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.
Although transition metal dichalcogenides such as MoS2 have been recognized as highly potent two-dimensional nanomaterials, general methods to chemically functionalize them are scarce. Herein, we demonstrate a functionalization route that results in organic groups bonded to the MoS2 surface via covalent C-S bonds. This is based on lithium intercalation, chemical exfoliation and subsequent quenching of the negative charges residing on the MoS2 by electrophiles such as diazonium salts. Typical degrees of functionalization are 10-20 atom % and are potentially tunable by the choice of intercalation conditions. Significantly, no further defects are introduced, and annealing at 350 °C restores the pristine 2H-MoS2. We show that, unlike both chemically exfoliated and pristine MoS2, the functionalized MoS2 is very well dispersible in anisole, confirming a significant modification of the surface properties by functionalization. DFT calculations show that the grafting of the functional group to the sulfur atoms of (charged) MoS2 is energetically favorable and that S-C bonds are formed.
In order to fulfil their potential for applications, it will be necessary to develop large-scale production methods for two-dimensional (2D) inorganic nanosheets. Here we demonstrate the large-scale shear-exfoliation of molybdenum disulphide nanosheets in aqueous surfactant solution using a kitchen blender. Using standard procedures, we measure how the MoS2 concentration and production rate scale with processing parameters. However, we also use recently developed methods based on optical spectroscopy to simultaneously measure both nanosheet lateral size and thickness, allowing us to also study the dependence of nanosheet dimensions on processing parameters. We found the nanosheet concentration and production rates to depend sensitively on the mixing parameters (the MoS2 concentration, Ci; the mixing time, t; the liquid volume, V; and the rotor speed, N). By optimising mixing parameters, we achieved concentrations and production rates as high as 0.4 mg/ml and 1.3 mg/min respectively. Conversely, the nanosheet size and thickness were largely invariant with these parameters. The nanosheet concentration is also extremely sensitive to the surfactant concentration. However, more interestingly the nanosheet lateral size and thickness also varied strongly with the surfactant concentration. This allows the mean nanosheet dimensions to be controlled during shear exfoliation at least in the range ~40-220 nm for length and ~2-12 layers for thickness. We demonstrate the importance of this by showing that the MoS2 nanosheets prepared using different surfactant concentrations, and so displaying different nanosheets sizes, perform differently when used as hydrogen evolution catalysts. We find the nanosheets produced using high surfactant concentrations, which gives smaller flake sizes, perform significantly better, consistent with catalysis occurring at nanosheet edges. Finally, we also demonstrate that shear exfoliation using a kitchen blender is not limited to MoS2 but can also be achieved for boron nitride and tungsten disulphide. ToC fig3
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.
The successful commercialization of smart wearable garments is hindered by the lack of fully integrated carbon-based energy storage devices into smart wearables. Since electrodes are the active components that determine the performance of energy storage systems, it is important to rationally design and engineer hierarchical architectures atboth the nano- and macroscale that can enjoy all of the necessary requirements for a perfect electrode. Here we demonstrate a large-scale flexible fabrication of highly porous high-performance multifunctional graphene oxide (GO) and rGO fibers and yarns by taking advantage of the intrinsic soft self-assembly behavior of ultralarge graphene oxide liquid crystalline dispersions. The produced yarns, which are the only practical form of these architectures for real-life device applications, were found to be mechanically robust (Young's modulus in excess of 29 GPa) and exhibited high native electrical conductivity (2508 ± 632 S m(-1)) and exceptionally high specific surface area (2605 m(2) g(-1) before reduction and 2210 m(2) g(-1) after reduction). Furthermore, the highly porous nature of these architectures enabled us to translate the superior electrochemical properties of individual graphene sheets into practical everyday use devices with complex geometrical architectures. The as-prepared final architectures exhibited an open network structure with a continuous ion transport network, resulting in unrivaled charge storage capacity (409 F g(-1) at 1 A g(-1)) and rate capability (56 F g(-1) at 100 A g(-1)) while maintaining their strong flexible nature.
Here we demonstrate that the performance of catalytic electrodes, fabricated from liquid exfoliated MoS2 nanosheets, can be optimized by maximizing the electrode thickness coupled with the addition of carbon nanotubes. We find the current, and so the H2 generation rate, at a given potential to increase linearly with electrode thickness to up ∼5 μm after which saturation occurs. This linear increase is consistent with a simple model which allows a figure of merit to be extracted. The magnitude of this figure of merit implies that approximately two-thirds of the possible catalytically active edge sites in this MoS2 are inactive. We propose the saturation in current to be partly due to limitations associated with transporting charge through the resistive electrode to active sites. We resolve this by fabricating composite electrodes of MoS2 nanosheets mixed with carbon nanotubes. We find both the electrode conductivity and the catalytic current at a given potential to increase with nanotube content as described by percolation theory.
Here we demonstrate significant improvements in the performance of supercapacitor electrodes based on 2D MnO2 nano-platelets by the addition of carbon nanotubes. Electrodes based on MnO2 nano-platelets do not display high areal capacitance because the electrical properties of such films are poor, limiting the transport of charge between redox sites and the external circuit.In addition, the mechanical strength is low, limiting the achievable electrode thickness, even in the presence of binders. By adding carbon nanotubes to the MnO2-based electrodes, we have increased the conductivity by up to eight orders of magnitude, in line with percolation theory.The nanotube network facilitates charge transport, resulting in large increases in capacitance, especially at high rates, around 1 V/s. The increase in MnO2 specific capacitance scaled with nanotube content in a manner fully consistent with percolation theory. Importantly, the mechanical robustness was significantly enhanced, allowing the fabrication of electrodes that were 10 times thicker than could be achieved in MnO2-only films. This resulted in composite films with areal capacitances up to 40 times higher than could be achieved with MnO2-only electrodes.
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