In Situ N-Doped Graphene and Mo Nanoribbon Formation from Mo2 Ti2 C3 MXene Monolayers.

Since the advent of monolayered 2D transition metal carbide and nitrides (MXenes) in 2011, the number of different monolayer systems and the study thereof have been on the rise. Mo2 Ti2 C3 is one of the least studied MXenes and new insights to this material are of value to the field. Here, the stability of Mo2 Ti2 C3 under electron irradiation is investigated. A transmission electron microscope (TEM) is used to study the structural and elemental changes in situ. It is found that Mo2 Ti2 C3 is reasonably stable for the first 2 min of irradiation. However, structural changes occur thereafter, which trigger increasingly rapid and significant rearrangement. This results in the formation of pores and two new nanomaterials, namely, N-doped graphene membranes and Mo nanoribbons. The study provides insight into the stability of Mo2 Ti2 C3 monolayers against electron irradiation, which will allow for reliable future study of the material using TEM. Furthermore, these findings will facilitate further research in the rapidly growing field of electron beam driven chemistry and engineering of nanomaterials.

Charge Density Waves Driven by Peierls Instability at the Interface of Two-Dimensional Lateral Heterostructures.

The origin of charge density wave (CDW) observed in low-dimensional systems is, for long, a subject of intensive debate in contemporary condensed matter physics. Specifically, a simple and well established model, namely, the Peierls instability is often (but not always) used to clearly explain CDW states in real systems. Here, first-principles density functional theory calculations are used to show CDW formation at a one-dimensional interface embedded in a lateral heterostructure comprising blue and black phosphorene, even at room temperature. The CDW formation is fully explained by the Peierls mechanism, including a double-periodicity lattice distortion energy lowering and a bandgap opening. The lattice distortion also substantially modifies the band alignment of the heterostructure. Comparison with a freestanding P chain shows that the structural distortion is confined to one dimension within the heterostructures, ruling out competing non-Peierls-type distortions in two dimensions. In addition, similar Peierls-type distortions for other lateral heterostructures are shown by using the example of a graphene-hexagonal boron nitride heterostructure, which may stimulate related studies in different 2D systems. These findings not only shed more light on the Peierls mechanism, but also have important implications for devices based on 2D lateral heterostructures.

Ternary CNTs@TiO2/CoO Nanotube Composites: Improved Anode Materials for High Performance Lithium Ion Batteries.

TiO2 nanotubes (NTs) synthesized by electrochemical anodization are discussed as very promising anodes for lithium ion batteries, owing to their high structural stability, high surface area, safety, and low production cost. However, their poor electronic conductivity and low Li⁺ ion diffusivity are the main drawbacks that prevent them from achieving high electrochemical performance. Herein, we report the fabrication of a novel ternary carbon nanotubes (CNTs)@TiO2/CoO nanotubes composite by a two-step synthesis method. The preparation includes an initial anodic fabrication of well-ordered TiO2/CoO NTs from a Ti-Co alloy, followed by growing of CNTs horizontally on the top of the oxide films using a simple spray pyrolysis technique. The unique 1D structure of such a hybrid nanostructure with the inclusion of CNTs demonstrates significantly enhanced areal capacity and rate performances compared to pure TiO2 and TiO2/CoO NTs, without CNTs tested under identical conditions. The findings reveal that CNTs provide a highly conductive network that improves Li⁺ ion diffusivity, promoting a strongly favored lithium insertion into the TiO2/CoO NT framework, and hence resulting in high capacity and an extremely reproducible high rate capability.

Growing three-dimensional biomorphic graphene powders using naturally abundant diatomite templates towards high solution processability.

Mass production of high-quality graphene with low cost is the footstone for its widespread practical applications. We present herein a self-limited growth approach for producing graphene powders by a small-methane-flow chemical vapour deposition process on naturally abundant and industrially widely used diatomite (biosilica) substrates. Distinct from the chemically exfoliated graphene, thus-produced biomorphic graphene is highly crystallized with atomic layer-thickness controllability, structural designability and less noncarbon impurities. In particular, the individual graphene microarchitectures preserve a three-dimensional naturally curved surface morphology of original diatom frustules, effectively overcoming the interlayer stacking and hence giving excellent dispersion performance in fabricating solution-processible electrodes. The graphene films derived from as-made graphene powders, compatible with either rod-coating, or inkjet and roll-to-roll printing techniques, exhibit much higher electrical conductivity (∼110,700 S m-1 at 80% transmittance) than previously reported solution-based counterparts. This work thus puts forward a practical route for low-cost mass production of various powdery two-dimensional materials.

Scalable Seashell-Based Chemical Vapor Deposition Growth of Three-Dimensional Graphene Foams for Oil-Water Separation.

A seashell-based CVD technique for preparing three-dimensional (3D) graphene foams is reported. The graphene sheets in thus-obtained foams are seamlessly interconnected into a 3D flexible network, forming highly porous materials with negligible non-carbon impurities, ultralow density, and outstanding mechanical flexibility and electrical conductivity. These 3D graphene foams demonstrate a fast adsorption performance toward various oils and organic solvents, with adsorption capacity up to 250-fold weight gain. The present approach offers a practical route for scalable construction of 3D graphene foams for versatile applications such as energy storage and water remediation.

Direct Synthesis of Few-Layer Graphene on NaCl Crystals.

Chemical vapor deposition is used to synthesize few-layer graphene on micro crystalline sodium chloride (NaCl) powder. The water-soluble nature of NaCl makes it convenient to produce free standing graphene layers via a facile and low-cost approach. Unlike traditional metal-catalyzed or oxygen-aided growth, the micron-size NaCl crystal planes play an important role in the nucleation and growth of few-layer graphene. Moreover, the possibility of synthesizing cuboidal graphene is also demonstrated in the present approach for the first time. Raman spectroscopy, optical microscopy, scanning electron microscopy, transmission electron microscopy, and atomic force microscopy are used to evaluate the quality and structure of the few-layer graphene along with cuboidal graphene obtained in this process. The few-layer graphene synthesized using the present method has an adsorption ability for anionic and cationic dye molecules in water. The present synthesis method may pave a facile way for manufacturing few-layer graphene on a large scale.

Low voltage transmission electron microscopy of graphene.

The initial isolation of graphene in 2004 spawned massive interest in this two-dimensional pure sp(2) carbon structure due to its incredible electrical, optical, mechanical, and thermal effects. This in turn led to the rapid development of various characterization tools for graphene. Examples include Raman spectroscopy and scanning tunneling microscopy. However, the one tool with the greatest prowess for characterizing and studying graphene is the transmission electron microscope. State-of-the-art (scanning) transmission electron microscopes enable one to image graphene with atomic resolution, and also to conduct various other characterizations simultaneously. The advent of aberration correctors was timely in that it allowed transmission electron microscopes to operate with reduced acceleration voltages, so that damage to graphene is avoided while still providing atomic resolution. In this comprehensive review, a brief introduction is provided to the technical aspects of transmission electron microscopes relevant to graphene. The reader is then introduced to different specimen preparation techniques for graphene. The different characterization approaches in both transmission electron microscopy and scanning transmission electron microscopy are then discussed, along with the different aspects of electron diffraction and electron energy loss spectroscopy. The use of graphene for other electron microscopy approaches such as in-situ investigations is also presented.

Synthesis and toxicity characterization of carbon coated iron oxide nanoparticles with highly defined size distributions.

BACKGROUND: Iron oxide nanoparticles hold great promise for future biomedical applications. To this end numerous studies on iron oxide nanoparticles have been conducted. One aspect these studies reveal is that nanoparticle size and shape can trigger different cellular responses through endocytic pathways, cell viability and early apoptosis. However, systematic studies investigating the size dependence of iron oxide nanoparticles with highly defined diameters across multiple cells lines are not available yet. METHODS: Iron oxide nanoparticles with well-defined size distributions were prepared. All samples were thoroughly characterized and the cytotoxicity for four standard cell lines (HeLa Kyoto, human osteosarcoma (U2OS), mouse fibroblasts (NIH 3T3) and mouse macrophages (J7442)) where investigated. RESULTS: Our findings show that small differences in size distribution (ca. 10nm) of iron oxide nanoparticles do not influence cytotoxicity, while uptake is size dependent. Cytotoxicity is dose-dependent. Broad distributions of nanoparticles are more easily internalized as compared to the narrow distributions for two of the cell lines tested (HeLa Kyoto and mouse macrophages (J7442)). CONCLUSION: The data indicate that it is not feasible to probe changes in cytotoxicity within a small size range (10nm). However, TEM investigations of the nanoparticles indicate that cellular uptake is size dependent. GENERAL SIGNIFICANCE: The present work compares narrow and broad distributions for various samples of carbon-coated iron oxide nanoparticles. The data highlights that cells differentiate between nanoparticle sizes as indicated by differences in cellular uptake. This information provides valuable knowledge to better understand the interaction of nanoparticles and cells.

Synthesis of carbon nanotubes with and without catalyst particles.

The initial development of carbon nanotube synthesis revolved heavily around the use of 3d valence transition metals such as Fe, Ni, and Co. More recently, noble metals (e.g. Au) and poor metals (e.g. In, Pb) have been shown to also yield carbon nanotubes. In addition, various ceramics and semiconductors can serve as catalytic particles suitable for tube formation and in some cases hybrid metal/metal oxide systems are possible. All-carbon systems for carbon nanotube growth without any catalytic particles have also been demonstrated. These different growth systems are briefly examined in this article and serve to highlight the breadth of avenues available for carbon nanotube synthesis.