Synthesis of gold-tin alloy nanoparticles with tunable plasmonic properties.

Plasmonic nanoparticles and nanocrystalline materials have broad applicability in catalysis, optoelectronics, sensing, and sustainability. Below, we detail a robust protocol for the synthesis of bimetallic Au-Sn nanoparticles in mild, aqueous conditions. This protocol describes the steps for synthesizing gold nanoparticle seeds, diffusing Sn into the seeds by chemical reduction, and the optical and structural analysis by UV-visible spectroscopy, X-ray diffraction, and electron microscopy. For complete details on the use and execution of this protocol, please refer to Fonseca Guzman et al.1.

Material strategies for function enhancement in plasmonic architectures.

Plasmonic materials are promising for applications in enhanced sensing, energy, and advanced optical communications. These applications, however, often require chemical and physical functionality that is suited and designed for the specific application. In particular, plasmonic materials need to access the wide spectral range from the ultraviolet to the mid-infrared in addition to having the requisite surface characteristics, temperature dependence, or structural features that are not intrinsic to or easily accessed by the noble metals. Herein, we describe current progress and identify promising strategies for further expanding the capabilities of plasmonic materials both across the electromagnetic spectrum and in functional areas that can enable new technology and opportunities.

An Integrated Electrochemistry Approach to the Design and Synthesis of Polyhedral Noble Metal Nanoparticles.

The synthesis of shaped metal nanoparticles to meet the precise needs of emerging applications requires intentional synthetic design directed by fundamental chemical principles. We report an integrated electrochemistry approach to nanoparticle synthetic design that couples current-driven growth of metal nanoparticles on an electrode surface-in close analogy to standard colloidal synthesis-with electrochemical measurements of both electrochemical and colloidal nanoparticle growth. A simple chronopotentiometry method was used to translate an existing colloidal synthesis for corrugated palladium (Pd) nanoparticles to electrochemical growth on a glassy carbon electrode, with minimal modification to the growth solution. The electrochemical synthesis method was then utilized to produce large Pd icosahedra, a shape whose synthesis is challenging in a colloidal growth environment. This electrochemical synthesis for Pd icosahedra was used to develop a corresponding colloidal growth solution by tailoring a weak reducing agent to the measured potential profile of the electrochemical synthesis. Finally, measurements of colloidal syntheses were employed as guides for the directed design of electrochemical syntheses for Pd cubes and octahedra. Together, this work provides a cyclical approach to shaped nanoparticle design that allows for the optimization of nanoparticles grown via a colloidal approach with a chemical reducing agent or synthesized with an applied current on an electrode surface as well as subsequent bidirectional translation between the two methods. The enhanced chemical flexibility and direct tunability of this electrochemical method relative to combinatorial design of colloidal syntheses have the potential to accelerate the synthetic design process for noble metal nanoparticles with targeted morphologies.

Halide-assisted metal ion reduction: emergent effects of dilute chloride, bromide, and iodide in nanoparticle synthesis.

Understanding the competing effects of growth-directing additives, such as halide ions, on particle formation in solution phase metal nanoparticle syntheses is an ongoing challenge. Further, trace halide impurities are known to have a drastic impact on particle morphology as well as reproducibility. Herein, we employ a "halide-free" platform as an analogue to commonly used halide-containing surfactants and metal precursors to isolate and study the effects of micromolar concentrations of halide ions (chloride, bromide, and iodide) on the rate of metal ion reduction. In the absence of competing halides from precursors and surfactants, we observe a catalytic effect of low concentrations of halide ions on the rate of metal ion reduction, an influence which is fundamentally different from the previously reported role of halides in metal nanoparticle growth. We propose that this halide-assisted metal ion reduction proceeds via the formation of a halide bridge which facilitates the adsorption of the metal precursor to a growing nanoparticle and, subsequently, electron transfer from the particle surface. We then demonstrate that this process is operative not only in the well-controlled "halide-free" platform, but also in syntheses involving high concentrations of halide-containing surfactants as well as metal precursors with halide ligands. Importantly, this study shows that halide-assisted metal ion reduction can be extended to bimetallic systems and provides a handle for the directed differential control of metal ion reduction in one-pot co-reduction syntheses.

Defects by design: synthesis of palladium nanoparticles with extended twin defects and corrugated surfaces.

Recent catalytic work has highlighted the importance of grain boundaries in the design of highly active catalyst materials due to the high energy of atoms at strained defect sites. In addition, undercoordinated atoms have long been known to contribute to the catalytic performance of metal nanoparticles. In this work, we describe a method for deliberately increasing the coverage of defect boundaries and undercoordinated atoms at the surfaces of well-defined, symmetric palladium nanoparticles. Careful control of the competitive interactions of chloride and bromide ions with the surface of twinned palladium nanoparticles is used to drive the growth of fin-like structures to extend the area of exposed twin boundaries while also inducing corrugation at the particle surface to add further undercoordinated sites. Mechanistic studies show surface passivation by bromide and etching by chloride in the presence of a low concentration of surfactant to be the key factors that tailor the surface of these nanoparticles, while the internal defect structure is controlled by reaction kinetics. Importantly, these basic principles of competition between surface passivation and etching as well as kinetic control of twin structure are not unique to palladium, and thus this method has the potential to be extended to the enhancement of surface defect density for nanoparticles composed of other catalytically relevant metals.

6,7-Di-chloro-2,3-bis(pyridin-2-yl)quinox-aline.

The title compound, C18H10Cl2N4, synthesized by the condensation reaction between 4,5-di-chloro-benzene-1,2-di-amine and 1,2-di(pyridin-2-yl)ethane-1,2-dione in boiling acetic acid, has a nearly planar quinoxaline moiety [maximum deviation = 0.070 (1) Å] whose mean plane makes dihedral angles of 40.51 (2) and 39.29 (3)° with the pyridine rings. Within the unit cell, there are no classical hydrogen bonds. Molecules in the structure pack with π-π stacking contacts between the quinoxaline units and nearby pyridine rings with an intercentroid distance of 3.7676 (9) Å.