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We performed nonequilibrium molecular dynamics (NEMD) simulations and solvent permeation experiments to unravel the mechanism of water transport in reverse osmosis (RO) membranes. The NEMD simulations reveal that water transport is driven by a pressure gradient within the membranes, not by a water concentration gradient, in marked contrast to the classic solution-diffusion model. We further show that water molecules travel as clusters through a network of pores that are transiently connected. Permeation experiments with water and organic solvents using polyamide and cellulose triacetate RO membranes showed that solvent permeance depends on the membrane pore size, kinetic diameter of solvent molecules, and solvent viscosity. This observation is not consistent with the solution-diffusion model, where permeance depends on the solvent solubility. Motivated by these observations, we demonstrate that the solution-friction model, in which transport is driven by a pressure gradient, can describe water and solvent transport in RO membranes.

State-of-the-art polymeric membranes are unable to perform the high-precision ion separations needed for technologies essential to a circular economy and clean energy future. Coordinative interactions are a mechanism to increase sorption of a target species into a membrane, but the effects of these interactions on membrane permeability and selectivity are poorly understood. We use a multilayered polymer membrane to assess how ion-membrane binding energies affect membrane permeability of similarly sized cations: Cu 2+ , Ni 2+ , Zn 2+ , Co 2+ , and Mg 2+ . We report that metals with higher binding energy to iminodiacetate groups of the polymer more selectively permeate through the membrane in multisalt solutions than single-salt solutions. In contrast, weaker binding species are precluded from diffusing into the polymer membrane, which leads to passage proportional to binding energy and independent of membrane thickness. Our findings demonstrate that selectivity of polymeric membranes can markedly increase by tailoring ion-membrane binding energy and minimizing membrane thickness.

Graphene material has found tremendous applications in water desalination, DNA sequencing and energy storage. Multiple nanopores are etched to create opening for water desalination and energy storage applications. The nanopores created are of the order of 3-5 nm allowing multiple ions to transport through the pore. In this paper, we present for the first time, molecular dynamics study of single ion transport, where only one ion passes through the graphene nanopore. The diameter of the graphene nanopore is of the same order as the hydration layers formed around each ion. Analogous to single electron transport resulting from ionic transport is observed for the first time. The current-voltage characteristics of such a device are similar to single electron transport in quantum dots. The current is blocked until a critical voltage, as the ions are trapped inside a hydration shell. The trapped ions have a high energy barrier compared to the applied input electrical voltage, preventing the ion to break free from the hydration shell. This region is called “Coulomb blockade region”. In this region, we observe zero transport of ions inside the nanopore. However, when the electrical voltage is beyond the critical voltage, the ion has sufficient energy to break free from the energy barrier created by the hydration shell to enter into the pore. Thus, the input voltage can control the transport of the ion inside the nanopore. The device therefore acts as a binary storage unit, storing 0 when no ion passes through the pore and storing 1 when a single ion passes through the pore. We therefore postulate that the device can be used for fluidic computing applications in chemistry and biology, mimicking a computer. Furthermore, the trapped ion stores a finite charge in the Coulomb blockade region; hence the device also acts a super capacitor.

Protein detection plays a key role in determining the single point mutations which can cause a variety of diseases. Nanopore sequencing provides a label-free, single base, fast and long reading platform, which makes it amenable for personalized medicine. A challenge facing nanopore technology is the noise in ionic current. Here, we show that a nanoporous single-layer molybdenum disulfide (MoS2) can detect individual amino acids in a polypeptide chain (16 units) with a high accuracy and distinguishability. Using extensive molecular dynamics simulations (with a total aggregate simulation time of 66 µs) and machine learning techniques, we featurize and cluster the ionic current and residence time of the 20 amino acids and identify the fingerprints of the signals. Using logistic regression, nearest neighbor, and random forest classifiers, the sensor reading is predicted with an accuracy of 72.45, 94.55, and 99.6%, respectively. In addition, using advanced ML classification techniques, we are able to theoretically predict over 2.8 million hypothetical sensor readings’ amino acid types. Molecular dynamics simulations combined with machine learning techniques enable the prediction of MoS2 nanopore sequencing capabilities. A team led by N. R. Aluru at the University of Illinois at Urbana-Champaign used logistic regression, nearest neighbor, and random forest classifiers to develop a machine learning-based platform capable of predicting the sensing capabilities of nanoporous, atomically thin MoS2. The material was shown to be able to identify individual amino acids in polypeptide chains with high accuracy and distinguishability. Twenty amino acids could be detected and categorized in different classes based on current-residence time training data, with an accuracy of up to 99.6%. These results show promise for the development of amino acid detection platforms with atomically thin materials assisted by machine learning.

Making use of the osmotic pressure difference between fresh water and seawater is an attractive, renewable and clean way to generate power and is known as 'blue energy'(1-3). Another electrokinetic phenomenon, called the streaming potential, occurs when an electrolyte is driven through narrow pores either by a pressure gradient(4) or by an osmotic potential resulting from a salt concentration gradient(5). For this task, membranes made of two-dimensional materials are expected to be the most efficient, because water transport through a membrane scales inversely with membrane thickness(5-7). Here we demonstrate the use of single-layer molybdenum disulfide (MoS2) nanopores as osmotic nanopower generators. We observe a large, osmotically induced current produced from a salt gradient with an estimated power density of up to 10(6) watts per square metre-a current that can be attributed mainly to the atomically thin membrane of MoS2. Low power requirements for nanoelectronic and optoelectric devices can be provided by a neighbouring nanogenerator that harvests energy from the local environment(8-11)-for example, a piezoelectric zinc oxide nanowire array(8) or single-layer MoS2 (ref. 12). We use our MoS2 nanopore generator to power a MoS2 transistor, thus demonstrating a self-powered nanosystem.

Spatially nonuniform strain is important for engineering the pseudomagnetic field and band structure of graphene. Despite the wide interest in strain engineering, there is still a lack of control on device-compatible strain patterns due to the limited understanding of the structure-strain relationship. Here, we study the effect of substrate corrugation and curvature on the strain profiles of graphene via combined experimental and theoretical studies of a model system: graphene on closely packed SiO2 nanospheres with different diameters (20-200 nm). Experimentally, via quantitative Raman analysis, we observe partial adhesion and wrinkle features and find that smaller nanospheres induce larger tensile strain in graphene, theoretically, molecular dynamics simulations confirm the same microscopic structure and size dependence of strain and reveal that a larger strain is caused by a stronger, inhomogeneous interaction force between smaller nanospheres and graphene. This molecular-level understanding of the strain mechanism is important for strain engineering of graphene and other two-dimensional materials., Comment: Nano Letters (2018)

A fully controllable nano-electro-mechanical device that can pump fluids at nanoscale is proposed. Using molecular dynamics simulations, we show that an applied electric field to an ion@C60 inside a water-filled carbon nanotube can pump water with excellent efficiency. The key physical mechanism governing the fluid pumping is the conversion of electrical energy into hydrodynamic flow with efficiencies as high as 64%. Our results show that water can be compressed up to 7% higher than its bulk value by applying electric fields. High flux of water (up to 13,000 molecules/ns) is obtained by the electro-mechanical, piston-cylinder-like moving mechanism of the ion@C60 in the CNT. This large flux results from the piston-like mechanism, compressibility of water (increase in density of water due to molecular ordering), orienting dipole along the electric field and efficient electrical to mechanical energy conversion. Our findings can pave the way towards efficient energy conversion, pumping of fluids at nanoscale, and drug delivery.

Efficient desalination of water continues to be a problem facing the society. Advances in nanotechnology have led to the development of a variety of nanoporous membranes for water purification. Here we show, by performing molecular dynamics simulations, that a nanopore in a single-layer molybdenum disulfide can effectively reject ions and allow transport of water at a high rate. More than 88% of ions are rejected by membranes having pore areas ranging from 20 to 60 Å2. Water flux is found to be two to five orders of magnitude greater than that of other known nanoporous membranes. Pore chemistry is shown to play a significant role in modulating the water flux. Pores with only molybdenum atoms on their edges lead to higher fluxes, which are ∼70% greater than that of graphene nanopores. These observations are explained by permeation coefficients, energy barriers, water density and velocity distributions in the pores., Nanopores in two-dimensional materials are arousing considerable interest as filtration membranes to solve the problem of providing fresh water to a growing population. Here, the authors evaluate the potential of single-layer MoS2 to effectively reject salt ions whilst maintaining high flow rates.