arXiv subjects

Yinghua Qiu

Publications and source records attributed to Yinghua Qiu.

At least 19 recordsLinked to original sources

arXiv2026

Giant and Continuous Ionic Current Oscillation Induced by Dynamic Surface Charge Regulation in Cylindrical Mesopores

Nanofluidic ionic oscillators based on the dynamic regulation of surface charges hold great promise for neuromorphic computing, biosensing, and ionic circuits. Here, by dynamically adjusting the local charge inversion on pore walls, we present a simple and effective strategy to achieve periodic current oscillations by harnessing the transient adsorption and desorption of Ca2+ ions in cylindrical mesopores under concentration gradients. Based on the combined precision current measurements and multiphysics simulations, we demonstrate that local overadsorption of Ca2+ ions may induce asymmetric bipolar charge distributions along the pore axis, which periodically reverses the direction of electroosmotic flow and modulates the local ion concentration inside the pore, generating highly regular current oscillations. Notably, both the oscillation frequency and the open-state probability of the pore vary nearly linearly with the applied voltage. Moreover, under dynamic voltage scanning, the system exhibits typical memristive hysteresis, and the switching between the open and closed states is highly reproducible. This work not only reveals the dynamic, heterogeneous surface charge regulation by divalent ions, but also provides a simple, material agnostic method for constructing ionic oscillators and memristors based on dynamic adsorption/desorption of multivalent ions.

physics.chem-ph↗

arXiv2025

Modulation of Electroosmotic Flow through Short Nanopores by Charged Exterior Surfaces

Electroosmotic flow (EOF) through nanoporous membranes has broad applications in micro- and nanofluidic systems, particularly in biomedical diagnostics and chemical analysis. The use of short nanopores enables high fluid flux, and the presence of exterior surface charges can further enhance ion flux through short nanopores. Here, systematic simulations are conducted to explore the modulation of EOF by exterior surface charges. Our results indicate that charged exterior surfaces can provide an additional effective pathway for fluid flow, significantly increasing both the EOF velocity and output pressure. By analyzing the dependence of EOF velocity on the area of the charged exterior surface, we derive the effective width (Lcs_eff) of the charged ring region extending beyond the pore boundary. This parameter is quantitatively examined under various nanopore configurations and applied conditions. Lcs_eff is found to be proportional to the pore diameter, surface charge density, and applied voltage, while inversely proportional to pore length and salt concentration. These findings provide valuable insights into the modulation of EOF by exterior surface charges and offer theoretical guidance for optimizing the structural and functional properties of nanoporous membranes in practical applications of EOF.

physics.chem-ph↗

arXiv2025

Modulation of Ionic Current Rectification in Short Unipolar Nanopores

With controlled ionic current rectification (ICR) achieved through a strategically designed non-uniform surface charge distribution, short unipolar nanopores exhibit promising applications in nanofluidic sensors, ionic circuits, and ion amplifiers. By systematically investigating how the charged length on inner pore walls modulates ion transport, we found that both the maximum ICR degree and the corresponding charged-length proportion were influenced by nanopore parameters and simulation conditions. For 100 nm-long unipolar nanopores, the highest ICR degree is obtained at a charged-length proportion of ~0.3, due to the corresponding most significant ion enrichment and depletion inside the nanopore under opposite biases. This charged-length proportion of ~0.3 consistently appears as a characteristic value across most considered cases. For short unipolar nanopores, the presence of exterior surface charges significantly enhances the ICR degree by facilitating ion transport through nanopores. The effective widths of charged regions beyond nanopore borders on outer surfaces exhibit direct proportionality to the pore diameter, surface charge density, and applied voltage, and inverse proportionality to the pore length and salt concentration. Our research may provide useful guidance for the design of unipolar nanopores and porous membranes incorporating such charge configurations.

physics.chem-ph↗

arXiv2025

Characteristics of mono-, di-, and trivalent cations in electric double layers: a molecular dynamic investigation

Ionic behaviors, including ion distributions and hydration characteristics at solid-liquid interfaces, are important research interests in many important applications, such as electric double-layer capacitors and water lubrication. Here, we systematically investigated the concentration distributions, hydration numbers, and screening properties of Li+, Na+, K+, Ca2+, Mg2+, and La3+ ions inside electric double layers (EDLs) at various charge densities. For the surface charge density weaker than -0.16 C m-2, monovalent cations mainly accumulate in the outer Helmholtz plane (OHP). As the charge density magnitude increases, monovalent cations start to dehydrate and migrate to the inner Helmholtz plane (IHP), following the order of K+, Na+, and Li+. This size-dependent behavior arises from the lower hydration energy of larger ions. While for the di- and trivalent ions, no obvious IHP appears. Based on ion distributions, the screening effect of counterions on surface charges is evaluated by analyzing the net charge distributions. As the charge density changes from 0 to -0.32 C m-2, due to the stronger accumulation of cations in EDLs, the location of the neutral plane changes from ~1.2 to ~0.4 nm. When the charge density reaches a threshold, excessive accumulation of cations can induce charge inversion. The threshold value and the maximum reversed charge are found to correlate with the ion size, cation valence, and concentration.

physics.chem-ph↗

arXiv2025

Modulation of Memristive Characteristics by Dynamic Nanoprecipitation inside Conical Nanopores

Nanofluidic memristors have demonstrated great potential for neuromorphic system applications with the advantages of low energy consumption and excellent biocompatibility. Here, an effective way is developed to regulate the memristive behavior of conical nanopores by leveraging the reversible formation and dissolution of nanoprecipitates induced by ion enrichment and depletion in nanopores under opposite voltages. Through the interplay between precipitation dynamics at the pore tip and the ion enrichment/depletion inside the nanopore, conical nanopores exhibit pronounced current hysteresis loops in the presence of CaHPO4, a slightly soluble inorganic salt. The memristive characteristics are found to be strongly dependent on the concentration of CaHPO4, besides the applied voltage amplitude and scan rate. Under the stimulation of pulse voltages, ionic current demonstrates stable learning and forgetting processes with robust switching stability and effective reset capability, which is similar to the short-term plasticity characteristics of biological synapses. Our research may provide a straightforward and tunable approach for the design of nanofluidic memristors.

physics.chem-ph↗

arXiv2025

Ion transport through differently charged nanoporous membranes: from a single nanopore to multi-nanopores

Nanoporous membranes, leveraging their high-throughput characteristics, have been widely applied in fields such as molecular separation and energy conversion. Due to interpore interactions, besides the applied voltage and solution environment, the ion transport properties in porous membranes are influenced by the pore number and spacing. Here, to understand and control the transport properties of nanopore arrays, we systematically investigate the ion transport characteristics through membranes with different charge properties, pore numbers, and interpore distances. Using numerical simulations, we analyzed local ionic concentrations and electric potential in nanopore arrays containing nanopores with uniformly charged walls as well as unipolar diodes i.e., pores containing a junction between a charged zone and a neutral zone, and showed significant ion concentration polarization (ICP) for all studied cases. As the number of pores increased and the interpore spacing decreased, the enhanced interpore interactions through ICP led to a greater deviation of the total ionic current from the linear superposition of single-pore currents. Conversely, in bipolar nanopores whose walls contain a junction between positively and negatively charged zones ICP becomes negligible, and interpore interactions are substantially reduced. Furthermore, for membranes with various charge properties, the total current through nanopore arrays presents different quantitative dependence on the pore number under varying pore spacings. Our findings clarify the mechanism of interpore interactions in modulating ion transport through porous membranes, providing critical insights for designing nanofluidic devices based on nanopore arrays, such as nanopore-array sensors.

cond-mat.soft↗

arXiv2025

Ionic current rectification under concentration gradients and its application in evaluating surface charge properties of micropores

Ionic current rectification (ICR) induced by electroosmotic flow (EOF) under concentration gradients can find many applications in micro/nanofluidic sensing and ionic circuits. Here, we focused on the cases with micropores of moderate length-diameter ratios, through experimental research and systematical simulations, the EOF-induced ICR was found to exhibit voltage-dependent ratios. In the considered cases with a weak EOF or strong ionic diffusion, a large deviation appears between the ion concentration inside the micropore and the bulk value, which fails the prediction by solution conductivity gradients. Based on our simulation results, effective equations were developed for the theoretical description of ion concentration distributions along the micropore axis under coupled concentration gradient and electric field. With the predicted ion distributions inside micropores, the ICR ratio can be conveniently calculated with the derived electrical resistance of the microfluidic system, which applies to micropores of 200 to 1000 nm in diameter. Because the surface charge density is the only unknown input parameter, our developed equations can be used to evaluate the surface charge density of micropores with the measured EOF-induced ICR ratio under concentration gradients.

physics.chem-ph↗

arXiv2024

Detection of Nanopores with the Scanning Ion Conductance Microscopy: A Simulation Study

During the dielectric breakdown process of thin solid-state nanopores, the application of high voltages may cause the formation of multi-nanopores on one chip, which number and sizes are important for their applications. Here, simulations were conducted to mimic the investigation of in situ nanopore detection with scanning ion conductance microscopy (SICM). Results show that SICM can provide accurate nanopore location and relative pore size. Detection resolution is influenced by the dimensions of the applied probe and separation between the probe and membranes, which can be enhanced under large voltages or a concentration gradient.

physics.chem-ph↗

arXiv2024

Ionic Selectivity of Nanopores: Comparison among Cases under the Hydrostatic Pressure, Electric Field, and Concentration Gradient

The ionic selectivity of nanopores is crucial for the energy conversion based on nanoporous membranes. It can be significantly affected by various parameters of nanopores and the applied fields driving ions through porous membranes. Here, with finite element simulations, the selective transport of ions through nanopores is systematically investigated under three common fields, i.e. the electric field (V), hydrostatic pressure (p), and concentration gradient (C). For negatively charged nanopores, through the quantitative comparison of the cation selectivity (t+) under the three fields, the cation selectivity of nanopores follows the order of t+V > t+c > t+p. This is due to the transport characteristics of cations and anions through the nanopores. Because of the strong transport of counterions in electric double layers under electric fields and concentration gradients, the nanopore exhibits a relatively higher selectivity to counterions. We also explored the modulation of t+ on the properties of nanopores and solutions. Under all three fields, t+ is directly proportional to the pore length and surface charge density, and inversely correlated to the pore diameter and salt concentration. Under both the electric field and hydrostatic pressure, t+ has almost no dependence on the applied field strength or ion species, which can affect t+ in the case of the concentration gradient. Our results provide detailed insights into the comparison and regulation of ionic selectivity of nanopores under three fields which can be useful for the design of high-performance devices for energy conversion based on nanoporous membranes.

cond-mat.soft↗

arXiv2024

Modulation of ionic current rectification in short bipolar nanopores

Bipolar nanopores, with asymmetric charge distributions, can induce significant ionic current rectification (ICR) at ultra-short lengths, finding potential applications in nanofluidic devices, energy conversion, and other related fields. Here, with simulations, we investigated the characteristics of ion transport and modulation of ICR inside bipolar nanopores. With bipolar nanopores of half-positive and half-negative surfaces, the most significant ICR phenomenon appears at various concentrations. In these cases, ICR ratios are independent of electrolyte types. In other cases where nanopores have oppositely charged surfaces in different lengths, ICR ratios are related to the mobility of anions and cations. The pore length and surface charge density can enhance ICR. As the pore length increases, ICR ratios first increase and then approach their saturation which is determined by the surface charge density. External surface charges of nanopores can promote the ICR phenomenon mainly due to the enhancement of ion enrichment inside nanopores by external surface conductance. The effective width of exterior charged surfaces under various conditions is also explored, which is inversely proportional to the pore length and salt concentration, and linearly related to the pore diameter, surface charge density, and applied voltage. Our results may provide guidance for the design of bipolar porous membranes.

physics.chem-ph↗

arXiv2024

Dynamic Response of Ionic Current in Conical Nanopores

Ionic current rectification (ICR) of charged conical nanopores has various applications in fields including nanofluidics, bio-sensing, and energy conversion, whose function is closely related to the dynamic response of nanopores. The occurrence of ICR originates from the ion enrichment and depletion in conical pores, whose formation is found to be affected by the scanning rate of voltages. Here, through time-dependent simulations, we investigate the variation of ion current under electric fields and the dynamic formation of ion enrichment and depletion, which can reflect the response time of conical nanopores. The response time of nanopores when ion enrichment forms i.e. at the on state is significantly longer than that with the formation of ion depletion i.e. at the off state. Our simulation results reveal the regulation of response time by different nanopore parameters including the surface charge density, pore length, tip, and base radius, as well as the applied conditions such as the voltage and bulk concentration. The response time of nanopores is closely related to the surface charge density, pore length, voltage, and bulk concentration. Our uncovered dynamic response mechanism of the ionic current can guide the design of nanofluidic devices with conical nanopores, including memristors, ionic switches, and rectifiers.

physics.chem-ph↗

arXiv2024

Low-cost and Convenient Fabrication of Polymer Micro/Nanopores with the Needle Punching Process and Their Applications in Nanofluidic Sensing

Solid-state micro/nanopores play an important role in the sensing field because of their high stability and controllable size. Aiming at problems of complex processes and high costs in pore manufacturing, we propose a convenient and low-cost micro/nanopore fabrication technique based on the needle punching method. The thin film is pierced by controlling the feed of a microscale tungsten needle, and the size variations of the micropore are monitored by the current feedback system. Based on the positive correlation between the micropore size and the current threshold, the size-controllable preparation of micropores is achieved. The preparation of nanopores is realized by the combination of needle punching and chemical etching. Firstly, a conical defect is prepared on the film with the tungsten needle. Then, nanopores are obtained by unilateral chemical etching of the film. Using the prepared conical micropores resistive-pulse detection of nanoparticles is performed. Significant ionic current rectification is also obtained with our conical nanopores. It is proved that the properties of micro/nanopores prepared by our method are comparable to those prepared by the track-etching method. The simple and controllable fabrication process proposed here will advance the development of low-cost micro/nanopore sensors.

physics.chem-ph↗

arXiv2024

Improved theoretical prediction of nanoparticle sizes with the resistive-pulse technique

With the resistive-pulse technique (RPT), nanopores serve as the nanofluidic sensors of various analytes for their many physical and chemical properties. Here, we focus on the size measurement and its theoretical prediction for sub-200 nm nanoparticles with RPT. Through systematical investigation of the current blockade of nanoparticles across cylindrical nanopores with simulations, Maxwell method considering the shape coefficient and access resistances agrees well with simulation results. However, the widely used integration method of the resistance has distinct deviations in various cases. With the introduction of a correction factor \b{eta} to the integration method, our revised equations can provide good predictions for simulation results. \b{eta} shows a strong dependence on the diameter ratio (d over D) of the nanoparticle and nanopore. Following the same strategy, modified equations are provided for the accurate size prediction for nanoparticles across conical nanopores, where the integration method is the default convenient way. The correction factor \b{eta}' relates to \b{eta} in cylindrical nanopores. \b{eta}' exhibits independence on the pore geometry parameters and diameters of nanoparticles, but dependence on the surface charge density of conical nanopores. Our improved equations can provide theoretical predictions for the accurate size detection of 100-200 nm diameter nanoparticles across cylindrical and conical nanopores.

physics.chem-ph↗

arXiv2024

Ion Transport through Short Nanopores Modulated by Charged Exterior Surfaces

Short nanopores find extensive applications capitalizing on their high throughput and detection resolution. Ionic behaviors through long nanopores are mainly determined by charged inner-pore walls. When pore lengths decrease to sub-200 nm, charged exterior surfaces provide considerable modulation to ion current. We find that the charge status of inner-pore walls affects the modulation of ion current from charged exterior surfaces. For 50-nm-long nanopores with neutral inner-pore walls, charged exterior surfaces on the voltage (surfaceV) and ground (surfaceG) sides enhance and inhibit ion transport by forming ion enrichment and depletion zones inside nanopores, respectively. For nanopores with both charged inner-pore and exterior surfaces, continuous electric double layers enhance ion transport through nanopores significantly. The charged surfaceV results in higher ion current by simultaneously weakening ion depletion at pore entrances and enhancing the intra-pore ion enrichment. The charged surfaceG expedites the exit of ions from nanopores, resulting in a decrease in ion enrichment at pore exits. Through adjustment in the width of charged-ring regions near pore boundaries, the effective charged width of the charged exterior is explored at ~20nm. Our results may provide a theoretical guide for further optimizing the performance of nanopore-based applications, like seawater desalination, biosensing, and osmotic energy conversion.

physics.chem-ph↗

arXiv2024

Characterization of the Surface Charge Property and Porosity of Track-etched Polymer Membranes

As an important property of porous membranes, the surface charge property determines many ionic behaviors of nanopores, such as ionic conductance and selectivity. Based on the dependence of electric double layers on bulk concentrations, ionic conductance through nanopores at high and low concentrations is governed by the bulk conductance and surface charge density, respectively. Here, through the investigation of ionic conductance inside track-etched single polyethylene terephthalate (PET) nanopores under various concentrations, the surface charge density of PET membranes is extracted as around 0.021 C per m2 at pH 10 over measurements with 40 PET nanopores. Simulations show that surface roughness can cause underestimation in surface charge density due to the inhibited electroosmotic flow. Then, the averaged pore size and porosity of track-etched multipore PET membranes are characterized by the developed ionic conductance method. Through coupled theoretical predictions in ionic conductance under high and low concentrations, the averaged pore size and porosity of porous membranes can be obtained simultaneously. Our method provides a simple and precise way to characterize the pore size and porosity of multipore membranes, especially for those with sub-100 nm pores and low porosities.

physics.chem-ph↗

arXiv2024

Influences of Divalent Ions in Natural Seawater/River Water on Nanofluidic Osmotic Energy Generation

Besides the dominant NaCl, natural seawater/river water contains trace multivalent ions, which can provide effective screening to surface charges. Here, in both negatively and positively charged nanopores, influences from divalent ions as counterions and coions have been investigated on the performance of osmotic energy conversion (OEC) under natural salt gradients. As counterions, trace Ca2+ ions can suppress the electric power and conversion efficiency significantly. The reduced OEC performance is due to the bivalence and low diffusion coefficient of Ca2 ions, instead of the uphill transport of divalent ions discovered in the previous work. Effectively screened charged surfaces by Ca2+ ions induce enhanced diffusion of Cl ions which simultaneously decreases the net ion penetration and ionic selectivity of the nanopore. While as coions, Ca2+ ions have weak effects on the OEC performance. The promotion from charged exterior surfaces on OEC processes for ultra-short nanopores is also studied, which effective region is ~200 nm in width beyond pore boundaries independent of the presence of Ca2+ ions. Our results shed light on the physical details of the nanofluidic OEC process under natural seawater/river water conditions, which can provide a useful guide for high-performance osmotic energy harvesting.

physics.chem-ph↗

arXiv2024

Modulation Mechanism of Ionic Transport through Short Nanopores by Charged Exterior Surfaces

Short nanopores have various applications in biosensing, desalination, and energy conversion. Here, the modulation of charged exterior surfaces on ionic transport is investigated through simulations with sub-200 nm long nanopores under applied voltages. Detailed analysis of ionic current, electric field strength, and fluid flow inside and outside nanopores reveals that charged exterior surfaces can increase ionic conductance by increasing both the concentration and migration speed of charge carriers. The electric double layers near charged exterior surfaces provide an ion pool and an additional passageway for counterions, which lead to enhanced exterior surface conductance and ionic concentrations at pore entrances and inside the nanopore. We also report that charges on the membrane surfaces increase electric field strengths inside nanopores. The effective width of a ring with surface charges placed at pore entrances (Lcs) is considered as well by studying the dependence of the current on Lcs. We find a linear relationship between the effective Lcs and the surface charge density and voltage, and an inverse relationship between the geometrical pore length and salt concentration. Our results elucidate the modulation mechanism of charged exterior surfaces on ionic transport through short nanopores, which is important for the design and fabrication of porous membranes.

cond-mat.soft↗

arXiv2024

Influences of Electroosmotic Flow on Ionic Current through Nanopores: a Comprehensive Understanding

Continuum simulations become an important tool to uncover the mysteries in nanofluidic experiments. However, fluid flow in simulation models is usually unconsidered. Here, systematical simulations are conducted to provide a quantitative understanding of influences from electroosmotic flow (EOF) on ionic transport through nanopores by both types of models with and without consideration of EOF. In nanopores of less than ~10 nm in diameter, counterions dominate ionic current which is always promoted obviously by the convective effect of EOF. In the diameter range from ~10 to ~30 nm, strong EOF induces ion concentration polarization or ion depletion inside nanopores which causes significant decreases in ionic current. For nanopores larger than ~30 nm, due to convective promotion and inhibition of EOF on the transport of counterions and anions, considerable nanopore selectivity to counterions maintains in cases with EOF. Though the difference in total current between both cases decreases with further pore size increasing, the difference in cation/anion current is still considerable. From our results under various pore parameters and applied conditions, the fluid flow should be considered in the simulation cases when EOF is strong. Our work may provide useful guidance for simulation conductance.

physics.chem-ph↗