Andrei N. Khlobystov

Supramolecular design of one-dimensional coordination polymers based on silver(I) complexes of aromatic nitrogen-donor ligands

Abstract This review discusses the design and structure of coordination polymers derived from Ag(I) with N-donor ligands and their role in the investigation of weak non-covalent interactions in the solid state. These forces include arene–arene, metal–anion, metal–arene and metal–metal interactions. The main purpose of this review is to classify and discuss the supramolecular forces which define the overall observed structure (topology, geometry and packing arrangement) of coordination polymers by comparison of a series of structurally related compounds when one parameter of the multi-component system (choice of anion, ligand or solvent) is varied. Design criteria for one-dimensional polymers are given and discussed with respect to the fundamental importance of these compounds for understanding and further development of supramolecular synthetic strategies.

High-Quality Thin Graphene Films from Fast Electrochemical Exfoliation

Flexible and ultratransparent conductors based on graphene sheets have been considered as one promising candidate for replacing currently used indium tin oxide films that are unlikely to satisfy future needs due to their increasing cost and losses in conductivity on bending. Here we demonstrate a simple and fast electrochemical method to exfoliate graphite into thin graphene sheets, mainly AB-stacked bilayered graphene with a large lateral size (several to several tens of micrometers). The electrical properties of these exfoliated sheets are readily superior to commonly used reduced graphene oxide, which preparation typically requires many steps including oxidation of graphite and high temperature reduction. These graphene sheets dissolve in dimethyl formamide (DMF), and they can self-aggregate at air-DMF interfaces after adding water as an antisolvent due to their strong surface hydrophobicity. Interestingly, the continuous films obtained exhibit ultratransparency (∼96% transmittance), and their sheet resistance is <1k Ω/sq after a simple HNO3 treatment, superior to those based on reduced graphene oxide or graphene sheets by other exfoliation methods. Raman and STM characterizations corroborate that the graphene sheets exfoliated by our electrochemical method preserve the intrinsic structure of graphene.

Noncovalent interactions of molecules with single walled carbon nanotubes

In this critical review we survey non-covalent interactions of carbon nanotubes with molecular species from a chemical perspective, particularly emphasising the relationship between the structure and dynamics of these structures and their functional properties. We demonstrate the synergistic character of the nanotube-molecule interactions, as molecules that affect nanotube properties are also altered by the presence of the nanotube. The diversity of mechanisms of molecule-nanotube interactions and the range of experimental techniques employed for their characterisation are illustrated by examples from recent reports. Some practical applications for carbon nanotubes involved in non-covalent interactions with molecules are discussed.

Graphene-modified LiFePO4 cathode for lithium ion battery beyond theoretical capacity

The specific capacity of commercially available cathode carbon-coated lithium iron phosphate is typically 120-160 mAh g(-1), which is lower than the theoretical value 170 mAh g(-1). Here we report that the carbon-coated lithium iron phosphate, surface-modified with 2 wt% of the electrochemically exfoliated graphene layers, is able to reach 208 mAh g(-1) in specific capacity. The excess capacity is attributed to the reversible reduction-oxidation reaction between the lithium ions of the electrolyte and the exfoliated graphene flakes, where the graphene flakes exhibit a capacity higher than 2,000 mAh g(-1). The highly conductive graphene flakes wrapping around carbon-coated lithium iron phosphate also assist the electron migration during the charge/discharge processes, diminishing the irreversible capacity at the first cycle and leading to ~100% coulombic efficiency without fading at various C-rates. Such a simple and scalable approach may also be applied to other cathode systems, boosting up the capacity for various Li batteries.

Direct transformation of graphene to fullerene

Although fullerenes can be efficiently generated from graphite in high yield, the route to the formation of these symmetrical and aesthetically pleasing carbon cages from a flat graphene sheet remains a mystery. The most widely accepted mechanisms postulate that the graphene structure dissociates to very small clusters of carbon atoms such as C(2), which subsequently coalesce to form fullerene cages through a series of intermediates. In this Article, aberration-corrected transmission electron microscopy directly visualizes, in real time, a process of fullerene formation from a graphene sheet. Quantum chemical modelling explains four critical steps in a top-down mechanism of fullerene formation: (i) loss of carbon atoms at the edge of graphene, leading to (ii) the formation of pentagons, which (iii) triggers the curving of graphene into a bowl-shaped structure and which (iv) subsequently zips up its open edges to form a closed fullerene structure.

Self-assembly of a sulphur-terminated graphene nanoribbon within a single-walled carbon nanotube

The ability to tune the properties of graphene nanoribbons (GNRs) through modification of the nanoribbons width and edge structure widens the potential applications of graphene in electronic devices. Although assembly of GNRs has been recently possible, current methods suffer from limited control of their atomic structure, or require the careful organization of precursors on atomically flat surfaces under ultra-high vacuum conditions. Here we demonstrate that a GNR can self-assemble from a random mixture of molecular precursors within a single-walled carbon nanotube, which ensures propagation of the nanoribbon in one dimension and determines its width. The sulphur-terminated dangling bonds of the GNR make these otherwise unstable nanoribbons thermodynamically viable over other forms of carbon. Electron microscopy reveals elliptical distortion of the nanotube, as well as helical twist and screw-like motion of the nanoribbon. These effects suggest novel ways of controlling the properties of these nanomaterials, such as the electronic band gap and the concentration of charge carriers.

Transmission electron microscopy at 20 kV for imaging and spectroscopy

The electron optical performance of a transmission electron microscope (TEM) is characterized for direct spatial imaging and spectroscopy using electrons with energies as low as 20 keV. The highly stable instrument is equipped with an electrostatic monochromator and a C(S)-corrector. At 20 kV it shows high image contrast even for single-layer graphene with a lattice transfer of 213 pm (tilted illumination). For 4 nm thick Si, the 200 reflections (271.5 pm) were directly transferred (axial illumination). We show at 20 kV that radiation-sensitive fullerenes (C(60)) within a carbon nanotube container withstand an about two orders of magnitude higher electron dose than at 80 kV. In spectroscopy mode, the monochromated low-energy electron beam enables the acquisition of EELS spectra up to very high energy losses with exceptionally low background noise. Using Si and Ge, we show that 20 kV TEM allows the determination of dielectric properties and narrow band gaps, which were not accessible by TEM so far. These very first results demonstrate that low kV TEM is an exciting new tool for determination of structural and electronic properties of different types of nano-materials.

Carbon Nanotubes: From Nano Test Tube to Nano-Reactor

Confinement of molecules and atoms inside carbon nanotubes provides a powerful strategy for studying structures and chemical properties of individual molecules at the nanoscale. In this issue of ACS Nano, Allen et al. explore the nanotube as a template leading to the formation of unusual supramolecular and covalent structures. The potential of carbon nanotubes as reactors for synthesis on the nano- and macroscales is discussed in light of recent studies.

van der Waals Interactions between Nanotubes and Nanoparticles for Controlled Assembly of Composite Nanostructures

We have demonstrated that ubiquitous van der Waals forces are significant in controlling the interactions between nanoparticles and nanotubes. The adsorption of gold nanoparticles (AuNPs) on nanotubes (MWNTs) obeys a simple quadratic dependence on the nanotube surface area, regardless of the source of AuNPs and MWNTs. Changes in the geometric parameters of the components have pronounced effects on the affinity of nanoparticles for nanotubes, with larger, more polarizable nanostructures exhibiting stronger attractive interactions, the impact of which changes in the following order MWNT diameter > AuNP diameter > MWNT length.

Anion exchange in co-ordination polymers: a solid-state or a solvent-mediated process?

Interconversion of chain co-ordination polymers {[Ag(4,4′-bipy)](X)}∞ (X = NO3− or BF4−) in aqueous media has been studied by IR and 1H NMR spectroscopy, transmission electron (TEM) and atomic force (AFM) microscopies and by X-ray powder diffraction (PXRD). The exchange leads to the formation of a pure crystalline phase of a new co-ordination polymer, and detailed TEM and AFM studies indicate a solvent-mediated rather than a solid-state mechanism for the exchange process.