Ballistic molecular transport through two-dimensional channels.

Gas permeation through nanoscale pores is ubiquitous in nature and has an important role in many technologies1,2. Because the pore size is typically smaller than the mean free path of gas molecules, the flow of the gas molecules is conventionally described by Knudsen theory, which assumes diffuse reflection (random-angle scattering) at confining walls3-7. This assumption holds surprisingly well in experiments, with only a few cases of partially specular (mirror-like) reflection known5,8-11. Here we report gas transport through ångström-scale channels with atomically flat walls12,13 and show that surface scattering can be either diffuse or specular, depending on the fine details of the atomic landscape of the surface, and that quantum effects contribute to the specularity at room temperature. The channels, made from graphene or boron nitride, allow helium gas flow that is orders of magnitude faster than expected from theory. This is explained by specular surface scattering, which leads to ballistic transport and frictionless gas flow. Similar channels, but with molybdenum disulfide walls, exhibit much slower permeation that remains well described by Knudsen diffusion. We attribute the difference to the larger atomic corrugations at molybdenum disulfide surfaces, which are similar in height to the size of the atoms being transported and their de Broglie wavelength. The importance of this matter-wave contribution is corroborated by the observation of a reversed isotope effect, whereby the mass flow of hydrogen is notably higher than that of deuterium, in contrast to the relation expected for classical flows. Our results provide insights into the atomistic details of molecular permeation, which previously could be accessed only in simulations10,14, and demonstrate the possibility of studying gas transport under controlled confinement comparable in size to the quantum-mechanical size of atoms.

Molecular transport through capillaries made with atomic-scale precision.

Nanometre-scale pores and capillaries have long been studied because of their importance in many natural phenomena and their use in numerous applications. A more recent development is the ability to fabricate artificial capillaries with nanometre dimensions, which has enabled new research on molecular transport and led to the emergence of nanofluidics. But surface roughness in particular makes it challenging to produce capillaries with precisely controlled dimensions at this spatial scale. Here we report the fabrication of narrow and smooth capillaries through van der Waals assembly, with atomically flat sheets at the top and bottom separated by spacers made of two-dimensional crystals with a precisely controlled number of layers. We use graphene and its multilayers as archetypal two-dimensional materials to demonstrate this technology, which produces structures that can be viewed as if individual atomic planes had been removed from a bulk crystal to leave behind flat voids of a height chosen with atomic-scale precision. Water transport through the channels, ranging in height from one to several dozen atomic planes, is characterized by unexpectedly fast flow (up to 1 metre per second) that we attribute to high capillary pressures (about 1,000 bar) and large slip lengths. For channels that accommodate only a few layers of water, the flow exhibits a marked enhancement that we associate with an increased structural order in nanoconfined water. Our work opens up an avenue to making capillaries and cavities with sizes tunable to ångström precision, and with permeation properties further controlled through a wide choice of atomically flat materials available for channel walls.

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.

Anomalously low dielectric constant of confined water.

The dielectric constant ε of interfacial water has been predicted to be smaller than that of bulk water (ε ≈ 80) because the rotational freedom of water dipoles is expected to decrease near surfaces, yet experimental evidence is lacking. We report local capacitance measurements for water confined between two atomically flat walls separated by various distances down to 1 nanometer. Our experiments reveal the presence of an interfacial layer with vanishingly small polarization such that its out-of-plane ε is only ~2. The electrically dead layer is found to be two to three molecules thick. These results provide much-needed feedback for theories describing water-mediated surface interactions and the behavior of interfacial water, and show a way to investigate the dielectric properties of other fluids and solids under extreme confinement.

Scalable and efficient separation of hydrogen isotopes using graphene-based electrochemical pumping.

Thousands of tons of isotopic mixtures are processed annually for heavy-water production and tritium decontamination. The existing technologies remain extremely energy intensive and require large capital investments. New approaches are needed to reduce the industry's footprint. Recently, micrometre-size crystals of graphene are shown to act as efficient sieves for hydrogen isotopes pumped through graphene electrochemically. Here we report a fully-scalable approach, using graphene obtained by chemical vapour deposition, which allows a proton-deuteron separation factor of around 8, despite cracks and imperfections. The energy consumption is projected to be orders of magnitude smaller with respect to existing technologies. A membrane based on 30 m2 of graphene, a readily accessible amount, could provide a heavy-water output comparable to that of modern plants. Even higher efficiency is expected for tritium separation. With no fundamental obstacles for scaling up, the technology's simplicity, efficiency and green credentials call for consideration by the nuclear and related industries.

Size effect in ion transport through angstrom-scale slits.

In the field of nanofluidics, it has been an ultimate but seemingly distant goal to controllably fabricate capillaries with dimensions approaching the size of small ions and water molecules. We report ion transport through ultimately narrow slits that are fabricated by effectively removing a single atomic plane from a bulk crystal. The atomically flat angstrom-scale slits exhibit little surface charge, allowing elucidation of the role of steric effects. We find that ions with hydrated diameters larger than the slit size can still permeate through, albeit with reduced mobility. The confinement also leads to a notable asymmetry between anions and cations of the same diameter. Our results provide a platform for studying the effects of angstrom-scale confinement, which is important for the development of nanofluidics, molecular separation, and other nanoscale technologies.

Wrapping bacteria by graphene nanosheets for isolation from environment, reactivation by sonication, and inactivation by near-infrared irradiation.

Bioactivity of Escherichia coli bacteria (as a simple model for microorganisms) and interaction of them with the environment were controlled by their capturing within aggregated graphene nanosheets. The oxygen-containing functional groups of chemically exfoliated single-layer graphene oxide nanosheets were reduced by melatonin as a biocompatible antioxidant. While each one of the graphene (oxide) suspension and melatonin solution did not separately show any considerable inactivation effects on the bacteria, aggregation of the sheets in the melatonin-bacterial suspension resulted in trapping the bacteria within the aggregated sheets, i.e., a kind of inactivation. The bacteria trapped within the aggregated sheets were biologically disconnected from their environment, because they could not proliferate in a culture medium and consume the glucose of their environment. However, after removing the sheets from the surface of the microorganisms by using sonication, they could again interact with their environment. The reactivated bacteria consumed glucose and could be proliferated; i.e., they were alive within the aggregated graphene sheets (here, at least for 24 h). The trapped alive bacteria could be photothermally inactivated forever by near-infrared irradiation at 808 nm. These results suggest that graphene nanosheets may potentially serve as an encapsulating material for delivery of such microorganisms and as an effective photothermal agent for inactivation of the graphene-wrapped microorganisms.