Mechanical exfoliation of large area 2D materials from vdW crystals

Monolayer two-dimensional (2D) materials, such as graphene and transition metal dichalcogenides (TMDCs), provide a versatile platform for exploring novel physical phenomena at the 2D limit, and show great promise for next-generation electronic, optoelectronic, and quantum devices. To overcome the weak van der Waals interaction in the bulk layered crystal and achieve high quality single-crystal monolayers is a crucial task in top-down mechanical exfoliation. Tape exfoliation has long been the dominant approach to obtain single-crystal monolayers with high quality. More recently, there has been a fast development of using metals as an intermediate to enhance monolayer area and exfoliation yield. This review will provide a survey of mechanical exfoliation strategies of tape and metal-assisted exfoliations, particularly for the most popular graphene and TMDC materials. The interfacial interaction and lateral strain between monolayer and other materials such as oxides and metals play a crucial role in monolayer selectivity and yield. The challenges and opportunities will be highlighted for future development of exfoliating procedures to achieve large-area and high-quality 2D material monolayers and artificial stacks.     

Luminescent and Magnetic Tb-MOF Flakes Deposited on Silicon

The synthesis of a terbium-based 2D metal–organic framework (MOF), of formula [Tb(MeCOO)(PhCOO)₂] (1), a crystalline material formed by neutral nanosheets held together by Van der Waals interactions, is presented. The material can be easily exfoliated by sonication and deposited onto different substrates. Uniform distributions of Tb-2D MOF flakes onto silicon were obtained by spin-coating. We report the luminescent and magnetic properties of the deposited flakes compared with those of the bulk. Complex 1 is luminescent in the visible and has a sizeable quantum yield of QY = 61% upon excitation at 280 nm. Photoluminescence measurements performed using a micro-Raman set up allowed us to characterize the luminescent spectra of individual flakes on silicon. Magnetization measurements of flakes-on-silicon with the applied magnetic field in-plane and out-of-plane display anisotropy. Ac susceptibility measurements show that 1 in bulk exhibits field-induced slow relaxation of the magnetization through two relaxation paths and the slowest one, with a relaxation time of τ_lf ≈ 0.5 s, is assigned to a direct process mechanism. The reported exfoliation of lanthanide 2D-MOFs onto substrates is an attractive approach for the development of multifunctional materials and devices for different applications.     

Stacking of Exfoliated Two‐Dimensional Materials: A Review

In recent years, two‐dimensional (2D) atomic crystals represented by graphene have opened up new fields of 2D physics. Layered materials with atomic layer thickness are self‐assembled into van der Waals heterostructures by weak van der Waals forces without considering lattice matching. Van der Waals heterostructures can not only enhance the performance of its constituent materials but also show new characteristics. High‐quality heterostructures require mechanically cleaved intrinsic 2D materials and flexible 2D material stacking techniques. Here, we summarize in detail the reliable exfoliation methods for large‐area single‐layer 2D materials and the dry and wet stacking techniques with high success rates. The twisted bilayer graphene is used as an example to briefly introduce the single‐crystal tearing method, which is currently the most practical method for preparing isotropic twisted heterostructures with high‐precision rotation angles. We hope to provide a valuable reference for researchers of 2D materials.     

Noncovalent Functionalization of Black Phosphorus

Black phosphorus (BP) was functionalized with organic moieties on the basis of liquid exfoliation. The treatment of BP with electron‐withdrawing 7,7,8,8‐tetracyano‐p‐quinodimethane (TCNQ) led to electron transfer from BP to the organic dopant. On the other hand, the noncovalent interaction of BP with a perylene diimide was mainly due to van der Waals interactions but also led to considerable stabilization of the BP flakes against oxygen degradation.     

Jahn–Teller Disproportionation Induced Exfoliation of Unit-Cell Scale ϵ-MnO2

Exfoliation of non-layered (structurally) bulk materials at the nanoscale is challenging because of the strong chemical bonds in the lattice, as opposed to the weak van der Waals (vdW) interactions in layered materials. We propose a top-down method to exfoliate ϵ-MnO₂ nanosheets in a family of charge-ordered La_1−xAE_xMnO₃ (AE=Ca, Sr, Ba) perovskites, taking advantage of the Jahn–Teller disproportionation effect of Mn³⁺ and bond-strength differences. ϵ-MnO₂ crystallized into a nickel arsenide (NiAs) structure, with a thickness of 0.91 nm, displays thermal metastability and superior water oxidation activity compared to other manganese oxides. The exfoliation mechanism involves a synergistic proton-induced Mn³⁺ disproportionation and structural reconstruction. The synthetic method could also be potentially extended to the exfoliation of other two-dimensional nanosheet materials with non-layered structures.     

二维材料范德华间隙的利用

Since their discovery, two-dimensional (2D) materials have attracted significant research attention owing to their excellent and controllable physical and chemical properties. These materials have emerged rapidly as important material system owing to their unique properties such as electricity, optics, quantum properties, and catalytic properties. 2D materials are mostly bonded by strong ionic or covalent bonds within the layers, and the layers are stacked together by van der Waals forces, thereby making it possible to peel off 2D materials with few or single layers. The weak interaction between the layers of 2D materials also enables the use of van der Waals gaps for regulating the electronic structure of the system and further optimizing the material properties. The introduction of guest atoms can significantly change the interlayer spacing of the original material and coupling strength between the layers. Also, interaction between the guest and host atom also has the potential to change the electronic structure of the original material, thereby affecting the material properties. For example, the electron structure of a host can be modified by interlayer guest atoms, and characteristics such as carrier concentration, optical transmittance, conductivity, and band gap can be tuned. Organic cations intercalated between the layers of 2D materials can produce stable superlattices, which have great potential for developing new electronic and optoelectronic devices. This method enables the modulation of the electrical, magnetic, and optical properties of the original materials, thereby establishing a family of 2D materials with widely adjustable electrical and optical properties. It is also possible to introduce some new properties to the 2D materials, such as magnetic properties and catalytic properties, by the intercalation of guest atoms. Interlayer storage, represented by lithium-ion batteries, is also an important application of 2D van der Waals gap utilization in energy storage, which has also attracted significant research attention. Herein, we review the studies conducted in recent years from the following aspects: (1) changing the layer spacing to change the interlayer coupling; (2) introducing the interaction between guest and host atoms to change the physico-chemical properties of raw materials; (3) introducing the guest substances to obtain new properties; and (4) interlayer energy storage. We systematically describe various interlayer optimization methods of 2D van der Waals gaps and their effects on the physical and chemical properties of synthetic materials, and suggest the direction of further development and utilization of 2D van der Waals gaps.     

Poly(methyl methacrylate)-Assisted Exfoliation of Graphite and Its Use in Acrylonitrile-Butadiene-Styrene Composites

One of the applications of graphene in which its scalable production is of utmost importance is the development of polymer composites. Among the techniques used to produce graphene flakes, the liquid-phase exfoliation (LPE) of graphite stands out due to its versatility and scalability. However, solvents suitable for the LPE process are generally toxic and have a high boiling point, making the processing challenging. The use of low boiling point solvents could be convenient for the processing, due to the easiness of their removal. In this study, the use of poly(methyl methacrylate) (PMMA) as a stabilizing agent is proposed for the production of graphene flakes in a low boiling point solvent, that is, acetone. The graphene dispersions produced in the mixture acetone-PMMA have higher concentration, +175 %, and contain a higher percentage of few-layer graphene flakes (<5 layers), that is, +60 %, compared to the dispersions prepared in acetone. The as-produced graphene dispersions are used to develop graphene/acrylonitrile-butadiene-styrene composites. The mechanical properties of the pristine polymer are improved, that is, +22 % in the Young's modulus, by adding 0.01 wt. % of graphene flakes. Moreover, a decrease of ≈20 % in the oxygen permeability is obtained by using 0.1 wt. % of graphene flakes filler, compared to the unloaded matrix.     

基于自组装技术的纳米功能材料研究进展

纳米自组装技术的迅速发展拓宽了纳米材料的应用领域. 利用自组装合成纳米新材料是一种有效且具有发展前景的方法. 本综述介绍了纳米自组装技术的研究价值及近年来新兴的制备方法, 重点论述了驱动纳米自组装的作用类型, 包括范德华力、 静电作用、 磁力作用、 氢键、 熵效应以及疏溶剂相互作用、 DNA碱基互补配对等其它相互作用, 同时也对纳米自组装体的应用情况进行了阐述, 并探讨了利用纳米自组装技术研制新材料所面临的机遇和挑战.     

Thermal conductivity of exfoliated graphite nanocomposites

Since the late 1990’s, research has been reported where intercalated, expanded, and/or exfoliated graphite nanoflakes could also be used as reinforcements in polymer systems. The key point to utilizing graphite as a platelet nanoreinforcement is in the ability to exfoliate graphite using Graphite Intercalated Compounds (GICs). Natural graphite is still abundant and its cost is quite low compared to the other nano–size carbon materials, the cost of producing graphite nanoplatelets is expected to be ~$5/lb. This is significantly less expensive than single wall nanotubes (SWNT) (>$45000/lb) or vapor grown carbon fiber (VGCF) ($40–50/lb), yet the mechanical, electrical, and thermal properties of crystalline graphite flakes are comparable to those of SWNT and VGCF. The use of exfoliated graphite flakes (xGnP) opens up many new applications where electromagnetic shielding, high thermal conductivity, gas barrier resistance or low flammability are required. A special thermal treatment was developed to exfoliate graphite flakes for the production of nylon and high density polypropylene nanocomposites. X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to assess the degree of exfoliation of the graphite platelets and the morphology of the nanocomposites. The thermal conductivity of these composites was investigated by three different methods, namely, by DSC, modified hot wire, and halogen flash lamp methods. The addition of small amounts of exfoliated graphite flakes showed a marked improvement in thermal and electrical conductivity of the composites.     

Determination of van der Waals forces in monolayer films of lipids & biopolymers. Equation of state for two-dimensional films

Amphiphile molecules are characterized by the dual property arising from the interactions between the apolar [alkyl] and the polar part and the surrounding solvent, i.e., water. In assemblies which amphiphiles form in diverse systems, e.g., micelles, soap bubbles, monolayers or bilayers at interfaces, the attractive forces are attributed to the van der Waals forces. It is not easy to estimate the magnitude of van der Waals forces in some of these systems by any direct method.The magnitude of van der Waals forces in spread monolayers of lipids and biopolymers has been reported to be estimated from experimental data. The magnitude of these forces has been estimated by using an equation of state of a very general form, as delineated herein. In the current literature no such attempt has been reported in the analyses of these monolayers spread on aqueous surfaces. These analyses suggest that the predominant surface forces arise from van der Waals interactions, if the magnitude of electrostatic charge repulsions is weak. The equation-of-state as derived indicates that it is useful in providing information about the molecular interaction in monolayers, for both lipids and biopolymers.     

High‐Yield and Damage‐free Exfoliation of Layered Graphdiyne in Aqueous Phase

The two‐dimensional carbon material graphdiyne (GDY) holds great promise as a semiconductor and porous material, however, exfoliation of bulk GDY into single‐ or few‐layered GDY in the aqueous phase remains a challenge. We report an efficient method for the damage‐free exfoliation of bulk GDY into single‐ or few‐layered GDY with high yield in an aqueous solution of inorganic salts (e.g., Li₂SiF₆). This was confirmed by spherical‐aberration‐corrected scanning transmission electron microscopy, scanning/transmission electron microscopy, atomic force microscopy, Fourier transform infrared/Raman spectroscopy, X‐ray photoelectron spectroscopy. The method gives high exfoliation efficiency (75 wt %) without creating additional structural defects or oxides in the exfoliated GDY. Theoretical calculations suggest that non‐covalent adsorption of the anion, diffusion of the cation, and subsequent repulsive forces between adjacent flakes are the main driving force for the efficient exfoliation.     

Exfoliation of 2D Materials for Energy and Environmental Applications

The fascinating properties of single-layer graphene isolated by mechanical exfoliation have inspired extensive research efforts toward two-dimensional (2D) materials. Layered compounds serve as precursors for atomically thin 2D materials (briefly, 2D nanomaterials) owing to their strong intraplane chemical bonding but weak interplane van der Waals interactions. There are newly emerging 2D materials beyond graphene, and it is becoming increasingly important to develop cost-effective, scalable methods for producing 2D nanomaterials with controlled microstructures and properties. The variety of developed synthetic techniques can be categorized into two classes: bottom-up and top-down approaches. Of top-down approaches, the exfoliation of bulk 2D materials into single or few layers is the most common. This review highlights chemical and physical exfoliation methods that allow for the production of 2D nanomaterials in large quantities. In addition, remarkable examples of utilizing exfoliated 2D nanomaterials in energy and environmental applications are introduced.     

Dielectrophoretic placement of quasi-zero-, one-, and two-dimensional nanomaterials into nanogap for electrical characterizations

DEP is one of promising techniques for positioning nanomaterials into the desirable location for nanoelectronic applications. In contrast, the lithography technique is commonly used to make ultra-thin conducting wires and narrow gaps but, due to the limit of patterning resolution, it is not feasible to make electrical contacts on ultra-small nanomaterials for a bottom-up device fabrication. Thus, integrating the lithography and dielectrophoresis, a real bottom-up fabrication can be achieved. In this work, the device with the nanogap in between two nanofinger-electrodes is made using electron-beam lithography from top down and the ultra-small nanomaterials, such as colloidal PbSe quantum dots, polyaniline nanofibers, and reduced-graphene-oxide flakes, are placed in the nanogap by DEP from bottom up. The threshold electric field for the DEP placement of PbSe nanocrystals was roughly estimated to be about 8.3 × 10(4) V/cm under our experimental configuration. After the DEP process, several procedures for reducing contact resistances are attempted and measurements of intrinsic electron transport in versatile nanomaterials are performed. It is experimentally confirmed that electron transport in both PbSe nanocrystal arrays and polyaniline nanofibers agrees well with Prof. Ping Sheng's model of granular metallic conduction. In addition, electron transport in reduced-graphene-oxide flakes follows Mott's 2D variable-range-hopping model. This study illustrates an integration of the electron-beam lithography and the DEP techniques for a precise manipulation of nanomaterials into electronic circuits for characterization of intrinsic properties.     

Hydrogen-bonding versus van der Waals interactions in self-assembled monolayers of substituted isophthalic acids

Self-assembled monolayers of a series of isophthalic acids (5-octadecyloxyisophthalic acid, 5-decyloxyisophthalic acid, 5-hexyloxyisophthalic acid, and 5-pentyloxyisophthalic acid) formed on highly ordered pyrolytic graphite (HOPG) at the solid-liquid interface were studied using scanning tunneling microscopy (STM). Although these molecules have the same dicarboxyl headgroup, their hydrocarbon tails are of different lengths. Hydrogen-bonding between headgroups and van der Waals interactions between the hydrocarbon tails control the final morphology of the monolayer. The STM images show that both van der Waals interactions (vdWs) and hydrogen-bonding (H-B) compete to control the structure, but the final structure of the monolayer is determined by balance between the two interactions.     

High‐Concentration Graphene Dispersions with Minimal Stabilizer: A Scaffold for Enzyme Immobilization for Glucose Oxidation

Modified acrylate polymers are able to effectively exfoliate and stabilize pristine graphene nanosheets in aqueous media. Starting with pre‐exfoliated graphite greatly promotes the exfoliation level. The graphene concentration is significantly increased up to 11 mg mL^?1 by vacuum evaporation of the solvent from the dispersions under ambient temperature. TEM shows that 75 % of the flakes have fewer than five layers with about 18 % of the flakes consisting of monolayers. Importantly, a successive centrifugation and redispersion strategy is developed to enable the formation of dispersions with exceptionally high graphene‐to‐stabilizer ratio. Characterization by high‐resolution transmission electron microscopy, X‐ray photoelectron spectroscopy, X‐ray diffraction, and Raman spectroscopy shows the flakes to be of high quality with very low levels of defects. These dispersions can act as a scaffold for the immobilization of enzymes applied, for example, in glucose oxidation. The electrochemical current density was significantly enhanced to be approximately six times higher than an electrode in the absence of graphene, thus showing potential applications in enzymatic biofuel cells.     

Functional Molecular Junctions Derived from Double Self‐Assembled Monolayers

Information processing using molecular junctions is becoming more important as devices are miniaturized to the nanoscale. Herein, we report functional molecular junctions derived from double self‐assembled monolayers (SAMs) intercalated between soft graphene electrodes. Newly assembled molecular junctions are fabricated by placing a molecular SAM/(top) electrode on another molecular SAM/(bottom) electrode by using a contact‐assembly technique. Double SAMs can provide tunneling conjugation across the van der Waals gap between the terminals of each monolayer and exhibit new electrical functions. Robust contact‐assembled molecular junctions can act as platforms for the development of equivalent contact molecular junctions between top and bottom electrodes, which can be applied independently to different kinds of molecules to enhance either the structural complexity or the assembly properties of molecules.     

Electron Transfer through Monolayers of Mixed Long-chain Aliphatic Acids and Alcohols

Properties of monolayers of cetyl, stearyl, and eicosyl alcohols and stearic and behenic acids and their mixtures are studied, along with the kinetics of a redox reaction of hemin adsorbed on these monolayers. Three-dimensional computer models of corresponding monolayers are constructed and compared with their electrochemical behavior. Properties of monolayers of cetyl alcohol in acid and alkaline solutions and stearyl alcohol in acid solutions correspond to package of molecules in a stretched conformation oriented normally to the electrode surface; for the other one-component systems, the monolayer structure is less regular. The hemin redox reaction rate has no correlation whatsoever with the monolayer thickness and is defined by the length of the electron transfer path (over a chain of covalent bonds and through van der Waals contacts between molecules). The stronger the deviation of the conformation of molecules from the stretched one, the shorter the effective path of the electron transfer. In mixed films of stearic acid and cetyl alcohol (1 : 6), it is sometimes possible to keep molecules of stearic acid in a stretched conformation, thus inhibiting the electron transfer along the hydrocarbon chain of this molecule to a maximum extent. The other mixed systems, while making the conformation more stretched, fail to provide for a completely regular structure.     

微波固相剥离法制备功能化石墨烯及其电化学电容性能研究(英文)

通过微波固相剥离氧化石墨制备了功能化石墨烯材料。石墨烯的剥离,是由于微波加热过程中氧化石墨烯片上的官能团分解为CO2和H2O,产生的压力超过了片层间的范德华力。形貌表征显示了石墨烯的有效剥离和纳米孔结构的形成。红外光谱分析结果表明微波剥离的功能化石墨烯仍然有少量的官能团残留。N2等温吸附-脱附测试结果表明样品具有高比表面积(412.9m2·g-1)和大孔容(1.91cm3·g-1)。电化学测试结果表明功能化石墨烯具有良好的电化学电容行为和207.5F·g-1的比电容。     

Making equation of state models predictive: Part 2: An improved PCP-SAFT equation of state

We use the PCP-SAFT equation of state, which is of the Van der Waals type and has a sound physical basis, to predict mixture properties, such as vapor–liquid and liquid–liquid equilibria, as well as excess enthalpies. We use molecular properties, such as dipole moment, quadrupole moment, polarizability and dispersion interaction coefficients, that have been determined quantum mechanically in Part I of this publication and adjust the remaining three pure compound parameters to pure compound data. We finally present a new combination rule for the dispersion energy parameter ? that is based on the quantum mechanically determined data. The predictions based on quantum mechanically determined pure compound properties along with the new combination rule show an improved performance compared to the original PCP-SAFT combination rule.     

Layered inorganic-organic frameworks based on the 2,2-dimethylsuccinate ligand: structural diversity and its effect on nanosheet exfoliation and magnetic properties

The structures of four new 2,2-dimethylsuccinate frameworks suitable for exfoliation into nanosheets using ultrasonication are reported. These hybrid compounds contain either monovalent (Li(+)) or divalent (Co(2+) and Zn(2+)) cations, and they all feature hydrophobically capped covalently bonded layers that only interact with each other via weak van der Waals forces. Critically this shows that the use of this dicarboxylate ligand generally yields two dimensional compounds suitable for simple and affordable nanosheet exfoliation. This extends the range of frameworks that can be exfoliated and highlights the 2,2-dimethylsuccinate ligand as an excellent versatile platform for the production of nanosheets. The topologies of the layers in each framework were found to vary significantly and this appears to have a significant effect on the relative size of the nanosheets produced; increased space between methyl groups and more extensive inorganic connectivity appears to favour the formation of thin nanosheets with larger lateral dimensions. Additionally the magnetic properties of two of these frameworks were examined, and it was found that both exhibit strong low dimensional antiferromagnetic coupling despite their well-separated layers preventing three dimensional magnetic order.