One sentence summary:We describe a general liquid-phase method to exfoliate layered compounds to give monoand few-layer flakes in large quantities. TMDs consist of hexagonal layers of metal atoms, M, sandwiched between two layers of chalcogen atoms, X, with stoichiometry MX 2 . While the bonding within these tri-layer sheets is covalent, adjacent sheets stack via van der Waals interactions to form a 3D crystal. TMDs occur in more than 40 different types (2, 3) depending on the combination of chalcogen (S, Se or Te) and transition metal(3). Depending on the co-ordination and oxidation state of the metal atoms, TMDs can be metallic, semi-metallic or semiconducting(2, 3), e.g. WS 2 is a semiconductor while NbSe 2 is a metal(3). In addition, superconductivity(4) and charge density wave effects(5) have been observed in some TMDs. This versatility makes them potentially useful in many areas of electronics.However, like graphene(6), layered materials must be exfoliated to fulfil their full potential. For example, films of exfoliated Bi 2 Te 3 should display enhanced thermoelectric efficiency by suppression of thermal conductivity(7). Exfoliation of 2D topological insulators such as Bi 2 Te 3 and Bi 2 Se 3 would reduce residual bulk conductance, 4 highlighting surface effects. In addition, we can expect changes in electronic properties as the number of layers is reduced e.g. the indirect bandgap of bulk MoS 2 becomes direct in few-layer flakes(8). Although exfoliation can be achieved mechanically on a small scale(9, 10), liquid phase exfoliation methods are required for many applications(11).Critically, a simple liquid exfoliation method would allow the formation of novel hybrid and composite materials. While TMDs can be chemically exfoliated in liquids(12-14), this method is time consuming, extremely sensitive to the environment and incompatible with most solvents.We demonstrate exfoliation of bulk TMD crystals in common solvents to give mono-and few layer nano-sheets. This method is insensitive to air and water and can potentially be scaled up to give large quantities of exfoliated material. In addition, we show that this procedure allows the formation of hybrid films with enhanced properties.We initially sonicated commercial MoS 2 , WS 2 and BN (15, 16) powders in a number of solvents with varying surface tensions. The resultant dispersions were centrifuged and the supernatant decanted (Section S3). Optical absorption spectroscopy showed that the amount of material retained (characterised by / A l C α = , where A/l is the absorbance per length, α is the extinction coefficient and C is the concentration) was maximised for solvents with surface tension close to 40 mJ/m 2 (17, 18) ( Fig. 1A-C). Detailed analysis, within the framework of Hansen solubility parameter theory(19), shows successful solvents to be those with dispersive, polar and H-bonding components of the cohesive energy density within certain well-defined ranges (Section S4, Figs. S2-S3). This can be interpreted to mean that successful solvents are those w...

Abstract:In order to progress from the lab to commercial applications it will be necessary to develop industrially scalable methods to produce large quantities of defect-free graphene.Here we show that high-shear mixing of graphite in suitable, stabilizing liquids results in large-scale exfoliation to give dispersions of graphene nanosheets. XPS and Raman spectroscopy show the exfoliated flakes to be unoxidised and free of basal plane defects. We have developed a simple model which shows exfoliation to occur once the local shear rate exceeds 10 4 s -1 . By fully characterizing the scaling behaviour of the graphene production rate, we show that exfoliation can be achieved in liquid volumes from 100s of ml up to 100s of litres and beyond. The graphene produced by this method performs well in applications from composites to conductive coatings. This method can be applied to exfoliate BN, MoS2 and a range of other layered crystals. Main Text:Due to its ultra-thin, 2-dimensional nature and its unprecedented combination of physical properties, graphene has become the most studied of all nano-materials. In the next decade graphene is likely to find commercial applications in many areas from high-frequency electronics to smart coatings.

A method is demonstrated to prepare graphene dispersions at high concentrations, up to 1.2 mg mL(-1), with yields of up to 4 wt% monolayers. This process relies on low-power sonication for long times, up to 460 h. Transmission electron microscopy shows the sonication to reduce the flake size, with flake dimensions scaling as t(-1/2). However, the mean flake length remains above 1 microm for all sonication times studied. Raman spectroscopy shows defects are introduced by the sonication process. However, detailed analysis suggests that predominantly edge, rather than basal-plane, defects are introduced. These dispersions are used to prepare high-quality free-standing graphene films. The dispersions can be heavily diluted by water without sedimentation or aggregation. This method facilitates graphene processing for a range of applications.

We have developed methods to exfoliate MoS 2 in large quantities in surfactant-water solutions. This method can be extended to a range of other layered compounds. The layered material tends to be exfoliated as relatively defect free flakes with lateral sizes of 100s of nm. 2With high surface area and novel properties, two-dimensional (2D) materials are potentially useful for a range of applications. In addition to graphene, many 2D compounds exist with BN, MoS 2 and Bi 2 Te 3 generating renewed interest. Such materials are found stacked in layered crystals and can be metals, semiconductors or insulators.[ tend to bond via van der Waals interactions, stacking to form 3D crystals. These materials span the whole gamut of electronic structures from insulator to metal [1] and display interesting properties [6] such as superconductivity, [3] thermoelectricity [2] and topological insulator effects.[4]While micro-mechanically exfoliated [7] single flakes of materials such as MoS 2 are ideal for electronic devices, [8] large scale liquid-phase exfoliation methods will lead to a range of thin film applications such as nano-scale hybrids for use in thermoelectrics, [9] supercapacitors [10] or Li-ion batteries [11] . One advantage of such applications is that, as the electronic properties of TMDs vary relatively slowly with layer number, [12,13] full exfoliation to monolayers is not necessary; dispersed few-layer flakes are sufficient.While a number of layered compounds can be exfoliated by ion intercalation, [14][15][16][17] this method is time consuming, extremely sensitive to environmental conditions and results in structural deformations in some TMDs.[18] Furthermore, removal of the ions results in re-aggregation of the layers.[19] More promisingly, it has recently been shown that both TMDs [20] and BN can be exfoliated in organic solvents. [21][22][23][24] However, for large-scale applications, exfoliation in an aqueous environment would be hugely advantageous. While BN can be dispersed in water due to sonication-assisted hydrolysis, this method cannot be extended to other layered compounds.[25] The discovery of a facile, scalable method to exfoliate a range of layered materials in water would assist the production and 3 characterisation of a range of new materials and greatly facilitate the potential transfer of such technology to industry. In this work we show that a number of layered crystals can be exfoliated in water, resulting in thin flakes stabilised by a surfactant coating. This method is robust, can be carried out in ambient conditions, is scalable and allows the preparation of films, hybrids and composites.One possible reason why ion intercalation has been prevalent for TMDs rather than other liquid based dispersion methods is the relatively high exfoliation (surface) energy of TMDs. Computational studies have estimated this as greater than 250 mJ/m 2 for both MoS 2 and WS 2 ; [26,27] many times greater than that of graphene [28] or BN [29] . We suggest that sonication can be used to exfoliate TMDs in water,...

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 .

Employing high-yield production of layered materials by liquid-phase exfoliation, molybdenum disulfide (MoS2) dispersions with large populations of single and few layers were prepared. Electron microscopy verified the high quality of the two-dimensional MoS2 nanostructures. Atomic force microscopy analysis revealed that ~39% of the MoS2 flakes had thicknesses of less than 5 nm. Linewidth and frequency difference of the E(1)2g and A1g Raman modes confirmed the effective reduction of flake thicknesses from the bulk MoS2 to the dispersions. Ultrafast nonlinear optical (NLO) properties were investigated using an open-aperture Z-scan technique. All experiments were performed using 100 fs pulses at 800 nm from a mode-locked Ti:sapphire laser. The MoS2 nanosheets exhibited significant saturable absorption (SA) for the femtosecond pulses, resulting in the third-order NLO susceptibility Imχ((3)) ~ 10(-15) esu, figure of merit ~10(-15) esu cm, and free-carrier absorption cross section ~10(-17) cm(2). Induced free carrier density and the relaxation time were estimated to be ~10(16) cm(-3) and ~30 fs, respectively. At the same excitation condition, the MoS2 dispersions show better SA response than the graphene dispersions.

Monitoring of human bodily motion requires wearable sensors that can detect position, velocity and acceleration. They should be cheap, lightweight, mechanically compliant and display reasonable sensitivity at high strains and strain rates. No reported material has simultaneously demonstrated all the above requirements. Here we describe a simple method to infuse liquid-exfoliated graphene into natural rubber to create conducting composites. These materials are excellent strain sensors displaying 10(4)-fold increases in resistance and working at strains exceeding 800%. The sensitivity is reasonably high, with gauge factors of up to 35 observed. More importantly, these sensors can effectively track dynamic strain, working well at vibration frequencies of at least 160 Hz. At 60 Hz, we could monitor strains of at least 6% at strain rates exceeding 6000%/s. We have used these composites as bodily motion sensors, effectively monitoring joint and muscle motion as well and breathing and pulse.

Solvent exfoliation of inorganic layered compounds is likely to be important for a range of applications. However, this method generally gives dispersions of small nanosheets at low concentrations. Here we describe methods, based on sonication of powdered MoS 2 in the solvent N-methyl-pyrrolidone, to prepare dispersions with significantly increased lateral nanosheet size and dispersed concentration. We find the concentration to scale linearly with starting MoS 2 mass allowing the definition of a yield. This yield can be increased to ~40% by controlling the sonication time, resulting in concentrations as high as 40 mg/ml. We find the nanosheet size to increase initially with sonication time reaching ~700 nm (for a concentration of ~7.5 mg/ml). At longer sonication times the nanosheets size falls off due to sonication induced scission. The nanosheets produced by such methods are relatively thin and have no observable defects. We can separate the dispersed nanosheets by size using controlled centrifugation. This allows us to produce dispersions with mean flake size of up to ~2m. However, such large flakes are noticeably thicker than the standard nanosheets. We demonstrate that such nanosheets can be mixed with polymers to form composites. While standard nanosheets result in no improvement in composite mechanical properties, addition of size-selected nanosheets results in significant improvements in composite modulus and strength.