Hydrophobic Nanopores Research Articles

Triboelectrification During Water Intrusion–Extrusion into‐from Hydrophobic Nanopores

AbstractTriboelectrification is of great importance for many classical (petroleum, pharmaceutical, polymers) and emerging (generators, sensors) technologies. For energy generation, the contact area between the materials experiencing tribocharging is a key parameter: in addition to the nature of the materials, tribocharging scales with contact area. In this work, an approach is proposed to maximize tribocharging contact area by exploring the cycle of water intrusion–extrusion into–from hydrophobic nanopores with surface area orders of magnitude higher compared to flat or even nanotextured surfaces. Here this study reports the first experimental evidence of electrical energy generation upon water intrusion‐extrusion cycle under bias voltage‐free conditions. Combining these experiments with hierarchical molecular dynamic simulations/ab initio calculations, a microscopic mechanism of triboelectrification is hypothesized for water and grafted silica. The proposed approach provides a methodological alternative to studying solid–liquid contact electrification and an alternative root for a noticeable increase of specific contact area for solid–liquid triboelectric nanogenerators.

Energetic Characteristics of Hydrophobic Porous Materials as Candidates for Manufacturing of Nanorockets.

A new propulsion mechanism for nano- and microrocket engines is hypothesized. It is based on the instantaneous expulsion from hydrophobic nanopores triggered by irradiation from electromagnetic microwaves, ultrasound, or sudden pressure release. A large energy output is needed for the propulsion of a nanoparticle, and the value can be determined experimentally and by means of atomistic simulations. As such, we measured the heat of intrusion of water into ITQ-29 (LTA) pure silica zeolite with cage structure of pores. The heat effect is exothermic and equal to -7.3 ± 0.8 J/g of zeolite. Similar values were reported for chabazite, ZIF-8, and grafted mesoporous silica EVA. All these materials have cage structures of pores. In contrast, silicalite-1 (MFI) zeolite with a channel structure of pores exhibits endothermic intrusion. Molecular dynamics simulations of pure silica zeolites with LTA, CHA, and MFI topologies at a broad range of water loadings show that water becomes thermodynamically stable in cage-shaped pores while it is unstable in channel-shaped pores. A large energy release is expected during water expulsion from channel-type pores.

Mechanisms of ice crystal growth in nanoconfined spaces of cementitious composites at low temperatures: Insights from molecular dynamics simulations

AbstractThis study investigates the dynamics of ice crystal growth and stress distribution in nanoconfined spaces using molecular dynamics simulations. First, the interaction between the pore wall and coarse‐grained water is modified, leading to the development of pore models with varying wettability. Subsequently, the process of ice crystal growth within pores of 10 nm diameter is examined under different temperatures and hydrophobicity conditions. Results unveil that ice crystal growth induces substantial energy and enthalpy alterations within the system. Hydrophobic nanopores demonstrate a protective function by limiting ice crystal growth and water transport, thereby mitigating freezing damage. However, hydrophobic nanopores exhibit increased stress levels when saturated with water. The study employs the Zener pinning theory and mass transfer rates to qualitatively scrutinize the thermodynamic and kinetic interplay between the ice crystal interface and the degree of supercooling. These findings offer insights into the mechanisms of ice formation and stress evolution in nanoconfined environments.

Partial Water Intrusion and Extrusion in Hydrophobic Nanopores for Thermomechanical Energy Dissipation.

Forced wetting (intrusion) and spontaneous dewetting (extrusion) of hydrophobic/lyophobic nanoporous materials by water/nonwetting liquid are of great importance for a broad span of technological and natural systems such as shock-absorbers, molecular springs, separation, chromatography, ion channels, nanofluidics, and many more. In most of these cases, the process of intrusion-extrusion is not complete due to the stochastic nature of external stimuli under realistic operational conditions. However, understanding of these partial processes is limited, as most of the works are focused on an idealized complete intrusion-extrusion cycle. In this work, we show an experimental system operating under partial intrusion/extrusion conditions and present a simple model that captures its main features. We rationalize these operational conditions in terms of the pore entrance and cavity size distributions of the material, which control the range of intrusion/extrusion pressures.

Interplay of the forces governing steroid hormone micropollutant adsorption in vertically-aligned carbon nanotube membrane nanopores

Vertically-aligned carbon nanotube (VaCNT) membranes allow water to conduct rapidly at low pressures and open up the possibility for water purification and desalination, although the ultralow viscous stress in hydrophobic and low-tortuosity nanopores prevents surface interactions with contaminants. In this experimental investigation, steroid hormone micropollutant adsorption by VaCNT membranes is quantified and explained via the interplay of the hydrodynamic drag and friction forces acting on the hormone, and the adhesive and repulsive forces between the hormone and the inner carbon nanotube wall. It is concluded that a drag force above 2.2 × 10−3 pN overcomes the friction force resulting in insignificant adsorption, whereas lowering the drag force from 2.2 × 10−3 to 4.3 × 10−4 pN increases the adsorbed mass of hormones from zero to 0.4 ng cm−2. At a low drag force of 1.6 × 10−3 pN, the adsorbed mass of four hormones is correlated with the hormone−wall adhesive (van der Waals) force. These findings explain micropollutant adsorption in nanopores via the forces acting on the micropollutant along and perpendicular to the flow, which can be exploited for selectivity.

Spontaneous Dipole Reorientation in Confined Water and Its Effect on Wetting/Dewetting of Hydrophobic Nanopores.

The properties of nanoconfined fluids are important for a broad range of natural and engineering systems. In particular, wetting/dewetting of hydrophobic nanoporous materials is crucial due to their broad applicability for molecular separation and liquid purification; energy storage, conversion, recuperation, and dissipation; for catalysis, chromatography, and so on. In this work, a rapid, orchestrated, and spontaneous dipole reorientation was observed in hydrophobic nanotubes of various pore sizes d (7.9-16.5 Å) via simulations. This phenomenon leads to the fragmentation of water clusters in the narrow nanopores (d = 7.9, 10 Å) and strongly affects dewetting through cluster repulsion. The cavitation in these pores has an electrostatic origin. The dependence of hydrogen-bonded network properties on the tube aperture is obtained and is used to explain wetting (intrusion)-dewetting (extrusion) hysteresis. Computer simulations and experimental data demonstrate that d equals ca. 12.5 Å is a threshold between a nonhysteretic (spring) behavior, where intrusion-extrusion is reversible, and a hysteretic one (shock absorber), where hysteresis is prominent. This work suggests that water clustering and the electrostatic nature of cavitation are important factors that can be effectively exploited for controlling the wetting/dewetting of nanoporous materials.

Tuning Wetting-Dewetting Thermomechanical Energy for Hydrophobic Nanopores via Preferential Intrusion.

Heat and the work of compression/decompression are among the basic properties of thermodynamic systems. Being relevant to many industrial and natural processes, this thermomechanical energy is challenging to tune due to fundamental boundaries for simple fluids. Here via direct experimental and atomistic observations, we demonstrate, for fluids consisting of nanoporous material and a liquid, one can overcome these limitations and noticeably affect both thermal and mechanical energies of compression/decompression exploiting preferential intrusion of water from aqueous solutions into subnanometer pores. We hypothesize that this effect is due to the enthalpy of dilution manifesting itself as the aqueous solution concentrates upon the preferential intrusion of pure water into pores. We suggest this genuinely subnanoscale phenomenon can be potentially a strategy for controlling the thermomechanical energy of microporous liquids and tuning the wetting/dewetting heat of nanopores relevant to a variety of natural and technological processes spanning from biomedical applications to oil-extraction and renewable energy.

Voltage controlled iontronic switches: a computational method to predict electrowetting in hydrophobically gated nanopores

ABSTRACT Reliable and controllable switches are crucial in nanofluidics and iontronics. Ion channels found in nature serve as a rich source of inspiration due to their intricate mechanisms modulated by stimuli like pressure, temperature, chemical species, and voltage. The artificial replication of the properties of these channels is challenging due to their complex chemistry, limited stability range, and intricate moving parts, allosterically modulated. Nonetheless, we can harness some of the gating mechanisms of ion channels for nanofluidic and iontronic purposes. This theoretical and computational study explores the use of electrowetting in simple hydrophobic nanopores to control their conductance using an external applied voltage. We employ restrained molecular dynamics to calculate the free energy required for wetting a model nanopore under different voltages. Utilizing a simple theory, we generate free energy profiles across a wide voltage range. We also computed transition rates between conductive and non-conductive states, showing their voltage dependence and how this behavior can impair memory to the system, resembling the memristor behavior voltage-gated channels in the brain. The proposed framework provides a promising avenue for designing and controlling hydrophobic nanopores via electrowetting, enabling potential applications in neuromorphic iontronics.

Study on the slip behavior of CO2-crude oil on nanopore surfaces with different wettability

Unconventional reservoirs are characterized by a significant amount of micro and nanopores, which pose a critical challenge in accurately assessing the microscopic fluid transport behaviors to enhance oil and gas recovery in such reservoirs. CO2 injection is a promising recovery method for unconventional resources, hence the transport mechanism of CO2-crude oil at the nanoscale deserves further exploration. In this work, the flow and transport behaviors of CO2 and multicomponent crude oil in hydrophilic, neutral, and hydrophobic nanopores were investigated by the molecular dynamics simulation (MD) method. The CO2-crude oil shows a negative slip flow on hydrophilic surfaces, while it has a slip flow on neutral and hydrophobic surfaces. By illustrating the distribution structure of each component in the fluid and the solid-liquid interaction energy, the inherent causes of the slip mechanism of different wettability surfaces were revealed. The transport capacity and permeability of CO2-crude oil in the pores with different wettability were investigated. Modifying the Hagen-Poiseuille equation based on slip characteristics can effectively improve the prediction ability of nanopore permeability. This study is helpful to understand the flow and slip behavior of CO2-crude oil in nanopores of unconventional reservoirs, which provides a theoretical basis for accurately predicting the migration of reservoir fluid in nanopores.

Nanoconfined Water-Ion Coordination Network for Flexible Energy Dissipation Device.

Water-ion interaction in a nanoconfined environment that deeply constrains spatial freedoms of local atomistic motion with unconventional coupling mechanisms beyond that in a free, bulk state is essential to spark designs of a broad spectrum of nanofluidic devices with unique properties and functionalities. Here, wereport that the interaction between ions and water molecules in a hydrophobic nanopore forms a coordination network with an interaction density that is nearly four-fold as that of the bulk counterpart. Such strong interaction facilitates the connectivity of the water-ion network and is uncovered by corroborating the formation of ion clusters and the reduction of particle dynamics. Wedesign a liquid-nanopore energy dissipation system and demonstrate in both molecular simulations and experiments that the formed coordination network controls the outflow of confined electrolytes along with a pressure reduction, capable of providing flexible protection to personnel and devices and instrumentations against external mechanical impacts and attacks. This article is protected by copyright. All rights reserved.

Confined water–encapsulated activated carbon for capturing short-chain perfluoroalkyl and polyfluoroalkyl substances from drinking water

The global ecological crisis of perfluoroalkyl and polyfluoroalkyl substances (PFASs) in drinking water has gradually shifted from long-chain to short-chain PFASs; however, the widespread established PFAS adsorption technology cannot cope with the impact of such hydrophilic pollutants given the inherent defects of solid-liquid mass transfer. Herein, we describe a reagent-free and low-cost strategy to reduce the energy state of short-chain PFASs in hydrophobic nanopores by employing an in situ constructed confined water structure in activated carbon (AC). Through direct (driving force) and indirect (assisted slip) effects, the confined water introduced a dual-drive mode in the confined water-encapsulated activated carbon (CW-AC) and completely eliminated the mass transfer barrier (3.27 to 5.66 kcal/mol), which caused the CW-AC to exhibit the highest adsorption capacity for various short-chain PFASs (C-F number: 3-6) among parent AC and other adsorbents reported. Meanwhile, benefiting from the chain length- and functional group-dependent confined water-binding pattern, the affinity of the CW-AC surpassed the traditional hydrophobicity dominance and shifted toward hydrophilic short-chain PFASs that easily escaped treatment. Importantly, the ability of CW-AC functionality to directly transfer to existing adsorption devices was verified, which could treat 21,000 bed volumes of environment-related high-load (~350 ng/L short-chain PFAS each) real drinking water to below the World Health Organization's standard. Overall, our results provide a green and cost-effective in situ upgrade scheme for existing adsorption devices to address the short-chain PFAS crisis.

Confinement effects on distribution and transport of neutral solutes in a small hydrophobic nanopore

Confinement effects on distribution and transport of neutral solutes in a small hydrophobic nanopore

Quantifying the effects of dissolved nitrogen and carbon dioxide on drying pressure of hydrophobic nanopores.

The effects of a dissolved gas on the behavior of liquid in cylindrical nanopores are investigated in the framework of Gibbsian composite system thermodynamics and classical nucleation theory. An equation is derived relating the phase equilibrium of a mixture of a subcritical solvent and a supercritical gas to the curvature of the liquid-vapor interface. Both the liquid and the vapor phases are treated nonideally, which is shown to be important for the accuracy of the predictions in the case of water with dissolved nitrogen or carbon dioxide. The behavior of water in nanoconfinement is found to be only affected when the gas amount is significantly more than the saturation concentration of these gases at atmospheric conditions. However, such concentrations can be easily reached at high pressures during intrusion if there is sufficient gas present in the system, especially considering gas oversolubility in confinement. By including an adjustable line tension term in the free energy equation (-44pJ/m for all points), the theory can make predictions in line with the few data points available from recent experimental work. However, we note that such a fitted value empirically accounts for multiple effects and should not be interpreted as the energy of the three-phase contact line. Compared to molecular dynamics simulations, our method is easy to implement, requires minimal computational resources, and is not limited to small pore sizes and/or short simulation times. It provides an efficient path for first-order estimation of the metastability limit of water-gas solutions in nanopores.

An atomistically informed multiscale approach to the intrusion and extrusion of water in hydrophobic nanopores.

Understanding intrusion and extrusion in nanoporous materials is a challenging multiscale problem of utmost importance for applications ranging from energy storage and dissipation to water desalination and hydrophobic gating in ion channels. Including atomistic details in simulations is required to predict the overall behavior of such systems because the statics and dynamics of these processes depend sensitively on microscopic features of the pore, such as the surface hydrophobicity, geometry, and charge distribution, and on the composition of the liquid. On the other hand, the transitions between the filled (intruded) and empty (extruded) states are rare events that often require long simulation times, which are difficult to achieve with standard atomistic simulations. In this work, we explored the intrusion and extrusion processes using a multiscale approach in which the atomistic details of the system, extracted from molecular dynamics simulations, informed a simple Langevin model of water intrusion/extrusion in the pore. We then used the Langevin simulations to compute the transition times at different pressures, validating our coarse-grained model by comparing it with nonequilibrium molecular dynamics simulations. The proposed approach reproduces experimentally relevant features such as the time and temperature dependence of the intrusion/extrusion cycles, as well as specific details about the shape of the cycle. This approach also drastically increases the timescales that can be simulated, reducing the gap between simulations and experiments and showing promise for more complex systems.

Unusual Water Flow in Ultra-Tight Porous Media: Integration of Profession and Innovation

Hydraulic fracturing is an effective method for stimulating reservoirs, making the economic development of ultra-tight shale gas and coalbed methane reservoirs possible. These formations are rich in nanopores, in which the fracturing fluid, such as fresh water, the flow, and the behavior of this flow differ significantly from those described in the classic Navier-Stokes formula. In bulk space, the interaction force exerted by the solid phase can be ignored, but the solid–fluid interaction plays a dominant role in nanoconfinement spaces in which the pore size is comparable to the molecular diameter. Nanoconfined water molecules tend to approach the water-wet pore surface, enhancing the water viscosity, which is a key parameter affecting the water flow capacity. Conversely, water molecules tend to stay in the middle of nanopores when subjected to a hydrophobic surface, leading to a decrease in viscosity. Thus, nanoconfined water viscosity is a function of the strength of the surface–fluid interaction, rather than a constant parameter, in classic theory. However, the influence of varying the viscosity on the nanoscale water flow behavior is still not fully understood. In this research, we incorporate wettability-dependent viscosity into a pore network modeling framework for stable flow for the first time. Our results show that: (a) the increase in viscosity under hydrophilic nanoconfinement could reduce the water flow capacity by as much as 11.3%; (b) the boundary slip is the primary mechanism for boosting the water flow in hydrophobic nanopores, as opposed to the slight enhancement contributed by a viscosity decline; and (c) water flow characterization in nanoscale porous media must consider both the pore size and surface wettability. Revealing the varying viscosity of water flow confined in nanopores can advance our microscopic understanding of water behavior and lay a solid theoretical foundation for fracturing-water invasion or flowback simulation.

Dynamic molecular ordering in multiphasic nanoconfined ionic liquids detected with time-resolved diffusion NMR

Molecular motion in nanosized channels can be highly complicated. For example, water molecules in ultranarrow hydrophobic nanopores move rapidly and coherently in a single file, whereas by increasing the pore size they organize into coaxial tubes, displaying stratified diffusion. Interestingly, an analogous complex motion is predicted in viscous charged fluids, such as room temperature ionic liquids (RTILs) confined in nanoporous carbon or silica; however, experimental evidence is still pending. Here, by combining 1H NMR diffusion experiments in different relaxation windows with molecular dynamics simulations, we show that the imidazolium-based RTIL [BMIM]+[TCM]−, entrapped in the MCM-41 silica nanopores, exhibits an intricate dynamic molecular ordering; adsorbed RTIL molecules form a fluctuating charged layer near the pore walls, while in the bulk pore space they diffuse discretely in coaxial tubular shells, with molecular mean square displacement following a nearly ∼τ0.5 time dependence, characteristic of single file diffusion.

Nanofluidic Attenuation of Metal-Organic Frameworks

Porous materials with energy absorption characteristics have been used for attenuation against hazardous vibrations and noises. The intrusion of liquid water and aqueous solutions into hydrophobic nanoporous materials such as metal-organic frameworks (MOFs) present an attractive pathway to engineering new attenuation technologies. In this process, hydrostatic pressure forces water to intrude hydrophobic nanopores, thereby converting mechanical work into interfacial energy through nanoscale interfacial interactions. Once the external pressure is removed, water molecules can flow out of the nanopores spontaneously, making the system reversible. We envision that this mechanism has the potential of innovating attenuation technologies, so in this work we provided a preliminary study in this direction. We investigated a material system consisting of water and a commonly used MOF, zeolitic imidazolate framework-8 (ZIF-8), and demonstrated its reversibility and stability under cyclic pressurization, considered its performance at various peak pressures and frequencies, its tunability in terms of intrusion pressure, and its potential in hydrogel forms. These features are important for potential attenuation technologies based on this novel mechanism.

The impact of secondary channels on the wetting properties of interconnected hydrophobic nanopores

Pores in nanoporous materials can be interconnected in different ways; preliminary evidence exists that connecting channels can affect the overall hydrophobicity of the material thus providing an additional parameter in designing applications that require controlled wetting properties. In this work, we show that the length of secondary channels is a key parameter to tune the overall hydrophobicity of the material: short secondary channels make the main pore effectively more hydrophilic than a simple cylindrical pore, while long secondary channels enhance its hydrophobicity, producing the macroscopic effect of superhydrophobic textures. This rich behavior is rooted in the spontaneous filling of the secondary channels, which is unexpected based on classical capillarity. This length-dependent filling is explained by the formation of hydrogen bonds bridging the main pores which becomes less frequent with longer channels. These findings could be useful for designing nanoporous materials with tailored wetting properties.

Progress of water desalination applications based on wettability and surface characteristics of graphene and graphene oxide: A review

Seawater desalination techniques have been continuously developed to tackle the water scarcity problems. This review article provides comprehensive discussion on the progress of water desalination applications that utilize the unique wettability and surface characteristics of graphene and graphene oxides, which are being employed as ultrafiltration membranes in either a monolayer or multilayer nanosheet configuration. The interaction of water with graphene materials and their wetting characteristics as well as the controlling factors are examined. Particularly, the designs and roles of hydrophilic and hydrophobic nanopores and nanochannels are discussed. A focus is also made on recent developments of graphene membrane with respect to water flow, salt rejection and durability.

Confinement Effects on Distribution and Transport of Neutral Solutes in a Small Hydrophobic Nanopore.

Molecular dynamics simulations are used to study confinement effects in small cylindrical silica pores with extended hydrophobic surface functionalization as realized, for example, in reversed-phase liquid chromatography (RPLC) columns. In particular, we use a 6 nm cylindrical and a 10 nm slit pore bearing the same C18 stationary phase to compare the conditions inside the smaller-than-average pores within an RPLC column to column-averaged properties. Two small, neutral, apolar to moderately polar solutes are used to assess the consequences of spatial confinement for typical RPLC analytes with water (W)-acetonitrile (ACN) mobile phases at W/ACN ratios between 70/30 and 10/90 (v/v). The simulated data show that true bulk liquid behavior, as observed over an extended center region in the 10 nm slit pore, is not recovered within the 6 nm cylindrical pore. Instead, the ACN-enriched solvent layer around the C18 chain ends (the ACN ditch), a general feature of hydrophobic interfaces equilibrated with aqueous-organic liquids, extends over the entire pore lumen of the small cylindrical pore. This renders the entire pore a highly hydrophobic environment, where, contrary to column-averaged behavior, neither the local nor the pore-averaged sorption and diffusion of analytes scales directly with the W/ACN ratio of the mobile phase. Additionally, the solute polarity-related discrimination between analytes is enhanced. The consequences of local ACN ditch overlap in RPLC columns are reminiscent of ion transport in porous media with charged surfaces, where electrical double-layer overlap occurring locally in smaller pores leads to discrimination between co- and counterionic species.