Mechanical Properties of WS2 Nanotubes

Their mesoscopic dimensions (including a nanometer scale diameter and a micrometer scale length) make nanotubes a unique and attractive object of study, including the study of their mechanical properties and fracture in particular. The investigation of the mechanical properties of individual WS₂ nanotubes is a challenging task due to their small size. Hence, various microscopy based techniques were used to overcome this challenge. The Young’s modulus was studied by techniques like atomic force microscope (AFM) and scanning electron microscope (SEM); it was also calculated by using the density-functional-based tight-binding (DFTB) method. Tensile tests and bending tests of individual WS₂ nanotubes were performed as well. Furthermore, the shock wave resistance of these nanotubes was tested. The Young’s modulus of WS₂ nanotubes was found to be in the range of 150–170 GPa, which is in good agreement with DFTB calculations. WS₂ nanotubes also showed tensile strength as high as 16 GPa and fracture strain of 14%. These results indicate the high quality of these nanotubes which reach their theoretical strength. The interlayer shear (sliding) modulus was found to be ca. 2 GPa, this value is in good agreement with DFTB calculations. Moreover, the nanotubes were able to withstand shock waves as high as 21 GPa.     

Synthesis of tungsten disulfide (WS2) nanoflakes for lithium ion battery application

A novel method (a rheological phase reaction) was used to synthesize WS₂ nanoflakes by adding oxalic acid as a reducing reagent. High resolution electron microscopy observations revealed that the as-prepared WS₂ nanoflakes had started to curve and that WS₂ nanotubes were partly formed. The lithium intercalation/deintercalation behavior of as-prepared WS₂ electrode was also investigated. It was found that the WS₂ nanoflake electrode exhibited higher specific capacity with very good cycling stability compared to WS₂ nanotube or nanoparticle electrodes. The reasons for the improved electrochemical performance of the nanoflake electrodes are also discussed.     

Preparation of WS2 nanocomposites via mussel-inspired chemistry and their enhanced dispersion stability and tribological performance in polyalkylene glycol

A novel biomimetic surface modification method utilizing mussel-inspired chemistry was used to prepare tungsten disulfide (WS₂) nanocomposites, which enhanced the dispersion stability and tribological performance of WS₂ in polyalkylene glycol (PAG). Herein, WS₂-polydopamine-methoxypolyethylene glycol amine (WS₂-PDA-MPGA) was first synthesized via mussel-inspired chemistry and used as a lubricant additive in PAG. After modification, the dispersion stability of WS₂ nanosheets in PAG was obviously improved. Moreover, the tribological performance of WS₂-PDA-MPGA in PAG at high temperature was evaluated by the oscillating reciprocating tribometer. Compared to pure PAG, the lubricant composition containing WS₂-PDA-MPGA exhibited excellent performance in friction reduction and anti-wear properties at high temperature. The optimal tribological performance could be obtained when the percentage of additives was 0.9?wt%. The tribological results indicate that WS₂-PDA-MPGA, with its good dispersion stability, has better friction reduction and anti-wear properties than does WS₂ in PAG base oil. The chemical composition analysis of the wear surface indicated that a stable protective film had been formed by physical adsorption and tribo-chemical reactions. Therefore, the surface modification strategy is an effective way to improve the dispersion stability of WS₂ in PAG, which can be expanded application of WS₂ in the tribological field.     

Phonon spectra,electronic, and thermodynamic properties of WS2 nanotubes

Hybrid density functional theory calculations are performed for the first time on the phonon dispersion and thermodynamic properties of WS₂‐based single‐wall nanotubes. Symmetry analysis is presented for phonon modes in nanotubes using the standard (crystallographic) factorization for line groups. Symmetry and the number of infra‐red and Raman active modes in achiral WS₂ nanotubes are given for armchair and zigzag chiralities. It is demonstrated that a number of infrared and Raman active modes is independent on the nanotube diameter. The zone‐folding approach is applied to find out an impact of curvature on electron and phonon band structure of nanotubes rolled up from the monolayer. Phonon frequencies obtained both for layers and nanotubes are used to compute the thermal contributions to their thermodynamic functions. The temperature dependences of energy, entropy, and heat capacity of nanotubes are estimated with respect to those of the monolayer. The role of phonons in the stability estimation of nanotubes is discussed based on Helmholtz free energy calculations. © 2017 Wiley Periodicals, Inc.     

Modification of WS2 nanosheets with beta-cyclodextrone and N-isopropylacrylamide polymers for tamoxifen adsorption and investigation of in vitro drug release

In this research, tungsten disulfide (WS₂) nanosheets were modified with beta-cyclodextrone (βCD) N-isopropylacrylamide polymers (NIPAAP) for adsorption of tamoxifen (TAM) drug. The synthesized WS₂/βCD/NIPAAP samples were characterized by field-emission scanning electron microscopy (FE-SEM), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and X-ray diffraction (XRD) analyses. The adsorption experiments of TAM on WS₂/βCD/NIPAAP were performed as a function of pH, reaction contact time, temperature and drug concentration. The adsorption kinetic data were well fitted to the pseudo-second-order model. Also, the equilibrium data were well described by Langmuir isotherm model. The maximum adsorption capacity of WS₂/βCD/NIPAAP for TAM drug was found to be 62.0 mg/g. The results of regeneration tests showed that the synthesized WS₂/βCD/NIPAAP adsorbent can be easily reused after 6 cycles of adsorption–desorption. Furthermore, TAM drug release was investigated in a simulated system with pH 7.4 at different temperatures. The results showed that the release of TAM drug from WS₂/βCD/NIPAAP carrier at 50 °C and 37 °C was greater than TAM release at 25 °C. Also, the experimental data of drug release were studied by Higuchi, Ritger-Peppas, zero-order and first-order models. The release data were well fitted to the zero-order model indicating a case II transport. The results showed a high stability for TAM drug.

     

Comparative study on the properties of poly(trimethylene terephthalate) ‐based nanocomposites containing multi‐walled carbon (MWCNT) and tungsten disulfide (INT‐WS2) nanotubes

Multi‐walled carbon (MWCNT) and tungsten disulfide (INT‐WS₂) nanotubes are materials with excellent mechanical properties, high electrical and thermal conductivity. These special properties make them excellent candidates for high strength and electrically conductive polymer nanocomposite applications. In this work, the possibility of the improvement of mechanical, thermal and electrical properties of poly(trimethylene terephthalate) (PTT) by the introduction of MWCNT and INT‐WS₂ nanotubes was investigated. The PTT nanocomposites with low loading of nanotubes were prepared by in situ polymerization method. Analysis of the nanocomposites' morphology carried out by SEM and TEM has confirmed that well‐dispersed nanotubes in the PTT matrix were obtained at low loading (<0.5 wt%). Thermal and thermo‐oxidative stability of nanocomposites was not affected by the presence of nanotubes in PTT matrix. Loading with INT‐WS₂ up to 0.5 wt% was insufficient to ensure electrical conductivity of PTT nanocomposite films. In the case of nanocomposites filled with MWCNT, it was found that nanotube incorporation leads to increase of electrical conductivity of PTT films by 10 orders of magnitude, approaching a value of 10^?3 S/cm at loading of 0.3 wt%. Tensile properties of amorphous and semicrystalline (annealed samples) nanocomposites were affected by the presence of nanotubes. Moreover, the increase in the brittleness of semicrystalline nanocomposites with the increase in MWCNT loading was observed, while the nanocomposites filled with INT‐WS₂ were less brittle than neat PTT. Copyright © 2016 John Wiley & Sons, Ltd.     

Construction of 2D-2D TiO2 nanosheet/layered WS2 heterojunctions with enhanced visible-light-responsive photocatalytic activity

Constructing nanocomposites that combine the advantages of composite materials, nanomaterials, and interfaces has been regarded as an important strategy to improve the photocatalytic activity of TiO₂. In this study, 2D-2D TiO₂ nanosheet/layered WS₂ (TNS/WS₂) heterojunctions were prepared via a hydrothermal method. The structure and morphology of the photocatalysts were systematically characterized. Layered WS₂ (～4 layers) was wrapped on the surface of TiO₂ nanosheets with a plate-to-plate stacked structure and connected with each other by W=O bonds. The as-prepared TNS/WS₂ heterojunctions showed higher photocatalytic activity for the degradation of RhB under visible-light irradiation, than pristine TiO₂ nanosheets and layered WS₂. The improvement of photocatalytic activity was primarily attributed to enhanced charge separation efficiency, which originated from the perfect 2D-2D nanointerfaces and intimate interfacial contacts between TiO₂ nanosheets and layered WS₂. Based on experimental results, a double-transfer photocatalytic mechanism for the TNS/WS₂ heterojunctions was proposed and discussed. This work provides new insights for synthesizing highly efficient and environmentally stable photocatalysts by engineering the surface heterojunctions.     

Electrochemical behavior of horseradish peroxidase on WS2 nanosheet‐modified electrode and electrocatalytic investigation

In this paper, a WS₂ nanosheet was modified on the surface of a carbon ionic liquid electrode (CILE), and horseradish peroxidase (HRP) was further fixed on the electrode with a Nafion film. Direct electrochemistry and bioelectrocatalysis of HRP incorporated on the modified electrode were investigated in detail. On Nafion/HRP/WS₂/CILE, a pair of well‐defined quasi‐reversible redox peaks appeared on the cyclic voltammogram, indicating that the presence of the WS₂ nanosheet on the electrode surface could provide a specific interface with large surface area for HRP and its direct electron transfer rate was greatly enhanced. The formal potential (E⁰) obtained was –0.179 V, which was the typical feature of heme Fe(III)/Fe(II) in HRP. The electron transfer coefficient (α) and the heterogeneous electron transfer rate constant (k_s) of HRP were calculated as 0.44 and 1.01 s^–1, respectively. This HRP‐modified electrode showed excellent electrocatalytic activity for the reduction of trichloroacetic acid and NaNO₂ with a wide linear range and low detection limit. Real samples were detected by this proposed method, indicating the successful fabrication of a new third‐generation electrochemical enzyme sensor utilizing the WS₂ nanosheet.     

Formation and Stability of Gaseous WS2Cl2, WS2Br2 and WS2I2 – A Combined Experimental and Theoretical Study

Gaseous WS₂Cl₂ and WS₂Br₂ are formed by the reaction of solid WS₂ with chlorine resp. bromine at temperatures of about 1000 K. This could be shown by mass spectrometric measurements. The heats of formation and entropies of WS₂Cl₂ and WS₂Br₂ have been determined by means of mass spectrometry (MS) and quantum chemical calculations (QC). WS₂I₂ could not be detected by experimental methods. This is in line with the quantum chemically determined equilibrium constant of the formation reaction. The following values are given:, Δ_fH⁰₂₉₈(WS₂Cl₂) = –230.8 kJ · mol^–1 (MS), Δ_fH⁰₂₉₈(WS₂Cl₂) = –235.0 kJ · mol^–1 (QC),, S⁰₂₉₈(WS₂Cl₂) = 370.7 J · K^–1 · mol^–1 (QC) and, c_p⁰_T(WS₂Cl₂) = 103.78 + 7.07 × 10^–3 T – 0.93 × 10⁵ T^–2 – 3.25 × 10^–6 T² (298.15 K < T < 1000 K) (QC). Δ_fH⁰₂₉₈(WS₂Br₂) = –141.9 kJ · mol^–1 (MS), Δ_fH⁰₂₉₈(WS₂Br₂) = –131.5 kJ · mol^–1 (QC),, S⁰₂₉₈(WS₂Br₂) = 393.9 J · K^–1 · mol^–1 (QC) and, c_p⁰_T(WS₂Br₂) = 104.84 + 5.32 × 10^–3 T – 0.75 × 10⁵ T^–2 – 2.45 × 10^–6 T² (298.15 K < T < 1000 K) (QC). Δ_fH⁰₂₉₈(WS₂I₂) = –18.0 kJ · mol^–1 (QC), S⁰₂₉₈(WS₂I₂) = 409.9 J · K^–1 · mol^–1 (QC) and, c_p⁰_T(WS₂I₂) = 105.17 + 4.77 × 10^–3 T – 0.67 × 10⁵ T^–2 – 2.19 × 10^–6 T² (298.15 K < T < 1000 K) (QC). These molecules have the expected C_2v‐symmetry.     

Highly enhanced thermoelectric performance of WS2 nanosheets upon embedding PEDOT:PSS

Two‐dimensional (2D) WS₂ nanosheets (NSs) as a promising thermoelectric (TE) material have gained great concern recently. The low electrical conductivity significantly limits its further development. Herein, we reported an effective method to enhance the TE performance of WS₂ NSs by combining poly(3,4‐ethylenedioxythiophene):poly(4‐styrenesulfonate) (PEDOT:PSS). The restacked WS₂ NSs thin film with 1T phase structure obtained by a common chemical lithium intercalation show a high Seebeck coefficient of 98 μV K^?1 and a poor electrical conductivity of 12.5 S cm^?1. The introduction of PEDOT:PSS with different contents obviously improve the electrical conductivity of WS₂ NSs thin films. Although a declining Seebeck coefficient was observed, an optimized TE power factor of 45.2 μW m^?1 k^?1 was achieved for WS₂/PEDOT:PSS composite thin film. Moreover, the as‐prepared WS₂/PEDOT:PSS thin film can be easily peeled off and transferred to other substrate leading to a more promising application. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55 , 997–1004     

Cytotoxicity of Exfoliated Transition‐Metal Dichalcogenides (MoS2, WS2, and WSe2) is Lower Than That of Graphene and its Analogues

Studies involving transition‐metal dichalcogenides (TMDs) have been around for many decades and in recent years, many were focused on using TMDs to synthesize inorganic analogues of carbon nanotubes, fullerene, as well as graphene and its derivatives with the ultimate aim of employing these materials into consumer products. In view of this rising trend, we investigated the cytotoxicity of three common exfoliated TMDs (exTMDs), namely MoS₂, WS₂, and WSe₂, and compared their toxicological effects with graphene oxides and halogenated graphenes to find out whether these inorganic analogues of graphenes and derivatives would show improved biocompatibility. Based on the cell viability assessments using methylthiazolyldiphenyl‐tetrazolium bromide (MTT) and water‐soluble tetrazolium salt (WST‐8) assays on human lung carcinoma epithelial cells (A549) following a 24 h exposure to varying concentrations of the three exTMDs, it was concluded that MoS₂ and WS₂ nanosheets induced very low cytotoxicity to A549 cells, even at high concentrations. On the other hand, WSe₂ exhibited dose‐dependent toxicological effects on A549 cells, reducing cell viability to 31.8 % at the maximum concentration of 400 μg mL^?1; the higher cytotoxicity displayed by WSe₂ might be linked to the identity of the chalcogen. In comparison with graphene oxides and halogenated graphenes, MoS₂ and WS₂ were much less hazardous, whereas WSe₂ showed similar degree of cytotoxicity. Future in‐depth studies should be built upon this first work on the in vitro cytotoxicity of MoS₂ and WS₂ to ensure that they do not pose acute toxicity. Lastly, nanomaterial‐induced interference control experiments revealed that exTMDs were capable of reacting with MTT assay viability markers in the absence of cells, but not with WST‐8 assay. This suggests that the MTT assay is not suitable for measuring the cytotoxicity of exTMDs because inflated results will be obtained, giving false impressions that the materials are less toxic.     

Generation of High Peak Power Mode-Locked Green Pulses Based on WS2 and EOM: Experiment and Theory

Based on an as-prepared high-quality WS₂ film and an electro-optic modulator (EOM), a dual-loss-modulated low repetition rate mode-locking laser at 0.53 μm with high peak power is presented for the first time. The laser characteristics versus the pump power are investigated experimentally and theoretically. At a pump power of 10.67 W, the shortest pulse duration of 305 ps can be measured, corresponding to the highest peak power of 931 kW, which is much higher than those of the single passive modulated lasers with WS₂-SA. A simple rate equation simulation was used to describe this dual-loss-modulated mode-locking green laser based on WS₂ and EOM. The results of the numerical simulation are basically in accordance with the experimental values.     

Übergangsmetallchalkogenverbindungen. Über CuNH4WS4 und Cu2WS4 und andere Übergangsmetallchalkogenmetallate

Transition metal chalkogen compounds. On CuNH₄WS₄, Cu₂WS₄ and other transition metal chalkogenometallates The preparation, vibrational and electronic spectra of CuNH₄WS₄, Cu₂WS₄ and other transition metal compounds, which could not be isolated in a pure form, are reported. The X-ray data of CuNH₄WS₄ are given.     

WS2纳米颗粒的合成及摩擦学性能研究

将自制的WO₃纳米颗粒前驱体与S粉混合,在自制的反应装置氢气氛中,于550～750 ℃下煅烧得到二硫化钨纳米颗粒,反应中用H₂代替H₂S以减少对周围环境的污染。该合成路线简单且产物纯度高。用XRD、SEM、TEM和HRTEM对二硫化钨纳米结构进行了表征和分析,并将WS₂纳米颗粒作为添加剂添加到N40基础油中,在MS-T3000摩擦磨损仪测试其摩擦学性能。结果显示:制备的二硫化钨颗粒平均粒径在50 nm以内,其形状为球形或类球形。WS₂纳米颗粒作为普通润滑油的纳米级固体添加剂表现出了较优异的摩擦学性能。     

Fabrication of Two‐Dimensional Lateral Heterostructures of WS2/WO3⋅H2O Through Selective Oxidation of Monolayer WS2

Two‐dimensional (2D) lateral heterostructures have emerged as a hot topic in the fast evolving field of advanced functional materials , but their fabrication is challenging. The layer‐structured WS₂ was theoretically demonstrated to be inert to oxidation except for the monolayer, which can be selectively oxidized owing to the simultaneous interaction of oxygen with both sides. Combined with the theoretical calculations, a new method was developed for the successful construction of 2D lateral heterostructures of WS₂/WO₃?H₂O in an ambient environment, based on a simple liquid‐phase solution exfoliation. These lateral heterostructures of WS₂/WO₃?H₂O have interesting properties, as indicated by enhanced photocatalytic activity toward the degradation of methyl orange (MO).     

ChemInform Abstract: Formation and Stability of Gaseous WS2Cl2, WS2Br2 and WS2I2 — A Combined Experimental and Theoretical Study.

The reactions of solid WS₂ with gaseous Cl₂, Br₂ and I₂ are monitored by mass spectrometry.     

WS2 Nanowires as a High‐Performance Anode for Sodium‐Ion Batteries

We report the synthesis and anode application for sodium‐ion batteries (SIBs) of WS₂ nanowires (WS₂ NWs). WS₂ NWs with very thin diameter of ≈25 nm and expanded interlayer spacing of 0.83 nm were prepared by using a facile solvothermal method followed by a heat treatment. The as‐prepared WS₂ NWs were evaluated as anode materials of SIBs in two potential windows of 0.01–2.5 V and 0.5–3 V. WS₂ NWs displayed a remarkable capacity (605.3 mA h g^?1 at 100 mA g^?1) but with irreversible conversion reaction in the potential window of 0.01–2.5 V. In comparison, WS₂ NWs showed a reversible intercalation mechanism in the potential window of 0.5–3 V, in which the nanowire‐framework is well maintained. In the latter case, the interlayers of WS₂ are gradually expanded and exfoliated during repeated charge–discharge cycling. This not only provides more active sites and open channels for the intercalation of Na⁺ but also facilitates the electronic and ionic diffusion. Therefore, WS₂ NWs exhibited an ultra‐long cycle life with high capacity and rate capability in the potential window of 0.5–3 V. This study shows that WS₂ NWs are promising as the anode materials of room‐temperature SIBs.     

Physicochemcial characteristic of CdS-anchored porous WS2 hybrid in the photocatalytic degradation of crystal violet under UV and visible light irradiation

In this work, we report the synthesis of CdS-incorporated porous WS₂ by a simple hydrothermal method. The structural, morphological, and optical properties of the samples were examined by X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), Fourier transform infrared spectroscopy (FTIR), high resolution X-ray photoelectron spectroscopy (XPS) and UV–visible spectrometry. The photocatalytic activities were established for degradation of crystal violet (CV) under UV and visible light irradiation. The CdS-incorporated porous WS₂ hybrid demonstrated high photocatalytic activity for degradation of CV pollutant compared to pure CdS nanoparticles and porous WS₂ sheets. This result implies that the CdS-incorporated porous WS₂ promoted more electron-hole pair transformation under UV and visible light irradiation. This significant enhancement of photocatalytic efficiency of CdS-incorporated porous WS₂ photocatalyst under visible light can be ascribed to the presence of CdS nanospheres on the meshed-like WS₂ sheets which potentially improves absorption in the visible range enabled by surface plasmon resonance effect of CdS nanospheres. The photostability and reusability of the CdS-porous WS₂ were examined through recycling experiments.     

Influence of inorganic fullerene‐like WS2 nanoparticles on the thermal behavior of isotactic polypropylene

A new family of thermoplastic nanocomposites based on isotactic polypropylene (iPP) and inorganic fullerene‐like tungsten disulfide (IF‐WS₂) has been successfully prepared. A very efficient dispersion of IF‐WS₂ material was obtained by mixing in the melted polymer without using modifiers or surfactants. The addition of IF‐WS₂ nanoparticles induces a remarkable enhancement of the thermal stability of iPP, as well as an increase in the crystallization rate of the matrix when compared with pure iPP. The nucleating efficiency of IF‐WS₂ solid lubricant nanoparticles on the α‐phase of iPP reaches very high values (60–70%), the highest values observed hitherto for polypropylene nanocomposites. The incorporation of IF‐WS₂ has also been observed to increase the size and stability of the crystals formed. The melting behavior of the nanocomposites indicates the formation of more perfect crystals as determined by differential scanning calorimetry and time‐resolved synchrotron X‐ray scattering experiments. The new nanocomposites show an increase in the storage modulus with respect to pure iPP measured by dynamic mechanical analysis. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2309–2321, 2007     

Vanadium‐Doped WS2 Nanosheets Grown on Carbon Cloth as a Highly Efficient Electrocatalyst for the Hydrogen Evolution Reaction

Two‐dimensional transition‐metal dichalcogenides have been widely studied as electrocatalysts for the hydrogen evolution reaction (HER). However, limited active sites and poor conductivity hinder their application. To solve these disadvantages, heteroatom doping has attracted wide attention because it can not only increase the active sites but also affect the intrinsic catalytic properties of the electrocatalyst. Herein, we grew vanadium‐doped WS₂ nanosheets on carbon cloth (V‐WS₂/CC) as an electrocatalyst for HER under acidic and alkaline conditions. With a proper vanadium doping concentration, the electrochemical surface areas of V_0.065‐WS₂/CC were 9.6 and 2.6 times as large as that of pure WS₂ electrocatalyst under acidic and alkaline conditions, respectively. In addition, the charge‐transfer resistance also decreased with moderate vanadium doping. Based on this, the synthesized vanadium‐doped WS₂ nanosheets exhibited good stability with high HER catalytic activity and could reach a current density of 10 mA cm⁻² at overpotentials of 148 and 134 mV in 0.5 m H₂SO₄ and 1 m KOH, respectively. The corresponding Tafel slopes were 71 and 85 mV dec⁻¹. Therefore, our synthesized vanadium‐doped WS₂ nanosheets can be a promising electrocatalyst for the production of hydrogen over a wide pH range.