We discuss how an improved industrial manufacturability has been achieved for a hybrid water-treatment membrane that exhibits high water permeance, prolonged high salt and dye rejection under ...cross-flow conditions and better resistance to chlorine treatment.
By creating nanoscale pores in a layer of graphene, it could be used as an effective separation membrane due to its chemical and mechanical stability, its flexibility and, most importantly, its ...one-atom thickness. Theoretical studies have indicated that the performance of such membranes should be superior to state-of-the-art polymer-based filtration membranes, and experimental studies have recently begun to explore their potential. Here, we show that single-layer porous graphene can be used as a desalination membrane. Nanometre-sized pores are created in a graphene monolayer using an oxygen plasma etching process, which allows the size of the pores to be tuned. The resulting membranes exhibit a salt rejection rate of nearly 100% and rapid water transport. In particular, water fluxes of up to 10(6) g m(-2) s(-1) at 40 °C were measured using pressure difference as a driving force, while water fluxes measured using osmotic pressure as a driving force did not exceed 70 g m(-2) s(-1) atm(-1).
There is a demand for the manufacture of two-dimensional (2D) materials with high-quality single crystals of large size. Usually, epitaxial growth is considered the method of choice
in preparing ...single-crystalline thin films, but it requires single-crystal substrates for deposition. Here we present a different approach and report the synthesis of single-crystal-like monolayer graphene films on polycrystalline substrates. The technological realization of the proposed method resembles the Czochralski process and is based on the evolutionary selection
approach, which is now realized in 2D geometry. The method relies on 'self-selection' of the fastest-growing domain orientation, which eventually overwhelms the slower-growing domains and yields a single-crystal continuous 2D film. Here we have used it to synthesize foot-long graphene films at rates up to 2.5 cm h
that possess the quality of a single crystal. We anticipate that the proposed approach could be readily adopted for the synthesis of other 2D materials and heterostructures.
We show that graphene chemical vapor deposition growth on copper foil using methane as a carbon source is strongly affected by hydrogen, which appears to serve a dual role: an activator of the ...surface bound carbon that is necessary for monolayer growth and an etching reagent that controls the size and morphology of the graphene domains. The resulting growth rate for a fixed methane partial pressure has a maximum at hydrogen partial pressures 200–400 times that of methane. The morphology and size of the graphene domains, as well as the number of layers, change with hydrogen pressure from irregularly shaped incomplete bilayers to well-defined perfect single layer hexagons. Raman spectra suggest the zigzag termination in the hexagons as more stable than the armchair edges.
Proton transfer across single-layer graphene proceeds with large computed energy barriers and is therefore thought to be unfavourable at room temperature unless nanoscale holes or dopants are ...introduced, or a potential bias is applied. Here we subject single-layer graphene supported on fused silica to cycles of high and low pH, and show that protons transfer reversibly from the aqueous phase through the graphene to the other side where they undergo acid-base chemistry with the silica hydroxyl groups. After ruling out diffusion through macroscopic pinholes, the protons are found to transfer through rare, naturally occurring atomic defects. Computer simulations reveal low energy barriers of 0.61-0.75 eV for aqueous proton transfer across hydroxyl-terminated atomic defects that participate in a Grotthuss-type relay, while pyrylium-like ether terminations shut down proton exchange. Unfavourable energy barriers to helium and hydrogen transfer indicate the process is selective for aqueous protons.
Despite the frequent use of noble gas ion irradiation of graphene, the atomistic-scale details, including the effects of dose, energy, and ion bombardment species on defect formation, and the ...associated dynamic processes involved in the irradiations and subsequent relaxation have not yet been thoroughly studied. Here, we simulated the irradiation of graphene with noble gas ions and the subsequent effects of annealing. Lattice defects, including nanopores, were generated after the annealing of the irradiated graphene, which was the result of structural relaxation that allowed the vacancy-type defects to coalesce into a larger defect. Larger nanopores were generated by irradiation with a series of heavier noble gas ions, due to a larger collision cross section that led to more detrimental effects in the graphene, and by a higher ion dose that increased the chance of displacing the carbon atoms from graphene. Overall trends in the evolution of defects with respect to a dose, as well as the defect characteristics, were in good agreement with experimental results. Additionally, the statistics in the defect types generated by different irradiating ions suggested that the most frequently observed defect types were Stone-Thrower-Wales (STW) defects for He+ irradiation and monovacancy (MV) defects for all other ion irradiations.
All large-scale graphene films contain extended topological defects dividing graphene into domains or grains. Here, we spatially map electronic transport near specific domain and grain boundaries in ...both epitaxial graphene grown on SiC and CVD graphene on Cu subsequently transferred to a SiO2 substrate, with one-to-one correspondence to boundary structures. Boundaries coinciding with the substrate step on SiC exhibit a significant potential barrier for electron transport of epitaxial graphene due to the reduced charge transfer from the substrate near the step edge. Moreover, monolayer–bilayer boundaries exhibit a high resistance that can change depending on the height of substrate step coinciding at the boundary. In CVD graphene, the resistance of a grain boundary changes with the width of the disordered transition region between adjacent grains. A quantitative modeling of boundary resistance reveals the increased electron Fermi wave vector within the boundary region, possibly due to boundary induced charge density variation. Understanding how resistance change with domain (grain) boundary structure in graphene is a crucial first step for controlled engineering of defects in large-scale graphene films.
Free-standing graphene is inherently crumpled in the out-of-plane direction due to dynamic flexural phonons and static wrinkling. We explore the consequences of this crumpling on the effective ...mechanical constants of graphene. We develop a sensitive experimental approach to probe stretching of graphene membranes under low applied stress at cryogenic to room temperatures. We find that the in-plane stiffness of graphene is 20-100 N m(-1) at room temperature, much smaller than 340 N m(-1) (the value expected for flat graphene). Moreover, while the in-plane stiffness only increases moderately when the devices are cooled down to 10 K, it approaches 300 N m(-1) when the aspect ratio of graphene membranes is increased. These results indicate that softening of graphene at temperatures <400 K is caused by static wrinkling, with only a small contribution due to flexural phonons. Together, these results explain the large variation in reported mechanical constants of graphene devices and pave the way towards controlling their mechanical properties.
Single- and multiple-nanopore membranes are both highly interesting for biosensing and separation processes, as well as their ability to mimic biological membranes. The density of pores, their shape, ...and their surface chemistry are the key factors that determine membrane transport and separation capabilities. Here, we report silicon nitride (SiN) membranes with fully controlled porosity, pore geometry, and pore surface chemistry. An ultrathin freestanding SiN platform is described with conical or double-conical nanopores of diameters as small as several nanometers, prepared by the track-etching technique. This technique allows the membrane porosity to be tuned from one to billions of pores per square centimeter. We demonstrate the separation capabilities of these membranes by discrimination of dye and protein molecules based on their charge and size. This separation process is based on an electrostatic mechanism and operates in physiological electrolyte conditions. As we have also shown, the separation capabilities can be tuned by chemically modifying the pore walls. Compared with typical membranes with cylindrical pores, the conical and double-conical pores reported here allow for higher fluxes, a critical advantage in separation applications. In addition, the conical pore shape results in a shorter effective length, which gives advantages for single biomolecule detection applications such as nanopore-based DNA analysis.
Two-dimensional (2D) van der Waals (vdW) heterostructures are a family of artificially structured materials that promise tunable optoelectronic properties for devices with enhanced functionalities. ...Compared to transferring, direct epitaxy of vdW heterostructures is ideal for clean interlayer interfaces and scalable device fabrication. Here we report the synthesis and preferred orientations of 2D GaSe atomic layers on graphene (Gr) by vdW epitaxy. GaSe crystals are found to nucleate predominantly on random wrinkles or grain boundaries of graphene, share a preferred lattice orientation with underlying graphene, and grow into large (tens of micrometers) irregularly shaped, single-crystalline domains. The domains are found to propagate with triangular edges that merge into the large single crystals during growth. Electron diffraction reveals that approximately 50% of the GaSe domains are oriented with a 10.5 ± 0.3° interlayer rotation with respect to the underlying graphene. Theoretical investigations of interlayer energetics reveal that a 10.9° interlayer rotation is the most energetically preferred vdW heterostructure. In addition, strong charge transfer in these GaSe/Gr vdW heterostructures is predicted, which agrees with the observed enhancement in the Raman E2 1g band of monolayer GaSe and highly quenched photoluminescence compared to GaSe/SiO2. Despite the very large lattice mismatch of GaSe/Gr through vdW epitaxy, the predominant orientation control and convergent formation of large single-crystal flakes demonstrated here is promising for the scalable synthesis of large-area vdW heterostructures for the development of new optical and optoelectronic devices.
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