We demonstrate rectification of ionic transport in a nanofluidic diode fabricated by introducing a surface charge discontinuity in a nanofluidic channel. Device current-voltage (I-V) characteristics agree qualitatively with a one-dimensional model at moderate to high ionic concentrations. This study illustrates ionic flow control using surface charge patterning in nanofluidic channels under high bias voltages.
Transmembrane proteins often contain nanoscale channels through which ions and molecules can pass either passively (by diffusion) or actively (by means of forced transport). These proteins play important roles in selective mass transport and electrical signalling in many biological processes. Fluidic nanochannels that are 1-2 nm in diameter act as functional mimics of protein channels, and have been used to explore the transport of ions and molecules in confined liquids. Here we report ion transport in 2-nm-deep nanochannels fabricated by standard semiconductor manufacturing processes. Ion transport in these nanochannels is dominated by surface charge until the ion concentration exceeds 100 mM. At low concentrations, proton mobility increases by a factor of four over the bulk value, possibly due to overlapping of the hydrogen-bonding network of the two hydration layers adjacent to the hydrophilic surfaces. The mobility of K+/Na+ ions also increases as the bulk concentration decreases, although the reasons for this are not completely understood.
In an aqueous solution, the surface of inorganic nanochannels acquires charges from ionization, ion adsorption, and ion dissolution. These surface charges draw counter-ions toward the surface and repel co-ions. In the presence of a concentration gradient, counter-ions are transported through nanochannels much more easily than co-ions, which results in a net charge migration of one type of ions. The Gibbs free energy of mixing, which forces ion diffusion, thus can be converted into electrical energy by using inorganic ion-selective nanochannels. Silica nanochannels with heights of 4, 26, and 80 nm were used in this study. We experimentally investigated the power generation from these nanochannels placed between two potassium chloride solutions with various combinations of concentrations. The power generation per unit channel volume increases when the concentration gradient increases, and also increases as channel height decreases. The highest power density measured was 7.7 W/m 2 . Our data also indicate that the energy conversion efficiency and the ion selectivity increase with a decrease of concentrations and channel height. The best efficiency obtained was 31%. Power generation from concentration gradients in inorganic ion-selective nanochannels could be used in a variety of applications, including micro batteries and micro power generators.
Superfast water transport discovered in graphitic nanoconduits, including carbon nanotubes and graphene nanochannels, implicates crucial applications in separation processes and energy conversion. Yet lack of complete understanding at the single-conduit level limits development of new carbon nanofluidic structures and devices with desired transport properties for practical applications. Here, we show that the hydraulic resistance and slippage of single graphene nanochannels can be accurately determined using capillary flow and a novel hybrid nanochannel design without estimating the capillary pressure. Our results reveal that the slip length of graphene in the graphene nanochannels is around 16 nm, albeit with a large variation from 0 to 200 nm regardless of the channel height. We corroborate this finding with molecular dynamics simulation results, which indicate that this wide distribution of the slip length is due to the surface charge of graphene as well as the interaction between graphene and its silica substrate.
Thanks to its unique features at the nanoscale, nanofluidics, the study and application of fluid flow in nanochannels/nanopores with at least one characteristic size smaller than 100 nm, has enabled the occurrence of many interesting transport phenomena and has shown great potential in both bio- and energy-related fields. The unprecedented growth of this research field is apparently attributed to the rapid development of micro/nanofabrication techniques. In this review, we summarize recent activities and achievements of nanofabrication for nanofluidic devices, especially those reported in the past four years. Three major nanofabrication strategies, including nanolithography, microelectromechanical system based techniques, and methods using various nanomaterials, are introduced with specific fabrication approaches. Other unconventional fabrication attempts which utilize special polymer properties, various microfabrication failure mechanisms, and macro/microscale machining techniques are also presented. Based on these fabrication techniques, an inclusive guideline for materials and processes selection in the preparation of nanofluidic devices is provided. Finally, technical challenges along with possible opportunities in the present nanofabrication for nanofluidic study are discussed.
Cavitation, known as the formation of vapor bubbles when liquids are under tension, is of great interest both in condensed matter science as well as in diverse applications such as botany, hydraulic engineering, and medicine. Although widely studied in bulk and microscale-confined liquids, cavitation in the nanoscale is generally believed to be energetically unfavorable and has never been experimentally demonstrated. Here we report evaporation-induced cavitation in water-filled hydrophilic nanochannels under enormous negative pressures up to −7 MPa. As opposed to receding menisci observed in microchannel evaporation, the menisci in nanochannels are pinned at the entrance while vapor bubbles form and expand inside. Evaporation in the channels is found to be aided by advective liquid transport, which leads to an evaporation rate that is an order of magnitude higher than that governed by Fickian vapor diffusion in macro-and microscale evaporation. The vapor bubbles also exhibit unusual motion as well as translational stability and symmetry, which occur because of a balance between two competing mass fluxes driven by thermocapillarity and evaporation. Our studies expand our understanding of cavitation and provide new insights for phase-change phenomena at the nanoscale.nanobubbles | confined fluids | confined water | bubble dynamics | bubble formation
Capillary evaporation in nanoscale conduits is an efficient heat/mass transfer strategy that has been widely utilized by both nature and mankind. Despite its broad impact, the ultimate transport limits of capillary evaporation in nanoscale conduits, governed by the evaporation/condensation kinetics at the liquid-vapor interface, have remained poorly understood. Here we report experimental study of the kinetic limits of water capillary evaporation in two dimensional nanochannels using a novel hybrid channel design. Our results show that the kinetic-limited evaporation fluxes break down the limits predicated by the classical Hertz-Knudsen equation by an order of magnitude, reaching values up to 37.5 mm/s with corresponding heat fluxes up to 8500 W/cm. The measured evaporation flux increases with decreasing channel height and relative humidity but decreases as the channel temperature decreases. Our findings have implications for further understanding evaporation at the nanoscale and developing capillary evaporation-based technologies for both energy- and bio-related applications.
Evaporation from nanopores plays an important role in various natural and industrial processes that require efficient heat and mass transfer. The ultimate performance of nanopore-evaporation-based processes is dictated by evaporation kinetics at the liquid–vapor interface, which has yet to be experimentally studied down to the single nanopore level. Here we report unambiguous measurements of kinetically limited intense evaporation from individual hydrophilic nanopores with both hydrophilic and hydrophobic top outer surfaces at 22 °C using nanochannel-connected nanopore devices. Our results show that the evaporation fluxes of nanopores with hydrophilic outer surfaces show a strong diameter dependence with an exponent of nearly −1.5, reaching up to 11-fold of the maximum theoretical predication provided by the classical Hertz–Knudsen relation at a pore diameter of 27 nm. Differently, the evaporation fluxes of nanopores with hydrophobic outer surfaces show a different diameter dependence with an exponent of −0.66, achieving 66% of the maximum theoretical predication at a pore diameter of 28 nm. We discover that the ultrafast diameter-dependent evaporation from nanopores with hydrophilic outer surfaces mainly stems from evaporating water thin films outside of the nanopores. In contrast, the diameter-dependent evaporation from nanopores with hydrophobic outer surfaces is governed by evaporation kinetics inside the nanopores, which indicates that the evaporation coefficient varies in different nanoscale confinements, possibly due to surface-charge-induced concentration changes of hydronium ions. This study enhances our understanding of evaporation at the nanoscale and demonstrates great potential of evaporation from nanopores.
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