Impermeability of graphene and its applications
TL;DR: In this article, the authors discuss the genesis of impermeability in graphene and its extraordinary applications in fluid-encasement for wet electron-microscopy, selective gas-permeation, nanopore-bio-diffusion, and barrier coating against rusting and environmental hazards.
About: This article is published in Carbon.The article was published on 2013-10-01. It has received 580 citations till now. The article focuses on the topics: Graphene oxide paper & Graphene foam.
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TL;DR: This critical review assesses the recent developments in the use of graphene-based materials as sorbent or photocatalytic materials for environmental decontamination, as building blocks for next generation water treatment and desalination membranes, and as electrode materials for contaminant monitoring or removal.
Abstract: Graphene-based materials are gaining heightened attention as novel materials for environmental applications The unique physicochemical properties of graphene, notably its exceptionally high surface area, electron mobility, thermal conductivity, and mechanical strength, can lead to novel or improved technologies to address the pressing global environmental challenges This critical review assesses the recent developments in the use of graphene-based materials as sorbent or photocatalytic materials for environmental decontamination, as building blocks for next generation water treatment and desalination membranes, and as electrode materials for contaminant monitoring or removal The most promising areas of research are highlighted, with a discussion of the main challenges that we need to overcome in order to fully realize the exceptional properties of graphene in environmental applications
1,158 citations
TL;DR: This tutorial review aims to present the latest groundbreaking advances in both the theoretical and experimental chemical science and engineering of graphene-based membranes, including their design, fabrication and application.
Abstract: Graphene is a well-known two-dimensional material that exhibits preeminent electrical, mechanical and thermal properties owing to its unique one-atom-thick structure. Graphene and its derivatives (e.g., graphene oxide) have become emerging nano-building blocks for separation membranes featuring distinct laminar structures and tunable physicochemical properties. Extraordinary molecular separation properties for purifying water and gases have been demonstrated by graphene-based membranes, which have attracted a huge surge of interest during the past few years. This tutorial review aims to present the latest groundbreaking advances in both the theoretical and experimental chemical science and engineering of graphene-based membranes, including their design, fabrication and application. Special attention will be given to the progresses in processing graphene and its derivatives into separation membranes with three distinct forms: a porous graphene layer, assembled graphene laminates and graphene-based composites. Moreover, critical views on separation mechanisms within graphene-based membranes will be provided based on discussing the effect of inter-layer nanochannels, defects/pores and functional groups on molecular transport. Furthermore, the separation performance of graphene-based membranes applied in pressure filtration, pervaporation and gas separation will be summarized. This article is expected to provide a compact source of relevant and timely information and will be of great interest to all chemists, physicists, materials scientists, engineers and students entering or already working in the field of graphene-based membranes and functional films.
884 citations
TL;DR: In this paper, a review outlines the different mechanisms of wrinkle, ripple and crumple formation, and the interplay between wrinkles and ripples' attributes (wavelength/width, amplitude/height, length/size, and bending radius) and graphene's electronic properties and other mechanical, optical, surface, and chemical properties.
780 citations
TL;DR: Highly efficient mass transfer across physically perforated double-layer graphene is reported, having up to a few million pores with narrowly distributed diameters between less than 10 nanometers and 1 micrometer, in agreement with predictions of 2D transport theories.
Abstract: A two-dimensional (2D) porous layer can make an ideal membrane for separation of chemical mixtures because its infinitesimal thickness promises ultimate permeation. Graphene—with great mechanical strength, chemical stability, and inherent impermeability—offers a unique 2D system with which to realize this membrane and study the mass transport, if perforated precisely. We report highly efficient mass transfer across physically perforated double-layer graphene, having up to a few million pores with narrowly distributed diameters between less than 10 nanometers and 1 micrometer. The measured transport rates are in agreement with predictions of 2D transport theories. Attributed to its atomic thicknesses, these porous graphene membranes show permeances of gas, liquid, and water vapor far in excess of those shown by finite-thickness membranes, highlighting the ultimate permeation these 2D membranes can provide.
734 citations
TL;DR: Transport and mass spectroscopy measurements are reported which establish that monolayers of graphene and hexagonal boron nitride are highly permeable to thermal protons under ambient conditions, whereas no proton transport is detected for thicker crystals such as monolayer molybdenum disulphide, bilayer graphene or multilayer hBN.
Abstract: Measurements show that monolayers of graphene and hexagonal boron nitride are unexpectedly highly permeable to thermal protons and that their conductivity rapidly increases with temperature, but that no proton transport is detected for few-layer crystals. A perfect graphene sheet is impermeable to all atoms and molecules: even hydrogen, the smallest of atoms, is not expected to penetrate through graphene's dense electronic cloud within billions of years. This characteristic is thought to extend to other two-dimensional crystals such as hexagonal boron nitride and molybdenum disulphide. Sheng Hu and colleagues now show that, surprisingly, monolayers of graphene and hexagonal boron nitride (but not molybdenum disulphide) are highly permeable to protons. In combination with their stability, this establishes these monolayers as promising candidates for use in many hydrogen-based technologies. Graphene is increasingly explored as a possible platform for developing novel separation technologies1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19. This interest has arisen because it is a maximally thin membrane that, once perforated with atomic accuracy, may allow ultrafast and highly selective sieving of gases, liquids, dissolved ions and other species of interest2,9,10,11,12,13,14,15,16,17,18,19. However, a perfect graphene monolayer is impermeable to all atoms and molecules under ambient conditions1,2,3,4,5,6,7: even hydrogen, the smallest of atoms, is expected to take billions of years to penetrate graphene’s dense electronic cloud3,4,5,6. Only accelerated atoms possess the kinetic energy required to do this20,21. The same behaviour might reasonably be expected in the case of other atomically thin crystals22,23. Here we report transport and mass spectroscopy measurements which establish that monolayers of graphene and hexagonal boron nitride (hBN) are highly permeable to thermal protons under ambient conditions, whereas no proton transport is detected for thicker crystals such as monolayer molybdenum disulphide, bilayer graphene or multilayer hBN. Protons present an intermediate case between electrons (which can tunnel easily through atomically thin barriers24) and atoms, yet our measured transport rates are unexpectedly high4,5 and raise fundamental questions about the details of the transport process. We see the highest room-temperature proton conductivity with monolayer hBN, for which we measure a resistivity to proton flow of about 10 Ω cm2 and a low activation energy of about 0.3 electronvolts. At higher temperatures, hBN is outperformed by graphene, the resistivity of which is estimated to fall below 10−3 Ω cm2 above 250 degrees Celsius. Proton transport can be further enhanced by decorating the graphene and hBN membranes with catalytic metal nanoparticles. The high, selective proton conductivity and stability make one-atom-thick crystals promising candidates for use in many hydrogen-based technologies.
632 citations
References
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TL;DR: Monocrystalline graphitic films are found to be a two-dimensional semimetal with a tiny overlap between valence and conductance bands and they exhibit a strong ambipolar electric field effect.
Abstract: We describe monocrystalline graphitic films, which are a few atoms thick but are nonetheless stable under ambient conditions, metallic, and of remarkably high quality. The films are found to be a two-dimensional semimetal with a tiny overlap between valence and conductance bands, and they exhibit a strong ambipolar electric field effect such that electrons and holes in concentrations up to 10 13 per square centimeter and with room-temperature mobilities of ∼10,000 square centimeters per volt-second can be induced by applying gate voltage.
55,532 citations
"Impermeability of graphene and its ..." refers background in this paper
...[9] Novoselov KS, Geim AK, Morozov SV, Jiang D, Zhang Y, Dubonos SV, et al....
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TL;DR: Owing to its unusual electronic spectrum, graphene has led to the emergence of a new paradigm of 'relativistic' condensed-matter physics, where quantum relativistic phenomena can now be mimicked and tested in table-top experiments.
Abstract: Graphene is a rapidly rising star on the horizon of materials science and condensed-matter physics. This strictly two-dimensional material exhibits exceptionally high crystal and electronic quality, and, despite its short history, has already revealed a cornucopia of new physics and potential applications, which are briefly discussed here. Whereas one can be certain of the realness of applications only when commercial products appear, graphene no longer requires any further proof of its importance in terms of fundamental physics. Owing to its unusual electronic spectrum, graphene has led to the emergence of a new paradigm of 'relativistic' condensed-matter physics, where quantum relativistic phenomena, some of which are unobservable in high-energy physics, can now be mimicked and tested in table-top experiments. More generally, graphene represents a conceptually new class of materials that are only one atom thick, and, on this basis, offers new inroads into low-dimensional physics that has never ceased to surprise and continues to provide a fertile ground for applications.
35,293 citations
"Impermeability of graphene and its ..." refers background in this paper
...Therefore, for all practical purposes, graphene is impermeable [41,42]....
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TL;DR: This study reports an experimental study of a condensed-matter system (graphene, a single atomic layer of carbon) in which electron transport is essentially governed by Dirac's (relativistic) equation and reveals a variety of unusual phenomena that are characteristic of two-dimensional Dirac fermions.
Abstract: Quantum electrodynamics (resulting from the merger of quantum mechanics and relativity theory) has provided a clear understanding of phenomena ranging from particle physics to cosmology and from astrophysics to quantum chemistry. The ideas underlying quantum electrodynamics also influence the theory of condensed matter, but quantum relativistic effects are usually minute in the known experimental systems that can be described accurately by the non-relativistic Schrodinger equation. Here we report an experimental study of a condensed-matter system (graphene, a single atomic layer of carbon) in which electron transport is essentially governed by Dirac's (relativistic) equation. The charge carriers in graphene mimic relativistic particles with zero rest mass and have an effective 'speed of light' c* approximately 10(6) m s(-1). Our study reveals a variety of unusual phenomena that are characteristic of two-dimensional Dirac fermions. In particular we have observed the following: first, graphene's conductivity never falls below a minimum value corresponding to the quantum unit of conductance, even when concentrations of charge carriers tend to zero; second, the integer quantum Hall effect in graphene is anomalous in that it occurs at half-integer filling factors; and third, the cyclotron mass m(c) of massless carriers in graphene is described by E = m(c)c*2. This two-dimensional system is not only interesting in itself but also allows access to the subtle and rich physics of quantum electrodynamics in a bench-top experiment.
18,958 citations
"Impermeability of graphene and its ..." refers background in this paper
...[31] Novoselov KS, Geim AK, Morozov SV, Jiang D, Katsnelson MI, Grigorieva IV, et al....
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...Further, it possesses a unique electronic structure [31,32], which can be controlled chemically [33,34] and geometrically [35]....
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TL;DR: Graphene is established as the strongest material ever measured, and atomically perfect nanoscale materials can be mechanically tested to deformations well beyond the linear regime.
Abstract: We measured the elastic properties and intrinsic breaking strength of free-standing monolayer graphene membranes by nanoindentation in an atomic force microscope. The force-displacement behavior is interpreted within a framework of nonlinear elastic stress-strain response, and yields second- and third-order elastic stiffnesses of 340 newtons per meter (N m(-1)) and -690 Nm(-1), respectively. The breaking strength is 42 N m(-1) and represents the intrinsic strength of a defect-free sheet. These quantities correspond to a Young's modulus of E = 1.0 terapascals, third-order elastic stiffness of D = -2.0 terapascals, and intrinsic strength of sigma(int) = 130 gigapascals for bulk graphite. These experiments establish graphene as the strongest material ever measured, and show that atomically perfect nanoscale materials can be mechanically tested to deformations well beyond the linear regime.
18,008 citations
"Impermeability of graphene and its ..." refers background in this paper
...For example, the flexible [37] and stretchable [19] carbon–carbon bonds in graphene can allow conformal coating on corrugated surfaces to make them impermeable [12]....
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...The ability to withstand such pressure differences (6 atm) in graphene is a result of its high strength (breaking strength = 42 N/m) and Young’s modulus (1 TPa) [19], which retains the structural integrity of graphene....
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...[18], and high mechanical strength (strongest nanomaterial) [19]....
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TL;DR: The extremely high value of the thermal conductivity suggests that graphene can outperform carbon nanotubes in heat conduction and establishes graphene as an excellent material for thermal management.
Abstract: We report the measurement of the thermal conductivity of a suspended single-layer graphene. The room temperature values of the thermal conductivity in the range ∼(4.84 ± 0.44) × 103 to (5.30 ± 0.48) × 103 W/mK were extracted for a single-layer graphene from the dependence of the Raman G peak frequency on the excitation laser power and independently measured G peak temperature coefficient. The extremely high value of the thermal conductivity suggests that graphene can outperform carbon nanotubes in heat conduction. The superb thermal conduction property of graphene is beneficial for the proposed electronic applications and establishes graphene as an excellent material for thermal management.
11,878 citations
"Impermeability of graphene and its ..." refers background in this paper
...[18] Balandin AA, Ghosh S, Bao W, Calizo I, Teweldebrhan D, Miao F, et al....
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...enables graphene to be rolled into carbon nanotubes) allows the sheets to conformally form chambers at nano-, microand macro- scale, (d) mechanical strength [5,23]: graphene’s high yield-strength enables it to sustain the high pressure differences, similar to that between the fluidic region and external vacuum of a TEM, (e) high electrical conductivity [8,22]: the mobile p-electrons of graphene significantly reduce the electrostatic charge buildup under electron microscopy (EM), and (f) high thermal conductance [18]: graphene’s high phonon-conductivity dissipates the heat generated from electron bombardment....
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...[18], and high mechanical strength (strongest nanomaterial) [19]....
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