Search

Graphical Abstract:

Si/O/N-doped single-walled carbon nanotubes (SWNTs) are synthesized using aerosol-assisted chemical vapor deposition (AACVD). The samples are characterized by Raman spectroscopy, high-resolution transmission electron microscopy (HRTEM), electron energy loss spectroscopy (EELS), energy-dispersive X-ray spectroscopy (EDS), Auger electron spectroscopy (AES), and X-ray photoelectron spectroscopy (XPS). HRTEM and Raman spectroscopy studies indicate that doping plays a crucial role in the generation of stable small diameter SWNTs. In order to elucidate the role of the heterodoping (Si/N, O/N, and Si/O) on the electronic properties and stability of SWNTs, density functional theory (DFT) computations on semiconductor (10,0), semimetallic (9,0), and metallic (5,5) SWNTs are performed. It is found that in the heterodoped SWNTs substitutional nitrogen makes the inclusion of Si and O atoms more energetically favorable within the carbon lattice. Heterodoping with Si/O/N may have an important impact in the chemistry of SWNTs as they could be used for anchoring polymer chains, clusters, molecules, etc., thus leading to advanced composites and sensors.

[Display omitted]

Hybrid systems consisting of ZnO nanoparticles (ZnO-NPs) anchored on the surface of nitrogen-doped multiwalled carbon nanotubes (CNX-MWNTs) have been synthesized. The anchoring process consists of a self-assembly method involving the mixing of CNX-MWNTs in a solution with N,N-dimethylformamide, zinc acetylacetonate, and thiophene. Thiophene is used as a capping agent for controlling the size and distribution of ZnO-NPs, as well as an anchoring element between the NPs and the nanotube walls. Scanning and transmission electron microscopy characterization revealed that the ZnO-NPs are homogeneously deposited on the surface of CNX-MWNTs. X-ray powder diffraction analysis demonstrated that the ZnO-NPs exhibit a Wurtzite-type crystal structure with an average particle diameter of 5 nm. We also show that the ZnO-NPs do not exhibit a preferential growth direction with respect to the nanotube surface, and their formation is simply controlled by the concentration of the passivating agent. Density functional theory (DFT) calculations confirm that sulfur (from thiophene) is an effective passivating agent for ZnO by preferentially binding low-coordinated Zn atoms. However, the ZnO-NPs could be chemically bonded to the nanotubes through oxygen atoms close to the nitrogenated sites of the tubes. Our results also demonstrate that isolated and sulfur passivated ZnO-NPs become magnetic and exhibit half-metallicity (electronic states with only one spin component are present at the Fermi level). Sulfur-passivated ZnO retains these properties even after forming ZnO/CNX-MWNT hybrid materials.

Abstract

The isolation of few-layered transition metal dichalcogenides has mainly been performed by mechanical and chemical exfoliation with very low yields. In this account, a controlled thermal reduction–sulfurization method is used to synthesize large-area (∼1 cm2) WS2sheets with thicknesses ranging from monolayers to a few layers. During synthesis, WOxthin films are first deposited on Si/SiO2substrates, which are then sulfurized (under vacuum) at high temperatures (750–950 °C). An efficient route to transfer the synthesized WS2films onto different substrates such as quartz and transmission electron microscopy (TEM) grids has been satisfactorily developed using concentrated HF. Samples with different thicknesses have been analyzed by Raman spectroscopy and TEM, and their photoluminescence properties have been evaluated. We demonstrated the presence of single-, bi-, and few-layered WS2on as-grown samples. It is well known that the electronic structure of these materials is very sensitive to the number of layers, ranging from indirect band gap semiconductor in the bulk phase to direct band gap semiconductor in monolayers. This method has also proved successful in the synthesis of heterogeneous systems of MoS2and WS2layers, thus shedding light on the controlled production of heterolayered devices from transition metal chalcogenides.

We are reporting the fabrication of a very efficient electron source using millimeter-long and highly crystalline carbon nanotubes. These devices start to emit electrons at fields as low as 0.17 V/μm and reach threshold emission at 0.24 V/μm. In addition, these electron sources are very stable and can achieve a peak current density of 750 mA cm–2at only 0.45 V/μm. In order to demonstrate intense electron beam generation, these devices were used to produce visible light by cathodoluminescence. Finally, density functional theory calculations were used to rationalize the measured electronic field emission properties in open carbon nanotubes of different lengths. The modeling establishes a clear correlation between length and field enhancement factor.

We present a class of intramolecular graphene heterojunctions and use first-principles density functional calculations to describe their electronic, magnetic, and transport properties. The hybrid graphene and hybrid graphene nanoribbons have both armchair and zigzag features that are separated by an interface made up of pentagonal and heptagonal carbon rings. Contrary to conventional graphene sheets, the computed electronic density of states indicates that all hybrid graphene and nanoribbon systems are metallic. Hybrid nanoribbons are found to exhibit a remarkable width-dependent magnetic behavior and behave as spin polarized conductors.

We present a density functional theory study of the electronic structure, quantum transport and mechanical properties of recently synthesized phosphorus (P) and phosphorus−nitrogen (PN) doped single-walled carbon nanotubes. The results demonstrate that substitutional P and PN doping creates localized electronic states that modify the electron transport properties by acting as scattering centers. Nonetheless, for low doping concentrations (1 doping site per ∼200 atoms), the quantum conductance for metallic nanotubes is found to be only slightly reduced. The substitutional doping also alters the mechanical strength, leading to a 50% reduction in the elongation upon fracture, while Young’s modulus remains approximately unchanged. Overall, the PN- and P-doped nanotubes display promising properties for components in composite materials and, in particular, for fast response and ultra sensitive sensors operating at the molecular level.

Arrays of multiwalled carbon nanotubes doped with phosphorus (P) and nitrogen (N) are synthesized using a solution of ferrocene, triphenyl-phosphine, and benzylamine in conjunction with spray pyrolysis. We demonstrate that iron phosphide (Fe 3P) nanoparticles act as catalysts during nanotube growth, leading to the formation of novel PN-doped multiwalled carbon nanotubes. The samples were examined by high resolution electron microscopy and microanalysis techniques, and their chemical stability was explored by means of thermogravimetric analysis in the presence of oxygen. The PN-doped structures reveal important morphology and chemical changes when compared to N-doped nanotubes. These types of heterodoped nanotubes are predicted to offer many new opportunities in the fabrication of fast-response chemical sensors.

In nature there are numerous layered compounds, some of which could be curved so as to form fascinating nanoshapes with novel properties. Graphite is at present the main example of a very flexible layered structure, which is able to form cylinders (nanotubes) and cages (fullerenes), but there are others. While fullerenes possess positive curvature due to pentagonal rings of carbon, there are other structures which could include heptagonal or higher membered rings. In fact, fullerenes and nanotubes could display negative curvature, thus forming nanomaterials possessing unexpected electronic and mechanical properties. The effect of curvature in other nano–architectures, such as in boron nitride and metal dichalcogenides, is also discussed in this account. Electron irradiation is a tool able to increase the structural complexity of layered materials. In this context, we describe the coalescence of carbon nanotubes and C60molecules. The latter results now open up an alternative approach to producing and manipulating novel nanomaterials in the twenty–first century.

Cement pastes and mortars based on ordinary Portland cement containing nitrogen-doped multiwalled carbon nanotubes (MWCNT-Nx) or oxygen-functionalized multiwalled carbon nanotubes (MWCNT-Ox) are investigated. To incorporate MWCNTs into the cementitious matrix, the as-produced carpets are dispersed over periods of 1 and 2 hours in distilled water at pH levels of 1 and 7. The cement pastes are prepared by adding 0.1 wt% of MWCNTs to cement powder, followed by characterization with SEM and X-ray diffraction (XRD) at an early age (first hours of hydration). The mortars are mechanically characterized during the hydration process for a period of 28 days. SEM characterization of cement pastes revealed that the carbon nanotubes are well incorporated in the cementitious matrix, with the hydrated cement grains interconnected by long carbon nanotubes. XRD characterizations demonstrated that, during the hydration of cement pastes, different peaks emerged that were associated with ettringite, hydrated calcium silicate, and calcium hydroxide, among other structures. Results of the compressive strength measurements for mortars simultaneously mixed with MWCNT-Nx and MWCNT-Ox reached an increment of approximately 30% in compressive strength. In addition, density functional theory calculations were performed in nitrogen-doped and oxygen-functionalized carbon nanotubes interacting with a cement grain.