Scaling up the fabrication of wafer-scale Ni-MoS2/WS2 nanocomposite moulds using novel intermittent ultrasonic-assisted dual-bath micro-electroforming

In the scale-up fabrication process for electroformed Ni-MoS₂/WS₂ composite moulds, the formulation of nanosheets is critical, since the size, charge, and their distribution can largely affect the hardness, surface morphology and tribological properties of the moulds. Additionally, the long-term dispersion of hydrophobic MoS₂/WS₂ nanosheets in a nickel sulphamate solution is problematic. In this work, we studied the effect of ultrasonic power, processing time, surfactant types and concentrations on the properties of nanosheets to elaborate their dispersion mechanism and control their size and surface charge in divalent nickel electrolyte. The formulation of MoS₂/WS₂ nanosheets was optimized for effective electrodeposition along with nickel ions. A novel strategy of intermittent ultrasonication in the dual bath was proposed to resolve the problem of long-term dispersion, overheating, and deterioration of 2D material deposition under direct ultrasonication. Such strategy was then validated by electroforming 4-inch wafer-scale Ni-MoS₂/WS₂ nanocomposite moulds. The results indicated that the 2D materials were successfully co-deposited into composite moulds without any defects, along with the mould microhardness increasing by ∼2.8 times, the coefficient of friction reducing by two times against polymer materials, and the tool life increasing up to 8 times. This novel strategy will contribute to the industrial manufacturing of 2D material nanocomposites under ultrasonication process.     

A facile sonochemical route for the synthesis of MoS2/Pd composites for highly efficient oxygen reduction reaction

For the alkaline fuel cell cathode reaction, it is very essential to develop novel catalysts with superior catalytic properties. Here, we report the synthesis of highly active and stable MoS₂/Pd composites for the oxygen reduction reaction (ORR), via a simple, eco-friendly sonochemical method. The bulk MoS₂ was first transformed into single and few layers MoS₂ nanosheets through ultrasonic exfoliation. Then the exfoliated MoS₂ nanosheets served as supporting materials for the nucleation and further in-situ growth of Pd nanoparticles to form MoS₂/Pd composites via ultrasonic irradiation. Cyclic voltammetry and rotating disk voltammetry measurements demonstrate that as-prepared MoS₂/Pd composites which provides a direct four-electron pathway for the ORR, have better electrocatalytic activity, long-term operation stability than commercial Pt/C catalyst. We expect that the present work would provide a promising strategy for the development of efficient oxygen reduction electrocatalyst. In addition, this study can also be extended to the preparation of other hybrid with desirable morphologies and functions.     

High-efficiency preparation of oil-dispersible MoS<Subscript>2</Subscript> nanosheets with superior anti-wear property in ultralow concentration

Molybdenum disulfide (MoS₂) nanosheets are a promising lubricant additive for enhanced engine efficiency in cars. However, high-cost production methods and poor dispersion have limited their application in industry. In this study, the ball milling process is demonstrated as a low-cost and high-efficient method for fabrication of oil-dispersible MoS₂ nanosheet, and the ball milling parameters are optimized. Moreover, the lubrication effectiveness of ball-milled MoS₂ nanosheet was also evaluated. Results indicated that well-dispersed MoS₂ nanosheets with a size of 250 nm can be manufactured with optimized surfactants of zinc dialkyldithiphosphates (ZDDP) and polyisobutylene succinimide (PIBS) after being ball milled for 36 h. Tribological results revealed that a friction coefficient of white oil with 0.25% MoS₂ nanosheets reached 0.075, much lower than that of lubricant without nanosheets (0.16). The wear scar radius of 0.015% MoS₂ nanosheets was similar with that of Hertz contact, and the wear scar radius reduction reached 20% compared with that of 1% ZDDP. In addition, EDS and XPS results indicated the formation of a MoS₂ and FeS tribofilm on the wear surface.     

Templated synthesis of plate-like MoS<Subscript>2</Subscript> nanosheets assisted with HNTs and their tribological performance in oil

Two-dimensional MoS₂ nanosheets were synthesized by using halloysite nanotubes (HNTs) as template under the hydrothermal synthesis. The structure and morphology of the as-synthesized MoS₂ nanosheets were determined by a series of characterizations. The results showed that the as-synthesized MoS₂ nanosheets were of the plate-like structure with about five layers, and the basal spacing was about 0.63 nm. It was demonstrated that HNTs played a crucial template role in the formation of the plate-like MoS₂ nanosheets. The formation mechanism was proposed. Furthermore, the tribological performance of the as-prepared MoS₂ nanosheets in oil was intensively examined on the ball-on-ball wear tester. The testing results verified that the as-prepared MoS₂ nanosheets as additive could significantly improve the friction performance of oil, which exhibited the good antifriction, antiwear, and load-carrying properties.     

Enhanced Exfoliation Effect of Solid Auxiliary Agent On the Synthesis of Biofunctionalized MoS2 Using Grindstone Chemistry

Mass production and commercial availability are prerequisites for the viability and wide application of MoS₂. Here, we demonstrate enhanced grindstone chemistry for a one‐step synthesis of biofunctionalized MoS₂. By adding a SiO₂ auxiliary agent the exfoliation efficiency increases from 16.23% to 58.59% and a rapid and high‐yield exfoliation of MoS₂ is seen. SiO₂ exhibits a fragmentation effect, which reduces the lateral size and facilitates the exfoliation of MoS₂, thus inducing a high‐efficient paradigm in the top‐down fabrication of biofunctionalized MoS₂ nanosheets. The as‐prepared MoS₂‐chitosan (MoS₂‐CS) nanosheets display complete disaggregation and homogeneous dispersion, as well as a high content of chitosan (ca. 20 wt%). As a proof‐of‐concept application, the MoS₂‐CS nanosheets act as a biosorbent for Pb^II removal, exhibiting a good adsorption capacity and recyclability. This green and facile enhanced grindstone chemistry with minimal use of organic solvents and high‐throughput efficiency can be extended to the fabrication of other biocompatible inorganic 2D analogues for a variety of applications.     

Facile photo-ultrasonic assisted synthesis of flower-like Pt/N-MoS2 microsphere as an efficient sonophotocatalyst for nitrogen fixation

Semiconductor photocatalytic technology is a sustainable and less energy consuming one for nitrogen (N₂) reduction to produce ammonia (NH₃). In this study, flower-like hierarchical N doped MoS₂ (N-MoS₂) microsphere was synthesized as a photocatalyst by one-step solvothermal method, which was assembled by numerous interleaving nanosheets petals with thin thickness. Besides, Pt nanoparticles were loaded on the surface of N-MoS₂ via photo-ultrasonic reduction method. The as-prepared Pt/N-MoS₂ photocatalyst exhibited higher N₂ fixation ability than that over pure MoS₂ and N-MoS₂, which can be attributed to that the N doping narrows the band gap, and the Schottky barrier due to the existence of Pt nanoparticles improves the charge transfer and carrier separation. The reduction of N₂ with ultrasonic irradiation was also investigated under visible light irradiation to evaluate the sonophotocatalytic activity of the Pt/N-MoS₂ microsphere. The results showed that the N₂ reduction rate of sonophotocatalysis (133.8 µmol/g_(cat)h) was higher than that of sonocatalysis and photocatalysis, which can be ascribed to the synergistic effect of ultrasound and visible light irradiation. The effects of catalyst dosage, ultrasonic power and ultrasonic pulse on the photocatalytic efficiency were also studied. Meanwhile, a possible mechanism for improved sonophotocatalytic performance was also proposed.     

Photodeposition of ultrathin MoS<Subscript>2</Subscript> nanosheets onto cubic CdS for efficient photocatalytic H<Subscript>2</Subscript> evolution

In this work, the photocatalyst composed of ultrathin MoS₂ nanosheets onto the surface of cubic CdS nanoparticles with an average diameter of 7~10 nm has been successfully fabricated through a facile and mild photodeposition route. The ultrathin MoS₂ nanosheets as a cocatalyst were demonstrated to greatly boost photocatalytic H₂ evolution over cubic CdS upon visible light irradiation. It was clearly revealed that both the cubic CdS substrate and structure of ultrathin MoS₂ nanosheets play critical roles in the observed efficient H₂ evolution. The cubic CdS offers a strong adherence for ultrathin MoS₂ nanosheets to form a well contact interface, across which the photogenerated charge transfer and charge separation are achieved. The ultrathin MoS₂ nanosheets introduce a high density of unsaturated active S atoms for H₂ evolution.     

Robust Fabrication of Quantum Dots on Few‐Layer MoS2 by Soft Hydrogen Plasma and Post‐Annealing

Apart from unique properties of layered transition‐metal dichalcogenide nanosheets like MoS₂, quantum dots (QDs) from these layered materials promise novel science and applications due to their quantum confinement effect. However, the reported fabrication techniques for such QDs all involve the use of liquid organic solvents and the final material extraction from such liquid dispersions. Here a novel and convenient dry method for the synthesis of MoS₂ quantum dots interspersed on few‐layer MoS₂ using soft hydrogen plasma treatment followed by post‐annealing is demonstrated. The size of MoS₂ nanodots can be well controlled by adjusting the working pressure of hydrogen plasma and post‐thermal annealing. This method relies on the cumulative hydrogen ion bombardment effect which can destroy the hexagonal structure of the top MoS₂ layer and disintegrate the top layer into MoS₂ nanodots and even QDs. Post‐thermal annealing can further reduce the size. Such MoS₂ quantum dots interspersed on few‐layer MoS₂ exhibit two new photoluminescence peaks at around 575 nm because of the quantum confinement effect. This dry method is versatile, scalable, and compatible with the semiconductor manufacturing processes, and can be extended to other layered materials for applications in hydrogen evolution reaction, catalysis, and energy devices.     

Ultrasonication-assisted synthesis of 2D porous MoS2/GO nanocomposite catalysts as high-performance hydrodesulfurization catalysts of vacuum gasoil: Experimental and DFT study

In this study, a novel, simple, high yield, and scalable method is proposed to synthesize highly porous MoS₂/graphene oxide (M−GO) nanocomposites by reacting the GO and co-exfoliation of bulky MoS₂ in the presence of polyvinyl pyrrolidone (PVP) under different condition of ultrasonication. Also, the effect of ultrasonic output power on the particle size distribution of metal cluster on the surface of nanocatalysts is studied. It is found that the use of the ultrasonication method can reduce the particle size and increase the specific surface area of M−GO nanocomposite catalysts which leads to HDS activity is increased. These nanocomposite catalysts are characterized by XRD, Raman spectroscopy, SEM, STEM, HR-TEM, AFM, XPS, ICP, BET surface, TPR and TPD techniques. The effects of physicochemical properties of the M−GO nanocomposites on the hydrodesulfurization (HDS) reactions of vacuum gas oil (VGO) has been also studied. Catalytic activities of MoS₂-GO nanocomposite are investigated by different operating conditions. M9-GO nanocatalyst with high surface area (324 m²/g) and large pore size (110.3 Å), have the best catalytic performance (99.95%) compared with Co-Mo/γAl₂O₃ (97.91%). Density functional theory (DFT) calculations were also used to elucidate the HDS mechanism over the M−GO catalyst. It is found that the GO substrate can stabilize MoS₂ layers through weak van der Waals interactions between carbon atoms of the GO and S atoms of MoS₂. At both Mo- and S-edges, the direct desulfurization (DDS) is found as the main reaction pathway for the hydrodesulfurization of DBT molecules.     

Controlled Formation of TiO2/MoS2 Core–Shell Heterostructures with Enhanced Visible‐Light Photocatalytic Activities

Most recently, much attention has been devoted to photocatalytic materials that may help to solve the global energy crisis and may provide environmental protection. Herein, novel cocatalysts based on few layered MoS₂ and TiO₂ nanomaterials have been designed by growing MoS₂ nanosheets on the surface of TiO₂ nanospheres through a facile hydrothermal method. The method allows the formation of TiO₂/MoS₂ core–shell heterostructures of uniform morphologies and stable structure and provides a good control over shell thickness. The mechanism that forms these heterostructures is discussed in detail. In addition, as cocatalyst, MoS₂ nanosheets can enlarge the light harvesting window to include visible light and improve the photocatalytic ability of TiO₂. Using Rhodamine B as the model, the resultant heterostructure is demonstrated to possess excellent and stable photocatalytic activity in the degradation of organic pollutants under visible light illumination. The TiO₂/MoS₂ heterostructures possess this catalytic activity due to their large surface area and their excellent interface for separating holes and electrons. Therefore, this novel heterostructure nanomaterials possess potential applications in water treatment, degradation of dye pollutants, and environmental cleaning.     

Three‐Dimensional Multilayer Assemblies of MoS2/Reduced Graphene Oxide for High‐Performance Lithium Ion Batteries

Three‐dimensional (3D) multilayer molybdenum disulfide (MoS₂)/reduced graphene oxide (RGO) nanocomposites are prepared by a solution‐processed self‐assembly based on the interaction using different sizes of MoS₂ and GO nanosheets followed by in situ chemical reduction. 3D multilayer assemblies with MoS₂ wrapped by large RGO nanosheets and good interface are observed by transmission electron microscopy. The interaction of Na⁺ ions with oxygen‐containing groups of GO is also investigated. The measurement of lithium ion batteries (LIBs) shows that MoS₂/RGO anode nanocomposite with a weight ratio of MoS₂ to GO of 3:1 exhibits an excellent rate performance of 750 mAh g^?1 at 3 A g^?1 outperforming many previous studies and a high reversible capacity up to ≈1180 mAh g^?1 after 80 cycles at 100 mA g^?1. Good rate performance and high capacity of MoS₂/RGO with 3D unique layered‐structures are attributed to the combined effects of continuous conductive networks of RGO, good interface facilitating charge transfer, and strong RGO sheets preventing the volume expansion. Results indicate that 3D multilayer MoS₂/RGO prepared by a facile solution‐processed assembly can be developed to be an excellent nanoarchitecture for high‐performance LIBs.     

Flower-like MoS<Subscript>2</Subscript> supported on three-dimensional graphene aerogels as high-performance anode materials for sodium-ion batteries

Flower-like MoS₂ supported on three-dimensional graphene aerogel (MoS₂/GA) composite has been prepared by a facile hydrothermal method followed by subsequent heat-treatment process. Each of MoS₂ microflowers is surrounded by the three-dimensional graphene nanosheets. The MoS₂/GA composite is applied as an anode material of sodium-ion batteries (SIBs) and it exhibits high initial discharge/charge capacities of 562.7 and 460 mAh g^?1 at a current density of 0.1 A g^?1 and good cycling performance (348.6 mAh g^?1 after 30 cycles at 0.1 A g^?1). The good Na⁺ storage properties of the MoS₂/GA composite could be attributed to the unique structure which flower-like MoS₂ are homogeneously and tightly decorated on the surface of three-dimensional graphene aerogel. Our results demonstrate that as-prepared MoS₂/GA composite has a great potential prospect as anodes for SIBs.     

Ultrasonication-assisted liquid-phase exfoliation enhances photoelectrochemical performance in α-Fe2O3/MoS2 photoanode

This study successfully manufactured a p-n heterojunction hematite (α-Fe₂O₃) structure with molybdenum disulfide (MoS₂) to address the electron–hole transfer problems of conventional hematite to enhance photoelectrochemical (PEC) performance. The two-dimensional MoS₂ nanosheets were prepared through ultrasonication-assisted liquid-phase exfoliation, after which the concentration, number of layers, and thickness parameters of the MoS₂ nanosheets were respectively estimated by UV–vis, HRTEM and AFM analysis to be 0.37 mg/ml, 10–12 layers and around 6 nm. The effect of heterojunction α-Fe₂O₃/MoS₂ and the role of the ultrasonication process were investigated by the optimized concentration of MoS₂ in the forms of bulk and nanosheet on the surface of the α-Fe₂O₃ electrode while measuring the PEC performance. The best photocurrent density of the α-Fe₂O₃/MoS₂ photoanode was obtained at 1.52 and 0.86 mA.cm⁻² with good stability at 0.6 V vs. Ag/AgCl under 100 mW/cm² (AM 1.5) illumination from the back- and front-sides of α-Fe₂O₃/MoS₂; these values are 13.82 and 7.85-times higher than those of pure α-Fe₂O₃, respectively. The results of electrochemical impedance spectroscopy (EIS) and Mott-Schottky analysis showed increased donor concentration (2.6-fold) and decreased flat band potential (by 20%). Moreover, the results of IPCE, ABPE, and OCP analyses also supported the enhanced PEC performance of α-Fe₂O₃/MoS₂ through the formation of a p–n heterojunction, leading to a facile electron–hole transfer.     

Tailoring MoS2 Ultrathin Sheets Anchored on Graphene Flexible Supports for Superstable Lithium‐Ion Battery Anodes

2D MoS₂ has a significant capacity decay due to the stack of layers during the charge/discharge process, which has seriously restricted its practical application in lithium‐ion batteries. Herein, a simple preform‐in situ process to fabricate vertically grown MoS₂ nanosheets with 8–12 layers anchored on reduced graphene oxide (rGO) flexible supports is presented. As an anode in MoS₂/rGO//Li half‐cell, the MoS₂/rGO electrode shows a high initial coulomb efficiency (84.1%) and excellent capacity retention (84.7% after 100 cycles) at a current density of 100 mA g^?1. Moreover, the MoS₂/rGO electrode keeps capacity as high as 786 mAh g^?1 after 1000 cycles with minimum degradation of 54 µAh g^?1 cycle^?1 after being further tested at a high current density of 1000 mA g^?1. When evaluated in a MoS₂/rGO//LiCoO₂ full‐cell, it delivers an initial charge capacity of 153 mAh g^?1 at a current density of 100 mA g^?1 and achieves an energy density of 208 Wh kg^?1 under the power density of 220 W kg^?1.     

Water‐Soluble Monolayer Molybdenum Disulfide Quantum Dots with Upconversion Fluorescence

Uniform water‐soluble monolayer MoS₂ quantum dots (MQDs) with lateral sizes of ≈2.1 nm, a clearly zigzag‐terminated edge, and a hexagonal lattice structure are achieved using ammonium molybdate, thiourea, and N‐acetyl‐l ‐cysteine (NAC) as precursors and the capping reagent in a facile one‐pot hydrothermal approach. MQDs have good dispersity and high stability in aqueous suspension and exhibit a significantly larger direct bandgap (3.96 eV) compared to monolayer MoS₂ nanosheets (1.89 eV). Pronounced blue‐shifts in the wavelengths of both the excitonic absorption and intrinsic state emission with activated strong luminescence at room temperature beyond monolayer MoS₂ nanosheets is demonstrated. Unusual upconversion photoluminescence is also observed and is caused by two successive transfers of energy from the near‐infrared (NIR) absorption generated by the NAC capping reagent to the hexagonal structure of MQDs. Additional optical properties of MQDs may provide numerous exciting technological applications. Here, MQDs are demonstrated as a highly selective fluorescent reagent for detecting tetracycline hydrochloride under UV and NIR irradiation.     

One‐Pot Synthesis of Algae‐Like MoS2/PPy Nanocomposite: A Synergistic Catalyst with Superior Peroxidase‐Like Catalytic Activity for H2O2 Detection

A facile one‐pot synthetic route is reported to prepare algae‐like molybdenum disulfide/polypyrrole (MoS₂/PPy) nanocomposite through a redox reaction between ammonium tetrathiomolybdate and pyrrole monomer under a hydrothermal condition without any other templates. The as‐prepared unique algae‐like MoS₂/PPy nanocomposites are composed of few layer MoS₂ nanosheets, which are covered with PPy. Structural and morphological characterizations of this unique nanocomposite are investigated by Fourier‐transform infrared spectra, Raman spectra, X‐ray diffraction pattern, X‐ray photoelectron spectra, energy‐dispersive X‐ray spectroscopy, and transmission electron microscopy. The as‐prepared MoS₂/PPy nanocomposites exhibit an excellent peroxidase‐like catalytic activity toward the oxidation of 3,3,5,5‐tetramethylbenzidine (TMB) in the presence of hydrogen peroxide (H₂O₂) in acetate buffer solution (pH 4.0), which provides a facile strategy for the colorimetric detection of H₂O₂ with a high sensitivity.     

Facile synthesis of calcium silicate hydrate using sodium dodecyl sulfate as a surfactant assisted by ultrasonic irradiation

Calcium silicate hydrate (CSH) consisting of nanosheets has been successfully synthesized assisted by a tip ultrasonic irradiation (UI) method using calcium nitrate (Ca(NO₃)·4H₂O), sodium silicate (Na₂SiO₃·9H₂O) and sodium dodecyl sulfate (SDS) in water. Systematic studies found that reaction time of ultrasonic irradiation and concentrations of surfactant (SDS) in the system were important factors to control the crystallite size and morphologies. The products were characterized by X-ray power diffraction (XRD), field emission scanning electron microscopy (FESEM) and Fourier transform infrared spectrometry (FTIR). The size–strain plot (SSP) method was used to study the individual contributions of crystallite sizes and lattice strain on the peak broadening of the CSH. These characterization techniques revealed the successful formation of a crystalline phase with an average crystallite size of about 13 nm and nanosheet morphology at a reaction time of 10 min UI with 0.2 g SDS in solvent which were found to be optimum time and concentrations of SDS for the synthesis of CSH powders.     

Light Auxiliary Hydrogen‐Evolution Catalyst Based on Uniformly Pt Nanoparticles Decorated Molybdenum Sulfide Hybrids

The electrocatalytic splitting of water via hydrogen evolution reaction (HER) is one of the most efficient technologies for hydrogen production, while the massive consumption of precious Pt‐based catalysts hinders its commercialization, bringing an urgent task to explore low‐cost and earth‐abundant alternatives. Herein, a cost‐efficient system composed of metal Pt/molybdenum disulphide (MoS₂) nanosheets hybrids for the HER by auxiliary of solar light is reported. The uniformly Pt nanoparticle decorated MoS₂ sheets can be easily obtained under hydrothermal condition using oleylamine as capping agent and N,N‐dimethylmethanamide (DMF) as intercalation molecule for MoS₂ exfoliation. The Pt/MoS₂ hybrid shows a significantly enhanced HER activity compared with bare MoS₂ due to enhancing conductivity and reducing overpotential by electron transport between Pt and MoS₂. As a result, a Tafel slope of 38 mV per decade is obtained, suggesting a highly efficient Volmer–Heyrovsky reaction of hydrogen evolution.     

水热法合成纳米花状二硫化钼及其微观结构表征

本文以钼酸钠、硫代乙酰胺为前驱体, 硅钨酸为添加剂, 成功用水热法合成高纯度纳米花状二硫化钼. 产物特性用X射线衍射(XRD)、能量色散谱(EDS)、扫描电子显微镜(SEM)进行表征. XRD和EDS图显示实验产物为二硫化钼, 且其结晶度和层状堆垛良好. SEM图谱则表明二硫化钼为纳米花状结构, 颗粒直径300 nm左右, 由几十上百片花瓣组成, 每片花瓣厚度十个纳米左右. 通过以硅钨酸为变量的梯度实验, 研究发现, 硅钨酸对于纳米花状MoS₂的形成具有重要作用, 不添加硅钨酸, 无法形成纳米花状MoS₂, 此外, 硅钨酸的剂量会影响合成MoS₂的大小和形貌. 本文还对纳米花状二硫化钼的形成机理做了初步的讨论.     

Novel molybdenum disulfide nanosheets–decorated polyaniline: Preparation,characterization and enhanced electrocatalytic activity for hydrogen evolution reaction

Novel molybdenum disulfide nanosheets–decorated polyaniline (MoS₂/PANI) was synthesized and investigated as an efficient catalyst for hydrogen evolution reaction (HER). Compared with MoS₂, MoS₂/PANI nanocomposites exhibited higher catalytic activity and lower Tafel slope for HER in H₂SO₄ solution. The amount of 19 wt% PANI for coupling with MoS₂ resulted in a high current density of 80 mA cm⁻² at 400 mV (vs. RHE). In addition, the optimal MoS₂/PANI nanocomposite showed impressive long-term stability even after 500 cycles. The enhanced catalytic activity of MoS₂/PANI nanocomposites was primarily ascribed to the effective electron transport channels of PANI and the increase of electrochemically accessible surface area in composite materials, which was advantageous to facilitate the charge transfer at catalyst/electrolyte interface.