Polymer/layered silicate nanocomposites: a review from preparation to processing

Graphene’s success has shown that it is possible to create stable, single and few-atom-thick layers of van der Waals materials, and also that these materials can exhibit fascinating and technologically useful properties. Here we review the state-of-the-art of 2D materials beyond graphene. Initially, we will outline the different chemical classes of 2D materials and discuss the various strategies to prepare single-layer, few-layer, and multilayer assembly materials in solution, on substrates, and on the wafer scale. Additionally, we present an experimental guide for identifying and characterizing single-layer-thick materials, as well as outlining emerging techniques that yield both local and global information. We describe the differences that occur in the electronic structure between the bulk and the single layer and discuss various methods of tuning their electronic properties by manipulating the surface. Finally, we highlight the properties and advantages of single-, few-, and many-layer 2D materials in...

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Progress, Challenges, and Opportunities in Two-Dimensional Materials Beyond Graphene

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

Herein we report on the synthesis of two-dimensional transition metal carbides and carbonitrides by immersing select MAX phase powders in hydrofluoric acid, HF. The MAX phases represent a large (>60 members) family of ternary, layered, machinable transition metal carbides, nitrides, and carbonitrides. Herein we present evidence for the exfoliation of the following MAX phases: Ti2AlC, Ta4AlC3, (Ti0.5,Nb0.5)2AlC, (V0.5,Cr0.5)3AlC2, and Ti3AlCN by the simple immersion of their powders, at room temperature, in HF of varying concentrations for times varying between 10 and 72 h followed by sonication. The removal of the “A” group layer from the MAX phases results in 2-D layers that we are labeling MXenes to denote the loss of the A element and emphasize their structural similarities with graphene. The sheet resistances of the MXenes were found to be comparable to multilayer graphene. Contact angle measurements with water on pressed MXene surfaces showed hydrophilic behavior.

Two-dimensional transition metal carbides.

Layered double hydroxides (LDHs) are a class of ionic lamellar compounds made up of positively charged brucite-like layers with an interlayer region containing charge compensating anions and solvation molecules. Delamination of LDHs is an interesting route for producing positively charged thin platelets with a thickness of a few atomic layers, which can be used as nanocomposites for polymers or as building units for making new designed organic-inorganic or inorganic-inorganic nanomaterials. The synthesis of nanosized LDH platelets can be generally classified into two approaches, bottom-up and top-down. It requires modification of the LDH interlamellar environment and then selection of an appropriate solvent system. In DDS intercalated LDHs, the aliphatic tails of the DDS- anions exhibit a high degree of interdigitation in order to maximize guest-guest dispersive interactions. Bellezza reported that the LDH colloids can also been obtained by employing a reverse microemulsion approach.

Recent advances in the synthesis and application of layered double hydroxide (LDH) nanosheets.

Basic Properties of Mg2+1-xAl3+x Layered Double Hydroxides Intercalated by Carbonate, Hydroxide, Chloride, and Sulfate Anions

Layered materials with intracrystalline reactivity undergo intercalation and pillaring reactions to produce materials with useful properties for catalysis, electrodes for Li batteries and adsorbents. New possibilities for the use of layered inorganic solids came out from the layered structures capable of delamination. The exfoliated particles are considered a new class of nanomaterial based on single crystal nanosheets. Due to their unique morphological features and properties, these nanosheets can be used as building blocks for nanomaterials with innovative properties. In this feature article we describe the aspects related to layered niobate exfoliation and the new possibilities that arises from the use of niobate nanosheets in the manufacturing of thin films, layer-by-layer (LbL) assemblies, hybrid structures, sensors and other materials.

Layered niobate nanosheets: building blocks for advanced materials assembly

The polymerization of aniline intercalated into montmorillonite clay was monitored by in situ UV−vis−NIR and resonance Raman spectroscopies and in situ small-angle X-ray scattering. In the initial stages of the polymerization, it is observed the PANI−ES polaronic band at 750 nm in the UV−vis−NIR spectrum and also the characteristic PANI-ES resonance Raman spectrum (excited at 632.8 nm), which indicate that the head-to-tail coupling reactions between anilinium radical cations are occurring. Nevertheless, the resonance Raman spectrum excited at 488.0 nm presents bands at 1211, 1370, 1455, and 1608 cm-1, assigned to the benzidine dication species, which suggests that tail-to-tail coupling reactions are also occurring. In the final stages of polymerization, the presence of electronic absorption bands at 670 and 620 nm indicates the formation of new chromophoric species, which is also confirmed by its peculiar resonance Raman spectrum at 632.8 nm wavelength. The in situ SAXS results show that, during the anili...

Aniline Polymerization into Montmorillonite Clay: A Spectroscopic Investigation of the Intercalated Conducting Polymer

The specific activities of catalysts formed by thermal activation of the layered double hydroxide [Mg2.34Al (OH)6.68] (CO3)0.5·2.6H2O have been determined using 2-methyl-3-butyn-2-ol (MBOH) as an acid/base-selective substrate. Acetone and acetylene were the only reaction products formed over the temperature range 80–150°C, demonstrating that all of the LDHderived catalysts have highly basic selectivities. Thermal activation below the structural decomposition point of the LDH (⩽250°C) afforded catalysts with specific activities approximately an order of magnitude larger than the amorphous metal oxides and crystalline MgAl2U4 spinel-MgO mixtures formed by thermal activation at 450 and 890°C, respectively. Even the remnant LDH structure formed by partial decarbonation/dehydroxylation at 350°C was substantially more active than the more commonly used metal oxide derivatives.

Vera R. L. Constantino

Papers

Basic Properties of Mg2+1-xAl3+x Layered Double Hydroxides Intercalated by Carbonate, Hydroxide, Chloride, and Sulfate Anions

Layered niobate nanosheets: building blocks for advanced materials assembly

Aniline Polymerization into Montmorillonite Clay: A Spectroscopic Investigation of the Intercalated Conducting Polymer

Structure-reactivity relationships for basic catalysts derived from a Mg2+/A13+ /CO 3 ? layered double hydroxide

Adsorption of Acid Yellow 42 dye on calcined layered double hydroxide: Effect of time, concentration, pH and temperature