Thermally stable surfactant-free ceria nanocubes in silica aerogel.

Surfactant-mediated chemical routes allow one to synthesize highly engineered shape- and size-controlled nanocrystals. However, the occurrence of capping agents on the surface of the nanocrystals is undesirable for selected applications. Here, a novel approach to the production of shape-controlled nanocrystals which exhibit high thermal stability is demonstrated. Ceria nanocubes obtained by surfactant-mediated synthesis are embedded inside a highly porous silica aerogel and thermally treated to remove the capping agent. Powder X-ray Diffraction and Scanning Transmission Electron Microscopy show the homogeneous dispersion of the nanocubes within the aerogel matrix. Remarkably, both the size and the shape of the ceria nanocubes are retained not only throughout the aerogel syntheses but also upon thermal treatments up to 900 °C, while avoiding their agglomeration. The reactivity of ceria is measured by in situ High-Energy Resolution Fluorescence Detected - X-ray Absorption Near Edge Spectroscopy at the Ce L3 edge, and shows the reversibility of redox cycles of ceria nanocubes when they are embedded in the aerogel. This demonstrates that the enhanced reactivity due to their prominent {100} crystal facets is preserved. In contrast, unsupported ceria nanocubes begin to agglomerate as soon as the capping agent decomposes, leading to a degradation of their reactivity already at 275 °C.

Determining the maximum lanthanum incorporation in the fluorite structure of La-doped ceria nanocubes for enhanced redox ability.

Ceria nanocubes have been doped with increasing amounts of lanthanum to enhance their redox ability. X-ray diffraction and transmission electron microscopy techniques provide a consistent picture indicating that there is an upper limit to the lanthanum that can be incorporated in the fluorite structure of ceria nanocubes, which is close to 7.5 mol% La. This limited loading is nevertheless able to produce a significant enhancement of the ceria redox ability as evidenced by use of X-ray absorption spectroscopy to determine the Ce3+/Ce4+ ratio in samples submitted to a degassing treatment at room temperature.

CTAB-Influenced Electrochemical Dissolution of Silver Dendrites.

Dendrite formation on the electrodes of a rechargeable battery during the charge-discharge cycle limits its capacity and application due to short-circuits and potential ignition. However, understanding of the underlying dendrite growth and dissolution mechanisms is limited. Here, the electrochemical growth and dissolution of silver dendrites on platinum electrodes immersed in an aqueous silver nitrate (AgNO3) electrolyte solution was investigated using in situ liquid-cell transmission electron microscopy (TEM). The dissolution of Ag dendrites in an AgNO3 solution with added cetyltrimethylammonium bromide (CTAB) surfactant was compared to the dissolution of Ag dendrites in a pure aqueous AgNO3 solution. Significantly, when CTAB was added, dendrite dissolution proceeded in a step-by-step manner, resulting in nanoparticle formation and transient microgrowth stages due to Ostwald ripening. This resulted in complete dissolution of dendrites and "cleaning" of the cell of any silver metal. This is critical for practical battery applications because "dead" lithium is known to cause short circuits and high-discharge rates. In contrast to this, in a pure aqueous AgNO3 solution, without surfactant, dendrites dissolved incompletely back into solution, leaving behind minute traces of disconnected silver particles. Finally, a mechanism for the CTAB-influenced dissolution of silver dendrites was proposed based on electrical field dependent binding energy of CTA(+) to silver.

In-situ observations of nanoscale effects in germanium nanowire growth with ternary eutectic alloys.

Vapour-liquid-solid (VLS) techniques are popular routes for the scalable synthesis of semiconductor nanowires. In this article, in-situ electron microscopy is used to correlate the equilibrium content of ternary (Au0.75 Ag0.25 -Ge and Au0.65 Ag0.35 -Ge) metastable alloys with the kinetics, thermodynamics and diameter of Ge nanowires grown via a VLS mechanism. The shape and geometry of the heterogeneous interfaces between the liquid eutectic and solid Ge nanowires varies as a function of nanowire diameter and eutectic alloy composition. The behaviour of the faceted heterogeneous liquid-solid interface correlates with the growth kinetics of the nanowires, where the main growth facet at the solid nanowire-liquid catalyst drop contact line lengthens for faster nanowire growth kinetics. Pronounced diameter dependent growth kinetics, as inferred from liquid-solid interfacial behaviour, is apparent for the synthesised nanowires. Direct in-situ microscopy observations facilitates the comparison between the nanowire growth behaviour from ternary (Au-Ag-Ge) and binary (Au-Ge) eutectic systems.

Manipulating the growth kinetics of vapor-liquid-solid propagated Ge nanowires.

This article describes an innovative approach in which bimetallic alloy seeds of AuxAg1-x are used to enhance the growth kinetics of Ge nanowires, via a vapor-liquid-solid (VLS) growth technique. The decreased equilibrium concentration and increased supersaturation of Ge in the liquid alloy seeds, compared to pure Au seeds, results in favorable growth kinetics and the realization of high-aspect ratio millimeter-long Ge nanowires. Also detailed is the manifestation of the Gibbs-Thompson effect resulting in diameter-dependent nanowire growth rates as a function of the Au-Ag-Ge eutectic composition. Significantly, AuxAg1-x alloy seeds lower the critical diameter of the Ge nanowires in this liquid-seeded growth approach. In situ TEM heating experiments established the correlation between the growth kinetics and equilibrium eutectic compositions in the ternary growth systems. The fundamental insights of nanowire growth demonstrated with the ternary eutectic alloys opens up opportunities to engineer the aspect ratio and morphology of a range of semiconductor nanowires.