Inspired by recent studies of various two-dimensional (2D) metals such as Au, Fe and Ag, we study the growth of two-dimensional gold patches in graphene pores by density-functional theory. We find that at room temperature gold atoms diffuse readily on top of both graphene and two-dimensional gold with energy barriers less than $0.5$ eV. Furthermore, gold atoms move without barriers from the top of graphene to its edge and from the top of 2D gold to its edge. The energy barriers are absent even at the interface of 2D gold and graphene, so that the gold atoms move effortlessly across the interface. We hope our demonstration for the propensity of diffusing gold atoms to grow 2D gold patches in graphene pores will inspire the fabrication of these patches experimentally.
Two-dimensional (2D) materials can be used as stabilizing templates for exotic nanostructures, including pore-stabilized, free-standing patches of elemental metal monolayers. Although these patches represent metal clusters under extreme conditions and are thus bound for investigations, they are poorly understood as their energetic stability trends and the most promising elements remain unknown. Here, using density-functional theory simulations and liquid drop model to explore the properties of 45 elemental metal candidates, we identify metals that enable the largest and most stable patches. Si…
With the ability to selectively control ionic flux, biological protein ion channels perform a fundamental role in many physiological processes. For practical applications that require the functionality of a biological ion channel, graphene provides a promising solid-state alternative, due to its atomic thinness and mechanical strength. Here, we demonstrate that nanopores introduced into graphene membranes, as large as 50 nm in diameter, exhibit inter-cation selectivity with a ~20x preference for K+ over divalent cations and can be modulated by an applied gate voltage. Liquid atomic force micro…
Membranes act as selective barriers and play an important role in processes such as cellular compartmentalization and industrial-scale chemical and gas purification. The ideal membrane should be as thin as possible to maximize flux, mechanically robust to prevent fracture, and have well-defined pore sizes to increase selectivity. Graphene is an excellent starting point for developing size selective membranes because of its atomic thickness, high mechanical strength, relative inertness, and impermeability to all standard gases. However, pores that can exclude larger molecules, but allow smaller…
By limiting the carbon segregation at the copper surface defects, a pulsed chemical vapor deposition method for single layer graphene growth is shown to inhibit the formation of few-layer regions, leading to a fully single-layered graphene homogeneous at the centimeter scale. Graphene field-effect devices obtained after transfer of pulsed grown graphene on oxidized silicon exhibit mobilities above 5000 cm^2.V^-1.s^-1.
This paper reports on the topological effects of three-dimensional (3D) porous graphene with tunable pore sizes and a preserved 2D graphene system of Dirac quasiparticles on its electrical properties. This 3D architecture is characterized by the intrinsic curvature of smoothly interconcnected graphene sheets without edges, the structures and properties of which can be controlled with its pore sizes. The impact of pore size on the electrical transport properties was investigated through magnetoresistance measurements. We observed that 3D graphene with small pores exhibits transitioning to weak …
An ability to precisely regulate the quantity and location of molecular flux is of value in applications such as nanoscale 3D printing, catalysis, and sensor design. Barrier materials containing pores with molecular dimensions have previously been used to manipulate molecular compositions in the gas phase, but have so far been unable to offer controlled gas transport through individual pores. Here, we show that gas flux through discrete angstrom-sized pores in monolayer graphene can be detected and then controlled using nanometer-sized gold clusters, which are formed on the surface of the grap…
Selective ion transport is a hallmark of biological ion channel behavior but is a major challenge to engineer into artificial membranes. Here, we demonstrate, with all-atom molecular dynamics simulations, that bare graphene nanopores yield measurable ion selectivity that varies over one to two orders of magnitude simply by changing the pore radius and number of graphene layers. Monolayer graphene does not display dehydration-induced selectivity until the pore radius is small enough to exclude the first hydration layer from inside the pore. Bi- and tri-layer graphene, though, display such selec…
Using extensive room-temperature molecular dynamics simulations, we investigate selective aqueous cation trapping and permeation in graphene-embedded 18-crown-6 ether pores. We show that in the presence of suspended water-immersed crown-porous graphene, K+ ions rapidly organize and trap stably within the pores, in contrast with Na+ ions. As a result, significant qualitative differences in permeation between ionic species arise. The trapped ion occupancy and permeation behaviors are shown to be highly voltage-tunable. Interestingly, we demonstrate the possibility of performing conceptually stra…
With the technology of artificial defects creating, we can tune the band structure and transport properties of many two-dimensional (2D) layered materials. One prototype materials system is the antidoted graphene sheet, where periodical pores are made using focuses ion or electron beams in the nanoscale. We here study the electrical conductivity, thermopower, and active rates of cooling and refrigeration of antidoted graphene samples with different pore-radii and interporous distances. We use a calculation method that takes into consider the sensitivity of transport to charge carrier energy, w…
Water transport through graphene-derived membranes has gained much interest recently due to its promising potential in filtration and separation applications. In this work, we explore water permeation in graphene oxide membranes using atomistic simulations, by considering flow through interlayer gallery, expanded pores such as wrinkles of interedge spaces, and pores within the sheet. We find that although flow enhancement can be established by nanoconfinement, fast water transport through pristine graphene channels is prohibited by a prominent side-pinning effect from capillaries formed betwee…
Nanopores -- nanosized holes that can transport ions and molecules -- are very promising devices for genomic screening, in particular DNA sequencing. Both solid-state and biological pores suffer from the drawback, however, that the channel constituting the pore is long, viz. 10-100 times the distance between two bases in a DNA molecule (0.5 nm for single-stranded DNA). Here, we demonstrate that it is possible to realize and use ultrathin nanopores fabricated in graphene monolayers for single-molecule DNA translocation. The pores are obtained by placing a graphene flake over a microsize hole in…
Graphene nanomeshes (GNM's) formed by the creation of pore superlattices in graphene, are a possible route to graphene-based electronics due to their semiconducting properties, including the emergence of fractional eV band gaps. The utility of GNM's would be markedly increased if a scheme to stably and controllably dope them was developed. In this work, a chemically-motivated approach to GNM doping based on selective pore-perimeter passivation and subsequent ion chelation is proposed. It is shown by first-principles calculations that ion chelation leads to stable doping of the passivated GNM's…
Biological ion channels balance electrostatic and dehydration effects to yield large ion selectivities alongside high transport rates. These macromolecular systems are often interrogated through point mutations of their pore domain, limiting the scope of mechanistic studies. In contrast, we demonstrate that graphene crown ether pores afford a simple platform to directly investigate optimal ion transport conditions, i.e., maximum current densities and selectivity. Crown ethers are known for selective ion adsorption. When embedded in graphene, however, transport rates lie below the drift-diffusi…
Ion channels play a key role in regulating cell behavior and in electrical signaling. In these settings, polar and charged functional groups -- as well as protein response -- compensate for dehydration in an ion-dependent way, giving rise to the ion selective transport critical to the operation of cells. Dehydration, though, yields ion-dependent free-energy barriers and thus is predicted to give rise to selectivity by itself. However, these barriers are typically so large that they will suppress the ion currents to undetectable levels. Here, we establish that graphene displays a measurable deh…
We synthesized three-dimensional nanoporous graphene films by a chemical vapor deposition method with nanoporous copper as a catalytic substrate. The resulting nanoporous graphene has the same average pore size as the underlying copper substrate. Our surface-enhanced Raman scattering (SERS) investigation indicates that the nanoporosity of graphene significantly improves the SERS efficiency of graphene as a substrate as compared to planar graphene substrates.
Two-dimensional crystals with angstrom-scale pores are widely considered as candidates for a next generation of molecular separation technologies aiming to provide extreme, exponentially large selectivity combined with high flow rates. No such pores have been demonstrated experimentally. Here we study gas transport through individual graphene pores created by low intensity exposure to low kV electrons. Helium and hydrogen permeate easily through these pores whereas larger species such as xenon and methane are practically blocked. Permeating gases experience activation barriers that increase qu…
Flexoelectricity phenomenon is the response of electric polarization to an applied strain gradient and is developed as a consequence of crystal symmetry in all materials. In this study, we show that the presence of strain gradient in non-piezoelectric graphene sheet does not only affect the ionic positions, but also the asymmetric redistribution of the electron density, which induce strong polarization in the graphene sheet. Using quantum mechanics calculations, the resulting axial and normal piezoelectric coefficients of the graphene sheet were determined using two loading conditions: (i) a g…
Ionic transport in nano- to sub-nano-scale pores is highly dependent on translocation barriers and potential wells. These features in the free-energy landscape are primarily the result of ion dehydration and electrostatic interactions. For pores in atomically thin membranes, such as graphene, other factors come into play. Ion dynamics both inside and outside the geometric volume of the pore can be critical in determining the transport properties of the channel due to several commensurate length scales, such as the effective membrane thickness, radii of the first and the second hydration layers…
We present a numerically efficient technique to evaluate the Green's function for extended two dimensional systems without relying on periodic boundary conditions. Different regions of interest, or `patches', are connected using self energy terms which encode the information of the extended parts of the system. The calculation scheme uses a combination of analytic expressions for the Green's function of infinite pristine systems and an adaptive recursive Green's function technique for the patches. The method allows for an efficient calculation of both local electronic and transport properties,…
A fluid-based method is demonstrated for preparing graphene nanomeshes (GNMs) directly from pristine graphite flakes by a one-step process. The high efficiency is attributed to the combination of fluid-assisted exfoliation and perforation of the graphene sheets. Atomic force microscopy shows that the as-produced GNMs are less than 1.5 nm thick. The total area of the pores within 1 um2 of the GNM sheet is estimated as ~0.15 um2 and the pore density as ~22 um-2, The yield of GNMs from pristine graphite powder and the power consumption for per gram GNM synthesis are evaluated as 5 wt% and 120 kWh…
Permeation through nanometer pores is important in the design of materials for filtration and separation techniques and because of unusual fundamental behavior arising at the molecular scale. We found that submicron-thick membranes made from graphene oxide can be completely impermeable to liquids, vapors and gases, including helium, but allow unimpeded permeation of water (H2O permeates through the membranes at least 10^10 times faster than He). We attribute these seemingly incompatible observations to a low-friction flow of a monolayer of water through two dimensional capillaries formed by cl…
In the framework of density functional theory (DFT) calculations we investigate the electronic and thermal properties of porous graphene (PG) structures passivated with halogen atoms as possible candidates for efficient thermoelectric devices. Armchair and zig-zag halogenated PG nanoribbons are analyzed comparatively. The electronic properties are consistent with the expected behavior for the two types of terminations, however with marked influences introduced by the different halogen atoms. Depending on the pore sizes and halogen type pseudo-gaps in the phononic band structure are visible in …
Ion transport through nanopores permeates through many areas of science and technology, from cell behavior to sensing and separation to catalysis and batteries. Two-dimensional materials, such as graphene, molybdenum disulfide (MoS$_2$), and hexagonal boron nitride (hBN), are recent additions to these fields. Low-dimensional materials present new opportunities to develop filtration, sensing, and power technologies, encompassing ion exclusion membranes, DNA sequencing, single molecule detection, osmotic power generation, and beyond. Moreover, the physics of ionic transport through pores and con…
By stacking various two-dimensional (2D) atomic crystals [1] on top of each other, it is possible to create multilayer heterostructures and devices with designed electronic properties [2-5]. However, various adsorbates become trapped between layers during their assembly, and this not only affects the resulting quality but also prevents the formation of a true artificial layered crystal upheld by van der Waals interaction, creating instead a laminate glued together by contamination. Transmission electron microscopy (TEM) has shown that graphene and boron nitride monolayers, the two best charact…
The discovery of graphene some ten years ago was the first proof of a free-standing two-dimensional (2D) solid phase. Here, using quantum molecular dynamics simulations of nanoscale gold patches suspended in graphene pores, we predict the existence of an atomically thin, free-standing 2D liquid phase. The liquid phase, enabled by the exceptional planar stability of gold due to relativistic effects, demonstrates extreme fluxionality of metal nanostructures and opens possibilities for a variety of nanoscale phenomena.
Water wetting on a hydrophobic surface at ambient conditions is disallowed by the nonpolar nature of the surface and high vapor pressure of water. However, the presence of sub-millimeter sized hydrophilic patches allows the waxy wings of desert beetles to become wettable by morning mist. Here, we show that a sprinkle of graphene oxide nanoflakes (nanoGOs) is effective in condensing water nanodroplets and seeding ice epitaxy on graphite at ambient conditions. By controlling relative humidity and nanoGO density, we are able to study the formation of a complete ice wetting layer on a time scale o…
Graphdiyne is a novel two-dimensional material deriving from graphene that has been recently synthesized and featuring uniformly distributed sub-nanometer pores. We report accurate calculations showing that graphdiyne pores permit an almost unimpeded helium transport which can be used for its chemical and isotopic separation. Exceptionally high He/CH_4 selectivities are found which largely exceed the performance of the best membranes used to date for extraction from natural gas. Moreover, by exploiting slight differences in the tunneling probabilities of ^3He and ^4He, we also find promising r…
Recently, holey graphene (HG) has successfully synthesized at atomic precision of hole size and shape. This shows interesting physical and chemical properties for energy and environmental applications. Shaping of the pores also transforms semimetallic graphene to semiconductor holey graphene, which opens new door for its use in electronic applications. We systematically investigated the structural, electronic, optical and thermoelectric properties of HG structure using first-principles calculations. HG was found to have a direct band gap with 0.65 eV (PBE functional), 0.95 eV (HSE06 functional…
Recent experimental discoveries of graphene-stabilized patches of two-dimensional (2D) metals have motivated also their computational studies. However, so far the studies have been restricted to ideal and infinite 2D metallic monolayers, which is insufficient because in reality the properties of such metallic patches are governed by microstructures pervaded by edges, defects, and several types of perturbations. Here we use density-functional theory to calculate edge and vacancy formation energies of hexagonal and square lattices of 45 elemental 2D metals. We find that the edge and vacancy form…
Using first-principles quantum transport simulations, based on the nonequilibrium Green function formalism combined with density functional theory (NEGF+DFT), we examine changes in the total and local electronic currents within the plane of graphene nanoribbon with zigzag edges (ZGNR) hosting a nanopore which are induced by inserting a DNA nucleobase into the pore. We find a sizable change of the zero-bias conductance of two-terminal ZGNR + nanopore device after the nucleobase is placed into the most probable position (according to molecular dynamics trajectories) inside the nanopore of a smal…
Quantum phenomena are relevant to the transport of light atoms and molecules through nanoporous two-dimensional (2D) membranes. Indeed, confinement provided by (sub-)nanometer pores enhances quantum effects such as tunneling and zero point energy (ZPE), even leading to quantum sieving of different isotopes of a given element. However, these features are not always taken into account in approaches where classical theories or approximate quantum models are preferred. In this work we present an exact three-dimensional wave packet propagation treatment for simulating the passage of atoms through p…
Gas permeation through nanoscale pores is ubiquitous in nature and plays an important role in a plethora of technologies. Because the pore size is typically smaller than the mean free path of gas molecules, their flow is conventionally described by the Knudsen theory that assumes diffuse reflection (random-angle scattering) at confining walls. This assumption has proven to hold surprisingly well in experiment, and only a few cases of partially specular (mirror-like) reflection are known. Here we report gas transport through angstrom-scale channels with atomically-flat walls and show that surfa…
