Synthesis and nanostructural characterization of new layered compounds based on molybdenum disulfide and organic dyes

Preparation of new MoS₂ layered compounds, in which organic dyes (rhodamine 6G, oxazine 1, and thionine) were used as the guest components, was successfully realized in two reaction systems differing by the nature of molybdenum disulfide. In one system, MoS₂ was used in the form of single-layer dispersion in aqueous media; in the other system, it was taken in the form of nanodispersed powdered material, res-MoS₂, obtained by exfoliation-restacking procedure and suspended in non-aqueous solvent. Structures of prepared compounds are discussed on the basis of their compositions, X-ray diffraction and high-resolution transmission electron microscopy data. The hybrid compounds formed in single-layer dispersions were found to contain the MoS₂ layers, each of which alternate with dye layer, whereas, in the case of res-MoS₂ the same as well as the other sequences of organic and inorganic layers are formed depending on the reaction conditions. The vicinity of different-thickness domains was revealed within the guest layers of rhodamine and oxazine. It results from different packings of organic molecules and sufficient flexibility of molybdenum disulfide layers.     

Low-Temperature Plasma-Chemical Deposition of Nanocomposite Antifriction Molybdenum Disulfide (Filler)–Silicon Oxide (Matrix) Coatings

It was demonstrated experimentally that the spatial separation of two processes of chemical vapor deposition, one of which provides synthesis of filler (MoS₂) nanoparticles and the other yields the matrix (SiO₂) of the nanocomposite coating, performed ina common reactor, enables an independent control over two process rates and makes it possible to widely vary the composition of the films deposited in this way. The deposition was performed in a double-zone vertical tubular quartz reactor. Molybdenum disulfide particles were produced by pyrolysis of aerosols of ammonium thiomolybdate solutions in dimethylformamide in the upper zone of the reactor, and the plasma-chemical deposition of a nanocomposite coating occurred in the lower zone into which MoS₂ nanoparticles were transported by the gas flow and tetraethoxysilane was delivered. It was shown that the nanocomposite coatings composed of molybdenum disulfide (filler) and silicon oxide (matrix) possess improve the antifriction properties as compared with the matrix (SiO₂ layers), these properties being determined by the relative amounts of MoS₂ nanoparticles in the layer and by their average size.     

Synthesis and study of self-organization of organo-inorganic nanostructures based on cationic poly(meth)acrylates and molybdenum disulfide single layers

Poly(meth)acrylates of three types, namely, regular homopolymers containing side-chain tetraalkylammonium ionic groups with alkyl radicals of various lengths (C₆ and C₁₆), a copolymer with statistically distributed ionic and long-chain (C₁₈) alkyl groups, and a block copolymer of the same composition in which alkylammonium and alkyl groups are located in separate blocks, are synthesized with the use of controlled radical polymerization processes. The interaction of the polymers with molybdenum disulfide singlelayer dispersions yields self-organized organic-inorganic nanocomposites containing up to 40% polymer. As evidenced by powder X-ray diffraction and high-resolution transmission electron microscopy structural studies of the composites, they possess a crystalline layered structure with interlayer distances depending on the composition and structure of the polymer. Structures with the most regular alternation of organic and inorganic layers are formed in the case of homopolymers. The orientation of their alkylammonium fragments relative to MoS₂ layers depends on the length of the alkyl radical and corresponds to their parallel (C₆) or perpendicular (C₁₆) arrangement.     

A sensitive electrochemical aptasensor based on palladium nanoparticles decorated graphene–molybdenum disulfide flower-like nanocomposites and enzymatic signal amplification

In the present study, with the aggregated advantages of graphene and molybdenum disulfide (MoS₂), we prepared poly(diallyldimethylammonium chloride)–graphene/molybdenum disulfide (PDDA–G–MoS₂) nanocomposites with flower-like structure, large surface area and excellent conductivity. Furthermore, an advanced sandwich-type electrochemical assay for sensitive detection of thrombin (TB) was fabricated using palladium nanoparticles decorated PDDA–G–MoS₂ (PdNPs/PDDA–G–MoS₂) as nanocarriers, which were functionalized by hemin/G-quadruplex, glucose oxidase (GOD), and toluidine blue (Tb) as redox probes. The signal amplification strategy was achieved as follows: Firstly, the immobilized GOD could effectively catalyze the oxidation of glucose to gluconolactone, coupling with the reduction of the dissolved oxygen to H₂O₂. Then, both PdNPs and hemin/G-quadruplex acting as hydrogen peroxide (HRP)-mimicking enzyme could further catalyze the reduction of H₂O₂, resulting in significant electrochemical signal amplification. So the proposed aptasensor showed high sensitivity with a wide dynamic linear range of 0.0001 to 40 nM and a relatively low detection limit of 0.062 pM for TB determination. The strategy showed huge potential of application in protein detection and disease diagnosis.     

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.     

Water-processable nanocomposite based on polyaniline and 2D molybdenum disulfide for NIR-transparent ambipolar transport layers

Polymer nanocomposite based on stable water-dispersible polyaniline complex with poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PANI–PAMPSA) and 2D molybdenum disulphide (MoS₂) was developed. The nanocomposite layers obtained by drop-casting were characterized by Vis–NIR- and FTIR spectroscopies, as well as by atomic force, transmission electron, and Kelvin-probe microscopies, X-ray diffraction, cyclic voltammetry, Hall effect, and DC-conductivity measurements. It was shown that the preparation procedure allows easy adjusting of MoS₂ content in the nanocomposite resulting in the growth of DC conductivity by up to six times in the case of 20 wt% MoS₂ as compared with the additive-free PANI–PAMPSA complex. FTIR spectroscopy revealed the existence of hydrophobic interactions between PANI–PAMPSA and 2D MoS₂ nanophase, which facilitate interchain electron transfer. Hall effect studies showed that while increasing MoS₂ content in the nanocomposite, a transition occurs from monopolar hole transport, characteristic of PANI–PAMPSA, to ambipolar transport. This feature makes the obtained PANI–PAMPSA/MoS₂ composite a promising material for different optoelectronic devices, in particular tandem solar cells.     

利用光热电效应收集近红外光能的二硫化钼和热释电高分子纳米复合物

设计合成了一种基于二硫化钼（MoS₂）/热释电聚合物的柔性薄膜光热电纳米发电机（PTENG）。过渡金属硫族化合物作为薄层纳米薄片,可以捕获近红外（NIR）光,并将其转化为热能。同时,热释电聚合物将无机纳米片所收集的热能转化为电能。在近红外辐照下,PTENG可以瞬间产生电压和光电流,且输出长期保持在较高水平。通过光热效应与热释电效应的有效耦合,该体系具有较高的热电转换系数。我们还通过理论模拟分析了MoS₂在聚合物纳米复合材料中的作用。MoS₂的存在显著提高了热释电聚合物薄膜的温度变化率,提高了器件的光电响应。     

Side‐Chain‐Directed Dispersion of MoS2 Nanosheets by V‐Shaped Polyaromatic Compounds

Bulk molybdenum disulfide (MoS₂) itself is virtually insoluble in common organic solvents because of the tight stacks of multiple MoS₂ nanosheets. Here we report that V‐shaped polyaromatic compounds with non‐ionic side chains can efficiently exfoliate and disperse the inorganic nanosheets. Simple grinding and sonication (less than total 1 h) of MoS₂ powder with the V‐shaped compounds gave rise to large MoS₂ nanosheets highly dispersed in NMP through efficient host‐guest S–π interactions. DLS and AFM analyses revealed that the lateral sizes (ca. 150–270 nm) and thicknesses (ca. 2–8 nm) of the products depend on the identity of the non‐ionic side chains on the V‐shaped dispersant.     

Preparation and photoelectric properties of organoinorganic polymer nanocomposites on the basis of ultradispersed molybdenum disulfide particles

Photoconducting nanocomposites were prepared by incorporating nanoparticles obtained by monolayer dispersion of crystalline molybdenum disulfide into various polymer matrices (nonconducting and p-or n-type conducting). The shift of the absorption spectrum caused by changes in the concentration of MoS₂ nanoparticles demonstrated that such particles exhibit a quantum-size effect, the characteristics of which were found to be determined by the efficiency of their stabilization in each of the polymer matrices. Studying the photoelectric sensitivity of films of n-type-conduction composites on the basis of polymethylphenylsiloxane modified with 2,4,7-trinitrofluorenone (an electron acceptor) units demonstrated that molybdenum disulfide nanoparticles possess acceptor properties (characterized by an electron affinity energy of E _a > 2 eV, in agreement with the observation that composite films based on poly(N-epoxypropylcarbazole (a p-type-conduction matrix) doped with p-diethylaminobenzaldehyde-N,N-diphenylhydrazone (an effective donor), exhibit an enhancement in the proper photosensitivity of the p-type-conduction matrix in its absorption band (λ < 400 nm). For large molybdenum disulfide particles capable of absorbing light with λ > 600 nm (formed at a MoS₂ concentration of > 2.0 wt %), a weakening of the acceptor properties was observed, a feature responsible for decreases in the photosensitivity and the quantum yield of the photogeneration of holes and for the capture of holes in traps. A mechanism of the photogeneration of charge carriers with the participation of the phototransfer of electrons leading to the formation of electron-hole pairs was discussed.     

Modification of molybdenum disulfide (2H-MoS<Subscript>2</Subscript>) and synthesis of its intercalation compounds

We have shown that powdered molybdenum disulfide prepared as a result of the exfoliation (singlelayer dispersion) of a crystalline precursor (2H-MoS₂) and subsequent precipitation in an acid medium, is capable of forming intercalation compounds in reacting with salts of copper and tetramethylammonium, as well as diethylamine and triethylamine. We consider factors influencing the composition and type of the alternation of guest and host layers in the resulting layered compounds. Relationships between charge transfer to MoS₂ layers and the extraordinary reactivity of its modified species are discussed.     

Surface topography and the spectral and photoelectric properties of intercalated molybdenum disulfide films

The structural and photoelectric properties of nanodispersed molybdenum disulfide films intercalated with cationic organic compounds (rhodamine 6G, oxazine, triethylbenzylammonium, hexadecyltrimethylammonium, and polyvinylpyrrolidone) and hydroxocomplexes of Zn, Co, Ni, and Cd are studied. It is found that the greatest differences between the absorption spectra of MoS₂ films intercalated with compounds of various natures are observed in the range of 500–850 nm, and the conductivities (dark and photo-) of MoS₂ films intercalated with Ni or Co hydroxocomplexes rise by one or more orders of magnitude, respectively, compared to films of intercalated molybdenum disulfide. The correlation between photoconductivity and the corresponding values of dark conductivity is determined, proving that charge transport (and not generation processes) in films is the limiting step for photocurrent. It is concluded that highly conductive polycrystal films of intercalated MoS₂ with conductivities close to those in MoS₂ monocrystals are of interest for practical use in optoelectronics.     

In Situ Formation of a MoS2‐Based Inorganic–Organic Nanocomposite by Directed Thermal Decomposition

Nanocomposites based on molybdenum disulfide (MoS₂) and different carbon modifications are intensively investigated in several areas of applications due to their intriguing optical and electrical properties. Addition of a third element may enhance the functionality and application areas of such nanocomposites. Herein, we present a facile synthetic approach based on directed thermal decomposition of (Ph₄P)₂MoS₄ generating MoS₂ nanocomposites containing carbon and phosphorous. Decomposition at 250 °C yields a composite material with significantly enlarged MoS₂ interlayer distances caused by in situ formation of Ph₃PS bonded to the MoS₂ slabs through Mo?S bonds and (Ph₄P)₂S molecules in the van der Waals gap, as was evidenced by ³¹P solid‐state NMR spectroscopy. Visible‐light‐driven hydrogen generation demonstrates a high catalytic performance of the materials.     

Formation and tribological properties of composite Langmuir–Blodgett films of stearic acid with molybdenum disulfide and amorphous carbon

The morphology and tribological properties of Langmuir–Blodgett mono- and bilayers of stearic acid with particles of molybdenum disulfide (MoS₂) and amorphous carbon (С), prepared on silicon and steel substrates by horizontal deposition (stearic acid–MoS₂ and stearic acid–С monolayers) and by the “roll” technique (stearic acid–MoS₂/stearic acid–С bilayers), were studied. Incorporation of C and MoS₂ particles into the structure of a stearic acid film enhances its wear resistance by a factor of 2.8 and 5.5, respectively. The presence of MoS₂ and С particles and of their aggregates of size from ~220 nm to 16.3 μm in stearic acid layers was confirmed by atomic force microscopy.     

The influence of melamine phosphate modified MoS2 on the thermal and flammability of poly(butylene succinate) composites

This work reported a facile fabrication method to modify molybdenum disulfide (MoS₂) nanosheets with common flame retardant melamine phosphate (MAP) and then were incorporated into poly(butylene succinate) by melt blending method with the purpose of improving the thermal and flame retardancy properties. MAP modified MoS₂ nanosheets dispersed well in poly(butylene succinate) composites with intercalated structure. The incorporation of MAP modified MoS₂ nanosheets led to an increase of thermal degradation temperature and char formation as well as reduction of the peak heat release rate. Copyright © 2016 John Wiley & Sons, Ltd.     

Glassy Carbon Electrode Modified via Molybdenum Disulfide Decorated Multiwalled Carbon Nanotubes for Sensitive Voltammetric Detection of Aristolochic Acids

In this study, a molybdenum disulfide/multiwalled carbon nanotubes (MoS₂@MWCNTs) nanocomposite was synthesized by employing a simple hydrothermal method. The flower‐like structure of the MoS₂@MWCNTs was characterized via scanning electron microscopy (SEM) and transmission electron microscopy (TEM), and the load of crystalline MoS₂ was verified via X‐ray diffraction (XRD) and energy‐dispersive spectroscopy (EDS). The as‐prepared MoS₂@MWCNTs nanocomposite was used to modify glassy carbon electrode (GCE) as an electrochemical sensor for detecting aristolochic acids (AAs). With the optimized parameters, the proposed electrochemical sensor exhibited good sensitivity and a broad linear concentration range for detecting AAs from 0.2 to 10 μ mol/L and 10 to 100 μ mol/L, with the sensitivity of ?3.10 μ A/(μ mol/L) and ?0.91 μ A/(μ mol/L), respectively. The detection limit was also calculated as 0.06 μ mol/L (S/N=3) based on the low background signal. Furthermore, the modified electrochemical sensor exhibited good selectivity, repeatability, reproducibility, and stability, thus showing potential application for detecting AA in chinese herbs with good mean recovery and accuracy. In other words, the MoS₂@MWCNTs/GCE can be used as an excellent platform to detect AAs.     

Highly Sensitive and Selective Determination of Dopamine in the Presence of Ascorbic Acid Using Gold Nanoparticles‐Decorated MoS2 Nanosheets Modified Electrode

Herein, a novel nanocomposite has been synthesized by molybdenum disulfide (MoS₂) nanosheets and gold nanoparticles (AuNPs) via a microwave‐assisted hydrothermal method, which possesses the specific features of both MoS₂ and AuNPs. The AuNPs@MoS₂ nanocomposite modified electrode exhibits excellent electrocatalytic activity toward dopamine (DA). Its oxidation peak current shows a linear dependence over the DA concentration in the range from 0.1 to 200 µM, with a detection limit of 80 nM (S/N=3). More importantly, the AuNPs@MoS₂‐based sensor can detect DA in the presence of a large excess of ascorbic acid. The AuNPs@MoS₂‐based sensor shows good sensitivity, reproducibility and selectivity, suggesting that the AuNPs@MoS₂ nanocomposite is a promising candidate in electrochemical sensing and other electrocatalytic applications.     

类石墨烯二硫化钼及其在光电子器件上的应用

由单层或几层二硫化钼构成的类石墨烯二硫化钼(graphene-like MoS₂)是一种具有类似石墨烯结构和性能的新型二维(2D)层状化合物, 近年来以其独特的物理、化学性质而成为新兴的研究热点. 本文综述了近年来类石墨烯二硫化钼常见的几种制备方法, 包括以微机械力剥离、锂离子插层和液相超声法等为主的“自上而下”的剥离法, 以及以高温热分解、水热法等为主的“自下而上”的合成法; 介绍了其常用的结构表征方法, 包括原子力显微镜(AFM)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)和拉曼光谱等; 概述了类石墨烯二硫化钼的紫外-可见(UV-Vis)吸收、荧光发射等基本光物理性质及其相关机理; 总结了类石墨烯二硫化钼在二次电池、场效应晶体管、传感器、有机电致发光二极管和电存储等光电子器件领域的应用原理及其研究进展, 展望了这类新型二维层状化合物的研究前景.     

Platinum nanoparticles supported MoS2 nanosheet for simultaneous detection of dopamine and uric acid

Herein, platinum nanoparticles-decorated molybdenum disulfide(Pt NPs@MoS_2) nanocomposite has been synthesized via a microwave-assisted hydrothermal method, which was characterized by transmission electron microscopy(TEM) and powder X-ray diffraction(XRD). This MoS_2-based nanocomposite modified glass carbon electrode(Pt NPs@MoS_2/GCE) exhibited excellent electrocatalytic activity toward dopamine(DA) and uric acid(UA) due to their synergistic effect. Two well-defined oxidation peaks of DA and UA were obtained at Pt NPs@MoS_2/GCE with a large peak separation of 160 m V(DA-UA), suggesting that the modified electrode could individually or simultaneously analyze DA and AA. Under the optimal conditions, the peak currents of DA and UA were linearly dependent on their concentrations in the range of 0.5–150 and 5–1000 mmol/L with detection limit of 0.17 and 0.98 mmol/L, respectively. The proposed MoS_2-based sensor can also be employed to examine DA and UA in real samples with satisfactory results. Therefore, the Pt NPs@MoS_2 nanocomposite might offer a good possibility for electrochemical sensing and other electrocatalytic applications.     

Hierarchical MoS2/polyaniline binary hybrids with high performance for improving fire safety of epoxy resin

Here we report a facile strategy to fabricate phosphoric acid doped polyaniline/molybdenum disulfide (PANI/MoS₂) hybrids as high-performance nanofillers in epoxy (EP) resin for the first time. In situ growth of PANI on the surface of two-dimensional MoS₂ template resulted in the uniform dispersion and strong interfacial adhesion of PANI/MoS₂ hybrids within EP matrix, which can be confirmed by the obvious increase (13.5°C) in glass transition temperature (T_g) of EP composites. The MoS₂ nanosheets also acted as a critical component to generate synergistic effect with PANI on reducing the fire hazards of EP resin. It resulted in a remarkable removal of flammable decomposed products and a considerable reduction of toxic CO yield. The dramatical decreases in real-time smoke density and total smoke production, and high-graphitized char layer in condensed phase were obtained for EP composite with 5 wt% PANI/MoS₂ hybrids. The multiple synergistic effects (synergistic dispersion and synergistic char formation) are believed to be the primary source for these obvious enhancements of properties of EP composites. This facile strategy may achieve the potential application of functionalized MoS₂ in polymeric nanocomposites.     

Synthesis of intercalation compounds of molybdenum disulfide with nitrogen-containing organic molecules and study of their microstructure

Reactions of single-layer dispersions of molybdenum disulfide with 2,2-bipyridyl, para-phenylenediamine, and hexamethylenetetramine afford intercalation compounds consisting of alternating MoS₂ layers and layers formed by organic molecules. The structures of the intercalation compounds were characterized by X-ray powder diffraction and electron microscopy data. The influence of pH on the composition of resulting compounds and the packing of the intercalant was examined.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1837–1845, September, 2004.