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1.
Nano Lett ; 24(37): 11756-11762, 2024 Sep 18.
Artículo en Inglés | MEDLINE | ID: mdl-39236070

RESUMEN

Developing a nanofluidic membrane with simultaneously enhanced ion selectivity and permeability for high-performance osmotic energy conversion has largely been unexplored. Here, we tackle this issue by the confinement of highly space-charged hydrogels within an orderedly aligned nanochannel array membrane. The nanoconfinement effect endows the hydrogel-based membrane with excellent antiswelling property. Furthermore, experimental and simulation results demonstrate that such a nanoconfined hydrogel membrane exhibits massively enhanced cation selectivity and ion transport properties. Consequently, an amazingly high power density up to ∼52.1 W/m2 with an unprecedented energy conversion efficiency of 37.5% can be reached by mixing simulated salt-lake water (5 M NaCl) and river water (0.01 M NaCl). Both efficiency indexes surpass those of most of the state-of-the-art nanofluidic membranes. This work offers insights into the design of highly ion-selective membranes to achieve ultrafast ion transport and high-performance osmotic energy harvesting.

2.
Proc Natl Acad Sci U S A ; 121(38): e2407877121, 2024 Sep 17.
Artículo en Inglés | MEDLINE | ID: mdl-39259594

RESUMEN

Understanding the structure in the nanoscopic region of water that is in direct contact with solid surfaces, so-called contact layer, is key to quantifying macroscopic properties that are of interest to e.g. catalysis, ice nucleation, nanofluidics, gas adsorption, and sensing. We explore the structure of the water contact layer on various technologically relevant solid surfaces, namely graphene, MoS[Formula: see text], Au(111), Au(100), Pt(111), and Pt(100), which have been previously hampered by time and length scale limitations of ab initio approaches or force field inaccuracies, by means of molecular dynamics simulations based on ab initio machine learning potentials built using an active learning scheme. Our results reveal that the in-plane intermolecular correlations of the water contact layer vary greatly among different systems: Whereas the contact layer on graphene and on Au(111) is predominantly homogeneous and isotropic, it is inhomogeneous and anisotropic on MoS[Formula: see text], on Au(100), and on the Pt surfaces, where it additionally forms two distinct sublayers. We apply hydrodynamics and the theory of the hydrophobic effect, to relate the energy corrugation and the characteristic length-scales of the contact layer with wetting, slippage, the hydration of small hydrophobic solutes and diffusio-osmotic transport. Thus, this work provides a microscopic picture of the water contact layer and links it to macroscopic properties of liquid/solid interfaces that are measured experimentally and that are relevant to wetting, hydrophobic solvation, nanofluidics, and osmotic transport.

3.
Proc Natl Acad Sci U S A ; 121(38): e2318386121, 2024 Sep 17.
Artículo en Inglés | MEDLINE | ID: mdl-39264743

RESUMEN

Capillarity-driven transport in nanoporous solids is widespread in nature and crucial for modern liquid-infused engineering materials. During imbibition, curved menisci driven by high negative Laplace pressures exert an enormous contractile load on the porous matrix. Due to the challenge of simultaneously monitoring imbibition and deformation with high spatial resolution, the resulting coupling of solid elasticity to liquid capillarity has remained largely unexplored. Here, we study water imbibition in mesoporous silica using optical imaging, gravimetry, and high-resolution dilatometry. In contrast to an expected Laplace pressure-induced contraction, we find a square-root-of-time expansion and an additional abrupt length increase when the menisci reach the top surface. The final expansion is absent when we stop the imbibition front inside the porous medium in a dynamic imbibition-evaporation equilibrium, as is typical for transpiration-driven hydraulic transport in plants, especially in trees. These peculiar deformation behaviors are validated by single-nanopore molecular dynamics simulations and described by a continuum model that highlights the importance of expansive surface stresses at the pore walls (Bangham effect) and the buildup or release of contractile Laplace pressures as menisci collectively advance, arrest, or disappear. Our model suggests that these observations apply to any imbibition process in nanopores, regardless of the liquid/solid combination, and that the Laplace contribution upon imbibition is precisely half that of vapor sorption, due to the linear pressure drop associated with viscous flow. Thus, simple deformation measurements can be used to quantify surface stresses and Laplace pressures or transport in a wide variety of natural and artificial porous media.

4.
ACS Appl Mater Interfaces ; 16(39): 52358-52363, 2024 Oct 02.
Artículo en Inglés | MEDLINE | ID: mdl-39298559

RESUMEN

Here, we report an osmotic power generator (OPG) using a restacked membrane of vanadium pentoxide (V2O5) nanosheets and an ion-infused gelatin hydrogel. This gel osmotic power generator (GOPG) has several advantages over traditional liquid-based OPG in portability, power output, and spillage safety. Under a 1000-fold salinity gradient, the GOPG achieved an output power density of 0.13 W m-2. We have studied the effect of different ions, the concentration gradient, and the membrane thickness to achieve maximum power output. Notably, physical damage to the V2O5 membrane can be healed by adding a drop of water. Cracks or damage to the gelatin gel can be healed by reheating and cooling. The GOPGs can be easily connected in series and/or parallel to add up the voltage and/or current values generated by individual devices for practical powering applications. We have demonstrated lighting up an LED and powering a humidity meter using a series of combinations with the GOPG.

5.
ACS Nano ; 2024 Sep 10.
Artículo en Inglés | MEDLINE | ID: mdl-39253836

RESUMEN

In the field of nanoconfined fluids, there are striking examples of deformation/transport coupling in which mechanical solicitation of the confining solid and dynamics of the confined fluid impact each other. While this intriguing behavior can be harnessed for applications (e.g., energy storage, phase separation, catalysis), the underlying mechanisms remain to be understood. Here, using molecular simulations, we investigate fluid flow in deformable nanoporous materials subjected to external mechanical stresses. We show that the pore mechanical properties significantly affect fluid flow as they lead to significant pore deformations and different fluid organization at the solid surface. Despite such mechanical effects, we show that the fluid thermodynamic properties (i.e., adsorption) can be linked consistently to Darcy's law for the permeability by invoking a pore size definition based on the concept of Gibbs' dividing surface. In particular, regardless of the solid stiffness and applied external stress, all data can be rationalized by accounting for the fluid viscosity and slippage at the solid surface (independently of a specific pore size definition). Using such a formalism, we establish that the intimate relation─derived using the linear response theory─between collective diffusivity and hydraulic permeability remains valid. This allows linking consistently microscopic dynamics experiments and macroscopic permeability experiments on fluid flow in deformable nanoporous materials.

6.
Nanomaterials (Basel) ; 14(18)2024 Sep 19.
Artículo en Inglés | MEDLINE | ID: mdl-39330676

RESUMEN

The combination of micro- or nanofluidics and strong light-matter coupling has gained much interest in the past decade, which has led to the development of advanced systems and devices with numerous potential applications in different fields, such as chemistry, biosensing, and material science. Strong light-matter coupling is achieved by placing a dipole (e.g., an atom or a molecule) into a confined electromagnetic field, with molecular transitions being in resonance with the field and the coupling strength exceeding the average dissipation rate. Despite intense research and encouraging results in this field, some challenges still need to be overcome, related to the fabrication of nano- and microscale optical cavities, stability, scaling up and production, sensitivity, signal-to-noise ratio, and real-time control and monitoring. The goal of this paper is to summarize recent developments in micro- and nanofluidic systems employing strong light-matter coupling. An overview of various methods and techniques used to achieve strong light-matter coupling in micro- or nanofluidic systems is presented, preceded by a brief outline of the fundamentals of strong light-matter coupling and optofluidics operating in the strong coupling regime. The potential applications of these integrated systems in sensing, optofluidics, and quantum technologies are explored. The challenges and prospects in this rapidly developing field are discussed.

7.
Nano Lett ; 24(39): 12054-12061, 2024 Oct 02.
Artículo en Inglés | MEDLINE | ID: mdl-39167431

RESUMEN

We study the role of underlying substrates on interfacial heat transfer within supported graphene nanochannels. Due to graphene's translucency, the underlying substrate, apart from its known hydrodynamic impact on fluid flow, also influences heat transport. We introduce the term "thermal translucency" to describe this phenomenon in the context of interfacial heat transfer. Our findings reveal that the Kapitza resistance, RK, is dependent on the specific underlying substrate. The specific underlying substrate alters the water-graphene interface potential landscape due to graphene's translucency, leading to a breakdown in the inverse relationship between interfacial water density peaks and RK values, typically observed at water-graphene and water-graphite interfaces. Remarkably, higher interfacial water density peaks correlate with more ordered energy patterns, not necessarily tied to more hydrophilic substrates as the literature commonly suggests for lower RK values. The insights provided have implications for controlling and tuning thermal transport and heat storage in nanofluidic devices.

8.
Chempluschem ; : e202400133, 2024 Aug 26.
Artículo en Inglés | MEDLINE | ID: mdl-39185588

RESUMEN

The creation of ordered structures of molecules assembled from solution onto a substrate is a fundamental technological necessity across various disciplines, spanning from crystallography to organic electronics. However, achieving macroscopic order poses significant challenges, since the process of deposition is inherently impacted by factors like solvent evaporation and dewetting flows, which hinder the formation of well-organized structures. Traditional methods like drop casting or spin coating encounter limitations due to the rapid kinetics of solvent evaporation, leading to limited control over final uniformity and order. In response to these challenges, Solvent Vapour Annealing (SVA) has emerged as a promising solution for realizing ordered molecular structures at scales ranging from nano- to milli- meters. SVA decouples the self-assembly stage from the deposition stage by utilizing solvent vapours which can enable rearrangement, movement, and diffusion of large molecules on the surface even on a macroscopic scale. Essentially acting as "molecular lubricants," solvent vapours enable the formation of well-ordered molecular films. This review discusses the advancements, obstacles, and promising strategies associated with utilizing SVA for the development of innovative nanostructured thin films, and emphasizes the originality and effectiveness of molecular assembly on substrates achieved through this approach.

9.
ACS Nano ; 18(35): 24118-24127, 2024 Sep 03.
Artículo en Inglés | MEDLINE | ID: mdl-39172927

RESUMEN

We investigate the interfacial transport of water and hydrophobic solutes on van der Waals bilayers and heterostructures formed by stacking graphene, hBN, and MoS2 using extensive ab initio molecular dynamics simulations. We compute water slippage and the diffusio-osmotic transport coefficient of hydrophobic particles at the interface by combining hydrodynamics and the theory of the hydrophobic effect. We find that slippage is dominated by the layer that is in direct contact with water and only marginally altered by the second layer, leading to a so-called "slip opacity". The screening of the lateral forces, where the liquid does not feel the forces coming from the second nearest layer, is one of the factors leading to the "slip opacity" in our systems. The diffusio-osmotic transport of small hydrophobes (with a radius below 2.5 Å) is also affected by the slip opacity, being dramatically enhanced by slippage. Furthermore, the direction of diffusio-osmotic flow is controlled by the solute size, with the flow in the opposite direction of the concentration gradient for smaller hydrophobes, and vice versa for larger ones. We connect our findings to the wetting properties of two-dimensional materials, and we propose that slippage and wetting can be controlled separately: whereas the slippage is mostly determined by the layer in closer proximity to water, wetting can be finely tuned by stacking different two-dimensional materials. Our study advances the computational design of two-dimensional materials and van der Waals heterostructures, enabling precise control over wetting and slippage properties for applications in coatings and water purification membranes.

10.
Electrophoresis ; 2024 Jul 04.
Artículo en Inglés | MEDLINE | ID: mdl-38962855

RESUMEN

Miniaturized systems have attracted much attention with the recent advances in microfluidics and nanofluidics. From the capillary electrophoresis, the development of glass-based microfluidic and nanofluidic technologies has supported advances in microfluidics and nanofluidics. Most microfluidic systems, especially nanofluidic systems, are still simple, such as systems constructed with simple straight nanochannels and bulk-scale electrodes. One of the bottlenecks to the development of more complicated and sophisticated systems is to develop the locally integrated nano-electrodes. However, there are still issues with integrating nano-electrodes into nanofluidic devices because it is difficult to fit the nano-electrode size into a nanofluidic channel at the nanometer level. In this study, we propose a new method for the fabrication of local nano-electrodes in nanofluidic devices with nanofluidic and nano-electrochemistry-based experiments. An electroplating solution was introduced to a nanochannel with control of the flow and the electroplating reaction, by which nano-electrodes were successfully fabricated. In addition, a nanofluidic device was available for nanofluidic experiments with the application of 200 kPa. This method can be applied to any electroplating material such as gold and copper. The local nano-electrode will make a significant contribution to the development of more complicated and sophisticated nanofluidic electrophoresis systems and to local electric detection methods for various nanofluidic devices.

11.
Angew Chem Int Ed Engl ; 63(40): e202409349, 2024 Oct 01.
Artículo en Inglés | MEDLINE | ID: mdl-38962957

RESUMEN

Two-dimensional polymers (2DPs) and their layer-stacked 2D covalent organic frameworks (2D COFs) membranes hold great potential for harvesting sustainable osmotic energy. The nascent research has yet to simultaneously achieve high ionic flux and selectivity, primarily due to inefficient ion transport dynamics. This is directly related to ultrasmall pore size (<3 nm), much smaller than the duple Debye length in the diluted electrolyte (6-20 nm), as well as low charge density (<4.5 mC m-2). Here, we introduce a π-conjugated viologen-based 2DP (V2DP) membrane possessing a large pore size of 4.5 nm, strategically enhancing the overlapping of the electric double layer, coupled with an exceptional positive surface charge density (~6 mC m-2). These characteristics enable the membrane to facilitate high anion flux while maintaining ideal selectivity. Notably, V2DP membranes realize an impressive current density of 5.5×103 A m-2, surpassing benchmarks set by previously reported nanofluidic membranes. In the practical application scenario involving the mixing of artificial seawater and river water, the V2DP membranes exhibit a considerable ion transference number of 0.70 towards Cl-, contributing to an outstanding power density of ~55 W m-2. Theoretical calculations reveal the important role of the large quantity of anion transport sites, which act as binding sites evenly located in the positively charged N-containing pyridine rings. These binding sites enable kinematic coupling and decoupling between anions and the V2DP skeleton, establishing a continuous Cl- ion transport pathway. This work demonstrates the great promise of large-area ultrathin 2DP membranes featuring highly organized charged ion transport networks when applied for osmotic energy conversion.

12.
Nanomaterials (Basel) ; 14(14)2024 Jul 16.
Artículo en Inglés | MEDLINE | ID: mdl-39057885

RESUMEN

Under ideal conditions, nanotubes with a fixed negative tube-wall charge will reject anions and transport-only cations. Because many proposed nanofluidic devices are optimized in this ideally cation-permselective state, it is important to know the experimental conditions that produce ideal responses. A parameter called Ccrit, the highest salt concentration in a contacting solution that still produces ideal cation permselectivity, is of particular importance. Pioneering potentiometric studies on gold nanotubes were interpreted using an electrostatic model that states that Ccrit should occur when the Debye length in the contacting salt solution becomes equivalent to the tube radius. Since this "double-layer overlap model" (DLOM), treats all same-charge ions as identical point charges, it predicts that all same-charged cations should produce the same Ccrit. However, the effect of cation on Ccrit in gold nanotubes was never investigated. This knowledge gap has become important because recent studies with a polymeric cation-permselective nanopore membrane showed that DLOM failed for every cation studied. To resolve this issue, we conducted potentiometric studies on the effect of salt cation on Ccrit for a 10 nm diameter gold nanotube membrane. Ccrit for all cations studied were, within experimental error, the same and identical, with values predicted by DLOM. The reason DLOM prevailed for the gold nanotubes but failed for the polymeric nanopores stems from the chemical difference between the fixed negative charges of these two membranes.

13.
Small ; : e2402188, 2024 Jun 20.
Artículo en Inglés | MEDLINE | ID: mdl-38899397

RESUMEN

Ionic diodes provide ionic current rectification (ICR), which is useful for micro-/nanofluidic devices for ionic current-mediated applications. However, the modulation of ICR is not fully developed, and current challenges include limited active control and localized modulation for further multiplexing of micro-/nanofluidic ionic diodes. Herein, a microfluidic device integrated with particle-assembly-based ionic diodes (PAIDs) and a gas-flow channel above them is presented. Exploiting in-situ gas permeation through a polymeric film, precise control over the physiochemical conditions of the nanopores within the PAIDs, leading to the modulation of ICR is demonstrated. The investigation not only characterizes the rectification properties of the PAIDs but also unveils their capacitor-like behavior and the ability to actively modulate ICR using various gas flows. Furthermore, the reversible modulation of ICR through dynamic switching of gas-dissolved solutions, enabling ion-signal amplification is showcased. This pioneering approach of in situ gas-permeation offers programmable manipulation of ion transport along PAIDs, thereby positioning ionic diodes as versatile nanofluidic components. Looking ahead, the development of multiplexed PAIDs in an addressable manner on a chip holds promise for practical applications across diverse fields, including ion signaling, ion-based logic, chemical reactors, and (bio)chemical sensing.

14.
Talanta ; 277: 126331, 2024 Sep 01.
Artículo en Inglés | MEDLINE | ID: mdl-38823324

RESUMEN

Recognition and separation of chiral isomers are of great importance in both industrial and biological applications. However, owing to identical molecular formulas and chemical properties of enantiomers, signal transduction and amplification are still two major challenges in chiral sensing. In this study, we developed an enantioselective device by integrating chiral covalent organic framework nanosheets (CONs) with nanochannels for sensitive identification and quantification of enantiomers. Using 3,4-dihydroxyphenylalanine (DOPA) as the model analyte, the as-prepared chiral nanofluidic device exhibits a remarkable chiral recognition ability to l-DOPA than d-DOPA. More importantly, due to the chelation of DOPA with Fe3+ ions, it can efficiently block the ion transport through channel and shield the channel surface charge, which will amplify the difference in the electrochemical response of l-DOPA and d-DOPA. Therefore, a sensitive chiral recognition can be achieved using the present nanofluidic device coupled using electrochemical amplification strategy. Notably, using this method, an ultra-low concentration of l-DOPA (as low as 0.21 pM) can be facilely and successfully detected with a linear range of 1 pM-10 µM. This study provides a reliable and sensitive approach for achieving highly selective detection of chiral molecules.

15.
ACS Nano ; 18(25): 16141-16150, 2024 Jun 25.
Artículo en Inglés | MEDLINE | ID: mdl-38856748

RESUMEN

Foundations of nanofluidics can enable advances in diverse applications such as water desalination, energy harvesting, and biological analysis. Dynamically manipulating nanofluidic properties, such as diffusion and friction, is an area of great scientific interest. Twisted bilayer graphene, particularly at the magic angle, has garnered attention for its unconventional superconductivity and correlated insulator behavior due to strong electronic correlations. The impact of the electronic properties of moiré patterns in twisted bilayer graphene on structural and dynamic properties of water remains largely unexplored. Computational challenges, stemming from simulating large unit cells using density functional theory, have hindered progress. This study addresses this gap by investigating water behavior on twisted bilayer graphene, employing a deep neural network potential (DP) model trained with a data set from ab initio molecular dynamics simulations. It is found that as the twisted angle approaches the magic angle, interfacial water friction increases, leading to a reduced water diffusion. Notably, the analysis shows that at smaller twisted angles with larger moiré patterns, water is more likely to reside in AA stacking regions than AB (or BA) stacking regions, a distinction that diminishes with smaller moiré patterns. This study illustrates the potential for leveraging the distinctive properties of moiré systems to effectively control and optimize interfacial fluid behavior.

16.
ACS Nano ; 18(25): 16199-16207, 2024 Jun 25.
Artículo en Inglés | MEDLINE | ID: mdl-38860922

RESUMEN

Biological signaling correlates with the interrelation between ion and nanofluidic transportation pathways. However, artificial embodies with reconfigurable ion-fluid transport interaction aspects remain largely elusive. Herein, we unveiled an intimate interplay between nanopore-driven advancing flow and ion carriage for the spontaneous imbibition of aqueous solutions at the nanoporous thin film level. Ionic factors dominate transport phenomena processing and integration (ions influence fluid motion, which in turn governs the self-regulated ion traveling). We show an ion-induced translation effect that finely converts a chemical input, the nature of ions, into a related fluidic output: modulation of the extent of imbibition. We further find complex imbibition dynamics induced by the ion type and population. We peculiarly pinpoint a stop-and-go effective transport process with a programmable delay time triggered by selective guest-host interactions. The ion-fluid transport interplay is captured by a simple model that considers the counterbalance between the capillary infiltration and solution concentration, owing to water loss at the nanoporous film-air interface. Our results demonstrate that nanopore networks present fresh scenarios for understanding and controlling autonomous macroscopic liquid locomotion and offer a distinctive working principle for smart ion operation.

17.
Eur J Clin Microbiol Infect Dis ; 43(8): 1533-1543, 2024 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-38825624

RESUMEN

PURPOSE: This study compared the results of the new Sysmex PA-100 AST System, a point-of-care analyser, with routine microbiology for the detection of urinary tract infections (UTI) and performance of antimicrobial susceptibility tests (AST) directly from urine. METHODS: Native urine samples from 278 female patients with suspected uncomplicated UTI were tested in the Sysmex PA-100 and with reference methods of routine microbiology: urine culture for bacteriuria and disc diffusion for AST. RESULTS: The analyser delivered bacteriuria results in 15 min and AST results within 45 min. Sensitivity and specificity for detection of microbiologically confirmed bacteriuria were 84.0% (89/106; 95% CI: 75.6-90.4%) and 99.4% (155/156; 95% CI: 96.5-100%), respectively, for bacterial species within the analyser specifications. These are Escherichia coli, Klebsiella pneumoniae, Proteus mirabilis, Enterococcus faecalis and Staphylococcus saprophyticus, which are common species causing uncomplicated UTI. Overall categorical agreement (OCA) for AST results for the five antimicrobials tested in the Sysmex PA-100 (amoxicillin/clavulanic acid, ciprofloxacin, fosfomycin, nitrofurantoin and trimethoprim) ranged from 85.4% (70/82; 95%CI: 75.9-92.2%) for ciprofloxacin to 96.4% (81/84; 95% CI: 89.9-99.3%) for trimethoprim. The Sysmex PA-100 provided an optimal treatment recommendation in 218/278 cases (78.4%), against 162/278 (58.3%) of clinical decisions. CONCLUSION: This first clinical evaluation of the Sysmex PA-100 in a near-patient setting demonstrated that the analyser delivers phenotypic AST results within 45 min, which could enable rapid initiation of the correct targeted treatment with no further adjustment needed. The Sysmex PA-100 has the potential to significantly reduce ineffective or unnecessary antibiotic prescription in patients with UTI symptoms.


Asunto(s)
Antibacterianos , Bacteriuria , Pruebas de Sensibilidad Microbiana , Humanos , Femenino , Bacteriuria/diagnóstico , Bacteriuria/microbiología , Bacteriuria/tratamiento farmacológico , Pruebas de Sensibilidad Microbiana/instrumentación , Pruebas de Sensibilidad Microbiana/métodos , Antibacterianos/farmacología , Sensibilidad y Especificidad , Bacterias/efectos de los fármacos , Bacterias/aislamiento & purificación , Sistemas de Atención de Punto , Infecciones Urinarias/microbiología , Infecciones Urinarias/diagnóstico , Infecciones Urinarias/tratamiento farmacológico , Adulto , Persona de Mediana Edad , Anciano , Adulto Joven , Anciano de 80 o más Años , Adolescente
18.
Nano Lett ; 24(27): 8268-8276, 2024 Jul 10.
Artículo en Inglés | MEDLINE | ID: mdl-38940535

RESUMEN

The elegance and accuracy of biological ion channels inspire the fabrication of artificial devices with similar properties. Here, we report the fabrication of iontronic devices capable of delivering ions at the nanomolar (nmol) level of accuracy. The triangular nanofluidic device prepared with reconstructed vanadium pentoxide (VO) membranes of thickness 45 ± 5.5 µm can continuously deliver K+, Na+, and Ca2+ ions at the rate of 0.44 ± 0.24, 0.35 ± 0.06, and 0.03 nmol/min, respectively. The ionic flow rate can be further tuned by modulating the membrane thickness and salt concentration at the source reservoir. The triangular VO device can also deliver ions in minuscule doses (∼132 ± 9.7 nmol) by electrothermally heating (33 °C) with a nichrome wire (NW) or applying light of specific intensities. The simplicity of the fabrication process of reconstructed layered material-based nanofluidic devices allows the design of complicated iontronic devices such as the three-terminal-Ni-VO (3T-Ni-VO) devices.

19.
Adv Sci (Weinh) ; 11(31): e2400233, 2024 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-38885420

RESUMEN

Nanofluidic energy harvesting from salinity gradients is studied in 2D nanomaterials-based membranes with promising performance as high ion selectivity and fast ion transport. In addition, moving forward to scalable, feasible systems requires environmentally friendly materials to make the application sustainable. Clay-based membranes are attractive for being environmentally friendly, non-hazardous, and easy to manipulate materials. However, achieving underwater stability for clay-based membranes remains challenging. In this work, the synthetic clay Laponite is used to prepare clay-based membranes with high stability and excellent performance for osmotic energy harvesting. The Laponite membranes (Lap-membranes) are stabilized by low-temperature annealing treatment to effectively reduce the interlayer space, achieving a continuous operation under salinity gradients. Furthermore, the Lap-membranes conserve integrity while soaking in water for more than one month. The output power density improves from ≈4.97 W m-2 on the pristine membrane to ≈9.89 W m-2 in the membrane treated 12 h at 300 °C from a 30-fold concentration gradient. Especially, It is found that the presence of interlayer water to be favorable for ion transport. Different mechanisms are proposed in the Lap-membranes involved for efficient ion selectivity and the states found with varying annealing temperatures. This work demonstrates the potential application of Laponite based nanomaterials for nanofluidic energy harvesting.

20.
ACS Nano ; 18(23): 15025-15034, 2024 Jun 11.
Artículo en Inglés | MEDLINE | ID: mdl-38804641

RESUMEN

Iontronics that are capable of mimicking the functionality of biological systems within an artificial fluidic network have long been pursued for biomedical applications and ion-based intelligence systems. Here, we report on facile and robust realization of iontronic bipolar memristors featuring a three-layer polyelectrolyte gel structure. Significant memristive hysteresis of ion currents was successfully accomplished, and the memory time proved geometrically scalable from 200 to 4000 s. These characteristics were enabled by the ion concentration polarization-induced rectification ratio within the polyelectrolyte gels. The memristors exhibited memory dynamics akin to those observed in unipolar devices, while the bipolar structure notably enabled prolonged memory time and enhanced the ion conductance switching ratio with mesoscale (10-1000 µm) geometry precision. These properties endow the devices with the capability of effective neuromorphic processing with pulse-based input voltage signals. Owing to their simple fabrication process and superior memristive performance, the presented iontronic bipolar memristors are versatile and can be easily integrated into small-scale iontronic circuits, thereby facilitating advanced neuromorphic computing functionalities.

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