Search

Mesocrystals are superstructures of crystallographically aligned nanoparticles and are a rapidly emerging class of crystalline materials displaying sophisticated morphologies and properties, beyond those originating from size and shape of nanoparticles alone. This study reports the first synthesis of Cu 3 N mesocrystals employing structure-directing agents with a subtle tuning of the reaction parameters. Detailed structural characterizations carried out with a combination of transmission electron microscopy techniques (HRTEM, HAADF-STEM-EXDS) reveal that Cu 3 N mesocrystals form by non-classical crystallization, and variations in their sizes and morphologies are traced back to distinct attachment scenarios of corresponding mesocrystal subunits. In the presence of oleylamine, the mesocrystal subunits in the early reaction stages prealign in a crystallographic fashion and afterwards grow into the final mesocrystals, while in the presence of hexadecylamine the subunits come into contact through misaligned attachment, and subsequently, to some degree, realign in crystallographic register. Upon prolonged heating both types of mesocrystals undergo chemical conversion processes resulting in structural and morphological changes. A two-step mechanism of chemical conversion is proposed, involving Cu 3 N decomposition and anion exchange driven by the nanoscale Kirkendall effect, resulting first in multicomponent/heterostructured Cu 3 N-Cu 2 O mesocrystals, which subsequently convert into Cu 2 O nanocages. It is anticipated that combining nanostructured Cu 3 N and Cu 2 O in a mesocrystalline and hollow morphology will provide a platform to expand their application potential.

Since the discovery of the pseudocapacitive behavior in RuO 2 by Sergio Trasatti and Giovanni Buzzanca in 1971, materials with pseudocapacitance have been regarded as promising candidates for high-power energy storage. Pseudocapacitance-involving energy storage is predominantly based on faradaic redox reactions, but at the same time the charge storage is not limited by solid-state ion diffusion. Besides the search for pseudocapacitive materials, their implementation into non-aqueous hybrid capacitors stands for the strategy to increase power density by a rational design of the battery structure. Composed of a battery-type anode and a capacitor-type cathode, such devices show great promise to integrate the merits of both batteries and capacitors. Today, the availability of fast-charging technologies is of fundamental importance for establishing electric vehicles on a mass scale. Therefore, from the perspective of materials and battery design, understanding the basics and the recent developments of pseudocapacitive materials and non-aqueous hybrid capacitors is of great importance. With this goal in mind, we introduce here the fundamentals of pseudocapacitance and non-aqueous hybrid capacitors. In addition, we provide an overview of the latest developments in this fast growing research field.

Luminescent nanoparticles are researched for their potential impact in medical science, but no materials approved for parenteral use have been available so far. To overcome this issue, we demonstrate that Eu3+-doped hafnium dioxide nanocrystals can be used as non-toxic, highly stable probes for cellular optical imaging and as radiosensitive materials for clinical treatment. Furthermore, viability and biocompatibility tests on artificially stressed cell cultures reveal their ability to buffer reactive oxygen species, proposing an anti-cytotoxic feature interesting for biomedical applications.

Here we present a strategy to assemble one-dimensional nanostructures into a three-dimensional architecture with macroscopic size. With the assistance of centrifugation, we successfully gel ultrathin W18O49 nanowires with diameters of 1 to 2 nm and aspect ratios larger than 100 into 3D networks, which are transformed into monolithic aerogels by supercritical drying.

TiO2 has been considered as a promising anode material for lithium ion batteries. However, its poor rate capability originating from the intrinsically low lithium ion diffusivity and its poor electronic conductivity hampers putting such an application into practice. Both issues can be addressed by nanostructure engineering and conductive surface coating. Herein, we report a template-assisted synthesis of micron sized TiO2 fibers consisting of a mesoporous network of anatase nanoparticles of about 7.5 nm and coated by N doped carbon. In a first step, an amorphous layer of TiO2 was deposited on cobalt silicate nanobelts and subsequently transformed into crystalline anatase nanoparticles by hydrothermal treatment. The N doped carbon coating was realized by in situ polymerization of dopamine on the crystalline TiO2 followed by annealing under N2. After removal of the template, we obtained the final mesoporous TiO2 fibers@N doped carbon composite. Electrochemical tests revealed that the composite electrode exhibited excellent electrochemical properties in terms of specific capacity, rate performance and long term stability.

We use in situ X-ray absorption and diffraction studies to directly monitor the crystallization of different titania polymorphs in one and the same solution. We find that, despite the commonly accepted polymorphic-crossover from anatase to rutile triggered by the critical size of nanoparticles, in the solution their respective nucleation and growth are independent processes. Moreover, we find that 5.9 nm rutile nanoparticles are formed prior to the formation of 8.4 nm anatase nanoparticles. Our results suggest that the origins of this crystallization mechanism lie in the formation of an intermediate non-crystalline phase and in time-dependent changes in the chemical environment.

Texturing of magnetic ceramics and composites by aligning and fixing of colloidal particles in a magnetic field is a powerful strategy to induce anisotropic chemical, physical and especially mechanical properties into bulk materials. If porosity could be introduced, anisotropically structured magnetic materials would be the perfect supports for magnetic separations in biotechnology or for magnetic field-assisted chemical reactions. Aerogels, combining high porosity with nanoscale structural features, offer an exceptionally large surface area, but they are difficult to magnetically texture. Here we present the preparation of anatase-magnetite aerogel monoliths via the assembly of preformed nanocrystallites. Different approaches are proposed to produce macroscopic bodies with gradient-like magnetic segmentation or with strongly anisotropic magnetic texture.

We present a detailed study on the nonaqueous synthesis of tungstite nanostructures with the focus on crystallization processes and the evolution of particle morphology. Time-dependent transmission electron microscopy (TEM) revealed a complex, particle-based crystallization mechanism involving first the formation of spherical and single-crystalline primary particles of 2-8 nm, which are cross-linked to large and unordered agglomerates, followed by their organization into rod-like structures of 40 × 200-400 nm. These rods undergo an internal ordering process, during which crystallographically oriented stacks of platelets develop. In situ small angle X-ray scattering (SAXS) experiments confirm this pathway of particle formation. The scattering intensity is dominated by the fast formation of rod-like particles, which cause an inter-platelet peak in the SAXS pattern with ongoing internal ordering. With continuous reaction time, the platelet stacks start to fall apart forming shorter assemblies of just a few platelets or even single platelets.

Zinc oxide nanostructures are known to exist in a great variety of morphologies. However, the underlying mechanisms leading to these architectures are far from being fully understood. Here, we present a time dependent study of the generation of zinc oxide nanorods, which arrange into bundles with a fan- or bouquet-like structure, using the benzyl alcohol route. The structural evolution of the nanoparticles was monitored by electron microscopy techniques, whereas the progress of the chemical reaction was followed by quantification of the organic by-products using gas chromatography. With this study we give a detailed insight into the formation of the zinc oxide structures, which involves a complex pathway based on many in parallel occurring processes such as crystallization of primary particles, their oriented attachment and surface reconstruction inside the nanoparticulate agglomerates. However, in spite of such an intricate growth behavior, the ZnO nanostructures are surprisingly uniform in size and shape., (This journal is © The Royal Society of Chemistry 2012)

This Feature Article gives an overview of microwave-assisted liquid phase routes to inorganic nanomaterials. Whereas microwave chemistry is a well-established technique in organic synthesis, its use in inorganic nanomaterials' synthesis is still at the beginning and far away from having reached its full potential. However, the rapidly growing number of publications in this field suggests that microwave chemistry will play an outstanding role in the broad field of Nanoscience and Nanotechnology. This article is not meant to give an exhaustive overview of all nanomaterials synthesized by the microwave technique, but to discuss the new opportunities that arise as a result of the unique features of microwave chemistry. Principles, advantages and limitations of microwave chemistry are introduced, its application in the synthesis of different classes of functional nanomaterials is discussed, and finally expected benefits for nanomaterials' synthesis are elaborated.

Diluted magnetic semiconductors with a Curie temperature exceeding 300 K are promising candidates for spintronic devices and spin-based electronic technologies. We review recent achievements in the field of one of them: Co-doped ZnO at the nanoparticulate scale.