Gas-phase synthesis of inorganic fullerene-like structures and inorganic nanotubes

Following the discovery of fullerenes (C₆₀) and carbon nanotubes, it was shown that nanoparticles of inorganic layered compounds, like WS₂ and MoS₂, are unstable in the planar form and they form closed cage structures with polyhedral or nanotubular shapes. Although initially the method of synthesis for the formation of such closed caged structures and nanotubes involved starting from the respective oxides, it is now well established that the gas-phase synthetic route (using metal chlorides, carbonyls etc) provides an alternative which is suitable for the synthesis of very many closed caged structures and nanotubes hitherto unknown. Various issues with this method of synthesis, including its fundamentals, mechanism, and the properties of the inorganic fullerene-like structures produced are reviewed, together with some possible applications.      

Advances in the synthesis of inorganic nanotubes and fullerene-like nanoparticles

In analogy to graphite, nanoparticles of inorganic compounds with lamellar two-dimensional structure, such as MoS(2), are not stable against folding, and can adopt nanotubular and fullerene-like structures, nicknamed inorganic fullerenes or IF. Various applications for such nanomaterials were proposed. For instance, IF-WS(2) nanoparticles were shown to have beneficial effects as solid lubricants and as part of tribological surfaces. Further applications of IF for high-tensile-strength fibers, hydrogen storage, rechargeable batteries, catalysis, and in nanotechnology are being contemplated. This Minireview highlights some of the latest developments in the synthesis of inorganic nanotubes and fullerene-like structures. Some structural aspects and properties of IF, which are distinct from the bulk materials, are briefly discussed.     

Computational evidence for stable inorganic fullerene-like structures of ceramic and semiconductor materials

Theoretical electronic structure techniques have become an indispensible and powerful means for predicting molecular properties and designing new materials. Based on a density functional approach and guided by geometric considerations we provide evidence for some specific inorganic fullerene-like cage molecules of ceramic and semiconductor materials which exhibit high energetic stability and point group symmetry as well as nearly perfect spherical shape.     

Rare-Earth-compound nanowires, nanotubes, and fullerene-like nanoparticles: synthesis, characterization, and properties

Various low-dimensional nanostructures, such as nanowires, nanotubes, nanosheets, and fullerene-like nanoparticles have been selectively synthesized from rare-earth compounds (hydroxides, fluorides) based on a facile hydrothermal method. The subsequent dehydration, sulfidation, and fluoridation processes lead to the formation of rare-earth oxide, oxysulfide, and oxyhalide nanostructures, which can be functionalized further by doping with other rare-earth ions or by coating with metal nanoparticles. Owing to the interesting combination of novel nanostructures and functional compounds, these nanostructures can be expected to bring new opportunities in the vast research areas of and application in biology, catalysts, and optoelectronic devices.     

Inorganic materials from ionic liquids

Ionic liquids (ILs) can add value to many chemical processes. The electrochemistry and the (physical) organic chemistry communities in particular have extensively studied the structure, properties, and reactivities of various ILs and reactions therein. Inorganic and materials chemists are the newest addition to the IL community: over a number of years, various approaches to the fabrication of inorganic solids with unprecedented and sometimes unique structures and properties have been reported. This article summarizes the state of this particular sub-field of IL research and highlights a few promising approaches that not only reproduce conventional synthesis in ILs, but that provide pathways towards new, possibly unknown, inorganics with advantageous properties that cannot (or only with great difficulty) be made via conventional processes.     

Titanium disulfide nanotubes as hydrogen-storage materials

TiS2 nanotubes, which were synthesized through a chemical transport reaction, are very effective in reversible hydrogen absorption and desorption with the capacity of 2.5 wt %.     

Inorganic nanotubes formation through the synergic evolution of dynamic templates and metallophosphates: from vesicles to nanotubes

A novel synergic evolution of dynamic assembly, from vesicles to nanotubes, between the metallophosphates and organic amines, is disclosed, by which the multicomponent metallophosphate (Cu(2)(OH)PO(4)) nanotubes are synthesized for the first time.     

Inorganic p-type semiconductors and carbon materials based hole transport materials for perovskite solar cells

Incorporation of proper inorganic p-type semiconductors as hole transport layer has great potential to increase long-term stability while maintaining high power conversion efficiency of perovskite solar cells with low material cost.     

Inorganic fluorinated materials in France: recent developments

The purpose of this very short review is obviously not to give an extensive image of the activities carried out in France these last years in various domains related to inorganic fluorine chemistry. At the turn of the century, it will rather focus on a few examples obtained in French research groups, mostly this last decade, in the fields of the synthesis and discovery of some outstanding chemical and physical properties of inorganic fluorinated materials.     

Cluster-assembled materials based on M12N12 (M = Al, Ga) fullerene-like clusters

We report the results of density functional theory calculations on cluster-assembled materials based on M(12)N(12) (M = Al, Ga) fullerene-like clusters. Our results show that the M(12)N(12) fullerene-like structure with six isolated four-membered rings (4NRs) and eight six-membered rings (6NRs) has a T(h) symmetry and a large HOMO-LUMO gap, indicating that the M(12)N(12) cluster would be ideal building blocks for the synthesis of cluster-assembled materials. Via the coalescence of M(12)N(12) building blocks, we find that the M(12)N(12) clusters can bind into stable assemblies by either 6NR or 4NR face coalescence, which enables the construction of rhombohedral or cubic nanoporous framework of varying porosity. The rhombohedral-MN phase is energetically more favorable than the cubic-MN phase. The M(12)N(12) fullerene-like structures in both phases are maintained and the M-N bond lengths between M(12)N(12) monomers are slightly larger than that in isolated M(12)N(12) clusters and the bulk wurtzite phases. The band analysis of both phases reveals that they are all wide-gap semiconductors. Because of the nanoporous character of these phases, they could be used for gas storage, heterogeneous catalysis, filtration and so on.     

碳纳米管预处理及其在催化材料中应用

本文以碳纳米管作催化剂载体为出发点,回顾了大管径尤其是大内径碳纳米管制备,介绍了不同纯化处理工艺对碳纳米管性能的影响,综述了制备、预处理等因素对碳纳米管复合材料和碳纳米管负载型催化剂性能的影响。     

Inorganic electrochromic materials based on tungsten oxide and nickel oxide nanostructures

Electrochromic devices, which dynamically change color under applied potentials, are widely studied for use in energy-efficient smart windows. The operation of electrochromic materials and devices involves the gain or loss of electrons and simultaneous insertion/extraction of ions with opposite charges to balance the internal electric fields. The performance is therefore limited by kinetics of charge transport in the electrochromic materials as well as ion migration in the electrolyte, materials and at their interfaces. Nanostructured electrochromic materials have an extremely short charge transport distance facilitating charge transport in electrochromic devices and large specific surface area for interaction with electrolytes, and thus may provide fast charge and ions transport, high electrochemical activities and remarkable enhancement of electrochromic properties. The recent progress in application of nanostructures, including nanoparticles, 1D and 2D nanostructures, in metal oxide electrochromic materials and devices is reviewed. A perspective on the development trends in electrochromic materials and devices is also proposed.     

Toxic CO detection by Li-encapsulated fullerene-like BeO

Structural Chemistry - We report adsorption energies, structures, energy gap (E g), charge transfer, and electronic properties of carbon monoxide (CO) on primary, cation Li-, Li-, and two...     

Ionic liquids for soft functional materials with carbon nanotubes

A serendipitous finding that ionic liquids gel with carbon nanotubes has opened a new possibility of ionic liquids as modifiers for carbon nanotubes. Upon being ground into ionic liquids, carbon nanotube bundles are untangled, and the resultant fine bundles form a network structure. This is due to the possible specific interaction between the imidazolium ion component and the pi-electronic nanotube surface. The resultant gelatinous materials, consisting of highly electroconductive nanowires and fluid electrolytes, can be utilized for a wide variety of electrochemical applications, such as sensors, capacitors, and actuators. Ionic liquids allow for noncovalent and covalent modifications of carbon nanotubes and fabrication of polymer composites with enhanced physical properties. The processing of carbon nanotubes with ionic liquids is not accompanied by the disruption of the pi-conjugated nanotube structure and does not require solvents; therefore it can readily be scaled up. This article focuses on new aspects of ionic liquids for designer soft materials based on carbon nanotubes.     

Inorganic functional materials: optimization of properties by structural and compositional control

A review is given of the strategies used to dope inorganic solids and the consequences for properties such as ionic and electronic conductivity. Doping mechanisms involve either substitution of foreign ions onto lattice sites, creation of vacancies on either cation or anion sites, or population of normally empty interstitial sites by either anions or cations. Mechanisms for charge compensation associated with aliovalent doping are reviewed and examples are given in the fields of solid state ionics and high-temperature superconductivity. The strategies used for targeting materials with new properties are reviewed, including a surprising number of cases where startling new properties are encountered in well-known materials. Specific examples discussed include MgB2 superconductor, Na beta-alumina sodium ion conductor, Ca12Al14O33 oxide ion conductor, LiCoMnO4 lithium battery cathode, doped Li4SiO4 tunable lithium ion conductor, and La-doped BaTiO3 ferroelectric, which can be either semiconducting or insulating. Examples are also given of a curious observation that extraordinary properties are often encountered in materials that are on the edge of stability, either structurally or compositionally or at the crossover between different property types.     

Supramolecular organized structures of fullerene-based materials and organic functionalization of carbon nanotubes

Self-assembly and morphological organization of various fulleropyrrolidine derivatives affords different and individual supramolecular architectures. Nanospheres, tubules and bundles of nanorods are formed depending on the nature of the added group in the fullerene unit. The current work represents, in the nanometer scale, a novel connection between spherical-shaped fullerene-based materials and fibrous-structurally nanotubes. We also report on the organic functionalization of carbon nanotubes via 1,3-dipolar cycloaddition of azomethine ylides, which results in solubilization of the functionalized nanotubes in most common organic solvents. To cite this article: D. Tasis et al., C. R. Chimie 6 (2003).     

TiS2 nanotubes as the cathode materials of Mg-ion batteries

Titanium disulfide (TiS2) nanotubes were used as the cathode materials of rechargeable magnesium-ion batteries, showing potential low-cost, high-capacity, and good-reversibility properties.