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We report the synthesis of pentagonal- and hexagonal-shaped gold nanoparticles with controlled diameters ranging from 5 to 50 nm. These nanoparticles were prepared by a seeding growth approach. Sodium dodecyl sulfate (SDS) molecules served as the capping agent to restrict the particle size. In addition, the formation of highly faceted gold nanoparticles may be facilitated by the possibly ineffective capping interactions between the lamellar micellar structures formed by the SDS molecules and the gold nanoparticles. The crystal structure of the highly faceted particles was found to consist of mostly [111] surfaces as particle size increases, as revealed by both TEM and XRD results.

We have developed a general synthetic route to encapsulate small molecules in monodisperse zeolitic imid-azolate framework-8 (ZIF-8) nanospheres for drug delivery. Electron microscopy, powder X-ray diffraction, and elemental analysis show that the small-molecule-encapsulated ZIF-8 nanospheres are uniform 70 nm particles with single-crystalline structure. Several small molecules, including fluorescein and the anticancer drug camptothecin, were encapsulated inside of the ZIF-8 framework. Evaluation of fluorescein-encapsulated ZIF-8 nanospheres in the MCF-7 breast cancer cell line demonstrated cell internalization and minimal cytotoxicity. The 70 nm particle size facilitates cellular uptake, and the pH-responsive dissociation of the ZIF-8 framework likely results in endosomal release of the small-molecule cargo, thereby rendering the ZIF-8 scaffold an ideal drug delivery vehicle. To confirm this, we demonstrate that camptothecin encapsulated ZIF-8 particles show enhanced cell death, indicative of internalization and intracellular release of the drug. To demonstrate the versatility of this ZIF-8 system, iron oxide nanoparticles were also encapsulated into the ZIF-8 nanospheres, thereby endowing magnetic features to these nanospheres.

The effect of lattice strain on the catalytic properties of Pd nanoparticles is systematically studied. Synthetic strategies for the preparation of a series of shape-controlled Pd nanocrystals with lattice strain generated from different sources has been developed. All of these nanocrystals were created with the same capping agent under similar reaction conditions. First, a series of Pd nanoparticles was synthesized that were enclosed in {111} surfaces: Single-crystalline Pd octahedra, single-crystalline AuPd core–shell octahedra, and twinned Pd icosahedra. Next, various {100}-terminated particles were synthesized: Single-crystalline Pd cubes and single-crystalline AuPd core–shell cubes. Different extents of lattice strain were evident by comparing the X-ray diffraction patterns of these particles. During electrocatalysis, decreased potentials for CO stripping and increased current densities for formic-acid oxidation were observed for the strained nanoparticles. In the gas-phase hydrogenation of ethylene, the activities of the strained nanoparticles were lower than those of the single-crystalline Pd nanoparticles, perhaps owing to a larger amount of cetyl trimethylammonium bromide on the surface.

We probe the acoustic vibrations of silver nanoprisms and gold nano-octahedrons in aqueous solution with four-wave mixing. The nonlinear optical response shows two acoustic vibrational modes: an in-plane mode of nanoprisms with vertexial expansion and contraction; an extensional mode of nano-octahedrons with longitudinal expansion and transverse contraction. The particles were also analyzed with electron microscopy and the acoustic resonance frequencies were then calculated by the finite element analysis, showing good agreement with experimental observations. The experimental mode frequencies also fit with theoretical approximations, which show an inverse dependence of the mode frequency on the edge length, for both nanoprisms and nano-octahedrons. This technique is promising for in situ monitoring of colloidal growth.

Metal nanocrystals (NCs) comprising rhodium are heterogeneous catalysts for CO oxidation, NO reduction, hydrogenations, electro-oxidations, and hydroformylation reactions. It has been demonstrated that control of structure at the nanoscale can enhance the performance of a heterogeneous metal catalyst, such as Rh, but molecular-level control of NCs comprising this metal is less studied compared to gold, silver, platinum, and palladium. We report an iodide-mediated epitaxial overgrowth of Rh by using the surfaces of well-defined foreign metal crystals as substrates to direct the Rh surface structures. The epigrowth can be accomplished on different sizes, morphologies, and identities of metal substrates. The surface structures of the resulting bimetallic NCs were studied using electron microscopy, and their distinct catalytic behaviors were examined in CO stripping and the electro-oxidation of formic acid. Iodide was found to play a crucial role in the overgrowth mechanism. With the addition of iodide, the Rh epigrowth can even be achieved on gold substrates despite the rather large lattice mismatch of ~7%. Hollow Rh nanostructures have also been generated by selective etching of the core substrates. The new role of iodide in the overgrowth and the high level of control for Rh could hold the key to future nanoscale control of this important metal's architecture for use in heterogeneous catalysis.

A general synthetic strategy for yolk-shell nanocrystal@ZIF-8 nanostructures has been developed. The yolk-shell nanostructures possess the functions of nanoparticle cores, microporous shells, and a cavity in between, which offer great potential in heterogeneous catalysis. The synthetic strategy involved first coating the nanocrystal cores with a layer of Cu(2)O as the sacrificial template and then a layer of polycrystalline ZIF-8. The clean Cu(2)O surface assists in the formation of the ZIF-8 coating layer and is etched off spontaneously and simultaneously during this process. The yolk-shell nanostructures were characterized by transmission electron microscopy, scanning electron microscopy, X-ray diffraction, and nitrogen adsorption. To study the catalytic behavior, hydrogenations of ethylene, cyclohexene, and cyclooctene as model reactions were carried out over the Pd@ZIF-8 catalysts. The microporous ZIF-8 shell provides excellent molecular-size selectivity. The results show high activity for the ethylene and cyclohexene hydrogenations but not in the cyclooctene hydrogenation. Different activation energies for cyclohexene hydrogenation were obtained for nanostructures with and without the cavity in between the core and the shell. This demonstrates the importance of controlling the cavity because of its influence on the catalysis.

We report a seed-mediated synthesis method for the preparation of gold nanocrystals with systematic shape evolution from truncated cubic to cubic, trisoctahedral, and rhombic dodecahedral structures in aqueous solution for the first time. Nanocrystals with transitional morphologies were also synthesized. The combination of using cetyltrimethylammonium chloride (CTAC) surfactant and a very small amount of NaBr to control the bromide concentration in the growth solution was found to be critical to the formation of nanocubes. Variation in the volume of ascorbic acid added to the growth solution enabled the fine control of nanocrystal morphology. Nanocubes and rhombic dodecahedra with controlled sizes of 30-75 nm were prepared by adjusting the volume of the seed solution added to the growth solution. They can self-assemble into ordered packing structures on substrates because of their uniform sizes. XRD, TEM, and UV-vis absorption characterization of the different products synthesized have been performed. By increasing the bromide concentration 5-fold that used to make the nanocubes, unusual right bipyramids of gold bounded by six {100} faces were produced. The high product purity and excellent size control of this facile synthetic approach should make these novel gold nanostructures be readily available for a wide range of studies.

We have improved the device performance of polymer photovoltaic devices (OPVs) by blending Au nanoparticles (NPs) into the anodic buffer layer. The unique optical properties of localized surface plasmon resonance (LSPR), triggered by Au NPs, was beneficial for improving the photocurrent of OPVs. The excitation of LSPR increased not only the exciton generation rate but also the exciton dissociation probability. As a result, the power conversion efficiency of OPVs has been significantly enhanced from 3.57 to 4.24%.

We report a simple approach for the fabrication of cuprous oxide (Cu 2 O) nanocages and nanoframes. An aqueous solution of CuCl 2 , sodium dodecyl sulfate (SDS) surfactant, NH 2 OH·HCl reductant, HCl, and NaOH was prepared with reagents introduced in the order listed. Rapid seed particle aggregation and surface reconstruction of the intermediate structures resulted in the growth of type I nanoframes with just the {110} skeleton faces and empty {100} faces 45 minutes after mixing the reagents. Continued crystal growth for additional 75 min produced the nanocages with filled {100} faces. The nanocages have diameters of 350–400 nm, and their walls are thicker than those of the nanoframes. Selective acidic etching over the {110} faces of the nanocages by HCl via the addition of ethanol and then sonication of the solution led to the formation of type II nanoframes with elliptical pores on the {110} faces. The morphologies of these nanoframes have been carefully examined by electron microscopy. Without adding ethanol, random etching of the nanocages can occur at a slow rate. These composite materials should display interesting properties and functions.

The synthesis of gold nanoplates was carried out in an aqueous solution by thermal reduction of HAuCl(4) with trisodium citrate in the presence of cetyltrimethylammonium bromide (CTAB) surfactant in just 5-40 min. The sizes of the gold nanoplates can be varied from as small as tens of nanometers in width, to several hundreds of nanometers, and even a few microns in width by changing the reagent concentrations, solution temperature, and the reaction time. A [CTAB]/[HAuCl(4)] ratio of 6 in the reaction solution was found to be favorable for the formation of gold nanoplates. The nanoplates possess well-defined shapes with sharp edges. The small nanoplates exhibit mainly a triangular shape, while larger nanoplates show a mixture of triangular, hexagonal, truncated triangular, and other symmetrical structures. The nanoplates are composed of essentially (111) lattice planes, as revealed by both XRD and TEM results. Nanoplates with widths from several hundreds of nanometers to a few microns absorb light strongly in the near-infrared region. The growth mechanism of these nanoplates was investigated. The ability to synthesize gold nanoplates with these different size ranges in large scale in aqueous solution using simple CTAB capping surfactant should allow more diverse applications of gold nanoplates.

Synthesis of branched gold nanocrystals by a seeding growth approach is described. In this process, HAuCl4 aqueous solution was supplied stepwise to grow the gold seeds (approximately 2.5 nm) into larger nanoparticles with a highly faceted particle structure (approximately 15-20 nm in diameter). Sodium dodecyl sulfate (SDS) served as a capping agent to facilitate the formation of highly faceted nanoparticles, and ascorbic acid was used as a weak reducing agent. The highly faceted nanoparticles then transformed into branched nanocrystals (approximately 40 nm in length) by further addition of the SDS-HAuCl4 solution and ascorbic acid for particle growth. The branched nanocrystals show bipod, tripod, tetrapod, and pentapod structures and are composed of mainly (111) lattice planes. These multipods appear to grow along the twin boundaries of the initially formed highly faceted gold nanoparticles, as the twin boundaries on the pods originate from the centers of the branched nanocrystals. The concentration of ascorbate ions in the solution was found to have a profound influence on branch formation. These branched nanocrystals are stable to storage at low temperature (that is, 4 degrees C), but they may slowly evolve into a multitwinned faceted crystal structure (that is, pentagonal-shaped decahedral structure) when stored at 30 degrees C.

We have explored the effect of gold nanoparticle (Au NP)-induced surface plasmons on the performance of organic photovoltaic devices (OPVs). The power conversion efficiency of these OPVs was improved after blending the Au NPs into the anodic buffer layer. The addition of Au NPs increased the rate of exciton generation and the probability of exciton dissociation, thereby enhancing the short-circuit current density and the fill factor. We attribute the improvement in device performance to the local enhancement in the electromagnetic field originating from the excitation of the localized surface plasmon resonance.

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