linear chains formed from [(oleylamine)AuCl] complex via aurophilic interaction. The linear chains, with AuI...AuI bonds as the backbone and surrounded by oleylamines, can group together to form bundles of polymeric strands. When the AuI was reduced to Au0 by reacting with Ag nanoparticles in hexane, the polymeric strands functioned as both the source of Au and the template to mediate the nucleation and growth of Au nanowires. Using this method, we were able to produce Au nanowires with an average diameter of approximately 1.8 nm and an aspect ratio of >1000 in high yields (approximately 70%).

Facile Synthesis of Highly Faceted Multioctahedral Pt Nanocrystals through Controlled Overgrowth

Highly faceted Pt nanocrystals with a large number of interconnected arms in a quasi-octahedral shape were synthesized simply by reducing H2PtCl6 precursor with poly(vinyl pyrrolidone) in aqueous solutions containing a trace amount of FeCl3. The iron species (Fe(3+) or Fe(2+)) play a key role in inducing the formation of the multioctahedral structure by decreasing the concentration of Pt atoms and keeping a low concentration for the Pt seeds during the reaction. This condition favors the overgrowth of Pt seeds along their corners and thus the formation of multiarmed nanocrystals. Electron microscopy studies revealed that the multioctahedral Pt nanocrystals exhibit a large number of edge, corner, and surface step atoms. The size of the multioctahedral Pt nanocrystals can be controlled by varying the concentration of FeCl3 added to the reaction and/or the reaction temperature. These multioctahedral Pt nanocrystals were tested as electrocatalysts for the oxygen reduction reaction in a proton exchange membrane fuel cell and exhibited improved specific activity and durability compared to commercial Pt/C catalyst.

Tailoring Galvanic Replacement Reaction for the Preparation of Pt/Ag Bimetallic Hollow Nanostructures with Controlled Number of Voids

Here we report the synthesis of Pt/Ag bimetallic nanostructures with controlled number of void spaces via a tailored galvanic replacement reaction (GRR). Ag nanocubes (NCs) were employed as the template to react with Pt ions in the presence of HCl. The use of HCl in the GRR caused rapid precipitation of AgCl, which grew on the surface of Ag NCs and acted as a removable secondary template for the deposition of Pt. The number of nucleation sites for AgCl was tailored by controlling the amount of HCl added to the Ag NCs or by introducing PVP to the reaction. This strategy led to the formation of Pt/Ag hollow nanoboxes, dimers, multimers, or popcorn-shaped nanostructures consisting of one, two, or multiple hollow domains. Due to the presence of large void space and porous walls, these nanostructures exhibited high surface area and improved catalytic activity for methanol oxidation reaction.

Gold nanocages for cancer detection and treatment

Gold nanocages represent a novel class of biocompatible vectors with potential applications in drug delivery, tumor/tissue imaging and photothermal therapy. They are prepared through the galvanic-replacement reaction between Ag nanostructures and HAuCl(4). By controlling the amount of HAuCl(4) added, we can tune the surface-plasmon resonance peaks of the Au nanocages into the near-infrared, where the attenuation of light by blood and soft tissue is relatively low. Here, we highlight recent advances in the synthesis and utilization of Au nanocages for cancer detection and treatment. We have tailored the optical properties of Au nanocages for use as contrast agents in optical coherence tomography and as transducers for the selective photothermal ablation of cancer cells. Our results show improved optical coherence tomography image contrast when Au nanocages are added to tissue phantoms as well as the selective photothermal destruction of breast cancer cells in vitro when immunotargeted Au nanocages are used.

Electronic materials: Buckling down for flexible electronics

Inorganic nanoribbons can be attached to an elastic surface at selected positions to make wave-like structures that maintain their semiconducting properties when stretched or compressed. These nanostructures will prove to be immediately useful in flexible electronics.

Highly Symmetric Gold Nanostars: Crystallographic Control and Surface-Enhanced Raman Scattering Property

Gold nanostars have attracted widespread interest due to their remarkable properties and broad applications in plasmonics, spectroscopy, biomedicine, and energy conversion. However, current synthetic methods of Au nanostars have limited control over their symmetry; most existing nanostars are characterized by having uncertain number of arms with different lengths and random spatial arrangement. This morphological arbitrariness not only hampers the fundamental understanding of the properties of Au nanostars, but also lead to poor reproducibility in their applications. Here we demonstrate that, by using a robust solution-phase method, Au nanostars with unpreceded degree of symmetry control can be obtained in high yield and with remarkable monodispersity. Icosahedral seeds are used to dictate the growth of 3D evenly distributed arms in an Ih symmetric manner. Alkylamines serve as shape-control agent to regulate the growth of the hexagonal pyramidal arms enclosed by high-index facets. Benefiting from their high symmetry, the Au nanostars exhibit superior single-particle SERS performance compared to asymmetric Au nanostars, in terms of both intensity and reproducibility.