WS2 Nanotubes Research Articles

Electrochemical unzipping of multiple-walled WS2 nanotubes for synthesis of WS2 nanoribbons being an attractive H2 evolution catalyst

We report the unzipping of multiple-walled WS2 nanotubes (WS2-MWNTs) to produce WS2 nanoribbons by employing an electrochemical oxidation process. When conditioning the WS2-MWNTs in an acidic solution at 1.2 V vs. RHE, W-S bond was oxidized inducing a longitudinal unzipping of WS2 walls. The resultant WS2 nanoribbons displayed a significant superior catalytic activity in comparison to the WS2-MWNTs.

Force-field modeling of single-chirality-angle multi-walled WS2 nanotubes

The experimentally observed dependencies of the average interwall distances on the number of walls and diameters of multi-walled WS2 nanotubes were reproduced in molecular mechanics simulations based on a recently developed force field. A common chiral angle was used for all walls inside each nanotube to ensure its one-dimensional periodicity. The data obtained make it possible to determine the nature of changes in the diameters of single-wall components inside the nanotube and variations in the distances between the walls in its inner, middle and outer parts. The stability of multi-walled nanotubes with respect to WS2 nanolayers and free single-wall components was evaluated.

WS2 Nanotube Transistor for Photodetection and Optoelectronic Memory Applications.

Nanotube and nanowire transistors hold great promises for future electronic and optoelectronic devices owing to their downscaling possibilities. In this work, a single multi-walled tungsten disulfide (WS2) nanotube is utilized as the channel of a back-gated field-effect transistor. The device exhibits a p-type behavior in ambient conditions, with a hole mobility µp ≈ 1.4 cm2V-1s-1 and a subthreshold swing SS ≈ 10 V dec-1. Current-voltage characterization at different temperatures reveals that the device presents two slightly different asymmetric Schottky barriers at drain and source contacts. Self-powered photoconduction driven by the photovoltaic effect is demonstrated, and a photoresponsivity R ≈ 10 mAW-1 at 2V drain bias and room temperature. Moreover, the transistor is tested for data storage applications. A two-state memory is reported, where positive and negative gate pulses drive the switching between two different current states, separated by a window of 130%. Finally, gate and light pulses are combined to demonstrate an optoelectronic memory with four well-separated states. The results herein presented are promising for data storage, Boolean logic, and neural network applications.

Nanotubes from Transition Metal Dichalcogenides: Recent Progress in the Synthesis, Characterization and Electrooptical Properties.

Inorganic layered compounds (2D-materials), particularlytransition metal dichalcogenide (TMDC), are the focus of intensive research in recent years. Shortly after the discovery of carbon nanotubes (CNTs) in 1991, it was hypothesized that nanostructures of 2D-materials can also fold and seam forming, thereby nanotubes (NTs). Indeed, nanotubes (and fullerene-like nanoparticles) of WS2 and subsequently from MoS2 were reported shortly after CNT. However, TMDC nanotubes received much less attention than CNT until recently, likely because they cannot be easily produced as single wall nanotubes with well-defined chiral angles. Nonetheless, NTs from inorganic layered compounds have become a fertile field of research in recent years. Much progress has been achieved in the high-temperature synthesis of TMDC nanotubes of different kinds, as well as their characterization and the study of their properties and potential applications. Their multiwall structure is found to be a blessing rather than a curse, leading to intriguing observations. This concise minireview is dedicated to the recent progress in the research of TMDC nanotubes. After reviewing the progress in their synthesis and structural characterization, their contributions to the research fields of energy conversion and storage, polymer nanocomposites, andunique optoelectronic devices are being reviewed. These studies suggest numerous potential applications for TMDC nanotubes in various technologies, which are briefly discussed.

Mechanism of WS2 Nanotube Formation Revealed by in Situ/ex Situ Imaging.

Multiwall WS2 nanotubes have been synthesized from W18O49 nanowhiskers in substantial amounts for more than a decade. The established growth model is based on the "surface-inward" mechanism, whereby the high-temperature reaction with H2S starts on the nanowhisker surface, and the oxide-to-sulfide conversion progresses inward until hollow-core multiwall WS2 nanotubes are obtained. In the present work, an upgraded in situ SEM μReactor with H2 and H2S sources has been conceived to study the growth mechanism in detail. A hitherto undescribed growth mechanism, named "receding oxide core", which complements the "surface-inward" model, is observed and kinetically evaluated. Initially, the nanowhisker is passivated by several WS2 layers via the surface-inward reaction. At this point, the diffusion of H2S through the already existing outer layers becomes exceedingly sluggish, and the surface-inward reaction is slowed down appreciably. Subsequently, the tungsten suboxide core is anisotropically volatilized within the core close to its tips. The oxide vapors within the core lead to its partial out-diffusion, partially forming a cavity that expands with reaction time. Additionally, the oxide vapors react with the internalized H2S gas, forming fresh WS2 layers in the cavity of the nascent nanotube. The rate of the receding oxide core mode increases with temperatures above 900 °C. The growth of nanotubes in the atmospheric pressure flow reactor is carried out as well, showing that the proposed growth model (receding oxide core) is also relevant under regular reaction parameters. The current study comprehensively explains the WS2 nanotube growth mechanism, combining the known model with contemporary insight.

Implantation of Gallium into Layered WS2 Nanostructures is Facilitated by Hydrogenation.

Bombarding WS2 multilayered nanoparticles and nanotubes with focused ion beams of Ga+ ions at high doses, larger than 1016 cm-2, leads to drastic structural changes and melting of the material. At lower doses, when the damage is negligible or significantly smaller, the amount of implanted Ga is very small. A substantial increase in the amount of implanted Ga, and not appreciable structural damage, are observed in nanoparticles previously hydrogenated by a radio-frequency activated hydrogen plasma. Density functional calculations reveal that the implantation of Ga in the spaces between adjacent layers of pristine WS2 nanoparticles is difficult due to the presence of activation barriers. In contrast, in hydrogenated WS2, the hydrogen molecules are able to intercalate in between adjacent layers of the WS2 nanoparticles, giving rise to the expansion of the interlayer distances, that in practice leads to the vanishing of the activation barrier for Ga implantation. This facilitates the implantation of Ga atoms in the irradiationexperiments.

Polyetherimide (PEI) nanocomposite with WS2 nanotubes.

Nanocomposite materials, integrating nanoscale additives into a polymer matrix, hold immense promise for their exceptional property amalgamation. This study delves into the fabrication and characterization of polyetherimide (PEI) nanocomposite strings fortified with multiwall WS2 nanotubes. The manufacturing process capitalizes on the preferential alignment of WS2 nanotubes along the string axis, corroborated by scanning electron microscopy (SEM). Mechanical measurements unveil a remarkable acceleration of strain hardening in the nanocomposite strings, chiefly attributed to the WS2 nanotubes. Structural analyses via X-ray diffraction (XRD) and wide-angle X-ray scattering (WAXS) reveal intriguing structural alterations during tensile deformation. Notably a semi-crystalline framework ∼100 nm in diameter surrounding the WS2 nanotubes emerges, which is stabilized by the π-π interactions between the PEI chains. The amorphous majority phase (97% by volume) undergoes also major structural changes upon strain becoming more compact and closing-up of the distance beweeetn the PEI chains. Dynamic mechanical analysis (DMA) demonstrates improved thermal stability of the evolved semi-crystalline π-π oriented PEI molecules, characterized by delayed thermal "structural melting", underscoring the pivotal role of the WS2 nanotubes in reinforcing the nanocomposite. The insight gained in this study of WS2 nanotube-reinforced PEI nanocomposite strings, could offer diverse applications for such tailor-made polymeric materials.

Mechanism of WS2 nanotube formation revealed by in-situ/ex-situ imaging and cross-sectional sequences

Mechanism of WS2 nanotube formation revealed by in-situ/ex-situ imaging and cross-sectional sequences

Plasma-treated 1D transition metal dichalcogenides for efficient electrocatalytic hydrogen evolution reaction

Plasma traetment induces chemical modiifcation in 1D WS2 nanotubes, enhancing its electrocatalytic performances upon HER.

Encapsulation of Uranium Oxide in Multiwall WS2 Nanotubes.

Uranium is a high-value energy element, yet also poses an appreciable environmental burden. The demand for a straightforward, low energy, and environmentally friendly method for encapsulating uranium species can be beneficial for long-term storage of spent uranium fuel and a host of other applications. Leveraging on the low melting point (60°C) of uranyl nitrate hexahydrate and nanocapillary effect, a uranium compound is entrapped in the hollow core of WS2 nanotubes. Followingly, the product is reduced at elevated temperatures in a hydrogen atmosphere. Nanocrystalline UO2 nanoparticles anchor within the WS2 nanotube lumen are obtained through this procedure. Such methodology can find utilization in the processing of spent nuclear fuel or other highly active radionuclides as well as a fuel for deep space missions. Moreover, the low melting temperatures of different heavy metal-nitrate hydrates, pave the way for their encapsulation within the hollow core of the WS2 nanotubes, as demonstrated herein.

Semiconducting Transition Metal Dichalcogenide Heteronanotubes with Controlled Outer-Wall Structures.

Transition metal dichalcogenide (TMDC) nanotubes exhibit unique physical properties due to their nanotube structures. The development of techniques for synthesizing TMDC nanotubes with controlled structures is very important for their science and applications. However, structural control efforts have been made only for the homostructures of TMDC nanotubes and not for their heterostructures that provide an important platform for their two-dimensional counterparts. In this study, we synthesized heterostructures of TMDC nanotubes, MoS2/WS2 heteronanotubes, and demonstrated a technique for controlling features of their structures, such as diameters, layer numbers, and crystallinity. The diameter of the heteronanotubes could be tuned with inner nanotube templates and was reduced by using small-diameter WS2 nanotubes. The layer number and crystallinity of the MoS2 outer wall could be controlled by controlling their precursors and synthesis temperatures, resulting in the formation of high-crystallinity TMDC heteronanotubes with specific chirality. This study can expand the research of van der Waals heterostructures.

Submillimeter-Long WS2 Nanotubes: The Pathway to Inorganic Buckypaper.

WS2 nanotubes present many new technologies under development, including reinforced biocompatible polymers, membranes, photovoltaic-based memories, ferroelectric devices, etc. These technologies depend on the aspect ratio (length/diameter) of the nanotubes, which was limited to 100 or so. A new synthetic technique is presented, resulting in WS2 nanotubes a few hundred micrometers long and diameters below 50 nm (aspect ratios of 2000-5000) in high yields. Preliminary investigation into the mechanistic aspects of the two-step synthesis reveals that W5O14 nanowhisker intermediates are formed in the first step of the reaction instead of the ubiquitous W18O49 nanowhiskers used in the previous syntheses. The electrical and photoluminescence properties of the long nanotubes were studied. WS2 nanotube-based paper-like material was prepared via a wet-laying process, which could not be realized with the 10 μm long WS2 nanotubes. Ultrafiltration of gold nanoparticles using the nanotube-paper membrane was demonstrated.

Synthesis and optical properties of WS2 nanotubes with relatively small diameters

Tungsten disulfide (WS2) nanotubes exhibit various unique properties depending on their structures, such as their diameter and wall number. The development of techniques to prepare WS2 nanotubes with the desired structure is crucial for understanding their basic properties. Notably, the synthesis and characterization of multi-walled WS2 nanotubes with small diameters are challenging. This study reports the synthesis and characterization of small-diameter WS2 nanotubes with an average inner diameter of 6 nm. The optical absorption and photoluminescence (PL) spectra of the as-prepared nanotubes indicate that a decrease in the nanotube diameter induces a red-shift in the PL, suggesting that the band gap narrowed due to a curvature effect, as suggested by theoretical calculations.

Density functional and force field modeling of multi-walled WS2 nanotubes

A technique for constructing force fields based on the use of genetic algorithms is proposed. It is used to generate a force field designed to simulate multi-walled WS2 nanotubes, which is beyond the capabilities of ab initio methods. The resulting force field parameterization was successfully tested on single, double, and triple-walled nanotubes, which structure was determined using density functional calculations. The developed force field was applied to model the structure and stability of chiral and achiral multi-walled WS2 nanotubes. The interwall distances found by simulation are in good agreement with the results of recent measurements of these parameters for synthesized nanotubes. An analysis was made of the deviation of the shape of nanotubes from the cylindrical pattern.

(Invited) Optical Properties and Device Application of One-Dimensional Vdw Heterostructures Based on Single-Walled Carbon Nanotubes

A typical one-dimensional (1D) van der Waals (vdW) heterostructure consists of SWCNT, boron nitride nanotube (BNNT), and molybdenum disulfide nanotube (MoS2NT), grown coaxially by successive chemical vapor deposition (CVD) steps [1, 2]. The coaxially nested structure based on SWCNTs, which has diverse electronic properties (metallic or semiconducting), can expand the board application possibilities of 1D vdW heterostructures [3]. By comparing the optical properties of films of BNNT@MoS2NT and SWCNT@BNNT@MoS2NT, we found strong photoluminescence (PL) from monolayer MoS2NT and quenching of PL by coupling to SWCNT through thin BNNT [4]. The inter-tube excitons are demonstrated by ultrafast optical spectroscopy [5]. The inter-tube excitons, the counterpart of inter-layer excitons for 2D heterostructures, suggest a possibility of efficient photovoltaic applications of the 1D heterostructure [6]. In addition to MoS2 nanotubes, we will discuss the growth control of WS2 and NbS2 nanotubes. A general strategy we can tune the CVD condition from 2D flake to 1D tube is proposed. The junctions of MoS2 and WS2 nanotube are also realized as the outermost layer. More specific optical properties are studied for semiconductor SWCNTs and chirality-sorted SWCNTs [7,8]. Semiconductor SWCNT or chirality-sorted SWCNT wrapped with BNNT can be regarded as the ideal building blocks of field-effect transistors (FET) [9]. We have demonstrated the radial semiconductor–insulator–semiconductor (S-I-S) tunneling heterojunction diode by using a micrometer long 1D vdW heterostructure SWCNT@BNNT@MoS2NT [10]. We will discuss a more recent array of 1D heterostructure FET devices.Part of this work was supported by JSPS KAKENHI Grant Number JP20H00220, and by JST, CREST Grant Number JPMJCR20B5, Japan.

Direct growth of single-chiral-angle tungsten disulfide nanotubes using gold nanoparticle catalysts.

Transition metal dichalcogenide (TMD) nanotubes offer a unique platform to explore the properties of TMD materials at the one-dimensional limit. Despite considerable efforts thus far, the direct growth of TMD nanotubes with controllable chirality remains challenging. Here we demonstrate the direct and facile growth of high-quality WS2 and WSe2 nanotubes on Si substrates using catalytic chemical vapour deposition with Au nanoparticles. The Au nanoparticles provide unique accommodation sites for the nucleation of WS2 or WSe2 shells on their surfaces and seed the subsequent growth of nanotubes. We find that the growth mode of nanotubes is sensitive to the temperature. With careful temperature control, we realize ~79% WS2 nanotubes with single chiral angles, with a preference of 30° (~37%) and 0° (~12%). Moreover, we demonstrate how the geometric, electronic and optical properties of the synthesized WS2 nanotubes can be modulated by the chirality. We anticipate that this approach using Au nanoparticles as catalysts will facilitate the growth of TMD nanotubes with controllable chirality and promote the study of their interesting properties and applications.

Tungsten disulfide nanotubes enhanced nanocomposite paper-based aptasensor for label-free electrochemical detection of interferon-gamma

Interferon-Gamma (IFN-ɣ), a measurable biomarker is known to be related to Tuberculosis which is one of the major sanitation issues in the world. It is also a crucial indicator of the immune response to many infections and diseases. Measuring the concentration of IFN-γ can assist in disease diagnosis. Therefore, we have developed a cost-efficient, disposable, and highly sensitive paper-based electrochemical biosensor with probing aptamer immobilization that can detect IFN-ɣ with high sensitivity and selectivity. WS2 nanotubes (NTs) were modified on the nanocomposite conductive paper electrode to provide a large surface area, facilitating the efficient recognition of aptamer with IFN-ɣ, and yielded a high resistance to adsorption of non-targeted molecules. The step-wise modification of the sensing surface was characterized and then the electrode was examined by using differential pulse voltammetry (DPV) in different concentrations of IFN-ɣ samples. The peak current generated by the proposed sensor demonstrated a linear range from 3.125 to 100 pg mL−1, and the detection limit for IFN-ɣ was determined to be 1.13 pg mL−1. Moreover, this novel WS2 NTs enhanced nanocomposite conductive paper-based electrochemical biosensor was qualified to successfully measure IFN-ɣ in human serum samples, demonstrating its potential application as an efficient tool for Tuberculosis diagnosis.

The gold ticket to achiral WS2 nanotubes.

The gold ticket to achiral WS2 nanotubes.

Chiral Nanoparticle Chains on Inorganic Nanotube Templates.

Fabrication of chiral assemblies of plasmonic nanoparticles is a highly attractive and challenging task, with promising applications in light emission, detection, and sensing. So far, primarily organic chiral templates have been used for chirality inscription. Despite recent progress in using chiral ionic liquids in synthesis, the use of organic templates significantly limits the variety of nanoparticle preparation techniques. Here, we demonstrate the utilization of seemingly achiral inorganic nanotubes as templates for the chiral assembly of nanoparticles. We show that both metallic and dielectric nanoparticles can be attached to scroll-like chiral edges propagating on the surfaces of WS2 nanotubes. Such assembly can be performed at temperatures as high as 550 °C. This large temperature range significantly widens the portfolio of nanoparticle fabrication techniques, allowing us to demonstrate a variety of chiral nanoparticle assemblies, ranging from metals (Au, Ga), semiconductors (Ge), and compound semiconductors (GaAs) to oxides (WO3).

Negative differential resistance effect and current rectification in WS2 nanotubes: A density functional theory study

Electronic properties of (n,0) zigzag tungsten disulfide WS2 nanotubes and transport properties of (7,0) zigzag nanotube heterojunction are investigated by utilizing non-equilibrium Green's function formalism (NEGF). The results reveal that inclusion of the spin-orbit (SO) coupling significantly reduces the value of the band gap about 15.52\\%. Additionally, strong negative differential resistances take place in voltage regions between −0.2 and −0.4 V as well as between −0.5 and −0.6 V. Moreover, temperature dependent transport properties are elaborately investigated in this work. The results show that, as the temperature increases to 600 K the stronger negative differential resistance occurs in both positive and negative bias voltages. Finally, a reasonably large degree of rectification ratio can be established. Our analysis can provide a comprehensive perspective on the NDR effect and current rectification in WS2 nanotubes and can be used as a beneficial guide for future designing of novel logical and nanoelectronic and spintronic devices.