MoS2 nanosheets and bulk materials altered lipid profiles in 3D Caco-2 spheroids

MoS₂ nanosheets（NSs） are novel 2 D nanomaterials（NMs） with potential uses in many areas, and therefore oral exposure route to MoS₂ NSs is plausible. Currently, MoS₂ NSs are considered as biocompatible NMs, but there is lacking of systemic investigations to study the interactions of MoS₂ NSs with intestinal cells. In this study, we exposed the 3D Caco-2 spheroids to MoS₂ NSs or MoS₂ powders（denoted as MoS₂-bulk）, and inv...     

Preparation and electronic properties of MoS2 and WS2 single crystals grown in the presence of cobalt

Single crystals of MoS₂ and WS₂ were grown by chemical vapor transport in both the presence and absence of cobalt. Hall measurements indicate that cobalt cannot diffuse appreciably into the bulk of MoS₂ or WS₂ and, therefore, can be present only on the surface. Similar results were obtained for as-grown crystals annealed or sulfided in contact with Co₉S₈ or sulfided after being dipped in a 0.1M CoSO₄/methanol solution.     

TiO2 nanorods based self-supported electrode of 1T/2H MoS2 nanosheets decorated by Ag nano-particles for efficient hydrogen evolution reaction

Molybdenum disulfide (MoS₂) has shown significant promise as an economic hydrogen evolution reaction (HER) catalyst for hydrogen generation, but its catalytic performance is still lower than noble metal-based catalysists. Herein, a silver nanoparticles (Ag NPs)-decorated 1T/2H phase layered MoS₂ electrocatalyst grown on titanium dioxide nanorod arrays (Ag NPs/1T(2H) MoS₂/TNRs) was prepared through acid-tunable ammonium ion intercalation. Taking advantage of MoS₂ layered structure and crystal phase controllability, as-prepared Ag NPs/1T(2H) MoS₂/TNRs exhibited ultrahigh HER activity. As-proposed strategy combines facile hydrogen desorption (Ag NPs) with efficient hydrogen adsorption (1T/2H MoS₂) effectively circumventes the kinetic limitation of hydrogen desorption by 1T/2H MoS₂. The as-prepared Ag NPs/1T(2H) MoS₂/TNRs electrocatalyst exhibited excellent HER activity in 0.5 mol/L H₂SO₄ with low overpotential (118 mV vs. reversible hydrogen electrode (RHE)) and small Tafel slope (38.61 mV/dec). The overpotential exhibts no obvious attenuation after 10 h of constant current flow. First-principles calculation demonstrates that as-prepared 1T/2H MoS₂ exhibit a large capacity to store protons. These protons can be subsequently transferred to Ag NPs, which significantly increases the hydrogen coverage on the surface of Ag NPs in HER process and thus change the rate-determining step of HER on Ag NPs from water dissociation to hydrogen recombination. This study provides a unique strategy to improve the catalytic activity and stability for MoS₂-based electrocatalyst.     

Influence of polycrystalline MoS2 nanoflowers on mouse breast cancer cell proliferation via molten salt sintering

In this paper, polycrystalline molybdenum disulfide (MoS₂) nanoflowers were prepared by mixing ammonium molybdate tetrahydrate [(NH₄)₆Mo₇O₂₄·4H₂O] and potassium thiocyanate (KSCN) at 300 °C for 2 h via molten salt sintering method. Under scanning electron microscope (SEM) and high-resolution transmission electron microscope (HRTEM), MoS₂ showed popcorn-like shape, which surface distribution defects were easy to be further modified. MoS₂ as a nano-enzyme was used to inhibit the proliferation of mouse breast cancer cells (4 T1), which had 69.8 % inhibitory effect on 4 T1 cell proliferation. Electron spin resonance (ESR) analysis showed that MoS₂ could produce a large number of stable hydroxyl radicals (–OH). The disulfide bond in MoS₂ was highly sensitive to reactive oxygen species (ROS). High ROS level leads to the death of cancer cells under oxidative stress and inhibits the proliferation of 4 T1. This work demonstrates that MoS₂ is a potential anticancer drug or carrier for cancer treatment.     

Fast response speed of mechanically exfoliated MoS2 modified by PbS in detecting NO2

MoS₂, acting as a promising gas sensing material, has shown huge potential in monitoring of toxic and harmful gases at room temperature. However, MoS₂-based gas sensors still suffer from poor gas sensing performance such as poor sensitivity, long response time. Constructing the heterostructure is an effective approach to improve gas-sensing performance of MoS₂. Herein, PbS@MoS₂ composites synthesized by mechanical exfoliation combining with wet-chemical precipitation are used to investigate its performance in detecting NO₂ at room temperature. The response value of PbS@MoS₂ gas sensor against NO₂ is significantly improved compared with the pure MoS₂ gas sensor. At the same time, the modification with PbS also accelerates the response speed of MoS₂, and the response time is almost reduced by two orders of magnitude, from hundreds of seconds to less than ten seconds. The enhanced response value and fast response time are mainly benefited from the modulation effect of NO₂ to PbS@MoS₂ heterostructure and the mechanically exfoliated MoS₂ surface with few defects. This work can be expected to provide useful guidance for designing composite materials with excellent gas sensing properties.     

不同硫源水热合成的MoS2催化剂的形貌和加氢脱氧活性比较研究

分别采用硫脲、L-胱氨酸和硫磺为硫源水热合成了三种MoS₂催化剂,对其结构和形貌特征进行了表征,并以对甲酚为探针化合物,比较研究了三种MoS₂的加氢脱氧（HDO）催化活性。结果表明,硫源对MoS₂晶体结构的影响不大,但对其形貌和比表面积影响较大。与商业MoS₂相比,所制备的MoS₂催化剂都表现出更高的HDO活性;其中,以硫脲为原料合成的MoS₂具有较高的比表面积和花状结构,其催化活性最高,在300℃下进行对甲酚的HDO反应,脱氧度可达99.3%。     

Investigation on the Growth Mechanism of Cu2MoS4 Nanotube,Nanoplate and its use as a Catalyst for Hydrogen Evolution in Water

Cu₂MoS₄ is a ternary transition‐metal sulfide that shows great potential in the field of energy conversion and storage, namely catalytic H₂ evolution in water and Li‐, Na‐ or Mg‐ion battery. In this work, we report on a growth mechanism of the single‐crystalline Cu₂MoS₄ nanotube from (NH₄)₂MoS₄ salt and Cu₂O nanoparticle. By probing the nature and morphology of solid products generated in function of reaction conditions we find that the crystalline Cu(NH₄)MoS₄ nanorod is first generated at ambient conditions. The nanorod is then converted into Cu₂MoS₄ nanotube under hydrothermal treatment due to the Kirkendall effect or a selective etching of the Cu₂MoS₄ core. Extending the hydrothermal treatment causes a collapse of nanotube generating Cu₂MoS₄ nanoplate. The catalytic activities of these sulfides are investigated. The Cu₂MoS₄ shows superior catalytic activity to that of Cu(NH₄)MoS₄. Catalytic performance of the former largely depends on its morphology. The nanoplate shows superior catalytic activity to the nanotube, thanks to its higher specific electrochemical surface area.     

Electrochemical study of (NEt4)2Cl2FeS2MoS2 and (NEt4)2Cl2FeS2MoS2FeCl2

Summary The ability of [MoS₄]^2–, anions to be used as ligands for transition metal ions has been widely demonstrated, especially with Fe²⁺. The present study has been restricted to linear complexes such as (NEt₄)₂ [Cl₂FeS₂MoS₂] and (NEt₄)₂[Cl₂FeS₂MoS₂FeCl₂]. Their electrochemical properties are described: upon electrochemical reduction, these compounds yield MoS₂, as a black precipitate, and an iron complex in solution, assumed to be [SFeCl₂]^2–. The electrochemical reduction goes through two electron transfers, coupled with the breakdown of the molecular skeleton: a DISPl and an ECE mechanism. Depending on the solvent, the following equilibrium may be observed: [Cl₄Fe₂MoS₄]^2–[Cl₂FeMoS₄]^2–+FeCl₂. The equilibrium constant, K_D, was evaluated by differential pulse polarography. K_D is tightly related to the donor number of the solvent.     

Construction of a 2D Graphene‐Like MoS2/C3N4 Heterojunction with Enhanced Visible‐Light Photocatalytic Activity and Photoelectrochemical Activity

A novel graphene‐like MoS₂/C₃N₄ (GL‐MoS₂/C₃N₄) composite photocatalyst has been synthesized by a facile ethylene glycol (EG)‐assisted solvothermal method. The structure and morphology of this GL‐MoS₂/C₃N₄ photocatalyst have been investigated by a wide range of characterization methods. The results showed that GL‐MoS₂ was uniformly distributed on the surface of GL‐C₃N₄ forming a heterostructure. The obtained composite exhibited strong absorbing ability in the ultraviolet (UV) and visible regions. When irradiated with visible light, the composite photocatalyst showed high activity superior to those of the respective individual components GL‐MoS₂ and GL‐C₃N₄ in the degradation of methyl orange. The enhanced photocatalytic activity of the composite may be attributed to the efficient separation of electron–hole pairs as a result of the matching band potentials between GL‐MoS₂ and GL‐C₃N₄. Furthermore, a photocatalytic mechanism for the composite material has been proposed, and the photocatalytic reaction kinetics has been measured. Moreover, GL‐MoS₂/C₃N₄ could serve as a novel sensor for trace amounts of Cu²⁺ since it exhibited good selectivity for Cu²⁺ detection in water.     

Enhanced Photocatalytic Hydrogen Evolution over Hierarchical Composites of ZnIn2S4 Nanosheets Grown on MoS2 Slices

A highly active hierarchical MoS₂/ZnIn₂S₄ composite catalyst was synthesized in situ by using a facile controlled‐growth approach through a solvothermal process. During the solvothermal reaction, 2D ultrathin curled ZnIn₂S₄ nanosheets grew on the surface of MoS₂ slices, which could help to form a more‐homogeneous mixture, effective interfacial contact, and strong interactions between the ZnIn₂S₄ nanosheets and the MoS₂ slices. The intimate contact between ZnIn₂S₄ and MoS₂ favored the formation of junctions between the two components, thereby improving the charge separation and prolonging the mean lifetime of the electron–hole pairs. Moreover, growing ZnIn₂S₄ nanosheets by visible‐light catalysis on MoS₂ slices afforded a higher number of available catalytically active sites. So, the photocatalytic hydrogen‐evolution performance of the hierarchical MoS₂/ZnIn₂S₄ composite was significantly enhanced, owing to a synergistic effect of these factors. This work could provide new insights into the fabrication of a highly efficient and low‐cost non‐noble‐metal co‐catalyst for visible‐light H₂ generation.     

Structure Re‐determination and Superconductivity Observation of Bulk 1T MoS2

2H MoS₂ has been intensively studied because of its layer‐dependent electronic structures and novel physical properties. Though the metastable 1T MoS₂ with a [MoS₆] octahedron was observed over the microscopic area, the true crystal structure of 1T phase has not been strictly determined. Moreover, the true physical properties have not been demonstrated from experiments owing to the challenge for the preparation of pure 1T MoS₂ crystals. 1T MoS₂ single crystals were successfully synthesized and the crystal structure of 1T MoS₂ re‐determined from single‐crystal X‐ray diffraction. 1T MoS₂ crystallizes in the space group P m1 with a cell of a=b=3.190(3) Å and c=5.945(6) Å. The individual MoS₂ layer consists of MoS₆ octahedra sharing edges with each other. More surprisingly, the bulk 1T MoS₂ crystals undergo a superconducting transition of T_c=4 K, which is the first observation of superconductivity in pure 1T MoS₂ phase.     

Hierarchical MoS2@TiO2 Heterojunctions for Enhanced Photocatalytic Performance and Electrocatalytic Hydrogen Evolution

Hierarchical MoS₂@TiO₂ heterojunctions were synthesized through a one‐step hydrothermal method by using protonic titanate nanosheets as the precursor. The TiO₂ nanosheets prevent the aggregation of MoS₂ and promote the carrier transfer efficiency, and thus enhance the photocatalytic and electrocatalytic activity of the nanostructured MoS₂. The obtained MoS₂@TiO₂ has significantly enhanced photocatalytic activity in the degradation of rhodamine B (over 5.2 times compared with pure MoS₂) and acetone (over 2.8 times compared with pure MoS₂). MoS₂@TiO₂ is also beneficial for electrocatalytic hydrogen evolution (26 times compared with pure MoS₂, based on the cathodic current density). This work offers a promising way to prevent the self‐aggregation of MoS₂ and provides a new insight for the design of heterojunctions for materials with lattice mismatches.     

Selective modification of two-dimensional MoS2 nanosheets by polymer grafting

We reported on the direct creation of polymer brushes on two-dimensional molybdenum disulfide via the formation of C-S bond by UV-induced photopolymerization. The functionalization can be manipulated in forming polymer grafts on one side or both sides of the nanosheets.     

High-efficiency electrodeposition of polyindole nanocomposite using MoS2 nanosheets as electrolytes and their capacitive performance

Polyindole (PIn) has attracted extensive interest as promising energy storage materials owing to fairly good thermal stability, high redox activity and stability, however, it is challenging to prepare high-quality PIn in neutral solvents by electrochemical method. Herein, a simple route, based on MoS₂ nanosheets as electrolytes, has been developed for the electrochemical preparation of PIn/MoS₂ nanocomposite in acetonitrile solution. Due to the coordination interaction between indole and MoS₂, the onset oxidation potential of indole in this medium was reduced to 0.5 V from 0.75 V determined in acetonitrile/LiClO₄. The morphologies and structures of as-obtained PIn/MoS₂ nanocomposite were characterized using SEM, TEM, XRD, Raman and XPS. The results of thermal analysis indicated that the PIn/MoS₂ nanocomposite had an improved thermal stability relative to PIn and MoS₂ nanosheets. Moreover, the specific capacitance of PIn/MoS₂ nanocomposite was 8.3 times higher than that of PIn prepared acetonitrile/LiClO₄. To the best of our knowledge, this is the first report on the high-efficiency electrodeposition of PIn/MoS₂ nanocomposite in MoS₂-based acetonitrile solution, which will be a promising candidate as a high efficient electrode material in the application of supercapacitors.     

Chemischer Transport fester Lösungen. 23 [1] Der Chemische Transport von Mischphasen im System MoS2/MoSe2, MoS2/NbS2, MoSe2/NbSe2 und NbS2/NbSe2

Chemical Vapor Transport of Solid Solutions. 23 Chemical Vapor Transport of Mixed Phases in the System MoS₂/MoSe₂, MoS₂/NbS₂, MoSe₂/NbSe₂ and NbS₂/NbSe₂ X‐ray powder investigations have shown that MoS₂/MoSe₂, MoS₂/NbS₂, MoSe₂/NbSe₂ and NbS₂/NbSe₂ form mixed crystals without a miscibility gap. The mixed crystals can be prepared by heating the Elements for some days in the presence of small amounts of iodine as well as by chemical vapour transport. In the systems NbS₂/NbSe₂ and MoS₂/MoSe₂ the vapor transport occurs congruently, in the systems NbS₂/MoS₂ and NbSe₂/MoSe₂ however a strong enrichment of Niobium has been observed during the transport process. Mass spectrometric investigations and thermochemical calculations have shown that the transport occurs via NbI₄(g) and MoI₃(g).     

Engineering Chemically Exfoliated Large‐Area Two‐Dimensional MoS2 Nanolayers with Porphyrins for Improved Light Harvesting

Molybdenum disulfide (MoS₂) is a promising candidate for electronic and optoelectronic applications. However, its application in light harvesting has been limited in part due to crystal defects, often related to small crystallite sizes, which diminish charge separation and transfer. Here we demonstrate a surface‐engineering strategy for 2D MoS₂ to improve its photoelectrochemical properties. Chemically exfoliated large‐area MoS₂ thin films were interfaced with eight molecules from three porphyrin families: zinc(II)‐, gallium(III)‐, iron(III)‐centered, and metal‐free protoporphyrin IX (ZnPP, GaPP, FePP, H₂PP); metal‐free and zinc(II) tetra‐(N‐methyl‐4‐pyridyl)porphyrin (H₂T4, ZnT4); and metal‐free and zinc(II) tetraphenylporphyrin (H₂TPP, ZnTPP). We found that the photocurrents from MoS₂ films under visible‐light illumination are strongly dependent on the interfacial molecules and that the photocurrent enhancement is closely correlated with the highest occupied molecular orbital (HOMO) levels of the porphyrins, which suppress the recombination of electron–hole pairs in the photoexcited MoS₂ films. A maximum tenfold increase was observed for MoS₂ functionalized with ZnPP compared with pristine MoS₂ films, whereas ZnT4‐functionalized MoS₂ demonstrated small increases in photocurrent. The application of bias voltage on MoS₂ films can further promote photocurrent enhancements and control current directions. Our results suggest a facile route to render 2D MoS₂ films useful for potential high‐performance light‐harvesting applications.     

Electrolysis of solid MoS2 in molten CaCl2 for Mo extraction without CO2 emission

Sintered (300 °C) porous pellets of MoS₂ were electrolysed to elemental S and Mo in molten CaCl₂ (800–900 °C) under argon at 1.0–3.0 V for 1–20 h. On a graphite anode, the product was primarily S (but traces of CS₂ could not yet be excluded by this work) and evaporated from the molten salt, allowing the electrolysis to continue. It then condensed to solid at the lower temperature regions of the system. The anode remained intact after repeated uses. The MoS₂ pellet was highly conducting at high temperatures and could be fast electro-reduced to fine Mo powders (0.1–1.0 μm) in which the S content could be below 1000 ppm. No reduction occurred at voltages below 0.5 V. Partial reduction was seen at 0.5–0.7 V, and converted MoS₂ to a mixture of MoS₂ and Mo₃S₄, or Mo₃S₄ and Mo with the Mo content increasing with the voltage. Cyclic voltammetry of the MoS₂ powder in a Mo-cavity electrode, together with the electrolysis results, revealed the reduction mechanism to include two steps: MoS₂ to Mo₃S₄ at −0.28 V (potential vs. Ag/AgCl), and then to Mo at −0.43 V.     

Electronic Properties of Triangle Molybdenum Disulfide (MoS2) Clusters with Different Sizes and Edges

The electronic structures and transition properties of three types of triangle MoS₂ clusters, A (Mo edge passivated with two S atoms), B (Mo edge passivated with one S atom), and C (S edge) have been explored using quantum chemistry methods. The highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) gap of B and C is larger than that of A, due to the absence of the dangling of edge S atoms. The frontier orbitals (FMOs) of A can be divided into two categories, edge states from S_3p at the edge and hybrid states of Mo_4d and S_3p covering the whole cluster. Due to edge/corner states appearing in the FMOs of triangle MoS₂ clusters, their absorption spectra show unique characteristics along with the edge structure and size.     

Nanomechanical and nanotribological characterization of multilayer self-lubricating Ti/MoS2/Si/MoS2 nanocoating on aluminium-silicon substrate

Ti/MoS₂/Si/MoS₂ multilayer coating was fabricated by a pulse laser deposition method from a titanium, molybdenum disulphide, and silicon targets, and the coating was deposited in layers on aluminium-silicon substrates, at room temperature. The structural analysis and surface morphology of multilayer Ti/MoS₂/Si/MoS₂ coating were analysed using X-ray diffraction, Raman spectroscopy, and scanning electron microscopy integrated with energy dispersive X-ray spectroscopy. Nanomechanical tests were performed on Ti/MoS₂/Si/MoS₂ coating at small loads of 2000 to 6000 μN to study the effect of load on hardness and Young's modulus. Nanoscratch and nanowear tests were conducted on Ti/MoS₂/Si/MoS₂ coating at a low load of 1000 to 5000 μN and 100 to 500 μN, respectively, to study deformation and failure behaviours of coating/substrate system and also their nanotribological properties. The results show that hardness and Young's modulus of Ti/MoS₂/Si/MoS₂ coating decrease with increase in load. A low friction coefficient of 0.09 to 0.16 was observed, which proves that the Ti/MoS₂/Si/MoS₂ coating possesses self-lubricating property. The wear rate of Ti/MoS₂/Si/MoS₂ coating increases 3.3 × 10⁻¹⁰ to 7.8 × 10⁻¹⁰ mm³/Nm with increase in load. Ti/MoS₂/Si/MoS₂ multilayer coating shows a smooth wear track with no cracks and debris on the surface, which attributed plastic flow of softer coating material around the wear track.