A study of size-dependent properties of MoS2 monolayer nanoflakes using density-functional theory.
ABSTRACT: Novel physical phenomena emerge in ultra-small sized nanomaterials. We study the limiting small-size-dependent properties of MoS2 monolayer rhombic nanoflakes using density-functional theory on structures of size up to Mo35S70 (1.74?nm). We investigate the structural and electronic properties as functions of the lateral size of the nanoflakes, finding zigzag is the most stable edge configuration, and that increasing size is accompanied by greater stability. We also investigate passivation of the structures to explore realistic settings, finding increased HOMO-LUMO gaps and energetic stability. Understanding the size-dependent properties will inform efforts to engineer electronic structures at the nano-scale.
Project description:Photothermal cancer therapy has attracted considerable interest for cancer treatment in recent years, but the effective photothermal agents remain to be explored before this strategy can be applied clinically. In this study, we therefore develop flower-like molybdenum disulfide (MoS2) nanoflakes and investigate their potential for photothermal ablation of cancer cells. MoS2 nanoflakes are synthesized via a facile hydrothermal method and then modified with lipoic acid-terminated polyethylene glycol (LA-PEG), endowing the obtained nanoflakes with high colloidal stability and very low cytotoxicity. Upon irradiation with near infrared (NIR) laser at 808 nm, the nanoflakes showed powerful ability of inducing higher temperature, good photothermal stability and high photothermal conversion efficiency. The in vitro photothermal effects of MoS2-PEG nanoflakes with different concentrations were also evaluated under various power densities of NIR 808-nm laser irradiation, and the results indicated that an effective photothermal killing of cancer cells could be achieved by a low concentration of nanoflakes under a low power NIR 808-nm laser irradiation. Furthermore, cancer cell in vivo could be efficiently destroyed via the photothermal effect of MoS2-PEG nanoflakes under the irradiation. These results thus suggest that the MoS2-PEG nanoflakes would be as promising photothermal agents for future photothermal cancer therapy.
Project description:A deep understanding of the thermal properties of 2D materials is crucial to their implementation in electronic and optoelectronic devices. In this study, we investigated the macroscopic in-plane thermal conductivity (?) and thermal interface conductance (g) of large-area (mm2) thin film made from MoS2 nanoflakes via liquid exfoliation and deposited on Si/SiO2 substrate. We found ? and g to be 1.5?W/mK and 0.23?MW/m2K, respectively. These values are much lower than those of single flakes. This difference shows the effects of interconnections between individual flakes on macroscopic thin film parameters. The properties of a Gaussian laser beam and statistical optothermal Raman mapping were used to obtain sample parameters and significantly improve measurement accuracy. This work demonstrates how to address crucial stability issues in light-sensitive materials and can be used to understand heat management in MoS2 and other 2D flake-based thin films.
Project description:A simple one-pot hydrothermal method is developed for fabrication of MoS2@rGO nanoflakes using the economical MoO3 as the molybdenum source. Benefiting from the unique nanoarchitecture, high MoS2 loading (90.3?wt%) and the expanded interlayer spacing, the as-prepared MoS2@rGO nanoflakes exhibit greatly enhanced sodium storage performances including a high reversible specific capacity of 441?mAh g-1 at a current density of 0.2?A?g-1, high rate capability, and excellent capacity retention of 93.2% after 300 cycles.
Project description:This work primarily studies the crystallization condition of molybdenum disulfide (MoS2) in MoS2/graphene hybrids by a temperature-varying hydrothermal method from 150 to 240 °C. Flower-like MoS2 nanoflakes were successfully grown on graphene nanosheets and characterized to understand the temperature-dependent crystallization process and the electrochemical performance. The highest electrocatalytic efficiency for both the dye-sensitized solar cell and the hydrogen evolution reaction was obtained by preparing the hybrid at 180 °C, which benefits from balanced high reactivity and high conductivity. This research leads to a better understanding of temperature dependence of MoS2 crystallization and offers guidelines for better catalytic material design. Graphical abstract Temperature-dependent Crystallization of MoS2 Nanoflakes on Graphene Nanosheets for Electrocatalysis.
Project description:2D or 3D layered materials, such as graphene, graphite, and molybdenum disulfide, usually exhibit superlubricity properties when sliding occurs between the incommensurate interface lattices. This study reports the superlubricity between graphite and silica under ambient conditions, induced by the formation of multiple transferred graphene nanoflakes on the asperities of silica surfaces after the initial frictional sliding. The friction coefficient can be reduced to as low as 0.0003 with excellent robustness and is independent of the surface roughness, sliding velocities, and rotation angles. The superlubricity mechanism can be attributed to the extremely weak interaction and easy sliding between the transferred graphene nanoflakes and graphite in their incommensurate contact. This finding has important implications for developing approaches to achieve superlubricity of layered materials at the nanoscale by tribointeractions.
Project description:Achieving tunability of two dimensional (2D) transition metal dichalcogenides (TMDs) functions calls for the introduction of hybrid 2D materials by means of localized interactions with zero dimensional (0D) materials. A metal-semiconductor interface, as in gold (Au) - molybdenum disulfide (MoS2), is of great interest from the standpoint of fundamental science as it constitutes an outstanding platform to investigate plasmonic-exciton interactions and charge transfer. The applied aspects of such systems introduce new options for electronics, photovoltaics, detectors, gas sensing, catalysis, and biosensing. Here we consider pristine MoS2 and study its interaction with Au nanoislands, resulting in local variations of photoluminescence (PL) in Au-MoS2 hybrid structures. By depositing monolayers of Au on MoS2, we investigate the electronic structure of the resulting hybrid systems. We present strong evidence of PL quenching of MoS2 as a result of charge transfer from MoS2 to Au: p-doping of MoS2. The results suggest new avenues for 2D nanoelectronics, active control of transport or catalytic properties.
Project description:Amorphous Cu <i><sub>x</sub></i> O nanoflakes with a thickness of 10-50 nm were synthesized through dye-assisted transformation of rhombic dodecahedral Cu<sub>2</sub>O nanocrystals using a facile solution process. The morphology evolution observed by electron microscopy is highly dependent on the reaction between the surface and the dye. The crystal grain shrinks during the process until the formation of a purely amorphous nanoflake. The amorphous Cu <i><sub>x</sub></i> O nanoflake consists of a combination of Cu(I) and Cu(II) with a ratio close to 1:1. It shows enhanced photocatalytic reactivity toward the degradation of methyl orange compared to that of rhombic dodecahedral Cu<sub>2</sub>O nanocrystals with all active (110):Cu facets. The chemical composition and architecture remain the same after repeating degradation tests. The high surface-to-volume ratio contributes to its superior photocatalytic performance, whereas its low surface energy, confirmed by density functional theory simulations, explains its improved stability. The nanoflakes also show the ability of degrading nitrobenzene effectively, thus demonstrating great promise as a highly stable and active photocatalyst for environmental applications.
Project description:We investigate the electronic properties of graphene nanoflakes on Ag(111) and Au(111) surfaces by means of scanning tunneling microscopy and spectroscopy as well as density functional theory calculations. Quasiparticle interference mapping allows for the clear distinction of substrate-derived contributions in scattering and those originating from graphene nanoflakes. Our analysis shows that the parabolic dispersion of Au(111) and Ag(111) surface states remains unchanged with the band minimum shifted to higher energies for the regions of the metal surface covered by graphene, reflecting a rather weak interaction between graphene and the metal surface. The analysis of graphene-related scattering on single nanoflakes yields a linear dispersion relation E(k), with a slight p-doping for graphene/Au(111) and a larger n-doping for graphene/Ag(111). The obtained experimental data (doping level, band dispersions around EF, and Fermi velocity) are very well reproduced within DFT-D2/D3 approaches, which provide a detailed insight into the site-specific interaction between graphene and the underlying substrate.
Project description:Recent research interest in two-dimensional (2D) materials has led to an emerging new group of materials known as transition metal dichalcogenides (TMDs), which have significant electrical, optical, and transport properties. MoS2 is one of the well-known 2D materials in this group, which is a semiconductor with controllable band gap based on its structure. The hydrothermal process is known as one of the scalable methods to synthesize MoS2 nanostructures. In this study, the gas sensing properties of flower-shaped MoS2 nanoflakes, which were prepared from molybdenum trioxide (MoO3) by a facile hydrothermal method, have been studied. Material characterization was performed using X-ray diffraction, Brunauer-Emmett-Teller surface area measurements, elemental analysis using energy dispersive X-ray spectroscopy, and field-emission scanning electron microscopy. The gas sensing characteristics were evaluated under exposure to various concentrations of xylene and methanol vapors. The results reveal higher sensitivity and shorter response times for methanol at temperatures below 200 °C toward 200 to 400 ppm gas concentrations. The sensing mechanisms for both gases are discussed based on simulation results using density functional theory and charge transfer.
Project description:Nano energetic materials have attracted great attention recently owing to their potential applications for both civilian and military purposes. By introducing silicon microchannel plates (Si-MCPs) three-dimensional (3D)-ordered structures, monocrystalline MnMoO<sub>4</sub> with a size of tens of micrometres and polycrystalline MnMoO<sub>4</sub> nanoflakes are produced on the surface and sidewall of nickel-coated Si-MCP, respectively. The MnMoO<sub>4</sub> crystals ripen controllably forming polycrystalline nanoflakes with lattice fringes of 0.542?nm corresponding to the [Formula: see text] plane on the sidewall. And these MnMoO<sub>4</sub> nanoflakes show apparent thermite performance which is rarely reported and represents MnMoO<sub>4</sub> becoming a new category of energetic materials after nanocrystallization. Additionally, the nanocrystallization mechanism is interpreted by ionic diffusion caused by 3D structure. The results indicate that the Si-MCP is a promising substrate for nanocrystallization of energetic materials such as MnMoO<sub>4</sub>.