Open metal–organic frameworks are widely regarded as promising materials for applications1,2,3,4,5,6,7,8,9,10,11,12,13,14,15 in catalysis, separation, gas storage and molecular recognition. Compared to conventionally used microporous inorganic materials such as zeolites, these organic structures have the potential for more flexible rational design, through control of the architecture and functionalization of the pores. So far, the inability of these open frameworks to support permanent porosity and to avoid collapsing in the absence of guest molecules, such as solvents, has hindered further progress in the field14,15. Here we report the synthesis of a metal–organic framework which remains crystalline, as evidenced by X-ray single-crystal analyses, and stable when fully desolvated and when heated up to 300?°C. This synthesis is achieved by borrowing ideas from metal carboxylate cluster chemistry, where an organic dicarboxylate linker is used in a reaction that gives supertetrahedron clusters when capped with monocarboxylates. The rigid and divergent character of the added linker allows the articulation of the clusters into a three-dimensional framework resulting in a structure with higher apparent surface area and pore volume than most porous crystalline zeolites. This simple and potentially universal design strategy is currently being pursued in the synthesis of new phases and composites, and for gas-storage applications.

/pdf/design-and-synthesis-of-an-exceptionally-stable-and-highly-47du30tog6.pdf

Design and synthesis of an exceptionally stable and highly porous metal-organic framework

Rapid growth in nanotechnology is increasing the likelihood of engineered nanomaterials coming into contact with humans and the environment. Nanoparticles interacting with proteins, membranes, cells, DNA and organelles establish a series of nanoparticle/biological interfaces that depend on colloidal forces as well as dynamic biophysicochemical interactions. These interactions lead to the formation of protein coronas, particle wrapping, intracellular uptake and biocatalytic processes that could have biocompatible or bioadverse outcomes. For their part, the biomolecules may induce phase transformations, free energy releases, restructuring and dissolution at the nanomaterial surface. Probing these various interfaces allows the development of predictive relationships between structure and activity that are determined by nanomaterial properties such as size, shape, surface chemistry, roughness and surface coatings. This knowledge is important from the perspective of safe use of nanomaterials.

Understanding biophysicochemical interactions at the nano–bio interface

▪ Abstract Solution phase syntheses and size-selective separation methods to prepare semiconductor and metal nanocrystals, tunable in size from ∼1 to 20 nm and monodisperse to ≤5%, are presented. Preparation of monodisperse samples enables systematic characterization of the structural, electronic, and optical properties of materials as they evolve from molecular to bulk in the nanometer size range. Sample uniformity makes it possible to manipulate nanocrystals into close-packed, glassy, and ordered nanocrystal assemblies (superlattices, colloidal crystals, supercrystals). Rigorous structural characterization is critical to understanding the electronic and optical properties of both nanocrystals and their assemblies. At inter-particle separations 5–100 A, dipole-dipole interactions lead to energy transfer between neighboring nanocrystals, and electronic tunneling between proximal nanocrystals gives rise to dark and photoconductivity. At separations <5 A, exchange interactions cause otherwise insulating ass...

Synthesis and Characterization of Monodisperse Nanocrystals and Close-Packed Nanocrystal Assemblies

Small but strong: A review of the mechanical properties of carbon nanotube–polymer composites

We study the electronic states of graphite ribbons with edges of two typical shapes, armchair and zigzag, by performing tight binding band calculations, and find that the graphite ribbons show striking contrast in the electronic states depending on the edge shape. In particular, a zigzag ribbon shows a remarkably sharp peak of density of states at the Fermi level, which does not originate from infinite graphite. We find that the singular electronic states arise from the partly flat bands at the Fermi level, whose wave functions are mainly localized on the zigzag edge. We reveal the puzzle for the emergence of the peculiar edge state by deriving the analytic form in the case of semi-infinite graphite with a zigzag edge. Applying the Hubbard model within the mean-field approximation, we discuss the possible magnetic structure in nanometer-scale micrographite.

Peculiar Localized State at Zigzag Graphite Edge

The interpretation, in terms of dipole interactions, of the dependence on coverage of the stretching frequency of CO adsorbed of metal sufaces is re‐examined. We take into account substrate image effects and dielectric screening of the adsorbed layer. We also provide a theory of the statistical fluctuations in random, partially filled layers. The dipole interactions provide a frequency shift of about 10 cm−1, which is only about one third of that usually observed.

Collective vibrational modes of adsorbed CO

Fe-catalyzed carbon nanotube formation

Catalytic synthesis of carbon nanotubes using zeolite support

We report on the first measurements by high-resolution electron-energy-loss spectroscopy of the elementary excitations of ${\mathrm{C}}_{60}$ thin films deposited on Si(100). By varying the primary electron energy, the spectrum extending from the far ir to the far vuv has been investigated. Many spectral features are comparable to earlier observations by photon, photoelectron, and neutron spectroscopies. New molecular excitations are revealed including the lowest electronic excitation at 1.5 eV and collective excitations at 6.3 and 28 eV.

High-resolution electron-energy-loss spectroscopy of thin films of C60 on Si(100).

The growth of micron-size carbon fibres from thermal decomposition of hydrocarbons catalyzed by a metal has been widely studied. Coil-shaped fibres often grow among straight or twisted filaments. Their internal structure has not been studied in detail as yet. In the present work, the thermal cracking of acetylene on Co nanoparticles dispersed on porous silica has produced relatively well graphitized hollow nanotubules, including straight filaments and regular helices. The small diameter of the coiled tubules and the absence of an amorphous coating allowed a determination of their texture by transmission electron microscopy (TEM). The coiled tubules consist of regularly polygonized, coaxial graphene tubes whose angular bends are aligned. The bends are probably caused by the occurrence along the helix of pairs of pentagon-heptagon carbon rings in the hexagonal network. Such a structure was recently predicted to be a thermodynamically stable topology for helical, single-sheet carbon tubes. A molecular model, consistent with theoretical predictions on how to connect cylindrical tubule segments, is provided.

http://iopscience.iop.org/article/10.1209/0295-5075/27/2/011/pdf

Amand Lucas

Papers

Collective vibrational modes of adsorbed CO

Fe-catalyzed carbon nanotube formation

Catalytic synthesis of carbon nanotubes using zeolite support

High-resolution electron-energy-loss spectroscopy of thin films of C60 on Si(100).

The Texture of Catalytically Grown Coil-Shaped Carbon Nanotubules