Single-layer Nanosheets Research Articles

Single-layer MoSe2 based NH3 gas sensor

High performance chemical sensor is highly desirable to detect traces of toxic gas molecules. Two dimensional (2D) transition metal dichalcogenides (TMDC) semiconducting materials has attracted as high performance gas sensor device applications due to unique properties such as high surface to volume ratio. Here, we describe the utilization of single-layer MoSe2 as high-performance room temperature NH3 gas sensors. Our single-layer MoSe2 based gas sensor device shows comprehensible detection of NH3 gas down to 50 ppm. We also confirmed gas sensing measurement by recording the Raman spectra before and after exposing the device to NH3 gas, which subsequently shows the shift due to charger transfer and analyte gas molecule adsorption on surface of single-layer MoSe2 nanosheet. Our investigations show the potential use of single-layer and few layer thick MoSe2 and other TMDC as high-performance gas sensors.

One-pot synthesis of CdS nanocrystals hybridized with single-layer transition-metal dichalcogenide nanosheets for efficient photocatalytic hydrogen evolution.

Exploration of low-cost and earth-abundant photocatalysts for highly efficient solar photocatalytic water splitting is of great importance. Although transition-metal dichalcogenides (TMDs) showed outstanding performance as co-catalysts for the hydrogen evolution reaction (HER), designing TMD-hybridized photocatalysts with abundant active sites for the HER still remains challenge. Here, a facile one-pot wet-chemical method is developed to prepare MS2-CdS (M=W or Mo) nanohybrids. Surprisedly, in the obtained nanohybrids, single-layer MS2 nanosheets with lateral size of 4-10 nm selectively grow on the Cd-rich (0001) surface of wurtzite CdS nanocrystals. These MS2-CdS nanohybrids possess a large number of edge sites in the MS2 layers, which are active sites for the HER. The photocatalytic performances of WS2-CdS and MoS2-CdS nanohybrids towards the HER under visible light irradiation (>420 nm) are about 16 and 12 times that of pure CdS, respectively. Importantly, the MS2-CdS nanohybrids showed enhanced stability after a long-time test (16 h), and 70% of catalytic activity still remained.

Half-metallicity in single-layered manganese dioxide nanosheets by defect engineering.

Defect engineering is considered as one of the most efficient strategies to regulate the electronic structure of materials and involves the manipulation of the types, concentrations, and spatial distributions of defects, resulting in unprecedented properties. It is shown that a single-layered MnO2 nanosheet with vacancies is a robust half-metal, which was confirmed by theoretical calculations, whereas vacancy-free single-layered MnO2 is a typical semiconductor. The half-metallicity of the single-layered MnO2 nanosheet can be observed for a wide range of vacancy concentrations and even in the co-presence of Mn and O vacancies. This work enables the development of half-metals by defect engineering of well-established low-dimensional materials, which may be used for the design of next-generation paper-like spintronics.

Single-layer MnO2 nanosheets suppressed fluorescence of 7-hydroxycoumarin: mechanistic study and application for sensitive sensing of ascorbic acid in vivo.

In this study, we systematically investigate the mechanism of single-layer MnO2 nanosheets suppressing fluorescence of 7-hydroxycoumarin and, based on this, demonstrate a new fluorescent method for in vivo sensing of ascorbic acid (AA) in rat brain. The mechanism for the fluorescence suppression is attributed to a combination of inner filter effect (IFE) and static quenching effect (SQE), which is different from those reported for the traditional two-dimensional nanosheets, and Förster resonant energy transfer (FRET) mechanism reported for MnO2 nanosheets. The combination of IFE and SQE leads to an exponential decay in fluorescence intensity of 7-hydroxycoumarin with increasing concentration of MnO2 nanosheets in solution. Such a property allows optimization of the concentration of MnO2 nanosheets in such a way that the addition of reductive analyte (e.g., AA) will to the greatest extent restore the MnO2 nanosheets-suppressed fluorescence of 7-hydroxycoumarin through the redox reaction between AA and MnO2 nanosheets. On the basis of this feature, we demonstrate a fluorescent method for in vivo sensing of AA in the cerebral systems with an improved sensitivity. Compared with the turn-on fluorescent method through first decreasing the fluorescence to the lowest level by adding concentrated MnO2 nanosheets, the method demonstrated here possesses a higher sensitivity, lower limit of detection, and wider linear range. Upon the use of ascorbate oxidase to achieve the selectivity for AA, the turn-on fluorescence method demonstrated here can be used for in vivo sensing of AA in a simple but reliable way.

Two-dimensional synthetic templates

The isolation of atomic-thin graphene sheets from bulk graphite has led to the discovery of a number of novel properties of graphene that have enormously benefited the development of nanotechnology [1], which has inspired the exploration of other 2D materials, such as transition metal dichalcogenides (TMDs), hexagonal boron nitride (hBN), etc. [2]. To exfoliate a layered bulk crystal, the van der Waals interaction between the adjacent layers should be overcome, which can be realized by techniques like mechanical exfoliation [1] and solvent-assisted ultrasound exfoliation [3]. These two methods are relatively non-destructive so that the intrinsic properties of 2D materials could be preserved. However, the former method is mostly applied for fundamental studies and the latter one is difficult to produce high-yield single-layer nanosheets. The intercalation-based methods, on the other hand, are more effective and reliable in mass production of single-layer nanosheets. It was demonstrated decades ago that many chemical species, like alkali metals, transition-metal halides and amine molecules, can be intercalated into various layered materials [4]. As one of the most intensively studied intercalates, lithium, for example, can be inserted into the interlayer spaces of a layered crystal by soaking the crystal in n-butyl lithium solution at an elevated temperature (e.g. 100◦C) for a long time (e.g. 3 days). Alternatively, the electrochemical intercalation method (Fig. 1a–c), which employs electric 50 nm 5 nm (111)Pd

A novel biosensor based on single-layer MoS2 nanosheets for detection of Ag+

In this work, we use for the first time single layer MoS2 as the fluorescence quencher to design a detection method for Ag+ with excellent robustness, selectivity and sensitivity. To maintain the ultrathin MoS2, bulk MoS2 materials have been exfoliated by intercalation with lithium followed by reaction with water. As-prepared two-dimensional MoS2 not only has good water-solubility but also obtains high fluorescence quenching efficiency within 5min. Importantly, the detection limit of this assay for Ag+ (1nM) was lower than the maximum limitation guided by the United States Environmental Protection Agency (EPA) and the World Health Organization (WHO). Further, this new Ag+ probe was demonstrated in monitoring Ag+ in lake water samples with satisfactory results.

2-μm wavelength all-fiber Q-switched double-clad fiber laser using monopiece single-layer chemical-vapor-deposition graphene

We demonstrate a large-energy 2-μm double-clad Tm-doped fiber laser (DC-TDFL) Q-switched by a monopiece single-layer graphene nanosheet. The single-layer graphene is fabricated by the chemical vapor deposition (CVD) method, and then transferred onto the facet of a fiber ferrule for constructing a fiber-compatible saturable absorber (SA). The Q-switching operation of the DC-TDFL at 1980 nm is achieved and has a large pulse energy of 1.06 μJ (corresponding to the average output power of 28.6 mW). The narrowest pulse duration is 2.7 μs, and the pulse repetition rate can be tuned from 8 to 27 kHz by changing the pump power from 2.35 to 2.82 W. To the best of our knowledge, this work is not only the first demonstration of a 2-μm Q-switched all-fiber laser using monopiece single-layer CVD graphene as a SA, but also generates the largest pulse energy from graphene-based all-fiber DC-TDFLs. © 2014 Society of Photo-Optical Instrumentation Engineers (SPIE) (DOI: 10.1117/1.OE.53.10 .106103)

Redox control and high conductivity of nickel bis(dithiolene) complex π-nanosheet: a potential organic two-dimensional topological insulator.

A bulk material comprising stacked nanosheets of nickel bis(dithiolene) complexes is investigated. The average oxidation number is -3/4 for each complex unit in the as-prepared sample; oxidation or reduction respectively can change this to 0 or -1. Refined electrical conductivity measurement, involving a single microflake sample being subjected to the van der Pauw method under scanning electron microscopy control, reveals a conductivity of 1.6 × 10(2) S cm(-1), which is remarkably high for a coordination polymeric material. Conductivity is also noted to modulate with the change of oxidation state. Theoretical calculation and photoelectron emission spectroscopy reveal the stacked nanosheets to have a metallic nature. This work provides a foothold for the development of the first organic-based two-dimensional topological insulator, which will require the precise control of the oxidation state in the single-layer nickel bisdithiolene complex nanosheet (cf. Liu, F. et al. Nano Lett. 2013, 13, 2842).

A self-assembled macroporous coagulation graphene network with high specific capacitance for supercapacitor applications

A macroporous graphene network was prepared through polyethyleneimine-induced coagulation of graphene-oxide nanosheets from the dispersion. The as-prepared electrode made of graphene assemblies exhibited the high surface areal specific capacitance of 46.3 μF cm−2, excellent rate performance, and long cyclic life, which are attributed to the face-to-edge aggregation of exfoliated single-layer graphene nanosheets.

Dependence of electronic structure of g-C3N4 on the layer number of its nanosheets: A study by Raman spectroscopy coupled with first-principles calculations

Graphitic carbon nitride (g-C3N4) has attracted worldwide attention, because of its promising potential applications and theoretical prediction of its unique properties. Herein, 1-, 2- and 4-layer g-C3N4 nanosheets were synthesized in a well-crystallized form by controlling the intercalation time in a simple intercalation–exfoliation process. The electronic structures of the nanosheets were captured in their Raman spectra that clearly evolved with the layer number of the nanosheets for the first time. A clear correlation between the spectral properties and the layer number of the nanosheets was clarified by combining Raman spectra and the first-principles calculations. Raman vibrational modes of g-C3N4 were assigned. The layer–layer deformation vibrations and related in-plane twisting vibrations or symmetrical stretching vibrations reflected the change in the electronic structure of the nanosheets with different layers. The results may shed light on brand-new opportunities for significant improvements in the synthesis, structure, electronic and optical properties of single-layer and ultrathin g-C3N4 nanosheets toward desirable functional materials.

Stability characteristics of single-layered zinc oxide nanosheets under uniaxial loading

This paper is aimed to propose a three-dimensional model which would be used for investigation on the mechanical behavior of single-layered zinc oxide nanosheets. To develop this model, molecular mechanics is coupled with the density functional theory. Simulating the hexagonal lattices of nanosheets as a hexagonal mechanical structure composed of structural beam elements, the buckling behavior of zinc oxide nanosheets is studied. Effects of different parameters on the stability of armchair and zigzag nanosheets are examined. It is shown that the buckling forces of zigzag nanosheets are slightly greater than those of armchair ones. However, with increasing size of nanosheets the effect of atomic structure on the stability of nanosheets diminishes. By studying the effect of end conditions on the buckling behavior of nanosheets, it is shown the stability of nanosheets is affected significantly by boundary conditions.

Exfoliation of layered double hydroxides for enhanced oxygen evolution catalysis.

The oxygen evolution reaction is a key reaction in water splitting. The common approach in the development of oxygen evolution catalysts is to search for catalytic materials with new and optimized chemical compositions and structures. Here we report an orthogonal approach to improve the activity of catalysts without alternating their compositions or structures. Specifically, liquid phase exfoliation is applied to enhance the oxygen evolution activity of layered double hydroxides. The exfoliated single-layer nanosheets exhibit significantly higher oxygen evolution activity than the corresponding bulk layered double hydroxides in alkaline conditions. The nanosheets from nickel iron and nickel cobalt layered double hydroxides outperform a commercial iridium dioxide catalyst in both activity and stability. The exfoliation creates more active sites and improves the electronic conductivity. This work demonstrates the promising catalytic activity of single-layered double hydroxides for the oxygen evolution reaction.

High-Throughput Synthesis of Single-Layer MoS2 Nanosheets as a Near-Infrared Photothermal-Triggered Drug Delivery for Effective Cancer Therapy

We report here a simple, high-yield yet low-cost approach to design single-layer MoS2 nanosheets with controllable size via an improved oleum treatment exfoliation process. By decorating MoS2 nanosheets with chitosan, these functionalized MoS2 nanosheets have been developed as a chemotherapeutic drug nanocarrier for near-infrared (NIR) photothermal-triggered drug delivery, facilitating the combination of chemotherapy and photothermal therapy into one system for cancer therapy. Loaded doxorubicin could be controllably released upon the photothermal effect induced by 808 nm NIR laser irradiation. In vitro and in vivo tumor ablation studies demonstrate a better synergistic therapeutic effect of the combined treatment, compared with either chemotherapy or photothermal therapy alone. Finally, MoS2 nanosheets can also be used as a promising contrast agent in X-ray computed tomography imaging due to the obvious X-ray absorption ability of Mo. As a result, the high-throughput oleum treatment exfoliation process could be extended for fabricating other 2D nanomaterials, and the NIR-triggered drug release strategy was encouraging for simultaneous imaging-guided cancer theranostic application.

Highly luminescent two dimensional excitons in atomically thin CdSe nanosheets

Atomically thin Cadmium Selenide (CdSe) nanosheets have been synthesized using a surfactant mediated growth technique. The transmission electron microscopy studies confirm the presence of single layered nanosheets with thickness 1.31 nm and their stacking structures which are complemented by the small angle x-ray scattering measurements. The strongly bound and polarized character of two dimensional excitonic states with enhanced oscillator strength yielding distinct narrow blue luminescence has been observed from the CdSe nanosheets using room temperature based optical studies.

Sulfonic Acid-Functionalized α-Zirconium Phosphate Single-Layer Nanosheets as a Strong Solid Acid for Heterogeneous Catalysis Applications

Solid acids have received considerable attention as alternatives to traditional corrosive and hazardous homogeneous acids because of their advantages in practical applications, including their low corrosion of equipment and high catalytic activity and recyclability. In this work, a strong solid acid was prepared by anchoring thiol group terminated chains on layered α-zirconium phosphate (ZrP) single-layer nanosheets, followed by oxidation of thiol groups to form sulfonic acid groups. The obtained solid acids were thoroughly characterized and the results proved that sulfonic acid group terminated chains were successfully grafted onto the ZrP nanosheets with a high loading density. Such a strong solid acid based on inorganic nanosheets can be well-dispersed in polar solvents, leading to high accessibility to the acid functional groups. Meanwhile, it can be easily separated from the dispersion system by centrifugation or filtration. The strong solid acid can serve as an effective heterogeneous catalyst for various reactions, including the Bayer-Villiger oxidation of cyclohexanone to ε-caprolactone in the absence of organic solvents.

Gigantic Swelling of Inorganic Layered Materials: A Bridge to Molecularly Thin Two-Dimensional Nanosheets

Platy microcrystals of a typical layered material, protonated titanate, have been shown to undergo an enormous degree of swelling in aqueous solutions of various amines, including tertiary amines, quaternary ammonium hydroxides, and primary amines. Introducing these solutions expanded the crystal gallery height by up to ~100-fold. Through systematic analysis, we determined that ammonium ion intercalation is predominantly affected by the acid-base equilibrium and that the degree of swelling or inflow of H2O is controlled by the osmotic pressure balance between the gallery and the solution environment, both of which are relatively independent of electrolyte identity but substantially dependent on molarity. In solutions of tertiary amines and quaternary ammonium hydroxides, the uptake of ammonium ions increases nearly linearly with increasing external concentration before reaching a saturation plateau, i.e., ~40% relative to the cation-exchange capacity of the crystals used. The only exception is tetrabutylammonium ions, which yield a lower saturation value, ~30%, owing to steric effects. The swelling behaviors in some primary amine solutions differ as a result of the effect of attractive forces between amine solute molecules on the solution osmotic pressure. Although the swelling is essentially colligative in nature, the stability of the resultant swollen structure is heavily dependent on the chemical nature of the guest ions. Intercalated ions of higher polarity and smaller size help stabilize the swollen structure, whereas ions of lower polarity and larger size lead readily to exfoliation. The insight gained from this study sheds new light on both the incorporation of guest molecules into a gallery of layered structures in general and the exfoliation of materials into elementary single-layer nanosheets.

Single- and Double-Layered Organically Modified Nanosheets by Selective Interlayer Grafting and Exfoliation of Layered Potassium Hexaniobate

Organically modified niobate nanosheets are promising building blocks for the design of advanced hybrid materials. Nanosheets with controlled thickness and surface composition are important for precise structural design of the nanosheet-based materials. In this work, single-layered and double-layered niobate nanosheets functionalized by phenylphosphonate moieties were selectively prepared by interlayer grafting of A-type and B-type intercalation derivatives of potassium hexaniobate (K4Nb6O17·3H2O) with phenylphosphonic acid (PPA), followed by exfoliation by ultrasonication in acetonitrile. The interlayer grafting of PPA was monitored using X-ray diffraction (XRD), Fourier transform infrared (FTIR), and solid-state NMR spectroscopy, and the thicknesses of the exfoliated nanosheets were measured by atomic force microscopy (AFM). Transparent hybrid films were obtained by incorporating the single- and double-layered nanosheets into an epoxy matrix.

Ultrathin rhodium nanosheets

Despite significant advances in the fabrication and applications of graphene-like materials, it remains a challenge to prepare single-layered metallic materials, which have great potential applications in physics, chemistry and material science. Here we report the fabrication of poly(vinylpyrrolidone)-supported single-layered rhodium nanosheets using a facile solvothermal method. Atomic force microscope shows that the thickness of a rhodium nanosheet is <4 Å. Electron diffraction and X-ray absorption spectroscopy measurements suggest that the rhodium nanosheets are composed of planar single-atom-layered sheets of rhodium. Density functional theory studies reveal that the single-layered Rh nanosheet involves a δ-bonding framework, which stabilizes the single-layered structure together with the poly(vinylpyrrolidone) ligands. The poly(vinylpyrrolidone)-supported single-layered rhodium nanosheet represents a class of metallic two-dimensional structures that might inspire further fundamental advances in physics, chemistry and material science.

A facile wet chemistry approach towards unilamellar tin sulfide nanosheets from Li4xSn1−xS2solid solutions

We report on the facile production of single-layered tin sulfide nanosheets by a direct solid-state reaction, followed by quantitative liquid exfoliation in water. The new solid solution of SnS2 and Li2S with composition Li4xSn1−xS2 serves as a versatile solid-state precursor with tunable relative lithium and tin content. The end member Li2SnS3, corresponding to the solid solution composition Li3x[LixSn1−xS2], crystallizes in the well-known A2BO3 structure type with mixed Li/Sn layers alternating with pure Li layers in the cationic substructure, which is interleaved with sulfur layers. The bonding in the Li layers can be regarded as ionic, while the Sn–S bonds have substantial covalent character. The resulting inherent anisotropy allows for the facile production of unilamellar chalcogenide nanosheets with thicknesses below 1 nm and lateral sizes of tens of microns, simply by shaking the crystalline precursor in water. The quantitative exfoliation into single-layered nanosheets was confirmed using optical microscopy, AFM, TEM, as well as X-ray diffraction of freestanding films produced from the colloidal suspension by centrifugation. Upon annealing, the as-obtained nanosheets are converted into SnS2 without sacrificing their favorable dispersion properties in water. The presented method allows for the cheap and scalable production of unilamellar chalogenide nanosheets for various potential applications, such as in electronic devices, solar cells, sensors, or battery technology. We expect this method to be generic and transferable to the synthesis of other metal chalcogenides. The use of solid solutions as solid-state precursors, featuring a large compositional range and potential for doping with other metals, may ultimately allow for the controlled introduction of defect levels and rational band-gap engineering in nanosheet materials.

Versatile van der Waals epitaxy-like growth of crystal films using two-dimensional nanosheets as a seed layer: orientation tuning of SrTiO3 films along three important axes on glass substrates

One of the basic requirements for attaining a good epitaxy is a close structural matching between a substrate and a growing crystal epilayer. This restrictive requirement causes a major obstacle for its wide application to a range of functional crystal films in electronic, magnetic or optical devices. One approach for overcoming this problem is the so-called van der Waals epitaxy (VDWE) method, which can effectively implement the epitaxy of various crystals on cleaved faces of layered materials having no dangling bonds. The weak adatom–substrate interaction without directional covalent bonding plays a crucial role in the initial stage of VDWE, which drastically relaxes the lattice matching limitation. However, the method requires special materials for use as a substrate, thereby meaning that its applicability is limited. In this study, the concept is extended to the two-dimensional (2D) lattice of inorganic nanosheets, which are molecularly thin 2D crystals produced via artificial exfoliation of layered metal oxides. The nanosheets can neatly cover the surface of conventional substrates such as glass via a facile solution-based process. Similar to the above-mentioned cleaved faces of layered materials, such substrates can promote VDWE-like crystal growth because of their dangling bond-free nature. Based on this principle, we have demonstrated a selective deposition of highly textured (100), (110) and (111) SrTiO3 films, a fundamentally important archetype of functional crystals, on glass substrates covered with single-layer nanosheets with suitable 2D periodicities as a trigger for VDWE-like film growth. The rich varieties of nanosheet structures and their facile deposition onto almost any kinds of substrates provide a significant advantage, expanding potential applications for a range of devices based on functional crystal films.