Effects of green solvents and surfactants on the characteristics of few-layer graphene produced by dual-frequency ultrasonic liquid phase exfoliation technique

Appendix A. Supplementary data: available online at https://www.sciencedirect.com/science/article/pii/S0008622323000696?via%3Dihub#appsec1 .Copyright © 2023 The Authors. . Nowadays, one of the promising methods for scalable graphene production is ultrasound-aided liquid phase exfoliation (ULPE) of graphite. Two current limiting factors of ULPE are the use of harmful solutions (such as N-Methyl-2-pyrrolidone or Dimethylformamide) and a relatively low graphene yield. In this study, we demonstrate a new dual frequency (20 kHz and 1174 kHz) ULPE approach in various eco-friendly media, which enabled us to produce various few-layer graphene (FLG) solutions of high quality. By implementing sophisticated characterisation techniques consisting of Raman spectroscopy, UV–vis spectroscopy and high-resolution electron microscopy, the final graphene flakes structure was confirmed to correlate the properties of each individual solution. The thinner (∼3 layers) and larger (∼1.5 μm2) flakes were observed while using just water, with the highest yield (11%) of smaller FLG flakes to be achieved in the mixture of water and a surfactant. In order to understand the cavitation mechanism in different solutions, the ULPE process was investigated by acoustic measurements. This study demonstrates the crucial role of ethanol (as a solvent) and surfactants as it regulates the cavitation power and intensity of the ultrasonic field and, thereby, the cavitation effectiveness. It is suggested that the mixture of water, ethanol and a surfactant is the best medium for ULPE process where a high yield of low-defective FLG flakes can be obtained in a solution stable at least for 3 months (around 80%).This study is a part of the project “Sustainable and industrially scalable ultrasonic liquid phase exfoliation technologies for manufacturing 2D advanced functional materials” (EcoUltra2D) funded by the UK Engineering and Physical Sciences Research Council (EPSRC) under the grant nos. EP/R031665/1; EP/R031401/1; EP/R031819/1; EP/R031975/1

Temperature as a key parameter for graphene sono-exfoliation in water

Graphene dispersions in water are highly desirable for a range of applications such as biomedicines, separation membranes, coatings, inkjet printing and more. Recent novel research has been focussed on developing a green approach for scalable production of graphene. However, one important parameter, which is often neglected is the bulk temperature of the processing liquid. This paper follows our earlier work where optimal sono-exfoliation parameters of graphite in aqueous solutions were determined based on the measured acoustic pressure fields at various temperatures and input powers. Here, we take the next step forward and demonstrate using systematic characterisation techniques and acoustic pressure measurements that sonication-assisted liquid phase exfoliation (LPE) of graphite powder can indeed produce high quality few layer graphene flakes in pure water at a specific temperature, i.e. 40 °C, and at an optimised input generator power of 50%, within 2-h of processing. UV–vis analysis also revealed that the exfoliation, stability and uniformity of dispersions were improved with increasing temperature. We further confirmed the successful exfoliation of graphene sheets with minimal level of defects in the optimized sample with the help of Raman microscopy and transmission electron microscopy. This study demonstrated that understanding and controlling processing temperature is one of the key parameters for graphene exfoliation in water which offers a potential pathway for its large-scale production.UK Engineering and Physical Sciences Research Council (EPSRC), to the project “Sustainable and industrially scalable ultrasonic liquid phase exfoliation technologies for manufacturing 2D advanced functional materials” (EcoUltra2D), with the grant nos. EP/R031665/1; EP/R031401/1; EP/R031819/1; EP/R031975/1

An eco-friendly solution for liquid phase exfoliation of graphite under optimised ultrasonication conditions

Data availability: The data that supports the findings of this study are available upon request from the corresponding author.Appendix A. Supplementary data: available online at: https://www.sciencedirect.com/science/article/pii/S0008622322011125?via%3Dihub#appsec1 .Copyright © 2023 The Authors. Ultrasonic assisted liquid phase exfoliation (ULPE) is a promising method for the large scale production of 2D materials. Currently, toxic solvents such as N-Methyl-2-pyrrolidone (NMP) are commonly used for the production of graphene. In this paper four solvents; three green solvents (water, ethanol and water/ethanol) plus NMP for comparison, were sonicated and examined in terms of their bubble dynamics and acoustic emissions. Advanced fundamental analysis was conducted using high-speed imaging synchronised with acoustic pressure measurements complemented by shadowgraphic photography of the emitted shockwaves, in order to determine a suitable eco-friendly solvent medium from a cavitation bubbles dynamics perspective. Thereafter, ULPE of graphite in the optimum solvent took place for 2 h under controlled ultrasonication parameters. The produced graphene samples were characterised by employing a series of techniques consisting of Ultraviolet–visible (UV–Vis) and Raman spectroscopy as well as transmission electron microscopy (TEM). A mixture of deionised water and ethanol was shown to produce a yield twice that of pure water, comprising of high quality few layer graphene (3–5 Ls) with an average area of ∼1.15 (μm)2 and stability of ∼78% for the duration of six months. This combination is a promising eco-friendly substitute for future commercial manufacturing of graphene.UK Engineering and Physical Sciences Research Council (EPSRC), to the project “Sustainable and industrially scalable ultrasonic liquid phase exfoliation technologies for manufacturing 2D advanced functional materials” (EcoUltra2D), with the grant nos. EP/R031665/1; EP/R031401/1; EP/R031819/1; EP/R031975/1

Infrared-to-violet tunable optical activity in atomic films of GaSe, InSe, and their heterostructures

Two-dimensional semiconductors - atomic layers of materials with covalent intra-layer bonding and weak (van der Waals or quadrupole) coupling between the layers - are a new class of materials with great potential for optoelectronic applications. Among those, a special position is now being taken by post-transition metal chalcogenides (PTMC), InSe and GaSe. It has recently been found that the band gap in 2D crystals of InSe more than doubles in the monolayer compared to thick multilayer crystals, while the high mobility of conduction band electrons is promoted by their light in-plane mass. Here, we use Raman and PL measurements of encapsulated few layer samples, coupled with accurate atomic force and transmission electron microscope structural characterisation to reveal new optical properties of atomically thin GaSe preserved by hBN encapsulation. The band gaps we observe complement the spectral range provided by InSe films, so that optical activity of these two almost lattice-matched PTMC films and their heterostructures densely cover the spectrum of photons from violet to infrared. We demonstrate the realisation of the latter by the first observation of interlayer excitonic photoluminescence in few-layer InSe-GaSe heterostructures. The spatially indirect transition is direct in k-space and therefore is bright, while its energy can be tuned in a broad range by the number of layers.Comment: 8 pages 4 figure

Indirect to direct gap crossover in two-dimensional InSe revealed by ARPES

EPSRC, CDT Graphene-NOWNANO, the EPSRC Doctoral Prize Fellowship, e European Graphene Flagship Project, ERC Synergy Grarant Hetero2D,the ARCHER National UK Supercomputer RAP Project e547, Royal Society URF, and Llyod Register Foundation Nanotechnolog

High electron mobility, quantum Hall effect and anomalous optical response in atomically thin InSe

A decade of intense research on two-dimensional (2D) atomic crystals has revealed that their properties can differ greatly from those of the parent compound. These differences are governed by changes in the band structure due to quantum confinement and are most profound if the underlying lattice symmetry changes. Here we report a high-quality 2D electron gas in few-layer InSe encapsulated in hexagonal boron nitride under an inert atmosphere. Carrier mobilities are found to exceed 103cm2V-1s-1and 104cm2V-1s-1at room and liquid-helium temperatures, respectively, allowing the observation of the fully developed quantum Hall effect. The conduction electrons occupy a single 2D subband and have a small effective mass. Photoluminescence spectroscopy reveals that the bandgap increases by more than 0.5eV with decreasing the thickness from bulk to bilayer InSe. The band-edge optical response vanishes in monolayer InSe, which is attributed to the monolayer's mirror-plane symmetry. Encapsulated 2D InSe expands the family of graphene-like semiconductors and, in terms of quality, is competitive with atomically thin dichalcogenides and black phosphorus.EU, EPSRC. The Royal Societ

Dual frequency ultrasonic liquid phase exfoliation method for the production of few layer graphene in green solvents

Data availability: The data that supports the findings of this study are available upon request from the corresponding author.Supplementary data are available online at: https://www.sciencedirect.com/science/article/pii/S1350417724002025#s0095 .In this work, we implement a dual frequency (24 kHz and 1174 kHz) ultrasonic assisted liquid phase exfoliation (ULPE) technique in deionized water (DIW) and other eco-friendly solvents, to produce a variety of high-quality few-layer graphene (FLG) solutions under controlled ultrasonication conditions. The resulting FLG dispersions of variable sizes (∼0.2–1.5 μm2) confirmed by characterisation techniques comprising UV–Vis spectroscopy, Raman spectroscopy and high-resolution transmission electron microscopy (HR-TEM). For the first time we demonstrate that high yield of FLG flakes with minimal defects, stable for 6 + months in a solution (stability ∼ 70 %), can be obtained in less than 1-hour of treatment in either water/ethanol (DIW:EtOH) or water/isopropyl alcohol (DIW:IPA) eco-friendly mixtures. We also scrutinized the underlying mechanisms of cavitation using high-speed imaging synchronized with acoustic pressure measurements. The addition of ethanol or IPA to deionized water is proposed to play a central role in exfoliation as it regulates the extend of the cavitation zone, the intensity of the ultrasonic field and, thus, the cavitation effectiveness. Our study revealed that lateral sizes of the obtained FLG depend on the choice of exfoliating media and the diameter of a sonotrode used. This variability offers flexibility in producing FLG of different sizes, applicable in a wide spectrum of size-specific applications.UK Engineering and Physical Sciences Research Council (EPSRC), to the project “Sustainable and industrially scalable ultrasonic liquid phase exfoliation technologies for manufacturing 2D advanced functional materials” (EcoUltra2D), with the grant nos. EP/R031665/1; EP/R031401/1; EP/R031819/1; EP/R031975/1, Royal Society via the Isaac Newton International Fellowship to the project “Large Scale Exfoliation of 2D nanomaterials using an Environmentally Friendly Hybrid Cavitation Reactor” with grant number NIF\R1\221238 and EPSRC-PAAM project grant numbers (EP/W006774/1, EP/W006154/1 and EP/W00593X/1)

New insights into sono-exfoliation mechanisms of graphite: In situ high-speed imaging studies and acoustic measurements

© 2021 The Authors. The application of ultrasound and acoustic cavitation in liquid exfoliation of bulk layered materials is a widely used method. However, despite extensive research, the fundamental mechanisms remain far from being fully understood. A number of theories have been proposed to interpret the interactions between cavitation and bulk layered materials and hence to explain the mechanisms of ultrasound assisted exfoliation. Unfortunately, most of the research reported to date is ambiguous or inconclusive due to lack of direct real-time experimental evidence. In this paper, we report systematic work characterising cavitation emissions and observing the exfoliation of graphite in situ, in deionised water under the dynamic interaction with laser and ultrasound induced cavitation bubbles. Using ultra-high-speed optical imaging, we were able to determine the dynamic sequence of graphite exfoliation events on a time scale never reported before. Real-time observations also revealed that shock waves with a pressure magnitude up to 5 MPa and liquid-jets in the range of 80 ms−1, from transient cavitation bubble implosions, were essential for the initiation and propagation of the exfoliation process. On the other hand, bubble oscillations associated with stable cavitation were beneficial for promoting a gentler delamination of graphite layers.UK Engineering and Physical Sciences Research Council (EPSRC), (project “Sustainable and industrially scalable ultrasonic liquid phase exfoliation technologies for manufacturing 2D advanced functional materials” (EcoUltra2D), with the grant nos. EP/R031665/1; EP/R031401/1; EP/R031819/1; EP/R031975/1); Royal Society

Complete steric exclusion of ions and proton transport through confined monolayer water

It has long been an aspirational goal to create artificial structures that allow fast permeation of water but reject even the smallest hydrated ions, replicating the feat achieved by nature in protein channels (e.g., aquaporins). Despite recent progress in creating nanoscale pores and capillaries, these structures still remain distinctly larger than protein channels. We report capillaries made by effectively extracting one atomic plane from bulk crystals, which leaves a two-dimensional slit of a few angstroms in height. Water moves through these capillaries with little resistance, whereas no permeation could be detected even for such small ions as Na+ and Cl-. Only protons (H+) can diffuse through monolayer water inside the capillaries. These observations improve our understanding of molecular transport at the atomic scale

New insights into sono-exfoliation mechanisms of graphite: In situ high-speed imaging studies and acoustic measurements

The application of ultrasound and acoustic cavitation in liquid exfoliation of bulk layered materials is a widely used method. However, despite extensive research, the fundamental mechanisms remain far from being fully understood. A number of theories have been proposed to interpret the interactions between cavitation and bulk layered materials and hence to explain the mechanisms of ultrasound assisted exfoliation. Unfortunately, most of the research reported to date is ambiguous or inconclusive due to lack of direct real-time experimental evidence. In this paper, we report systematic work characterising cavitation emissions and observing the exfoliation of graphite in situ, in deionised water under the dynamic interaction with laser and ultrasound induced cavitation bubbles. Using ultra-high-speed optical imaging, we were able to determine the dynamic sequence of graphite exfoliation events on a time scale never reported before. Real-time observations also revealed that shock waves with a pressure magnitude up to 5 MPa and liquid-jets in the range of 80 ms−1, from transient cavitation bubble implosions, were essential for the initiation and propagation of the exfoliation process. On the other hand, bubble oscillations associated with stable cavitation were beneficial for promoting a gentler delamination of graphite layers