Investigation of multiple commercial electrocatalysts and electrocatalyst degradation for fuel cells in real vehicles.

Proton exchange membrane fuel cells (PEMFCs) are regarded as one of the promising new carbon mitigation strategies to realize carbon neutrality. However, efficient and robust electrocatalysts are vital for the commercialization of PEMFCs. Herein, three commercial Pt/C electrocatalysts were investigated including a carbon support and Pt nanoparticles (NPs) to identify their merits and disadvantages, which will help end users quickly select catalysts with excellent performances among the many brands of domestic and foreign catalysts to further better study and better utilize them. Subsequently, they were optimized for real automotive application for about 1800 h, and then the variations in the electrocatalysts on the MEA were analysed by transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The mean Pt particle size of the catalysts after operating for 1800 h (cathode, 9.9 ± 3.2 nm) was nearly 4-fold that before use (2.5 ± 0.6 nm), greatly reducing the exposure of metal sites, which was due to the violent three-phase interfacial reaction (ORR) occurring at the cathode side. Also, this assertion was supported by the negative shift in the Pt 4f peaks in the XPS spectra. Moreover, to determine the coalescent evolution of the Pt particles, an in situ TEM experiment was performed. This allowed us to perform fundamental Pt NP degradation studies on the carbon support, which can result in an improvement in the sustainability of catalysis.

Batchwise growth of silica cone patterns via self-assembly of aligned nanowires.

Silica-cone patterns self-assembled from well-aligned nanowires are synthesized using gallium droplets as the catalyst and silicon wafers as the silicon source. The cones form a triangular pattern array radially on almost the whole surface of the molten Ga ball. Detailed field-emission scanning electron microscopy (SEM) analysis shows that the cone-pattern pieces frequently slide off and are detached from the molten Ga ball surface, which leads to the exposure of the catalyst surface and the growth of a new batch of silicon oxide nanowires as well as the cone patterns. The processes of growth and detachment alternate, giving rise to the formation of a volcano-like or a flower-like structure with bulk-quantity pieces of cone patterns piled up around the Ga ball. Consequently, the cone-patterned layer grows batch by batch until the reaction is terminated. Different to the conventional metal-catalyzed growth model, the batch-by-batch growth of the triangular cone patterns proceeds on the molten Ga balls via alternate growth on and detachment from the catalyst surface of the patterns; the Ga droplet can be used continuously and circularly as an effective catalyst for the growth of amorphous SiO(x) nanowires during the whole growth period. The intriguing batchwise growth phenomena may enrich our understanding of the vapour-liquid-solid (VLS) growth mechanism for the catalyst growth of nanowires or other nanostructures and may offer a different way of self-assembling novel silica nanostructures.

Growth mechanism, photoluminescence, and field-emission properties of ZnO nanoneedle arrays.

ZnO nanoneedle arrays have been grown on a large scale with a chemical vapor deposition method at 680 degrees C. Zn powder and O(2) gas are employed as source materials, and catalyst-free Si plates are used as substrates. Energy-dispersive X-ray and X-ray diffraction analyses show that the nanoneedles are almost pure ZnO and preferentially aligned in the c-axis direction of the wurtzite structure. The growth mechanism of ZnO nanoneedle arrays is discussed with the thermodynamic theory and concluded to be the result of the co-effect of the surface tension and diffusion. Photoluminescence spectrum of the as-grown products shows a strong emission band centering at about 484 nm, which originates from oxygen vacancies. Field-emission examination exhibits that the ZnO nanoneedle arrays have a turn-on voltage at about 5.3 V/microm.

Structural, magnetic, and magnetoresistive properties of electrodeposited Ni5Zn21 alloy nanowires.

Ni5Zn21 alloy nanowires were fabricated through template-assisted electrochemical deposition method. The morphology and microstructures of as-deposited nanowires were determined by field-emission scanning electron microscope (FE-SEM), X-ray diffraction (XRD), high-resolution transmission electron microscope (HRTEM), electron diffraction (ED), and electron probe microanalysis (EPMA). The accurate composition was measured via induced coupling plasma atomic emission spectroscopy. SEM results show that Ni5Zn21 nanowires are deposited in most of the nanopores of the template, and they are continuous and dense throughout the whole length. The XRD result demonstrates that the nanowires are mainly composed of a cubic gamma phase Ni5Zn21 alloy, but there also exists a trace of Zn-rich eta phase. HRTEM and ED reveal that the alloy nanowires are polycrystalline with the crystallite size of several tens of nanometers. EPMA of a single nanowire illustrates that there exist Ni-rich microzones in as-deposited nanowires. Subsequent magnetic measurements of the array also confirmed the existence of them. In addition, it can be further inferred that the shape of Ni-rich microzones is probably barlike or disklike, from the anisotropy of zero field cooling/field cooling (ZFC/FC) curves as well as the vortex magnetization behavior of the Ni5Zn21 nanowire array. The low-temperature magnetoresistance of the Ni5Zn21 nanowire array was also measured. Giant magnetoresistance instead of anisotropic magnetoresistance is suggested to be responsible for contributing to the magnetoresistance.

Human fibrinogen adsorption onto single-walled carbon nanotube films.

The adsorption behavior of human fibrinogen (Hfg) on single-walled carbon nanotube (SWNT) films was investigated using scanning electron microscopy (SEM) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. It was shown in the SEM images that fibrinogen was adsorbed strongly on the surface of SWNT when the samples were incubated in the Hfg solutions for 10 min. The dependence of adsorption on the concentration of fibrinogen was also investigated and it was found that adsorption increased with increasing concentration. In order to further explore the adsorption of fibrinogen on SWNT surface, NEXAFS spectra were obtained at the N K-edge and the C K-edge. The results confirmed the conclusion regarding the dependence of adsorption on fibrinogen concentration. It is demonstrated that, due to its high sensitivity to the surface elements, NEXAFS spectroscopy is a powerful tool to investigate the adsorption of fibrinogen on SWNT films.

Synthesis of long indium nitride nanowires with uniform diameters in large quantities.

Large quantities of indium nitride (InN) nanowires are synthesized by the in situ nitriding of indium oxide (In(2)O(3)) powders in an ammonia (NH(3)) flux. Tens of milligrams of nanowires are obtained in one batch. Every 100 mg of In(2)O(3) starting powder can produce up to 65 mg of InN nanowires under the optimized conditions. The synthesized nanowires grow along the [001] direction with excellent crystallinity. They are of high purity and are 30-50 microm in length with an almost uniform diameter of about 100 nm. Photoluminescence measurements of the nanowires exhibit a strong peak at 707 nm. An optical bandgap of about 1.7 eV is estimated based on the absorption spectrum. The experimental results also demonstrate that the approach of nitriding In(2)O(3) powders in situ is feasible for the synthesis of high-purity InN nanowires in large quantities, with good reproducibility and without catalyst materials. The synthesis of InN nanowires in large quantities would be of benefit to the further study and understanding of their intrinsic properties, as well as being advantageous for their potential application in nanodevices.

Low-temperature growth and photoluminescence property of ZnS nanoribbons.

At a low temperature of 450 degrees C, ZnS nanoribbons have been synthesized on Si and KCl substrates by a simple chemical vapor deposition (CVD) method with a two-temperature-zone furnace. Zinc and sulfur powders are used as sources in the different temperature zones. X-ray diffraction (XRD), selected area electron diffraction (SEAD), and transmission electron microscopy (TEM) analysis show that the ZnS nanoribbons are the wurtzite structure, and there are two types-single-crystal and bicrystal nanoribbons. Photoluminescence (PL) spectrum shows that the spectrum mainly includes two parts: a purple emission band centering at about 390 nm and a blue emission band centering at about 445 nm with a weak green shoulder around 510 nm.

Enhanced optical responses of Au@Pd core/shell nanobars.

A Pd nanoshell was epitaxially grown on a Au nanorod (NR) via simple seed-mediated growth. Compared with the cylindrical shape of the Au NR, the Au core/Pd shell (Au@Pd) nanorods change to a rectangular shape due to the disappearance of {110} facets. The Au NRs exhibit a strong longitudinal surface plasmon resonance (LSPR). As Pd is deposited, damping and broadening occur to the LSPR band. Interestingly, the LSPR band maximum first shows a small red-shift (ca. 40 nm) which then is followed by a blue-shift as the amount of Pd is increased. A thickness-dependent LSPR feature of the Pd shell is believed to contribute to the shift. At a thinner Pd thickness, the Au@Pd nanobars exhibit a well-defined LSPR band in the visible and near-infrared region, which demonstrates a higher dielectric sensitivity than that of the corresponding Au NRs. It thus opens up the potential of Pd nanostructures for SPR-based sensing. Investigations on the surface-enhanced Raman scattering (SERS) indicate that the SERS activities of the Au@Pd nanobars at thicknesses smaller than 2.5 nm mainly originate from the Au cores; thus, the SERS activities can be improved by tuning the aspect ratio of the Au core and/or the Pd shell thickness.

Well-controlled synthesis of Au@Pt nanostructures by gold-nanorod-seeded growth.

Pt nanodots were formed on Au nanorods (NRs) by using a simple seed-mediated growth. Their density and distribution on the Au NR can be finely tuned by varying the reaction parameters. At lower Pt/Au ratios, the Pt nanodots mainly appear at endcaps and side edges of the Au rod. At higher Pt/Au ratios, they distribute homogeneously over the whole Au rod. The obtained Pt nanostructure is a single crystal owing to the epitaxial growth of Pt on the Au rod. Due to the unique surface plasmon resonance (SPR) features of the Au NRs, the Au core/Pt shell (Au@Pt) nanostructures also exhibit well-defined and red-shifted longitudinal SPR bands in the visible and near-infrared region. The position and intensity can be regulated by the thickness and amount of the Pt shell. At a thinner Pt thickness, the Au@Pt NRs show higher dielectric sensitivity than the corresponding Au NRs. It thus opens up the potential of Pt nanostructures for SPR-based sensing.

Gold nanorod-seeded growth of silver nanostructures: from homogeneous coating to anisotropic coating.

Single crystalline gold nanorods (Au NRs) dominated by {110} side facets were employed as seeds to tailor the deposition of Ag. Apart from homogeneous coating, anisotropic coating of Ag was observed and resulted in an orange slice-like shape for the Au@Ag nanocrystal. Different growth rates for the {110} side facets were responsible for this shape: among the four {110} facets, two of the neighboring {110} facets grew more quickly and another two grew more slowly, thus inducing the anisotropic deposition of Ag around the Au NR. This growth behavior is believed to be a consequence of competition between the strong stabilization of cetyltrimethylammomium bromide (CTAB) molecules to the {110} facets of Ag and minimization of the overall surface energy. Although the reason for the anisotropic coating remains to be clarified, our results lead to one important conclusion: The interaction of CTAB and metal can be utilized to tune the shapes of bimetallic structures.

Directly synthesized strong, highly conducting, transparent single-walled carbon nanotube films.

We report the direct synthesis of strong, highly conducting, and transparent single-walled carbon nanotube (SWNT) films. Systematically, tests reveal that the directly synthesized films have superior electrical and mechanical properties compared with the films made from a solution-based filtration process: the electrical conductivity is over 2000 S/cm and the strength can reach 360 MPa. These values are both enhanced by more than 1 order. We attribute these intriguing properties to the good and long interbundle connections. Moreover, by the help of an extrapolated Weibull theory, we verify the feasibility of reducing the interbundle slip by utilizing the long-range intertube friction and estimate the ultimate strength of macroscale SWNTs without binding agent.

Formation of rectangularly shaped Pd/Au bimetallic nanorods: evidence for competing growth of the Pd shell between the 110 and 100 side facets of Au nanorods.

In this letter, we report the competing growth of a Pd shell on the {110} and {100} facets of Au nanorods (Au NRs). This results in the disappearance of unstable {110} facets and the formation of rectangularly shaped Pd/Au bimetallic nanorods that show only four stable {100} side surfaces. The energy minimization to a more stable morphology is believed to be the driving force for the formation of the rectangular shape of the Pd shell.