Synthesis of Single-Crystalline Lead Sulfide Nanoframes and Nanorings

We present a colloidal synthesis strategy to obtain single-crystalline PbS nanorings. By controlling the ripening process in the presence of halide ions, a transformation of initial PbS nanosheets to framelike structures and finally to nanorings was achieved. We found that the competing ligands oleic acid, oleate, and halide ions play an important role in the formation of these nanostructures. Therefore, we propose a formation mechanism based on a thermally induced ripening of crystal facets dependent on the surface passivation. With this method, it became possible to synthesize colloidal nanorings of cubic crystal phase galena PbS. The synthesis was followed via TEM, and the products are characterized by XRD, AFM, and STEM tomography. Control of the initial nanoframe morphology allows adjusting the later nanoring dimensions

Colloidal lead iodide nanorings

Colloidal chemistry of nanomaterials experienced a tremendous development in the last decades. In the course of the journey 0D nanoparticles, 1D nanowires, and 2D nanosheets have been synthesized. They have in common to possess a simple topology. We present a colloidal synthesis strategy for lead iodide nanorings, with a non-trivial topology. First, two-dimensional structures were synthesized in nonanoic acid as the sole solvent. Subsequently, they underwent an etching process in the presence of trioctylphosphine, which determines the size of the hole in the ring structure. We propose a mechanism for the formation of lead iodide nanosheets which also explains the etching of the two-dimensional structures starting from the inside, leading to nanorings. In addition, we demonstrate a possible application of the as-prepared nanorings in photodetectors. These devices are characterized by a fast response, high gain values, and a linear relation between photocurrent and incident light power intensity over a large range. The synthesis approach allows for inexpensive large-scale production of nanorings with tunable properties.Comment: 26 pages, 7 figures, 2 scheme

Function Follows Form: From Semiconducting to Metallic toward Superconducting PbS Nanowires by Faceting the Crystal

In the realm of colloidal nanostructures, with its immense capacity for shape and dimensionality control, the form is undoubtedly a driving factor for the tunability of optical and electrical properties in semiconducting or metallic materials. However, influencing the fundamental properties is still challenging and requires sophisticated surface or dimensionality manipulation. In this work, we present such a modification for the example of colloidal lead sulphide nanowires. We show that the electrical properties of lead sulphide nanostructures can be altered from semiconducting to metallic with indications of superconductivity, by exploiting the flexibility of the colloidal synthesis to sculpt the crystal and to form different surface facets. A particular morphology of lead sulphide nanowires has been synthesized through the formation of {111} surface facets, which shows metallic and superconducting properties in contrast to other forms of this semiconducting crystal, which contain other surface facets ({100} and {110}). This effect, which has been investigated with several experimental and theoretical approaches, is attributed to the presence of lead rich {111} facets. The insights promote new strategies for tuning the properties of crystals as well as new applications for lead sulphide nanostructures.Comment: 23 pages, 6 figure

Low-Lanthanide-Content CeO2/MgO Catalysts with Outstandingly Stable Oxygen Storage Capacities: An In-Depth Structural Characterization by Advanced STEM Techniques

International audienceA novel CeO2/MgO catalyst with low ceria loading has been synthesized. This catalyst showed unique redox properties compared with conventional high and low surface area CeO2. Advanced (scanning) transmission electron microscopy techniques revealed the presence of a variety of highly dispersed ceria nanostructures: isolated CeOx entities, CeO2 clusters, as well as fairly small (<5nm) CeO2 nanoparticles. More interestingly, this CeO2/MgO catalyst showed outstanding stability in its redox response against high temperature aging treatments. Thus, after reduction in hydrogen at 950 degrees C and further oxidation at 500 degrees C, CeO2 reduction effects took still place at low temperatures, and no significant loss of oxygen storage capacity (OSC) was detected. Unique ceria-bilayer nanostructures were found and characterized in the aged catalyst. Their peculiar structural and chemical properties seem to be responsible for the large improvement observed in the stability of the redox response

Improved Oxidase Mimetic Activity by Praseodymium Incorporation into Ceria Nanocubes

Ceria nanocubes (NC) modified with increasing concentrations of praseodymium (5, 10, 15, and 20 mol %) have been successfully synthesized by a hydrothermal method. The as-synthesized Pr-modified ceria nanocubes exhibit an enhanced oxidase-like activity on the organic dye TMB within a wide range of concentrations and durations. The oxidase activity increases with increasing Pr amounts in Pr-modified ceria nanocubes within the investigated concentration range. Meanwhile, these Pr-modified ceria nanocubes also show higher reducibility than pure ceria nanocubes. The kinetics of their oxidase mimetic activity is fitted with the Michaelis–Menten equation. A mechanism has been proposed on how the Pr incorporation could affect the energy level of the bands in ceria and hence facilitate the TMB oxidation reaction. The presence of Pr³⁺ species on the surface also contributes to the increasing activity of the Pr-modified ceria nanocubes present higher oxidase activity than pure ceria nanocubes