Exfoliation of Two-Dimensional Nanosheets of Metal Diborides
Ahmed Yousaf, Matthew S. Gilliam, Shery L. Y. Chang, Mathias Augustin, Yuqi Guo, Fraaz Tahir, Meng Wang, Alexandra Schwindt, Ximo S. Chu, Duo O. Li, Suneet Kale… 展开作者
Ahmed Yousaf, Matthew S. Gilliam, Shery L. Y. Chang, Mathias Augustin, Yuqi Guo, Fraaz Tahir, Meng Wang, Alexandra Schwindt, Ximo S. Chu, Duo O. Li, Suneet Kale, Abhishek Debnath, Yongming Liu, Matthew D. Green, Elton J. G. Santos, Alexander A. Green, Qing Hua Wang
The metal diborides are a class of ceramic materials with crystal structures consisting of hexagonal sheets of boron atoms alternating with planes of metal atoms held together with mixed character ionic/covalent bonds. Many of the metal diborides are ultrahigh temperature ceramics like HfB$_2$, TaB$_2$, and ZrB$_2$, which have melting points above 3000$^\circ$C, high mechanical hardness and strength at high temperatures, and high chemical resistance, while MgB$_2$ is a superconductor with a transition temperature of 39 K. Here we demonstrate that this diverse family of non-van der Waals materials can be processed into stable dispersions of two-dimensional (2D) nanosheets using ultrasonication-assisted exfoliation. We generate 2D nanosheets of the metal diborides AlB$_2$, CrB$_2$, HfB$_2$, MgB$_2$, NbB$_2$, TaB$_2$, TiB$_2$, and ZrB$_2$, and use electron and scanning probe microscopies to characterize their structures, morphologies, and compositions. The exfoliated layers span up to micrometers in lateral dimension and reach thicknesses down to 2-3 nm, while retaining their hexagonal atomic structure and chemical composition. We exploit the convenient solution-phase dispersions of exfoliated CrB$_2$ nanosheets to incorporate them directly into polymer composites. In contrast to the hard and brittle bulk CrB$_2$, we find that CrB$_2$ nanocomposites remain very flexible and simultaneously provide increases in the elastic modulus and the ultimate tensile strength of the polymer. The successful liquid-phase production of 2D metal diborides enables their processing using scalable low-temperature solution-phase methods, extending their use to previously unexplored applications, and reveals a new family of non-van der Waals materials that can be efficiently exfoliated into 2D forms.
Manganese oxide nanosheets were synthesized using liquid phase exfoliation that achieved suspensions in isopropanol with concentrations of up to 0.45 mg/ml. A study of solubility parameters showed that the exfoliation was optimum in DMF followed by isopropanol and diethylene glycol. Isopropanol was the solvent of choice due to its environmentally friendly nature and ease of use for further processing. The 2D hybrid was synthesized in isopropanol suspensions with concentrations of up to 0.5 mg/ml and demonstrated stability against reaggregation for up to six months. The coexfoliation was found …
Bulk quantities of graphene nanosheets and nanodots have been selectively fabricated by mechanical grinding exfoliation of natural graphite in a small quantity of ionic liquids. The resulting graphene sheets and dots are solvent free with low levels of naturally absorbed oxygen, inherited from the starting graphite. The sheets are only two to five layers thick. The graphene nanodots have diameters in the range of 9-29 nm and heights in the range of 1-16 nm, which can be controlled by changing the processing time.
Liquid-phase exfoliation of two-dimensional materials is very attractive for large-scale applications. Although used extensively, isolating MoS2 layers (<10) with high efficiency is reported to be extremely difficult. Further, the importance of soaking has not yet been studied, and the surfactants' role in stabilizing MoS2 nanosheets is poorly understood1. Herein, we report a novel approach to exfoliating large quantities of MoS2 via high-pressure (HP) liquid-phase exfoliation (LPE) in deionized (DI) water. 4 to 7 layers of MoS2 nanosheets were obtained from 60 days-soaked samples and they wer…
Few layer black phosphorus is a new two-dimensional material which is of great interest for applications, mainly in electronics. However, its lack of stability severely limits our ability to synthesise and process this material. Here we demonstrate that high-quality, few-layer black phosphorus nanosheets can be produced in large quantities by liquid phase exfoliation in the solvent N-cyclohexyl-2-pyrrolidone (CHP). We can control nanosheet dimensions and have developed metrics to estimate both nanosheet size and thickness spectroscopically. When exfoliated in CHP, the nanosheets are remarkably…
Solution dispersions of two-dimensional (2D) black phosphorus (BP), often referred to as phosphorene, are achieved by solvent exfoliation. These pristine, electronic-grade BP dispersions are produced with anhydrous, organic solvents in a sealed tip ultrasonication system, which circumvents BP degradation that would otherwise occur via solvated oxygen or water. Among conventional solvents, n-methyl-pyrrolidone (NMP) is found to provide stable, highly concentrated (~0.4 mg/mL) BP dispersions. Atomic force microscopy, scanning electron microscopy, transmission electron microscopy, Raman spectrosc…
Producing monolayers and few-layers in high yield with environment-stability is still a challenge in hafnium disulphide (HfS2), which is a layered two-dimensional material of group-IV transition metal dichalcogenides, to reveal its unlocked electronic and optoelectronic applications. For the first time, to the best of our knowledge, we demonstrate a simple and cost-effective method to grow layered belt-like nano-crystals of HfS2 with surprisingly large interlayer spacing followed by its chemical exfoliation. Various microscopic and spectroscopic techniques reveal these as-grown crystals exfoli…
The rational design of transition metal dichalcogenide electrocatalysts for efficiently catalyzing hydrogen evolution reaction (HER) is believed to lead to the generation of a renewable energy carrier. To this end our work has made three main contributions. At first, we have demonstrated that exfoliation via ionic liquid assisted grinding combined with gradient centrifugation is an efficient method to exfoliate bulk WS2 to nanosheets with a thickness of a few atomic layers and lateral size dimensions in the range of 100 nm to 2 nm. These WS2 nanosheets decorated with scattered nanodots exhibit…
Ultrathin two-dimensional nanosheets raise a rapidly increasing interest due to their unique dimensionality-dependent properties. Most of the two-dimensional materials are obtained by exfoliation of layered bulk materials or are grown on substrates by vapor deposition methods. To produce free-standing nanosheets, solution-based colloidal methods are emerging as promising routes. In this work, we demonstrate ultrathin CdSe nanosheets with controllable size, shape and phase. The key of our approach is the use of halogenated alkanes as additives in a hot-injection synthesis. Increasing concentrat…
Surfactants are often used to stabilise two-dimensional (2D) materials in environmentally friendly solvents such as water. Aqueous-surfactant solutions prevent agglomeration of nanosheets through steric and electrostatic repulsion, facilitating the production of high concentration nanomaterial dispersions. Turbulent, shear-assisted liquid exfoliation of layered precursor materials produces defect-free nanosheets by promoting mixing and generating sufficiently high shear rates to overcome out-of-plane van der Waals bonds. In the presence of a liquid-gas interface, a consequence of using surfact…
We report the isolation of thin flakes of cylindrite, a naturally occurring van der Waals superlattice, by means of mechanical and liquid phase exfoliation. We find that this material is a heavily doped p-type semiconductor with a narrow gap (<0.85 eV) with intrinsic magnetic interactions that are preserved even in the exfoliated nanosheets. Due to its environmental stability and high electrical conductivity, cylindrite can be an interesting alternative to the existing two-dimensional magnetic materials.
Nano-thick metallic transition metal dichalcogenides such as VS$_{2}$ are essential building blocks for constructing next-generation electronic and energy-storage applications, as well as for exploring unique physical issues associated with the dimensionality effect. However, such 2D layered materials have yet to be achieved through either mechanical exfoliation or bottom-up synthesis. Herein, we report a facile chemical vapor deposition route for direct production of crystalline VS$_{2}$ nanosheets with sub-10 nm thicknesses and domain sizes of tens of micrometers. The obtained nanosheets fea…
Solution processable two-dimensional (2D) materials have provided an ideal platform for both fundamental studies and wearable electronic applications. Apart from graphene and 2D dichalcogenides, IVA-VI monochalcogenides (MMCs) has emerged recently as a promising candidate for next generation electronic applications. However, the dispersion behavior, which is crucial for the quality, solubility and stability of MMCs, has been quite unexplored. Here, the exfoliation and the dispersion behavior of Germanium (II) monosulfide (GeS) and Tin (II) monosulfide (SnS) nanosheets has been investigated in …
Thin films of noble-metal-based transition metal dichalcogenides, such as PtSe$_2$, have attracted increasing attention due to their interesting layer-number dependent properties and application potential. While it is difficult to cleave bulk crystals down to mono- and few-layers, a range of growth techniques have been established producing material of varying quality and layer number. However, to date, no reliable high-throughput characterization to assess layer number exists. Here, we use top-down liquid phase exfoliation (LPE) coupled with centrifugation to produce widely basal plane defect…
The current family of experimentally realized two-dimensional magnetic materials consist of 3$d$ transition metals with very weak spin-orbit coupling. In contrast, we report a new platform in a chemically bonded and layered 4$d$ oxide, with strong electron correlations and competing spin-orbit coupling. We synthesize ultra-thin sheets of SrRu$_2$O$_6$ using scalable liquid exfoliation. These exfoliated sheets are characterized by complementary experimental and theoretical techniques. The thickness of the nano-sheets varies between three to five monolayers, and within the first-principles calcu…
