Gate-All-Around Nanopore Osmotic Power Generators.

Nanofluidic channels in a membrane represent a promising avenue for harnessing blue energy from salinity gradients, relying on permselectivity as a pivotal characteristic crucial for inducing electricity through diffusive ion transport. Surface charge emerges as a central player in the osmotic energy conversion process, emphasizing the critical significance of a judicious selection of membrane materials to achieve optimal ion permeability and selectivity within specific channel dimensions. Alternatively, here we report a field-effect approach for in situ manipulation of the ion selectivity in a nanopore. Application of voltage to a surround-gate electrode allows precise adjustment of the surface charge density at the pore wall. Leveraging the gating control, we demonstrate permselectivity turnover to enhanced cation selective transport in multipore membranes, resulting in a 6-fold increase in the energy conversion efficiency with a power density of 15 W/m2 under a salinity gradient. These findings not only advance our fundamental understanding of ion transport in nanochannels but also provide a scalable and efficient strategy for nanoporous membrane osmotic power generation.

High-Q lasing via all-dielectric Bloch-surface-wave platform.

Controlling the propagation and emission of light via Bloch surface waves (BSWs) has held promise in the field of on-chip nanophotonics. BSW-based optical devices are being widely investigated to develop on-chip integration systems. However, a coherent light source that is based on the stimulated emission of a BSW mode has yet to be developed. Here, we demonstrate lasers based on a guided BSW mode sustained by a gain-medium guiding structure microfabricated on the top of a BSW platform. A long-range propagation length of the BSW mode and a high-quality lasing emission of the BSW mode are achieved. The BSW lasers possess a lasing threshold of 6.7 µJ/mm2 and a very narrow linewidth reaching a full width at half maximum as small as 0.019 nm. Moreover, the proposed lasing scheme exhibits high sensitivity to environmental changes suggesting the applicability of the proposed BSW lasers in ultra-sensitive devices.

Chiroptical Response Inversion and Enhancement of Room-Temperature Exciton-Polaritons Using 2D Chirality in Perovskites.

Although chiral semiconductors have shown promising progress in direct circularly polarized light (CPL) detection and emission, they still face potential challenges. A chirality-switching mechanism or approach integrating two enantiomers is needed to discriminate the handedness of a given CPL; additionally, a large material volume is required for sufficient chiroptical interaction. These two requirements pose significant obstacles to the simplification and miniaturization of the devices. Here, room-temperature chiral polaritons fulfilling dual-handedness functions and exhibiting a more-than-two-order enhancement of the chiroptical signal are demonstrated, by embedding a 40 nm-thick perovskite film with a 2D chiroptical effect into a Fabry-Pérot cavity. By mixing chiral perovskites with different crystal structures, a pronounced 2D chiroptical effect is accomplished in the perovskite film, featured by an inverted chiroptical response for counter-propagating CPL. This inversion behavior matches the photonic handedness switch during CPL circulation in the Fabry-Pérot cavity, thus harvesting giant enhancement of the chiroptical response. Furthermore, affected by the unique quarter-wave-plate effects, the polariton emission achieves a chiral dissymmetry of ±4% (for the emission from the front and the back sides). The room-temperature polaritons with the strong dissymmetric chiroptical interaction shall have implications on a fundamental level and future on-chip applications for biomolecule analysis and quantum computing.

Suppression of wetting transition on evaporative fakir droplets by using slippery superhydrophobic surfaces with low depinning force.

This study experimentally investigated the evaporation and wetting transition behavior of fakir droplets on five different microstructured surfaces. Diamond-like carbon was introduced as the substrate, and the influence of varying the width, height, and pitch of the micropillars was assessed. The experimental results showed that the interfacial properties of the surfaces change the evaporation behavior and the starting point of the wetting transition. An important result of this study is the demonstration of a slippery superhydrophobic surface with low depinning force that suppresses the transition from the Cassie-Baxter state to the Wenzel state for microdroplets less than 0.37 mm in diameter, without employing large pillar height or multiscale roughness. By selecting an appropriate pillar pitch and employing tapered micropillars with small pillar widths, the solid-liquid contact at the three-phase contact line was reduced and low depinning forces were obtained. The underlying mechanism by which slippery superhydrophobic surfaces suppress wetting transitions is also discussed. The accuracy of the theoretical models for predicting the critical transition parameters was assessed, and a numerical model was developed in the surface evolver to compute the penetration of the droplet bottom meniscus within the micropillars.

Enhancement of oxygen reduction reactivity on TiN by tuning the work function via metal doping.

Oxide layers on conductive TiN have recently been investigated to catalyse the oxygen reduction reaction (ORR) in acidic media. The ORR reactivity, i.e., activity and selectivity, has been correlated with the surface nitrogen atoms. A new strategy, optimising the work function via the doping of foreign metals, is revealed herein to enhance the reactivity.

A theoretical understanding of ionic current through a nanochannel driven by a viscosity gradient.

HYPOTHESIS: Different thermodynamic forces owing to the gradient of temperature, electrical potential, or concentration can drive ionic current through charged membranes. It has been recently shown that a viscosity gradient can drive an electrical current through a negatively charged nanochannel (Wiener and Stein, arXiv: 1807.09106). A model description of this phenomenon, based on the Maxwell-Stefan equation will help unravel the dominating physical mechanisms in so-called visco-migration. THEORY: To understand the physical mechanisms underlying this phenomenon, we employed the Maxwell-Stefan equation to develop a 1D model and obtain a relation between the flux of solvents and the driving forces. Viscosity gradients are known to drive transport, but the development of an electrical current has not been theoretically described prior to this work. FINDINGS: Our 1D model shows that the ionic current depends on the ideality of the solvent, though both ideal and non-ideal scenarios demonstrated good agreement with experimental data. We employed the model to understand the impact of solution bulk ionic strength and pH on the drift of ionic species with same reservoirs solution properties. Our modeling results unveiled the significant impact of bulk solution properties on the drift of ions which is in agreement with the experiments. Moreover, we have shown that the diffusion gradient along the nanochannel contributes significantly into driving ionic species if we even apply a small ionic concentration gradient to both reservoirs. Our modeling results may pave the way for finding novel applications for drift of ions in a diffusion gradient, which can be induced by connecting reservoirs of different viscosity fluids.

Review of component designs for post-COVID-19 HVAC systems: possibilities and challenges.

The globally occurring recurrent waves of the COVID-19 pandemic, primarily caused by the transmission of aerosolized droplets from an infected person to a healthy person in the indoor environment, has led to the urgency of designing new modes of indoor ventilation. To prevent cross-contaminations due to airborne viruses, bacteria, and other pollutants in indoor environments, heating ventilation and air-conditioning (HVAC) systems need to be redesigned with anti-pandemic components. The three vital anti-pandemic components for the post-COVID-19 HVAC systems, as identified by the authors, are: a biological contaminant inactivation unit, a volatile organic compound decomposition unit, and an advanced air filtration unit. The purpose of the current article is to provide an overview of the latest research outcomes toward designing these anti-pandemic components and pointing out the future promises and challenges. In addition, the role of personalized ventilation in minimizing the risk of indoor cross-contamination by employing various air terminal devices is discussed. The authors believe that this article will encourage HVAC designers to develop effective anti-pandemic components to minimize the indoor airborne transmission.

Evaluation of gas permeability in porous separators for polymer electrolyte fuel cells: Computational fluid dynamics simulation based on micro-x-ray computed tomography images.

Pore structures and gas transport properties in porous separators for polymer electrolyte fuel cells are evaluated both experimentally and through simulations. In the experiments, the gas permeabilities of two porous samples, a conventional sample and one with low electrical resistivity, are measured by a capillary flow porometer, and the pore size distributions are evaluated with mercury porosimetry. Local pore structures are directly observed with micro-x-ray computed tomography (CT). In the simulations, the effective diffusion coefficients of oxygen and the air permeability in porous samples are calculated using random walk Monte Carlo simulations and computational fluid dynamics (CFD) simulations, respectively, based on the x-ray CT images. The calculated porosities and air permeabilities of the porous samples are in good agreement with the experimental values. The simulation results also show that the in-plane permeability is twice the through-plane permeability in the conventional sample, whereas it is slightly higher in the low-resistivity sample. The results of this study show that CFD simulation based on micro-x-ray CT images makes it possible to evaluate anisotropic gas permeabilities in anisotropic porous media.

Investigation of entrance effects on particle electrophoretic behavior near a nanopore for resistive pulse sensing.

Resistive pulse sensing using solid-state nanopores provides a unique platform for detecting the structure and concentration of molecules of different types of analytes in an electrolyte solution. The capture of an entity into a nanopore is subject not only to the electrostatic force but also the effect of electroosmotic flow originating from the charged nanopore surface. In this study, we theoretically analyze spherical particle electrophoretic behavior near the entrance of a charged nanopore. By investigating the effects of pore size, particle-pore distance, and salt concentration on particle velocity, we summarize dominant mechanisms governing particle behavior for a range of conditions. In the literature, the Helmholtz-Smoluchowski equation is often adopted to evaluate particle translocation by considering the zeta potential difference between the particle and nanopore surfaces. We point out that, due to the difference of the electric field inside and outside the nanopore and the influence from the existence of the particle itself, the zeta potential of the particle, however, needs to be at least 30% higher than that of the nanopore to allow the particle to enter into the nanopore when its velocity is close to zero. Accordingly, we summarize the effective salt concentrations that enable successful particle capture and detection for different pore sizes, offering direct guidance for nanopore applications.

Multi-Walled Carbon Nanotube-Assisted Encapsulation Approach for Stable Perovskite Solar Cells.

Perovskite solar cells (PSCs) are regarded as the next-generation thin-film energy harvester, owing to their high performance. However, there is a lack of studies on their encapsulation technology, which is critical for resolving their shortcomings, such as their degradation by oxygen and moisture. It is determined that the moisture intrusion and the heat trapped within the encapsulating cover glass of PSCs influenced the operating stability of the devices. Therefore, we improved the moisture and oxygen barrier ability and heat releasing capability in the passivation of PSCs by adding multi-walled carbon nanotubes to the epoxy resin used for encapsulation. The 0.5 wt% of carbon nanotube-added resin-based encapsulated PSCs exhibited a more stable operation with a ca. 30% efficiency decrease compared to the ca. 63% decrease in the reference devices over one week under continuous operation. Specifically, the short-circuit current density and the fill factor, which are affected by moisture and oxygen-driven degradation, as well as the open-circuit voltage, which is affected by thermal damage, were higher for the multi-walled carbon nanotube-added encapsulated devices than the control devices, after the stability test.

Molecular dynamics study of water confined in MIL-101 metal-organic frameworks.

Molecular dynamics simulations of water adsorbed in Material Institute Lavoisier MIL-101(Cr) metal-organic frameworks are performed to analyze the kinetic properties of water molecules confined in the framework at 298.15 K and under different vapor pressures and clarify the water adsorption mechanism in MIL-101(Cr). The terahertz frequency-domain spectra (THz-FDS) of water are calculated by applying fast Fourier transform to the configurational data of water molecules. According to the characteristic frequencies in the THz-FDS, the dominant motions of water molecules in MIL-101(Cr) can be categorized into three types: (1) low-frequency translational motion (0-0.5 THz), (2) medium-frequency vibrational motion (2-2.5 THz), and (3) high-frequency vibrational motion (>6 THz). Each type of water motion is confirmed by visualizing the water configuration in MIL-101(Cr). The ratio of the number of water molecules with low-frequency translational motion to the total number of water molecules increases with the increase in vapor pressure. In contrast, that with medium-frequency vibrational motion is found to decrease with vapor pressure, exhibiting a pronounced decrease after water condensation has started in the cavities. That with the high-frequency vibrational motion is almost independent of the vapor pressure. The interactions between different types of water molecules affect the THz-FDS. Furthermore, the self-diffusion coefficient and the velocity auto-correlation function are calculated to clarify the adsorption state of the water confined in MIL-101(Cr). To confirm that the general trend of the THz-FDS does not depend on the water model, the simulations are performed using three water models, namely, rigid SPC/E, flexible SPC/E, and rigid TIP5PEw.

Nanoconfined Electrochemical Sensing of Single Silver Nanoparticles with a Wireless Nanopore Electrode.

Single entity electrochemistry (SEE) has emerged as a promising method for precise measurement and fundamental understanding of the heterogeneity of single entities. Herein, we propose the dual responsive SEE sensing of the silver nanoparticles (AgNPs) collisions through a wireless nanopore electrode (WNE). Given the high temporal resolution and low background noise features, the Faradaic and capacitive currents provide the AgNPs' collision response. The electron transfer between the AgNPs and the electrode surface is identified under a bipolar electrochemical mechanism. Compared to the ultramicroelectrode, multistep oxidation of 30 nm AgNPs is observed due to the decreased interaction of the nanoparticles to the electrode. Moreover, the nanoconfinement of WNE plays a vital role in the repeated capturing of nanoparticles from the nontunneling region into the tunneling region until a complete oxidation. As a comparison, the collision of 5 nm AgNPs with higher interaction at the electrode surface shows great decrease in the multistep events. Thus, we propose a nanoconfined interaction based SEE method which could be used for simultaneously capturing the Faradaic and capacitive response. The nanoconfined interaction based SEE method holds great promise in the better understanding of heterogeneity of single particles.

Electroosmotic flow: From microfluidics to nanofluidics.

Electroosmotic flow (EOF), a consequence of an imposed electric field onto an electrolyte solution in the tangential direction of a charged surface, has emerged as an important phenomenon in electrokinetic transport at the micro/nanoscale. Because of their ability to efficiently pump liquids in miniaturized systems without incorporating any mechanical parts, electroosmotic methods for fluid pumping have been adopted in versatile applications-from biotechnology to environmental science. To understand the electrokinetic pumping mechanism, it is crucial to identify the role of an ionically polarized layer, the so-called electrical double layer (EDL), which forms in the vicinity of a charged solid-liquid interface, as well as the characteristic length scale of the conducting media. Therefore, in this tutorial review, we summarize the development of electrical double layer models from a historical point of view to elucidate the interplay and configuration of water molecules and ions in the vicinity of a solid-liquid interface. Moreover, we discuss the physicochemical phenomena owing to the interaction of electrical double layer when the characteristic length of the conducting media is decreased from the microscale to the nanoscale. Finally, we highlight the pioneering studies and the most recent works on electro osmotic flow devoted to both theoretical and experimental aspects.

Joule Heating Effects on Transport-Induced-Charge Phenomena in an Ultrathin Nanopore.

Transport-induced-charge (TIC) phenomena, in which the concentration imbalance between cations and anions occurs when more than two chemical potential gradients coexist within an ultrathin dimension, entail numerous nanofluidic systems. Evidence has indicated that the presence of TIC produces a nonlinear response of electroosmotic flow to the applied voltage, resulting in complex fluid behavior. In this study, we theoretically investigate thermal effects due to Joule heating on TIC phenomena in an ultrathin nanopore by computational fluid dynamics simulation. Our modeling results show that the rise of local temperature inside the nanopore significantly enhances TIC effects and thus has a significant influence on electroosmotic behavior. A local maximum of the solution conductivity occurs near the entrance of the nanopore at the high salt concentration end, resulting in a reversal of TIC across the nanopore. The Joule heating effects increase the reversal of TIC with the synergy of the negatively charged nanopore, and they also enhance the electroosmotic flow regardless of whether the nanopore is charged. These theoretical observations will improve our knowledge of nonclassical electrokinetic phenomena for flow control in nanopore systems.

Augmenting the Carbon Dioxide Uptake and Selectivity of Metal-Organic Frameworks by Metal Substitution: Molecular Simulations of LMOF-202.

Metal organic frameworks (MOFs) are promising porous materials for the adsorption of CO2. Here, we report the study of a luminescent MOF (LMOF), called LMOF-202. We have employed Grand Canonical Monte Carlo (GCMC) simulations to understand and explain the adsorption phenomena inside LMOF-202, and based on the phenomena happening at the molecular level, we have varied the metal ions in LMOF-202 to increase the CO2 affinity and selectivity of the material. We show that the CO2 adsorption capacity and selectivity can be increased by approximately 1.5 times at 1 bar and 298 K by changing the metal ion from Zn to Ba. We also report the feasibility of using this material to capture CO2 from flue gas under realistic conditions (1 bar and 298 K). This work shows that LMOF-202 merits further consideration as a carbon capture adsorbent.

Li@C60 endohedral fullerene as a supraatomic dopant for C60 electron-transporting layers promoting the efficiency of perovskite solar cells.

C60:Li@C60 hybrid n-type semiconducting films were first fabricated. The Fermi level of 1% Li@C60-added C60 films was determined to be -4.52 eV, which was 0.12 eV higher than that of pristine C60 films. A fraction of Li@C60 is distributed uniformly within the C60 film. Its application in PSCs was demonstrated, in which the addition of Li@C60 into a C60 film improved the device performance.

Water Filling and Emptying Kinetics in Two-Dimensional Hexagonal Mesoporous Silica of the Same Pore Diameter but Different Pore Lengths.

The effect of pore length on the water filling and emptying rates was studied using mesoporous silica (MPS) with same pore diameter but different pore lengths. The pore diameter of the synthesized MPS was ∼8 nm, whereas the average pore lengths were 460, 1,770, and 4000 nm. The gravimetric method was employed to record the time course of the adsorbed mass of water in MPS at 298 K and 1 atm. In both the filling and emptying processes, the relaxation curves (time course of adsorbed mass of water per unit mass of sample) were not significantly related to the pore length. This independence of the initial adsorption and desorption rates on the pore length suggests that the surface of the MPS aggregates is the bottleneck in the overall adsorption and desorption processes and that the initial mass flux in each nanopore is inversely proportional to the pore length. Furthermore, because the relaxation times to reach the equilibrium state were independent of the pore length, the mass flux of water uptake, release, and transport probably increase with an increase in the pore length during the entire adsorption and desorption processes. A transport model to describe these phenomena was proposed.

Thermodynamic Stability Analysis of Microbubbles Confined in a Liquid Droplet.

A thermodynamic stability analysis of microbubbles in an enclosed volume of a volatile liquid-noncondensable gas solution was performed. The stability conditions for the formation of the bubbles and the relationship between the equilibrium bubble radius and the equilibrium bubble number were investigated. The calculation results show that even if the saturation vapor pressure of a volatile liquid is higher than the pressure of the liquid phase, stable noncondensable gas bubbles appear in a closed system. Under such a condition, if the initial pressure of the noncondensable gas, which is proportional to the total number of moles of a noncondensable gas in the system, increases, stable bubbles appear at a lower temperature. At a fixed parameter of h0, which is defined as the ratio of the saturation vapor pressure of the volatile liquid minus the pressure in the liquid phase to the initial pressure of the noncondensable gas, the equilibrium bubble radius increases with a decrease of the equilibrium bubble number.

Theory of Transport-Induced-Charge Electroosmotic Pumping toward Alternating Current Resistive Pulse Sensing.

In this work, we study transport-induced-charge electroosmosis toward alternating current resistive pulse sensing for the next generation of biomedical applications. Transport-induced-charge electroosmosis, being a new class of electrokinetic phenomenon, occurs as a salt concentration gradient works in synergy with an electric field in ultrathin nanopores. Apart from the conventional electric double layer-governed electroosmotic flow in which the flow behavior is subject to the surface charge, it is found that the transport-induced-charge electroosmotic flow behaves independently of surface charge magnitude but can be linearly regulated by the bulk salt concentration bias. The reversal of the electric field simultaneously inverses the induced charge allowing the establishment of a unidirectional flow under the application of a periodic alternating current field. This unique phenomenon permits continuous water and nanoparticles pumping through a two-dimensional material nanopore in spite of the reversal of the electric field. Built upon this mechanism, we propose a theoretical prototype of alternating current resistive pulse sensing in a two-dimensional nanopore system.

Molecular simulations of water adsorption and transport in mesopores with varying hydrophilicity arrangements.

The adsorption and transport of water in an open cylindrical mesopore with two different inner surface arrangements of hydrophilicities were examined by molecular simulations. The first model has a weak hydrophilic surface at both entrances of the pore and a stronger hydrophilic surface in the mid-section. The second pore has stronger hydrophilic surfaces at the entrances and weaker in the middle region. The simulation results show that the water adsorption isotherms obtained from Grand Canonical Monte Carlo simulations and pore filling curves acquired from Grand Canonical Molecular Dynamics simulations change depending on the arrangement of the strong and weak hydrophilic surfaces. In the first model, water condensation focuses on the mid-section forming a liquid bridge or a film, which creates a concave meniscus accelerating subsequent adsorption within the pore. Two bridges form in the entrance regions, where a cavity naturally occurs in between the films, in the second model. The different filling and emptying mechanisms clearly change the adsorption-desorption characteristics for the two pore types, but the second type generally showed faster transitions overall. Flux and meniscus analysis also reveals a circulating flow at the menisci of the interfaces within the pore. The results are expected to be valuable in understanding the effects of interior surface modification of nanopores in future applications.