Facile preparation of Carbon nanotubes and graphene sheets by a catalyst-free refluxing approach

A facile catalyst-free one-step approach for the preparation of carbon nanotubes and graphene sheets at ambient pressure and ?? 230 °C has been developed. Carbon nanotubes and graphene sheets are prepared by reducing tetrachloroethylene with sodium in paraffin oil under reflux. The as-prepared products can be easily purified just by washing with common solvents. No metallic contaminants or other impurities exist in the products. The products show unique optical properties and may find various applications such as optical light attenuators and catalyst supports. This high yield and economical process presents a possible strategy for the large-scale production of carbon nanotubes and graphene sheets for future applications.      

Redox-sensitive colorimetric polyaniline nanoprobes synthesized by a solvent-shift process

We have synthesized water-stable polyaniline nanoparticles coated with triarmed polyethylene glycol chains using a solvent-shift method and confirmed their colloidal size and aqueous solubility. Furthermore, we have demonstrated that the polyaniline nanoparticles can be doped with biological dopants to produce distinct color changes allowing the detection of live cancer cells.      

Nanoscale control of Ag nanostructures for plasmonic fluorescence enhancement of near-infrared dyes

Potential utilization of proteins for early detection and diagnosis of various diseases has drawn considerable interest in the development of protein-based detection techniques. Metal induced fluorescence enhancement offers the possibility of increasing the sensitivity of protein detection in clinical applications. We report the use of tunable plasmonic silver nanostructures for the fluorescence enhancement of a near-infrared (NIR) dye (Alexa Fluor 790). Extensive fluorescence enhancement of ～2 orders of magnitude is obtained by the nanoscale control of the Ag nanostructure dimensions and interparticle distance. These Ag nanostructures also enhanced fluorescence from a dye with very high quantum yield (7.8 fold for Alexa Fluor 488, quantum efficiency (Qy) = 0.92). A combination of greatly enhanced excitation and an increased radiative decay rate, leading to an associated enhancement of the quantum efficiency leads to the large enhancement. These results show the potential of Ag nanostructures as metal induced fluorescence enhancement (MIFE) substrates for dyes in the NIR “biological window” as well as the visible region. Ag nanostructured arrays fabricated by colloidal lithography thus show great potential for NIR dye-based biosensing applications.      

Coordinated buckling of thick multi-walled carbon nanotubes under uniaxial compression

Using a generalized quasi-continuum method, we characterize the post-buckling morphologies and energetics of thick multi-walled carbon nanotubes (MWCNTs) under uniaxial compression. Our simulations identify for the first time evolving post-buckling morphologies, ranging from asymmetric periodic rippling to a helical diamond pattern. We attribute the evolving morphologies to the coordinated buckling of the constituent shells. The post-buckling morphologies result in significantly reduced effective moduli that are strongly dependent on the aspect ratio. Our simulation results provide fundamental principles to guide the future design of high-performance, MWCNT-based nanodevices.      

Enhanced π-π interactions between a C60 fullerene and a buckle bend on a double-walled carbon nanotube

In situ low-voltage aberration corrected transmission electron microscopy (TEM) observations of the dynamic entrapment of a C₆₀ molecule in the saddle of a bent double-walled carbon nanotube is presented. The fullerene interaction is non-covalent, suggesting that enhanced π-π interactions (van der Waals forces) are responsible. Classical molecular dynamics calculations confirm that the increased interaction area associated with a buckle is sufficient to trap a fullerene. Moreover, they show hopping behavior in agreement with our experimental observations. Our findings further our understanding of carbon nanostructure interactions, which are important in the rapidly developing field of low-voltage aberration corrected TEM and nano-carbon device fabrication.      

A perspective on functionalizing colloidal quantum dots with DNA

This perspective provides an overview of the techniques that have been developed for the conjugation of DNA to colloidal quantum dots (QDs), or semiconductor nanocrystals. Methods described include: ligand exchange at the QD surface, covalent conjugation of DNA to the QD surface ligands, and one-step DNA functionalization on core QDs or during core/shell QD synthesis in aqueous solution, with an emphasis on the most recent progress in our lab. We will also discuss emerging trends in DNA-functionalized QDs for potential applications.      

Synthesis and characterization of WS2 inorganic nanotubes with encapsulated/intercalated CsI

WS₂ nanotubes have been filled and intercalated by molten phase caesium iodide. The presence of caesium iodide inside the WS₂ nanotubes has been determined using high-resolution transmission electron microscopy (HRTEM) coupled with electron energy-loss spectroscopy (EELS) and energy-dispersive X-ray spectroscopy (EDS). Noticeably, a Moiré pattern was observed due to the interference between encapsulated CsI and WS₂ layers. The intercalation of CsI into the host concentric WS₂ lattices resulted in an increase in the interplanar spacing.      

Curved carbon nanotubes: From unique geometries to novel properties and peculiar applications

Incorporating pentagons and heptagons into the hexagonal networks of pristine carbon nanotubes （CNTs） can form various CNT-based nanostructures, as pentagons and heptagons will bend or twist the CNTs by introducing positive and negative curvature, respectively. Some typical so-made CNT-based nanostructures are reviewed in this article, including zero-dimensional toroidal CNTs, and one-dimensional kinked and coiled CNTs. Due to the presence of non-hexagonal rings and curved geometries, such nanostructures possess rather different structural, physical and chemical properties from their pristine CNT counterparts, which are reviewed comprehensively in this article. Additionally, their synthesis, modelling studies, and potential applications are discussed.     

Nanobarrier-terminated growth of single-walled carbon nanotubes on quartz surfaces

Using carbon nanotubes as nanobarriers, the growth of single-walled carbon nanotubes (SWNTs) on a quartz surface can be terminated. First, carbon nanotube nanobarriers were grown on a quartz surface by the gas flow-directed growth mode. Then, the SWNTs were grown on the quartz surface via the lattice-oriented growth mode, in which growth of SWNTs can be terminated by hitting the nanotube nanobarriers. Moreover, using the carbon nanotube nanobarrier as a marker, the mechanism of the growth of SWNTs on the quartz surface can be studied; a base-growth mechanism is indicated. Based on this termination process and the base-growth mechanism, SWNT arrays with controlled lengths can be grown on a quartz surface by fixing the sites of both catalysts and nanobarriers.      

Impact of nanocrystallinity segregation on the growth and morphology of nanocrystal superlattices

A colloidal solution of 5 nm Au tetradecanethiol-coated nanoparticles is syn-thesized. After fast evaporation of one drop, ordered monolayers both composed of single domain and polycrystalline nanocrystals are obtained. On increasing the amount of materials and the evaporation time, nanocrystal films with irregular outlines are produced together with close-packed 3D superlattices exhibiting a truncated-tetrahedral shape. Using low-frequency micro-Raman scattering spectroscopy and electron microscopy the building block nanocrystallinity is characterized. Spontaneous nanocrystallinity segregation is revealed： the truncated-tetrahedral supracrystals are shown to mainly contain single domain building blocks while the supracrystalline films are composed of a mixture of single domain and polycrystalline nanocrystals. This observation points out the correlation between the nanocrystallinity segregation involved in the growth of the nanocrystal superlattices and their morphology.     

Selection of single-walled carbon nanotubes according to both their diameter and chirality via nanotweezers

Diameter- and chirality-dependent interactions between aromatic molecule-based nanotweezers and single-walled carbon nanotubes (SWNTs) are revealed by density functional theory calculations. We found that the threshold diameter of selected SWNTs is determined by the end-to-end distance of the nanotweezer. Large-diameter SWNTs are preferred by a nanotweezer with an obtuse folding angle, whereas small-diameter SWNTs are favored by a nanotweezer with an acute folding angle. The adsorption can be further stabilized by the orientational alignment of the hexagonal rings of the nanotweezer and the SWNT sidewall. Therefore, by taking advantage of the supramolecular recognition ability of the aromatic molecule-based nanotweezer, SWNTs can be enriched with both controllable diameter and chirality.      

Lithographically directed assembly of one-dimensional DNA nanostructures via bivalent binding interactions

In order to exploit the outstanding physical properties of one-dimensional (1D) nanostructures such as carbon nanotubes and semiconducting nanowires and nanorods in future technological applications, it will be necessary to organize them on surfaces with precise control over both position and orientation. Here, we use a 1D rigid DNA motif as a model for studying directed assembly at the molecular scale to lithographically patterned nanodot anchors. By matching the inter-nanodot spacing to the length of the DNA nanostructure, we are able to achieve nearly 100% placement yield. By varying the length of single-stranded DNA linkers bound covalently to the nanodots, we are able to study the binding selectivity as a function of the strength of the binding interactions. We analyze the binding in terms of a thermodynamic model which provides insight into the bivalent nature of the binding, a scheme that has general applicability for the controlled assembly of a broad range of functional nanostructures.      

Aptamer-conjugated upconversion nanoprobes assisted by magnetic separation for effective isolation and sensitive detection of circulating tumor cells

Detection of circulating tumor cells （CTCs） plays an important role in cancer diagnosis and prognosis. In this study, aptamer-conjugated upconversion nano- particles （UCNPs） are used for the first time as nanoprobes to recognize tumor cells, which are then enriched by attaching with magnetic nanoparticles （MNPs） and placing in the presence of a magnetic field. Owing to the autofluorescence- free nature of upconversion luminescence imaging, as well as the use of magnetic separation to further reduce background signals, our technique allows for highly sensitive detection and collection of small numbers of tumor cells spiked into healthy blood samples, and shows promise for CTC detection in medical diagnostics.     

Tunable D peak in gated graphene

We report the gate-modulated Raman spectrum of defective graphene. We show that the intensity of the D peak can be reversibly tuned by applying a gate voltage. This effect is attributed to chemical functionalization of the graphene crystal lattice, generated by an electrochemical reaction involving the water layer trapped at the interface between silicon and graphene.     

Facile design of Au@Pt core-shell nanostructures: Formation of Pt submonolayers with tunable coverage and their applications in electrocatalysis

A facile design of Pt nanostructures from submonolayer to monolayer has been realized by ion adsorption-in situ electrochemical reduction on Au nanoparticles supported on multiwall carbon nanotubes （CNTs）. The as prepared Au@Pt/CNTs catalysts display coverage-specific electrocatalysis. Au@Pt/CNTs with low Pt coverage is inactive towards methanol oxidation whereas it oxidizes formic acid effectively through a direct pathway with mass specific activity 90 times that of a commercial Pt/C catalyst. Due to its inertness to methanol, it shows high performance in the oxygen reduction reaction （ORR） with high methanol tolerance. In contrast, simply increasing the Pt coverage to above 40% switches the formic acid oxidation process to both direct and indirect catalytic pathways, and also results in high methanol oxidation activity.     

Light-controlled synthesis of uniform platinum nanodendrites with markedly enhanced electrocatalytic activity

We report a fast in situ seeding approach based on zinc（II） porphyrin （ZnP） under white light irradiation, leading to uniform spherical platinum nanodendrites with tunable sizes. The platinum nanodendrites exhibit significantly improved electrocatalytic activities toward oxygen reduction reaction （ORR） and methanol oxidation reaction （MOR） compared with commercial platinum black.     

Unexpected luminescence enhancement of upconverting nanocrystals by cation exchange with well retained small particle size

Highly luminescent upconversion nanoparticles （UCNPs） with small sizes are highly desirable for bioapplications. A facile in situ cation exchange strategy has been developed to greatly enhance the UC luminescence of hexagonal phase NaYF4 NPs while maintaining their small particle size and shape. Via a cation exchange treatment by hot-injecting Gd3＋ precursors into the as-prepared NPs solution without pre-separation, the naked-eye visible UC emission of the NPs was enhanced about 29 times under 980 nm near infrared （NIR） excitation with unchanged particle size. The cation exchange process was further demonstrated for the case of NaYF4 nanorods （NRs）. After the cation exchange, the nanorod was broken into two NPs with stronger emission. The cation exchanged hydrophobic UCNPs were further encapSulated with poly（amino acid） and successfully applied for targeted cancer cell UC luminescence imaging.     

Engineering manganese oxide/nanocarbon hybrid materials for oxygen reduction electrocatalysis

Manganese oxides are cost-effective and green materials with rich electrochemical properties. Continuous research efforts have been undertaken to obtain MnO _x materials with improved activity and stability for catalyzing the oxygen reduction reaction (ORR). Here, we have developed a novel ORR catalyst by nucleation and growth of Mn₃O₄ nanoparticles on graphene oxide (GO) sheets interconnected by electrically conducting multi-walled carbon nanotubes (MWCNTs). X-ray near edge absorption structure (XANES) spectroscopy revealed the partially reduced nature of GO and strong chemical coupling between the nanoparticles and the GO sheets. Incorporation of MWCNTs was found to improve the activity and stability of the hybrid by imparting higher conductivity to the hybrid material. Furthermore, surface oxidation of the manganese oxide nanoparticles through a calcination step was found to increase the density of ORR active sites. The strongly coupled and electrically interconnected Mn₃O₄/nanocarbon (Mn₃O₄/Nano-C) hybrid is one of the most active and stable manganese oxide-based ORR catalysts and shows promise for electrochemical energy conversion applications.      

Solution-processed bulk heterojunction solar cells based on interpenetrating CdS nanowires and carbon nanotubes

Incorporation of a bulk heterojunction is an effective strategy to enhance charge separation and carrier transport in solar cells, and has been adopted in polymeric and colloidal nanoparticle solar cells to improve energy conversion efficiency. Here, we report bulk heterojunction solar cells based on one-dimensional structures, fabricated by mixing CdS nanowires (CdS NWs) and single-walled carbon nanotubes (CNTs) to form a composite film with mutually interpenetrating networks through a simple solution-filtration process. Within the composite, the CNT network boosts charge separation by extracting holes generated from CdS NWs and also forms the transport path for carrier collection by the external electrode. At an optimized CNT loading of about 5 wt.%, the CdS NW/CNT bulk heterojunction solar cells showed three orders of magnitude increase in photocurrent and cell efficiency compared to a cell with the same materials arranged in a stacked layer configuration with a plain heterojunction. External quantum efficiency and photoluminescence studies revealed the efficient charge transfer process from photoexcited CdS NWs to CNTs in the mixed form. Our results indicate that the bulk heterojunction structure strategy can be extended to semiconductor NWs and CNTs and can greatly improve solar cell performance.      

Metal-film-assisted ultra-clean transfer of single-walled carbon nanotubes

Transfer printing of nanomaterials onto target substrates has been widely used in the fabrication of nanodevices, but it remains a challenge to fully avoid contamination introduced in the transfer process. Here we report a metal-film- assisted method to realize an ultra-clean transfer of single-walled carbon nanotubes （SWCNTs） mediated by poly（methyl methacrylate） （PMMA）. The amount of PMMA residue can be greatly reduced due to its strong physical adhesion to the metal film, leading to ultra-clean surfaces of both the SWCNTs and the substrates. This metal-film-assisted transfer method is efficient, nondestructive, and scalable. It is also suitable for the transfer of graphene and other nanostructures. Furthermore, the relatively low temperature employed allows this technique to be compatible with nanomaterial-based flexible electronics.