Direct Liquid-phase Exfoliation Research Articles

One-step simultaneous liquid phase exfoliation-induced chirality in graphene and their chirality-mediated microRNA delivery.

Graphene (G) has established itself as an exciting prospect for a broad range of applications owing to its remarkable properties. Recent innovations in chiral nanosystems have led to sensors, drug delivery, catalysis, etc. owing to the stereospecific interactions between various nanosystems and enantiomers. As the molecular structure of G itself is achiral introducing chirality in G by simple attachment of a functional group (a chiral ligand) on the G nanosheet may result in more diverse applications. Herein, we demonstrate direct liquid phase exfoliation and chiral induction in G nanosheets abbreviated as l-graphene and d-graphene in the presence of chiral l-tyrosine and d-tyrosine and by applying high-temperature sonication. The obtained exfoliated nanosheets demonstrated stable chirality confirmed by circular dichroism. Fourier transform infrared (FTIR) spectra, Raman spectroscopy, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and differential scanning calorimetry (DSC) showed functional, structural, morphological, surface, and thermal characteristics of l-graphene and d-graphene. The hemo-compatibility of these chiral graphenes was evaluated for the very first time utilizing human red blood cells. Lastly, for the very first time, an attempt was made to explore enantiomeric binding between chiral l-graphene and d-graphene with microRNA (miR-205) and their possibility towards chirality-mediated gene delivery in prostate cancerous cells.

Revisiting Solution-Based Processing of van der Waals Layered Materials for Electronics.

Following the significant discovery of van der Waals (vdW) layered materials with diverse electronic properties over more than a decade ago, the scalable production of high-quality vdW layered materials has become a critical goal to enable the transformation of fundamental studies into practical applications in electronics. To this end, solution-based processing has been proposed as a promising technique to yield vdW layered materials in large quantities. Moreover, the resulting dispersions are compatible with cost-effective device fabrication processes such as inkjet printing and roll-to-roll manufacturing. Despite these advantages, earlier works on solution-based processing methods (i.e., direct liquid-phase exfoliation or alkali-metal intercalation) have several challenges in achieving high-performance electronic devices, such as structural polydispersity in thickness and lateral size or undesired phase transformation. These challenges hinder the utilization of the solution-processed materials in the limited fields of electronics such as electrodes and conductors. In the meantime, the groundbreaking discovery of another solution-based approach, molecular intercalation-based electrochemical exfoliation, has shown significant potential for the use of vdW layered materials in scalable electronics owing to the nearly ideal structure of the exfoliated samples. The resulting materials are highly monodispersed, atomically thin, and reasonably large, enabling the preparation of electronically active thin-film networks via successful vdW interface formation. The formation of vdW interfaces is highly important for efficient plane-to-plane charge transport and mechanical stability under various deformations, which are essential to high-performance, flexible electronics. In this Perspective, we survey the latest developments in solution-based processing of vdW layered materials and their electronic applications while also describing the field's future outlook in the context of its current challenges.

The production of graphene by direct liquid phase exfoliation of graphite at moderate sonication power by using low boiling liquid media: The effect of liquid media on yield and optimization

There are many production methods for graphene production. One of the most successful production methods in terms of scale-up is liquid phase exfoliation (LPE) method. In this study, after optimizing the sonication time and sonication power that are effective in the production to increase the efficiency of the LPE method, the experiments were continued at moderate sonication powers and the effect of liquid media, another important parameter, was examined. In this study, hexagonal graphite powders were subjected to direct liquid phase exfoliation process by using different liquid media (N-Methyl-2-Pyrrolidone (NMP), N,N-Dimethylformamide (DMF), ethanol, 2-propanol, acetone, methanesulfonic acid, ethanol + Sodium dodecyl sulphate (SDS), 2-propanol + SDS) and the obtained samples were characterized. As a result of the characterization, the liquid media with the highest efficiency was determined to be NMP. Besides, it was observed that a new hybrid solvent obtained by adding a surfactant such as SDS into low-cost and environmentally friendly liquid media such as ethanol and 2-propanol showed a higher efficiency than NMP. It was observed that 3–5 layer graphene ranged between 15 and 19 wt% in either graphene produced by using hybrid solvents containing NMP or SDS. The amount of double or single-layer graphene was negligibly small. The production with the lowest efficiency was observed in the use of acetone. The produced graphenes were dispersed in the liquid and their sedimentation time was observed. The sedimentation time of graphenes, produced using NMP and SDS-doped hybrid solvents, in liquid was more than 120 days. The sedimentation time of graphene produced using acetone was less than 20 days. In the use of graphene as a reinforcing material or adsorbent, large amounts of graphene are needed. In such applications, mass production of graphene is important rather than the number or quality of sheets of graphene. Therefore, optimization of production parameters of LPE method, which is suitable for mass production, is significance.

Higher thermal conductivity and mechanical enhancements in hybrid 2D polymer nanocomposites

Nanocomposites based on graphene oxide (GO), hexagonal boron nitride (h-BN), and their hybrid GO/h-BN as nanofillers in polyurethane (PU) were prepared, and their structures and morphologies were studied. The efficient production of a few layers of nanofillers was completed using the direct liquid-phase exfoliation process. Mechanical and thermal tests were carried out to study the effect of the addition of GO, h-BN, and GO/h-BN at different wt% in the PU system. The tensile strength and Young's modulus showed an increase of up to 85% and 140%, respectively, for the composite containing 0.5 wt% of the hybrid GO/h-BN mixture. An impressive improvement of up to ~1450% in thermal conductivity was observed for the same sample when compared to neat polymer. In order to gain further insights regarding the mechanism behind the nanofiller dispersion and adhesion processes in PU, fully atomistic classical molecular dynamics simulations were carried out. Based on these simulations, it was possible to build structural models that help to explain the thermal and mechanical improvements in the hybrid GO/h-BN composites, with a focus on its stabilization energy.

Enhanced thermal and mechanical properties of poly (vinylidene fluoride) nanocomposites reinforced by liquid-exfoliated graphene

We report the preparation and enhanced thermal and mechanical properties of poly (vinylidine diflouride) (PVDF) nanocomposites reinforced by few-layer graphene flakes which are produced by the direct liquid-phase exfoliation of pristine graphite. Graphene flakes are found to homogeneously disperse in PVDF, reduce the bubble defects and thus the porosity of PVDF, and change PVDF’s crystallinity. Thermogravimetric analysis indicates that graphene can accelerate the fracture of hydrogen bond connecting PVDF and N-Methyl pyrrolidone molecules. 1.5 wt% graphene loading leads to around 20 °C enhancement in the melting temperature of PVDF. The mechanical properties like Young’s modulus (EIT), yield stress (σy), and hardness (H) of the nanocomposites are investigated by nanoindentation technique. A 1.0 wt% loading of graphene is found to increase EIT, σy, and H of PVDF by ∼337%, ∼102%, and ∼228%, respectively.HighlightsFew-layer graphene was produced by liquid-phase exfoliation.Graphene were added to PVDF to enhance thermal and mechanical properties of polymer.Mechanical properties of PVDF/graphene composite films were investigated by nanoindentation.

Direct Liquid Phase Exfoliation of Graphite to Produce Few-Layer Graphene by Microfluidization.

Graphene has attracted a great number of attentions due to the excellent physical and chemical properties. For the convenience of investigations and applications, it is crucial to produce the grapheme with high-quality and high-yield by an easy-obtained method. In this research, a promising method is demonstrated to produce a high-concentration few-layer graphene (FLG) dispersion by direct microfluidization in water/surfactant systems. The effects of surfactant selection, chamber pressure and microfluidization cycles on the graphitic material exfoliation efficiency are systematically studied. The FLG concentration and the quality of the as-prepared FLG were determined by a series of characterizations. The graphene dispersions, with an average lateral size of 0.6 μm and a few-layer structure, were stabilized by surfactants at a high concentration of up to 1.7 mg/mL and exhibited a relatively high quality (ID/IG = 0.07-0.56, C/O ~ 19.36) within a processing time of a few hours. This method should facilitate the mass production of high-quality graphene by liquid-phase exfoliation and promote the industrial application of graphene.

Correction: The treatment of femoral neck fracture using VEGF-loaded nanographene coated internal fixation screws.

[This corrects the article DOI: 10.1371/journal.pone.0187447.].

Production of mono- to few-layer MoS2 nanosheets in isopropanol by a salt-assisted direct liquid-phase exfoliation method

Here, we report a facile salt-assisted direct liquid-phase exfoliation method for mass production of MoS2 nanosheets. We choose organic solvent isopropanol (IPA) as exfoliation media and potassium ferrocyanide, potassium sodium tartrate, or sodium tartrate as salt, the assistant. The selected salts show universal and efficient assistant effect for the exfoliation of MoS2 in IPA. Especially, potassium ferrocyanide (K4Fe(CN)6) can enhance the exfoliation efficiency up to 73 times and a dispersion of MoS2 nanosheets with concentration as high as 0.240 mg mL−1 can be easily obtained in IPA-K4Fe(CN)6 system. Transmission electron microscopy, atomic force microscopy (AFM), and Raman spectroscopy show that bulk MoS2 has been successfully exfoliated into mono- to few-layer MoS2 nanosheets. AFM analysis indicates that nearly 60% flakes are monolayer in MoS2 dispersion.

The treatment of femoral neck fracture using VEGF-loaded nanographene coated internal fixation screws.

PurposePrevious studies have proved that vascular endothelial growth factor (VEGF) has a dual role in the promotion of new bone formation and blood vessel repair during fracture healing. However, how to introduce VEGF to a fracture site safely and effectively is still a challenge. This study aimed to prepare a VEGF-loaded nanographene coated internal fixation screw and to evaluate its effects in the treatment of femoral neck fracture.MethodsNanographene coated screws were prepared by direct liquid-phase exfoliation of the graphite method, and the surface characteristics were observed through scanning electron microscopy (SEM). VEGF was loaded on nanographene coatings through physical adsorption, and the VEGF controlled release was examined by ELISA. Then a canine femoral neck fracture model was built to examine both the angiogenic and osteogenic properties of the VEGF-loaded coated screws. X-ray, micro-CT-based microangiography, and histopathologic evaluation were used to assess the fracture healing progress.ResultsThe results demonstrated that nanographene could load VEGF effectively, and the accumulative release of VEGF clearly increased during the entire testing period (9 days) without burst release. In canine fracture models, the results of X-ray, microangiography, and histopathologic examination proved that the speed of fracture healing, new bone formation area, and revascularization of the fractured femoral heads in the VEGF-loaded coated screws groups were significantly higher than in the control groups.ConclusionOur study proved that VEGF-loaded nanographene coated screws were effective in the treatment of femoral neck fracture and prevention of avascular necrosis of femoral head.

High-quality graphene sheets decorated with ZIF-8 nanocrystals

Excellent-quality graphene sheets produced via the direct liquid phase exfoliation of highly crystalline graphite (avoiding any oxidative treatment), were employed for the first time as 2D scaffolds for the in-situ synthesis of zeolitic-imidazolate-framework (ZIF-8) material. Our synthetic approach involved the efficient, urea-assisted exfoliation of natural graphite (without using any acids), and the subsequent selective, mild functionalization of the resulting high-quality graphene sheets with benzoic acid functional groups. The graphene derivatives were next decorated via the in-situ development of ultrasmall (approx. 30 nm) ZIF-8 nanocrystals. We discuss the critical role of the functionalized graphene to the selective nucleation and crystal growth of ZIF-8 nanocrystals exclusively at their surface. In-depth gas sorption studies of different gases revealed that the novel ZIF-8@Graph nano-composites exhibited improved porosity (in terms of surface area and pore volume) compared to analogous Graphene Oxide/ZIF-8 hybrids. In addition, the gate effect of the ZIF-8 nanocrystals anchored onto the high-quality graphene, was found very different compared to bulk ZIF-8, a behavior that is attributed mainly to the significantly smaller crystal size and the perfect 2D confinement of ZIF-8 along graphene. Finally, preliminary CO2 adsorption properties of the synthesized novel nano-composites are reported, at near ambient temperature.

Chemical Exfoliation of Black Phosphorus for Nanoelectronics Applications

ABSTRACTChemically exfoliated two-dimensional (2D) materials have shown promise in a variety of applications such as thin film transistors and photovoltaic devices. Here, we present a scalable method for preparing black phosphorus membranes via direct liquid-phase exfoliation of the bulk crystal in organic solvents. The black phosphorus sheets are characterized by Raman and Photoluminescence (PL) spectroscopy, and optical microscopy. The properties of these chemically exfoliated black phosphorus was compared to mechanically exfoliated nanomembranes. The liquid-phase exfoliation nonetheless yields the potential for large-area scalability. Our results highlight the important aspects of forming solution dispersions of 2D black phosphorus which can subsequently be the stepping stone for future work on the ink-jet printing of such dispersions over a wide range of substrates.

Surface Tension Components Ratio: An Efficient Parameter for Direct Liquid Phase Exfoliation.

Direct liquid phase exfoliation (LPE) is generally regarded as an effective and efficient methodology for preparing single- to few-layered nanosheets on a large scale. Based on a previous finding that the polar and dispersive components of surface tension can be used as critical parameters for screening suitable solvents for LPE, in this study, we conducted in-depth research on direct LPE of two-dimensional (2D) materials by the extensive LPE of a series of 2D materials and the thorough comparison of their surfaces properties and LPE efficiencies. We rationally developed the surface tension component matching (STCM) theory, and in nature, its key point lies in the close ratio of polar to dispersive components (P/D) between the solvents and the aimed 2D materials. To this end, the surface tension components ratio is demonstrated to be an effective parameter for screening LPE solvents. In addition to the optimization of the LPE process for these 2D materials, this work has further greatly enlarged the comprehensive library for the solvent and 2D material matching pairs based on the improved STCM theory.

Internal fixation of femoral neck fracture using screws coated with vascular endothelial growth factorloaded nanographene

Objective To evaluate the internal fixation screws coated with vascular endothelial growth factor (VEGF)-loaded nanographene in the treatment of femoral neck fracture. Methods Screws with nanographene coating were prepared by direct liquidphase exfoliation of the graphite. After the surface characteristics were observed through scanning electron microscopy (SEM), the nanographene coating was loaded with VEGF through physical adsorption and controlled release of the VEGF was examined by ELISA. Femoral neck fracture models were built in 10 healthy adult canines to examine both the angiogenic and osteogenic properties of the screws coated with VEGF-loaded nanographene which were implanted at the experimental sides while the screws with mere nanographene coating at the contralateral sides as controls. X-ray and histopathologic evaluations were used to assess the fracture healing progress. Results SEM demonstrated that the screws were coated successfully with VEGF-loaded nanographene. The coating did not increase the cytotoxity of screws. The accumulative release of VEGF clearly increased during the entire testing period (9 days) with a maximum release of 9.51±0.23 ng. X-ray and histopathologic examination proved better fracture healing at the experimental sides than at the contralateral sides. The percentage of trabecular area at the experimental sides (50.8%±3.3%) was insignificantly larger than at the control sides (43.7%±3.9%), and the trabecular width at the experimental sides (146.8±19.5 μm) was insignificantly greater than at the control sides (129.0±10.2 μm) (P>0.05). The area of new bone trabecula at the experimental sides (17.3%±1.5%) was significantly larger than at the control sides (8.3%±1.6%), and the microvessel density (MVD) at the experimental sides (113.4±12.5) was also significantly greater than at the control sides (61.2±9.4) (P<0.05). Conclusions The nanographene coating can load and release VEGF effectively. The screws coated with VEGF-loaded nanographene possess a certain degree of bioactivity which may promote vascular repair in the treatment of femoral neck fracture. Key words: Femoral neck fractures; Fracture fixation, internal; Bone nails; Nanocomposites; Vascular endothelial growth factor

Surface Tension Components Based Selection of Cosolvents for Efficient Liquid Phase Exfoliation of 2D Materials.

A proper design of direct liquid phase exfoliation (LPE) for 2D materials as graphene, MoS2 , WS2 , h-BN, Bi2 Se3 , MoSe2 , SnS2 , and TaS2 with common cosolvents is carried out based on considering the polar and dispersive components of surface tensions of various cosolvents and 2D materials. It has been found that the exfoliation efficiency is enhanced by matching the ratio of surface tension components of cosolvents to that of the targeted 2D materials, based on which common cosolvents composed of IPA/water, THF/water, and acetone/water can be designed for sufficient LPE process. In this context, the library of low-toxic and low-cost solvents with low boiling points for LPE is infinitely enlarged when extending to common cosolvents. Polymer-based composites reinforced with a series of different 2D materials are compared with each other. It is demonstrated that the incorporation of cosolvents-exfoliated 2D materials can substantially improve the mechanical and thermal properties of polymer matrices. Typically, with the addition of 0.5 wt% of such 2D material as MoS2 nanosheets, the tensile strength and Young's modulus increased up to 74.85% and 136.97%, respectively. The different enhancement effect of 2D materials is corresponded to the intrinsic properties and LPE capacity of 2D materials.

Biomolecule-assisted exfoliation and dispersion of graphene and other two-dimensional materials: a review of recent progress and applications.

Direct liquid-phase exfoliation of layered materials by means of ultrasound, shear forces or electrochemical intercalation holds enormous promise as a convenient, cost-effective approach to the mass production of two-dimensional (2D) materials, particularly in the form of colloidal suspensions of high quality and micrometer- and submicrometer-sized flakes. Of special relevance due to environmental and practical reasons is the production of 2D materials in aqueous medium, which generally requires the use of certain additives (surfactants and other types of dispersants) to assist in the exfoliation and colloidal stabilization processes. In this context, biomolecules have received, in recent years, increasing attention as dispersants for 2D materials, as they provide a number of advantages over more conventional, synthetic surfactants. Here, we review research progress in the use of biomolecules as exfoliating and dispersing agents for the production of 2D materials. Although most efforts in this area have focused on graphene, significant advances have also been reported with transition metal dichalcogenides (MoS2, WS2, etc.) or hexagonal boron nitride. Particular emphasis is placed on the specific merits of different types of biomolecules, including proteins and peptides, nucleotides and nucleic acids (RNA, DNA), polysaccharides, plant extracts and bile salts, on their role as efficient colloidal dispersants of 2D materials, as well as on the potential applications that have been explored for such biomolecule-exfoliated materials. These applications are wide-ranging and encompass the fields of biomedicine (photothermal and photodynamic therapy, bioimaging, biosensing, etc.), energy storage (Li- and Na-ion batteries), catalysis (e.g., catalyst supports for the oxygen reduction reaction or electrocatalysts for the hydrogen evolution reaction), or composite materials. As an incipient area of research, a number of knowledge gaps, unresolved issues and novel future directions remain to be addressed for biomolecule-exfoliated 2D materials, which will be discussed in the last part of this review.

Surfactant mediated liquid phase exfoliation of graphene.

Commercialization of graphene based applications inevitably requires cost effective mass production. From the early days of research on graphene, direct liquid phase exfoliation (LPE) of graphite has been considered as the most promising strategy to produce high-quality mono or few-layer graphene sheets in solvent dispersion forms. Substantial success has been achieved thus far in the LPE of graphene employing numerous solvent systems and suitable surfactants. This invited review article principally showcase the recent research progress as well as shortcomings of surfactant assisted LPE of graphene. In particular, a comprehensive assessment of the quality and yield of the graphene sheets produced by different categories of the surfactants are summarized. Future direction of LPE methods is also proposed for the eventual success of commercial applications.

A surfactant-free water-processable all-carbon composite and its application to supercapacitor

An easy technique is proposed to prepare a new surfactant-free water-processable supercapacitive material composed of graphene oxide (GO) and pristine graphene (PG). GO and PG are prepared by a modified Hummer's method and direct liquid phase exfoliation of graphite in dimethyl sulfoxide (DMSO) respectively. Water-processable GO/PG composites can be conveniently fabricated by mixing colloidal GO/H2O and PG/DMSO dispersions. The GO/PG composites can be re-dispersed in water to form stable colloidal dispersions. Capacitive behaviors of GO, PG and GO/PG composites were tested by cyclic voltammetry, galvanostatic charge/discharge curves and electrochemical impedance spectroscopy in aqueous electrolyte solutions. GO/PG composites exhibited improved capacitive properties in terms of specific capacitance and cycling stability, compared to those of individual components. The enhanced performances of the GO/PG composites signify the importance of the surface chemical property and conductivity of carbon-based materials for supercapacitor applications.

From graphite to graphene: direct liquid-phase exfoliation of graphite to produce single- and few-layered pristine graphene

Graphene, a two-dimensional crystalline form of carbon, has attracted wide and intense interest owing to its excellent physical properties and because its surface and edges can be chemically modified readily. Development of a method for producing high-quality graphene in large quantities is essential for further investigation of its properties and applications. The direct liquid-phase exfoliation of graphite to produce graphene is a convenient method for generating ideal graphene samples in large quantities. This direct method, which involves the use of colloidal suspensions, is based on the one-step physical transformation of graphite into graphene and has many unique advantages. A large number of liquids have been employed as exfoliation media and show a range of exfoliation efficiencies. In this review, we highlight the recent progress made on the exfoliation of bulky graphite powders or flakes into single- and few-layered graphene sheets in various liquids, including organic solvents, ionic liquids, and water/surfactant solutions. The qualities and yields of the exfoliated graphene samples, as well as their use in various applications, are also reviewed. Furthermore, future research directions for the development of novel exfoliation media and more efficient techniques for producing well-exfoliated pristine graphene are proposed.