Interface Catalysts of Ni/Co2N for Hydrogen Electrochemistry.

The development of active, durable, and nonprecious electrocatalysts for hydrogen electrochemistry is highly desirable but challenging. In this work, we design and fabricate a novel interface catalyst of Ni and Co2N (Ni/Co2N) for hydrogen evolution reaction (HER) and hydrogen oxidation reaction (HOR). The Ni/Co2N interfacial catalysts not only achieve a current density of -10.0 mA cm-2 with an overpotential of 16.2 mV for HER but also provide a HOR current density of 2.35 mA cm-2 at 0.1 V vs reversible hydrogen electrode (RHE). Furthermore, the electrode couple made of the Ni/Co2N interfacial catalysts requires only a cell voltage of 1.57 V to gain a current density of 10 mA cm-2 for overall water splitting. Hybridizations in the three elements of Ni-3d, N-2p, and Co-3d result in charge transfer in the interfacial junction of the Ni and Co2N materials. Our density functional theory calculations show that both the interfacial N and Co sites of Ni/Co2N prefer to hydrogen adsorption in the hydrogen catalytic activities. This study provides a new approach for the construction of multifunctional catalysts for hydrogen electrochemistry.

Au-Cu-M (M = Pt, Pd, Ag) nanorods with enhanced catalytic efficiency by galvanic replacement reaction.

This work reports a general wet-chemistry method to produce Au-Cu-X (X = Pt, Pd, and Ag) trimetallic nanorods using galvanic replacement reaction with Au-Cu nanorods as the templates. The mild conditions, such as low temperature and slow injection of metal precursors, contributed to the slow galvanic replacement reaction and helped keep the rod structure intact. The distribution of Au, Cu and the doping metals was even in the rods as confirmed by elemental mapping. The alloyed trimetallic nanorods showed enhanced catalytic activity for p-nitrophenol reduction after incorporating the third metal. Remarkably, the Au-Cu-Pd and Au-Cu-Pt nanorods show more than an order of magnitude improvement in the mass activities compared to the Au-Cu nanorods. This facile and general synthetic method can be applied to fabricate other multimetallic nanoparticles with varying shapes and compositions.

Excitation Wavelength-Dependent Photoluminescence Decay of Hybrid Gold/Quantum Dot Nanostructures.

Hybrid nanostructures comprised of metal nanoparticles (MNPs) and quantum dots (QDs) have been found to exhibit unique, new optical properties due to the interaction that occurs between the MNPs and QDs. The aim of this work is to understand how the exciton-plasmon interaction in these systems is dependent on the excitation wavelength. The nanoassemblies consisted of gold (Au) NPs coated in a silica (SiO2) shell of a controlled thickness and core/shell CdSe/CdS QDs adsorbed onto the SiO2 shells. Our findings show that the photoluminescence lifetimes of the hybrid constructs are dependent on the excitation wavelength relative to the localized surface plasmon resonance (LSPR) of the Au NPs. When the excitation wavelength is closer to the LSPR, the photoluminescence decay of the hybrid structures is faster. We demonstrate that by tuning the excitation wavelength close to the resonance, there is an enhancement in the exciton-plasmon coupling between the Au NPs and QDs resulting in a shortening in the QD photoluminescence lifetime. We then propose a possible mechanism to explain this excitation wavelength-dependent phenomenon.

Formation of bimetallic dumbbell shaped particles with a hollow junction during galvanic replacement reaction.

The galvanic replacement reaction (GRR) has been shown to be an effective method to fine tune the structure of monometallic nanoparticles by controlling the precursor concentration and surface ligands. However, the structural evolution of nanoparticles is not well understood in multimetallic systems, where along with oxidation, dealloying and diffusion occur simultaneously. Here, we demonstrate that by controlling the rate of GRR in AuCu alloy nanorods, they can be transformed into either AuCu hollow rods or AuCu@Au core-shell spheroids. Interestingly, the transformation of rods into spheroids involved a critical intermediate state with a hollow junction and dumbbell shape. The formation of a hollow junction region was attributed to preferential diffusion of Cu atoms to the tips caused by the polycrystallinity and high curvature of the tips of the initial template. This structural transformation was also monitored in situ by single particle scattering spectroscopy. The coupling between the two ends of the dumbbell-shaped intermediate connected with a hollow metallic junction gives rise to additional plasmonic features compared with regular rods. Electrodynamic simulations showed that varying the dimensions of the hollow part by even one nanometer altered the plasmon resonance wavelength and lineshape drastically. This study shows that single particle plasmon resonance can be used as an exquisite tool to probe the internal structure of the nanoscale junctions.

An unconventional mechanism of hollow nanorod formation: asymmetric Cu diffusion in Au-Cu alloy nanorods during galvanic replacement reaction.

This study investigates how AuCu3 alloy nanorods transform into hollow rods during a galvanic replacement reaction. An unusual reaction intermediate was observed where the solid nanorod became partially hollow and Cu rich at one end. This was attributed to simultaneous galvanic replacement and asymmetric diffusion of Cu due to the Kirkendall effect. The hollow Au-Cu nanorods showed enhanced catalytic activity for p-nitrophenol reduction.

Structural defect induced peak splitting in gold-copper bimetallic nanorods during growth by single particle spectroscopy.

A single particle level study of bimetallic nanoparticle growth provides valuable information that is usually hidden in ensemble measurements, helping to improve the understanding of a reaction mechanism and overcome the synthetic challenges. In this study, we use single particle spectroscopy to monitor the changes in the scattering spectra of Au-Cu alloy nanorods during growth. We found that the unique features of the single particle scattering spectra were due to atomic level geometric defects in the nanorods. Electrodynamics simulations have demonstrated that small structural defects of a few atomic layers split the scattering peaks, giving rise to higher order modes, which do not exist in defect-free rods of similar geometry. The study shows that single particle scattering technique is as sensitive as high-resolution electron microscopy in revealing atomic level structural defects.

Synthesis, characterization and photoluminescence of cdS hyperbranched nanocrystals by a simple solution chemistry method.

We report the synthesis of CdS hyperbranched nanocrystals using a simple hot coordination solvents method. Transmission electron microscopy studies showed that the length of the arms and the angle of branching could be controlled by varying organic surfactants in terms of amount and type. It was found that long chain carboxylic acids favored the synthesis of CdS hyperbranched nanocrystals. Although their absorption spectra of CdS hyperbranched nanocrystals did not display sharp features, the photoluminescence spectra showed two emission peaks, i.e., the corresponding luminescence peak around 486 nm originates from the band edge and the broad band emission from 560 nm extended to the region of near infrared arises from trap-related recombination of as-prepared CdS hyperbranched nanocrystals.

Trioctylphosphine as Both Solvent and Stabilizer to Synthesize CdS Nanorods.

High quality CdS nanorods are synthesized reproducibly with cadmium acetate and sulfur as precursors in trioctylphosphine solution. The morphology, crystalline form and phase composition of CdS nanorods are characterized by transmission electron microscopy (TEM), high-resolution TEM and X-ray diffraction (XRD). CdS nanorods obtained are uniform with an aspect ratio of about 5:1 and in a wurtzite structure. The influence of reaction conditions on the growth of CdS nanorods demonstrates that low precursor concentration and high reaction temperature (260 degrees C) are favorable for the formation of uniform CdS nanorods with 85.3% of product yield.

Highly ordered self-assembly with large area of Fe3O4 nanoparticles and the magnetic properties.

Monodisperse Fe3O4 nanoparticles (NPs) with narrow size distribution are synthesized by a high-temperature solution-phase method. The diameter of the as-synthesized NPs is tuned from 2 to 14 nm by varying the reaction conditions. Highly ordered superlattice structures of the Fe3O4 NPs with areas extending over 0.8 microm x 0.7 microm have been successfully obtained. The magnetic properties are investigated in their different states, such as in the solid state and diluted in wax with different concentrations. Some magnetic properties enhanced by increasing interparticle distances, such as the remanent magnetization and coercive field at low temperature, were noticed. Furthermore, we also observed that the saturation magnetization changed with temperature as expected. The preliminary explanation for the properties mentioned above is proposed.

Morphologies and microstructures of nano-sized Cu(2)O particles using a cetyltrimethylammonium template.

Hollow polyhedra and cubes of nanostructured Cu(2)O particles have been synthesized by reduction of CuSO(4) with ascorbate acid in the solution phase. The nanostructures were obtained when the cetyltrimethylammonium (CTAB) concentration ranged from 0 to 0.03 M in the presence of NaOH. Structural characterizations, by means of x-ray photoelectron spectroscopy (XPS) for measuring Cu valence states and by electron microscopy for microstructure and chemical analyses, suggest that most Cu(2)O nanoparticles are covered with a thin CuO shell arising possibly from reaction of the adsorbed oxygen on the Cu(2)O particle surface. The blue shift is observed as microstructures of Cu(2)O nanoparticles changed from cubic to hollow in ultraviolet and visible (UV-visible) absorption spectra. Both the Cu(2)O hollow and cubic nanostructures show certain quantum-confined effects. A cationic CTAB template mechanism is proposed to interpret the formation of the Cu(2)O nanoparticles.