Few-layer black phosphorus (BP) is a new two-dimensional material which is of great interest for applications, mainly in electronics. However, its lack of environmental stability severely limits its synthesis and processing. Here we demonstrate that high-quality, few-layer BP nanosheets, with controllable size and observable photoluminescence, can be produced in large quantities by liquid phase exfoliation under ambient conditions in solvents such as N-cyclohexyl-2-pyrrolidone (CHP). Nanosheets are surprisingly stable in CHP, probably due to the solvation shell protecting the nanosheets from reacting with water or oxygen. Experiments, supported by simulations, show reactions to occur only at the nanosheet edge, with the rate and extent of the reaction dependent on the water/oxygen content. We demonstrate that liquid-exfoliated BP nanosheets are potentially useful in a range of applications from ultrafast saturable absorbers to gas sensors to fillers for composite reinforcement.
Two-dimensional nanomaterials such as MoS 2 are of great interest both because of their novel physical properties and their applications potential. Liquid exfoliation, an important production method, is limited by our inability to quickly and easily measure nanosheet size, thickness or concentration. Here we demonstrate a method to simultaneously determine mean values of these properties from an optical extinction spectrum measured on a liquid dispersion of MoS 2 nanosheets. The concentration measurement is based on the size-independence of the low-wavelength extinction coefficient, while the size and thickness measurements rely on the effect of edges and quantum confinement on the optical spectra. The resultant controllability of concentration, size and thickness facilitates the preparation of dispersions with pre-determined properties such as high monolayer-content, leading to first measurement of A-exciton MoS 2 luminescence in liquid suspensions. These techniques are general and can be applied to a range of two-dimensional materials including WS 2 , MoSe 2 and WSe 2 .
While liquid exfoliation is a powerful technique to produce defect-free nanosheets in large quantities, its usefulness is limited by broad nanosheet thickness distributions and low monolayer contents. Here we demonstrate liquid processing techniques, based on iterative centrifugation cascades, which can be designed to achieve either highly efficient nanosheet size-selection and/or monolayer enrichment. The resultant size-selected dispersions were used to establish quantitative metrics to determine monolayer volume fraction, as well as mean nanosheet size and thickness, from standard spectroscopic measurements. Such metrics allowed us to design and optimize centrifugation cascades to enrich liquid exfoliated WS2 dispersions up to monolayer contents of 75%. Monolayer-rich dispersions show relatively bright photoluminescence with narrow line widths (<35 meV) indicating the high quality of the nanosheets. The enriched dispersions display extinction spectra with distinct features, which also allow the direct estimation of monolayer contents.
Liquid phase exfoliation has become an important method for the production of large quantities of 2-dimensional nanosheets. This method is versatile, having been used to produce dozens of different 2D materials in a range of stabilizing liquids. The resultant liquidsuspended nanosheets have been characterized in great detail and have been processed into a number of structures for a wide range of applications. This has led to a growing number of researchers adopting this method. As a result, best practise in terms of experimental procedure has evolved rapidly over recent years. As experimental complexity has increased it has become more and more difficult to discuss the rational behind a chosen experimental procedure in full detail using standard "Methods" sections due to the frequent use of procedures developed in related prior reports. This can make it difficult to reproduce complex procedures and acts as a barrier to new researchers entering the field. To address this shortcoming, here we describe in detail the experimental methods and best practice used in our group when producing liquid exfoliated nanosheets.
Here we demonstrate the production of large quantities of gallium sulfide (GaS) nanosheets by liquid exfoliation of layered GaS powder. The exfoliation was achieved by sonication of the powder in suitable solvents. The variation of dispersed concentration with solvent was consistent with classical solution thermodynamics and showed successful solvents to be those with Hildebrand solubility parameters close to 21.5 MPa 1/2 . In this way, nanosheets could be produced at concentrations of up to ~0.2 mg/ml with lateral sizes and thicknesses of 50-1000 nm and 3-80 layers, respectively. The nanosheets appeared to be relatively defect free although oxygen was observed in the vicinity of the edges. Using controlled centrifugation techniques, it was possible to prepare dispersions containing size-selected nanosheets.Spectroscopic measurements showed the optical properties of the dispersions to vary strongly with nanosheet size, allowing the elucidation of spectroscopic metrics for in-situ estimation of nanosheet size and thickness. These techniques allow the production of nanosheets with controlled sizes which will be important for certain applications. To demonstrate this, we prepared films of GaS nanosheets of three different sizes for use as hydrogen evolution electrocatalysts. We found a clear correlation between performance and size showing small nanosheets to be more effective. This is consistent with the catalytically active sites residing on the nanosheet edges.
Liquid phase exfoliation is a powerful and scalable technique to produce defect-free mono- and few-layer graphene. However, samples are typically polydisperse and control over size and thickness is challenging. Notably, high throughput techniques to measure size and thickness are lacking. In this work, we have measured the extinction, absorption, scattering and Raman spectra for liquid phase exfoliated graphene nanosheets of various lateral sizes (90 ≤ 〈L〉 ≤ 810 nm) and thicknesses (2.7 ≤ 〈N〉 ≤ 10.4). We found all spectra to show well-defined dependences on nanosheet dimensions. Measurements of extinction and absorption spectra of nanosheet dispersions showed both peak position and spectral shape to vary with nanosheet thickness in a manner consistent with theoretical calculations. This allows the development of empirical metrics to extract the mean thickness of liquid dispersed nanosheets from an extinction (or absorption) spectrum. While the scattering spectra depended on nanosheet length, poor signal to noise ratios made the resultant length metric unreliable. By analyzing Raman spectra measured on graphene nanosheet networks, we found both the D/G intensity ratio and the width of the G-band to scale with mean nanosheet length allowing us to establish quantitative relationships. In addition, we elucidate the variation of 2D/G band intensities and 2D-band shape with the mean nanosheet thickness, allowing us to establish quantitative metrics for mean nanosheet thickness from Raman spectra.
ABSTRACT:Here we demonstrate a simple method to exfoliate layered molybdenum trioxide (MoO3) crystallites to give multi-layer MoO3 nanosheets dispersed in solvents. Exfoliation is achieved by sonicating MoO3 powder in the presence of suitable solvents followed by centrifugation to remove undispersed material. This procedure works well in a range of solvents with Hildebrand solubility parameters close to 21 MPa 1/2 , and is consistent with the predictions of classical solubility theory. We have fully optimised this process and demonstrated methods to separate the resultant nanosheets by size. Raman spectroscopy suggests the exfoliation process does not damage the MoO3. This is supported by measurements which show reaggregated nanosheets to display very similar photoluminescence to bulk MoO3. However, the dispersed nanosheets had distinctly different photoluminescence indicating a decoupling of the monolayers on exfoliation. We have used liquid exfoliated MoO3 to prepare supercapacitor electrodes which had relatively low capacitance (~2 F/g at 10 mV/s), due to the low electrical conductivity of the MoO3.However, addition of carbon nanotubes beyond the percolation threshold yielded a 100-fold increase in capacitance. Some MoO3/nanotube composites displayed capacitances as high as 540 F/g at 0.1 mV/s. This is the first example of solvent exfoliation of a layered metal oxide.We believe this work opens the way to liquid exfoliation of a wide range of layered compounds leading to an array of new solution processed 2D materials.
Advances in lithium ion batteries would facilitate technological developments inareas from electrical vehicles to mobile communications. While 2-dimensional systems like MoS2 are promising electrode materials due to their potentially high capacity, their poor ratecapability and low cycle-stability are severe handicaps. Here we study the electrical, mechanical and lithium storage properties of solution-processed MoS2/carbon nanotube anodes.Nanotube addition gives up to ×10 10 and ×40 increases in electrical conductivity and mechanical toughness respectively. The increased conductivity results in up to a ×100 capacity enhancement to ~1200 mAh/g (~3000 mAh/cm 3 ) at 0.1 A/g, while the improved toughness significantly boosts cycle stability. Composites with 20 wt% nanotubes combined high reversible capacity with excellent cycling stability (e.g. ~950 mAh/g after 500 cycles at 2 A/g) and high-rate capability (~600 mAh/g at 20 A/g). The conductivity, toughness and capacity scaled with nanotube content according to percolation theory while the stability increased sharply at the mechanical percolation threshold. We believe the improvements in conductivity and toughness obtained after addition of nanotubes can be transferred to other electrode materials such as silicon nanoparticles.Keywords: percolating, network, anode, mechanical 2 In recent years, lithium ion batteries (LIBs) have become the most common rechargeable power sources for portable electronic devices and electric vehicles. 1, 2 Nevertheless, they still suffer from several problems; their energy and especially power densities have not fulfilled their ultimate potential while their safety record is not unblemished. 3 A significant problem is that graphite, the dominant anode material used in LIBs, is limited by a relatively low theoretical capacity of 372 mAh/g. 4 As such, the development of the next-generation of LIBs, is expected to see the replacement of graphite-based anodes with alternative materials having higher capacity at similarly low cost. While a range of materials, including silicon, have been envisaged as future LIB anode materials, 4 of particular interest are 2-dimensional (2D) nanomaterials 5 such as graphene 6 and MoS2. 7 Over the last decade, 2D nano-materials have generated much excitement in the nanomaterials science community. [8][9][10] They come in many types including graphene, transition metal dichalcogenides (TMDs) and transition metal oxides (TMOs). These materials consist of covalently bonded monolayers which can stack via van der Waals interactions to form layered crystals. 8,9 Such 2D nanomaterials are often found as nanosheets with lateral size ranging from 10s of nm to microns and thickness of ~nm. 9 These materials have shown potential for applications 5 in both energy generation 11 and storage. 12 In the context of LIBs, exfoliated TMDs have received significant attention as prospective anode materials. 13,14 While bulk MoS2 was proposed 15 as a Li ion battery electrode material as early as 1980 due to its hi...
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