Ultrathin two-dimensional nanosheets of layered transition metal dichalcogenides (TMDs) are fundamentally and technologically intriguing. In contrast to the graphene sheet, they are chemically versatile. Mono- or few-layered TMDs - obtained either through exfoliation of bulk materials or bottom-up syntheses - are direct-gap semiconductors whose bandgap energy, as well as carrier type (n- or p-type), varies between compounds depending on their composition, structure and dimensionality. In this Review, we describe how the tunable electronic structure of TMDs makes them attractive for a variety of applications. They have been investigated as chemically active electrocatalysts for hydrogen evolution and hydrosulfurization, as well as electrically active materials in opto-electronics. Their morphologies and properties are also useful for energy storage applications such as electrodes for Li-ion batteries and supercapacitors.

http://nanotubes.rutgers.edu/PDFs/nchem_TMDs_2013.pdf

The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets

If they could be easily exfoliated, layered materials would become a diverse source of two-dimensional crystals whose properties would be useful in applications ranging from electronics to energy storage. We show that layered compounds such as MoS2, WS2, MoSe2, MoTe2, TaSe2, NbSe2, NiTe2, BN, and Bi2Te3 can be efficiently dispersed in common solvents and can be deposited as individual flakes or formed into films. Electron microscopy strongly suggests that the material is exfoliated into individual layers. By blending this material with suspensions of other nanomaterials or polymer solutions, we can prepare hybrid dispersions or composites, which can be cast into films. We show that WS2 and MoS2 effectively reinforce polymers, whereas WS2/carbon nanotube hybrid films have high conductivity, leading to promising thermoelectric properties.

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Two-Dimensional Nanosheets Produced by Liquid Exfoliation of Layered Materials

Graphene-Like Two-Dimensional Materials

Since the discovery of mechanically exfoliated graphene in 2004, research on ultrathin two-dimensional (2D) nanomaterials has grown exponentially in the fields of condensed matter physics, material science, chemistry, and nanotechnology. Highlighting their compelling physical, chemical, electronic, and optical properties, as well as their various potential applications, in this Review, we summarize the state-of-art progress on the ultrathin 2D nanomaterials with a particular emphasis on their recent advances. First, we introduce the unique advances on ultrathin 2D nanomaterials, followed by the description of their composition and crystal structures. The assortments of their synthetic methods are then summarized, including insights on their advantages and limitations, alongside some recommendations on suitable characterization techniques. We also discuss in detail the utilization of these ultrathin 2D nanomaterials for wide ranges of potential applications among the electronics/optoelectronics, electrocat...

Recent Advances in Ultrathin Two-Dimensional Nanomaterials

Background Since at least 400 C.E., when the Mayans first used layered clays to make dyes, people have been harnessing the properties of layered materials. This gradually developed into scientific research, leading to the elucidation of the laminar structure of layered materials, detailed understanding of their properties, and eventually experiments to exfoliate or delaminate them into individual, atomically thin nanosheets. This culminated in the discovery of graphene, resulting in a new explosion of interest in two-dimensional materials. Layered materials consist of two-dimensional platelets weakly stacked to form three-dimensional structures. The archetypal example is graphite, which consists of stacked graphene monolayers. However, there are many others: from MoS 2 and layered clays to more exotic examples such as MoO 3 , GaTe, and Bi 2 Se 3 . These materials display a wide range of electronic, optical, mechanical, and electrochemical properties. Over the past decade, a number of methods have been developed to exfoliate layered materials in order to produce monolayer nanosheets. Such exfoliation creates extremely high-aspect-ratio nanosheets with enormous surface area, which are ideal for applications that require surface activity. More importantly, however, the two-dimensional confinement of electrons upon exfoliation leads to unprecedented optical and electrical properties. Liquid exfoliation of layered crystals allows the production of suspensions of two-dimensional nanosheets, which can be formed into a range of structures. (A) MoS 2 powder. (B) WS 2 dispersed in surfactant solution. (C) An exfoliated MoS 2 nanosheet. (D) A hybrid material consisting of WS 2 nanosheets embedded in a network of carbon nanotubes. Advances An important advance has been the discovery that layered crystals can be exfoliated in liquids. There are a number of methods to do this that involve oxidation, ion intercalation/exchange, or surface passivation by solvents. However, all result in liquid dispersions containing large quantities of nanosheets. This brings considerable advantages: Liquid exfoliation allows the formation of thin films and composites, is potentially scaleable, and may facilitate processing by using standard technologies such as reel-to-reel manufacturing. Although much work has focused on liquid exfoliation of graphene, such processes have also been demonstrated for a host of other materials, including MoS 2 and related structures, layered oxides, and clays. The resultant liquid dispersions have been formed into films, hybrids, and composites for a range of applications. Outlook There is little doubt that the main advances are in the future. Multifunctional composites based on metal and polymer matrices will be developed that will result in enhanced mechanical, electrical, and barrier properties. Applications in energy generation and storage will abound, with layered materials appearing as electrodes or active elements in devices such as displays, solar cells, and batteries. Particularly important will be the use of MoS 2 for water splitting and metal oxides as hydrogen evolution catalysts. In addition, two-dimensional materials will find important roles in printed electronics as dielectrics, optoelectronic devices, and transistors. To achieve this, much needs to be done. Production rates need to be increased dramatically, the degree of exfoliation improved, and methods to control nanosheet properties developed. The range of layered materials that can be exfoliated must be expanded, even as methods for chemical modification must be developed. Success in these areas will lead to a family of materials that will dominate nanomaterials science in the 21st century.

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Liquid Exfoliation of Layered Materials

Large‐Scale Fabrication of Boron Nitride Nanosheets and Their Utilization in Polymeric Composites with Improved Thermal and Mechanical Properties

Large-Scale Fabrication of Boron Nitride Nanosheets and Their Utilization in Polymeric Composites with Improved Thermal and Mechanical Properties

Ultilizing boron nitride nanotubes (BNNTs) as fillers, composites are fabricated with poly(methyl methacrylate), polystyrene, poly(vinyl butyral), or poly(ethylene vinyl alcohol) as the matrix and their thermal, electrical, and mechanical properties are evaluated. More than 20-fold thermal conductivity improvement in BNNT-containing polymers is obtained, and such composites maintain good electrical insulation. The coefficient of thermal expansion (CTE) of the BNNT-loaded polymers is dramatically reduced because of interactions between the polymer chains and the nanotubes. Moreover, the composites possess good mechanical properties, as revealed by Vickers microhardness tests. This detailed study indicates that BNNTs are very promising nanofillers for polymeric composites, allowing the simultaneous achievement of high thermal conductivity, low CTE, and high electrical resistance, as required for novel and efficient heat-releasing materials.

Towards Thermoconductive, Electrically Insulating Polymeric Composites with Boron Nitride Nanotubes as Fillers

Highly faceted wurtzite-type ZnS nanotubes with hexagonal cross-section morphologies have been self-assembled via a controllable high-temperature thermal-chemical reaction route in work reported by Yin and co-workers on p. 1972. The self-assembly growth along c-axis to highly hexagonal-faceted ZnS single-crystalline nanotubes is associated with the crystallographic characteristics, such as the non-central and polar surfaces of the wurtzite-type ZnS structure. The faceted ZnS nanotubes grow along the direction, and are closed by low-index faces of non-polar {1000} faces. The inside cover and insets show electron microscopy and scanning electron microscopy images of the faceted ZnS nanotubes.

Inside Front Cover: Self‐Assembled Highly Faceted Wurtzite‐Type ZnS Single‐Crystalline Nanotubes with Hexagonal Cross‐Sections (Adv. Mater. 16/2005)

A novel metal–insulator heterostructure made of twinned Ga2O3 nanowires embedding discrete gold particles along the twin boundary was formed through a reaction between gold, gallium, and silica at 800 °C during simple thermal annealing. The Au-in-Ga2O3 peapods spontaneously crystallized under phase separation induced by the formation of twin boundaries. The nanostructures were analyzed by field emission scanning (FESEM) and transmission electron microscopes (FETEM), and their photoresponse was investigated using a double-frequency Nd:YAG laser with a wavelength of 532 nm on a designed single-nanowire device. The surface plasmon resonance (SPR) effects of embedded Au nanoparticles are proposed to be responsible for the remarkable photoresponse of these novel structures.

Dimitri Golberg

Papers

Large‐Scale Fabrication of Boron Nitride Nanosheets and Their Utilization in Polymeric Composites with Improved Thermal and Mechanical Properties

Large-Scale Fabrication of Boron Nitride Nanosheets and Their Utilization in Polymeric Composites with Improved Thermal and Mechanical Properties

Towards Thermoconductive, Electrically Insulating Polymeric Composites with Boron Nitride Nanotubes as Fillers

Inside Front Cover: Self‐Assembled Highly Faceted Wurtzite‐Type ZnS Single‐Crystalline Nanotubes with Hexagonal Cross‐Sections (Adv. Mater. 16/2005)

Nanophotonic Switch: Gold-in-Ga 2 O 3 Peapod Nanowires