Local Surface Charge Research Articles

Pore‐scale Study of Ion Transport Mechanisms in Inhomogeneously Charged Nanoporous Rocks: Impacts of Interface Properties on Macroscopic Transport

AbstractThe electrokinetic transport mechanisms of multispecies ions through 3‐D nanoporous rocks with chemical reaction at the solid‐aqueous solution interfaces are investigated. We systematically study the multiphysics transport phenomena by considering either inhomogeneous (local surface charge based on local pH and ion concentrations) or prescribed homogeneous surface charge at solid‐aqueous solution interface while the pores are screened via electric double layers. We develop a lattice Boltzmann numerical framework to solve the set of governing equations (Poisson‐Nernst‐Planck plus Navier–Stokes). Our modeling results reveal that the averaged local electric potential of the nanoporous rock is significantly underestimated (about 83%) when a homogeneous surface charge is prescribed based on the bulk solution properties. It is shown that increasing the porosity of the nanoporous media considerably increases the absolute values and inhomogeneity of the surface charge, which means that while the electric double layers screened the pores, increasing the porosity enhances the ion selectivity of the porous medium. When the scenario with inhomogeneous charge is taken into account, the predicted electroosmotic permeability and tortuosity are higher in comparison with the prescribed homogeneous case. Moreover, we have studied the electrostatic tortuosity, coupling coefficient, and the effective excess charge density of the nanoporous rocks. The results demonstrate that ignoring the inhomogeneity of surface charges may cause erroneous prediction of the ion transport through porous rocks with chemically active surfaces.

Synergic effect of adsorbed gas and charging on surface flashover

Flashover is a crucial issue in both high-voltage engineering and surface physics. It not only challenges the existing theories about its dynamic evolution, but also inhibits the clean energy revolution by limiting the accessible voltage rating of power equipment. It is of significance to elucidate the microscopic process along the interface to improve the flashover performance. In the present study, the synergic effect of adsorbed gas and surface charging is investigated, which reveals a long ignored factor for determining the flashover voltage. Depending on the relative amount of adsorbed gas, the flashover voltage varies, which exhibit different behavior from the bulk breakdown of the same gas. The amount of N2 gas adsorbed on epoxy resin (EP) surface is much larger than that on Al2O3 ceramic surface, corresponding to the observed higher flashover voltage on EP. It is proposed that the adsorbed gas molecules not only modify the local surface charging state via their interaction with the trapped charges, but also capture free electrons due to the distortion of their electronic distribution. Both effects suppress the free path length of electrons in the gas-solid interface. This work explores another possibility to improve the surface flashover performance.

In Situ Nanoscale Redox Mapping Using Tip-Enhanced Raman Spectroscopy.

Electrochemical atomic force microscopy tip-enhanced Raman spectroscopy (EC-AFM-TERS) was used for the first time to spatially resolve local heterogeneity in redox behavior on an electrode surface in situ and at the nanoscale. A structurally well-defined Au(111) nanoplate located on a polycrystalline ITO substrate was studied to examine nanoscale redox contrast across the two electrode materials. By monitoring the TERS intensity of adsorbed Nile Blue (NB) molecules on the electrode surface, TERS maps were acquired with different applied potentials. The EC-TERS maps showed a spatial contrast in TERS intensity between Au and ITO. TERS line scans near the edge of a 20 nm-thick Au nanoplate demonstrated a spatial resolution of 81 nm under an applied potential of -0.1 V vs Ag/AgCl. The intensities from the TERS maps at various applied potentials followed Nernstian behavior, and a formal potential ( E0') map was constructed by fitting the TERS intensity at each pixel to the Nernst equation. Clear nanoscale spatial contrast between the Au and ITO regions was observed in the E0' map. In addition, statistical analysis of the E0' map identified a statistically significant 4 mV difference in E0' on Au vs ITO. Electrochemical heterogeneity was also evident in the E0' distribution, as a bimodal distribution was observed in E0' on polycrystalline ITO, but not on gold. A direct comparison between an AFM friction image and the E0' map resolved the electrochemical behavior of individual ITO grains with a spatial resolution of ∼40 nm. The variation in E0' was attributed to different local surface charges on the ITO grains. Such site-specific electrochemical information with nanoscale spatial and few mV voltage resolutions is not available using ensemble spectroelectrochemical methods. We expect that in situ redox mapping at the nanoscale using EC-AFM-TERS will have a crucial impact on understanding the role of nanoscale surface features in applications such as electrocatalysis.

Optical Imaging of Charges with Atomically Thin Molybdenum Disulfide.

Mapping local surface charge distribution is critical to the understanding of various surface processes and also allows the detection of molecules binding to the surface. We show here that the optical absorption of monolayer MoS2 is highly sensitive to charge and demonstrate optical imaging of local surface charge distribution with this atomically thin material. We validate the imaging principle and perform charge sensitivity calibration with an electrochemical gate. We further show that binding of charged molecules to the atomically thin material leads to a large change in the image contrast, allowing determination of the charge of the adsorbed molecules. This capability opens possibilities for characterizing impurities and defects in two-dimensional materials and for label-free optical detection and charge analysis of molecules.

Bridging the Surface Charge and Catalytic Activity of a Defective Carbon Electrocatalyst

AbstractElectrocatalysis is dominated by reaction at the solid–liquid–gas interface; surface properties of electrocatalysts determine the electrochemical behavior. The surface charge of active sites on catalysts modulate adsorption and desorption of intermediates. However, there is no direct evidence to bridge surface charge and catalytic activity of active sites. Defects (active sites) were created on a HOPG (highly oriented pyrolytic graphite) surface that broke the intrinsic sp2‐hybridization of graphite by plasma, inducing localization of surface charge onto defective active sites, as shown by scanning ion conductance microscopy (SICM) and Kelvin probe force microscopy (KPFM). An electrochemical test revealed enhanced intrinsic activity by the localized surface charge. DFT calculations confirmed the relationship between surface charge and catalytic activity. This work correlates surface charge and catalytic activity, providing insights into electrocatalytic behavior and guiding the design of advanced electrocatalysts.

Bridging the Surface Charge and Catalytic Activity of a Defective Carbon Electrocatalyst.

Electrocatalysis is dominated by reaction at the solid-liquid-gas interface; surface properties of electrocatalysts determine the electrochemical behavior. The surface charge of active sites on catalysts modulate adsorption and desorption of intermediates. However, there is no direct evidence to bridge surface charge and catalytic activity of active sites. Defects (active sites) were created on a HOPG (highly oriented pyrolytic graphite) surface that broke the intrinsic sp2 -hybridization of graphite by plasma, inducing localization of surface charge onto defective active sites, as shown by scanning ion conductance microscopy (SICM) and Kelvin probe force microscopy (KPFM). An electrochemical test revealed enhanced intrinsic activity by the localized surface charge. DFT calculations confirmed the relationship between surface charge and catalytic activity. This work correlates surface charge and catalytic activity, providing insights into electrocatalytic behavior and guiding the design of advanced electrocatalysts.

Electric charge of nanopatterned silica surfaces.

The most recent technologies employ nanoscale surface patterning or roughening in order to engineer desired properties on a surface. Electrokinetic properties at the interface of such surfaces and ionic liquids show different behavior to the well-known theoretical descriptions. Basically, the ionic distribution on the surface differs due to electrical double layer overlap effects in the pits and curvature effects at the tips of surface structures. Generally, the charge density of a surface is assumed to be a material property and surface roughness effects are overlooked in most of the literature. In contrast, we properly calculated the local surface charges based on surface chemistry at the corresponding local ionic concentration (charge regulation) for various surface roughness and solution conditions. The results showed that the surface charge density of silica decreased at the pits but increased at the tips of surface patterns. Even for the simplest case of self-repeating surface structures, the average of local surface charges becomes lower than the theoretical predictions. Based on numerical calculations, a phenomenological model was developed as an extension to the existing flat surface theory, which can successfully predict the average surface charge on a nano patterned surface as a function of the surface pattern size, ionic concentration and pH.

Dust shedding from a dielectric surface in plasma as a result of charge fluctuations

If a body is in a plasma and/or is exposed to streams of charged particles with different signs, or is under UV electromagnetic radiation, etc., then the distribution of the different sign charges on the surface is random. As a result, the surface of the dielectric will be covered by microscopic “spots” with different signs and values of charges, continuously changing in shapes and sizes. A Coulomb force acting on a dust particle lying near the center of such a spot is proportional to the square of the local surface charge density. A stochastic differential equation describing the dynamics of an ensemble of these spots was derived and solved in the article. A solution was obtained also for the dependence of the average spot size, its lifetime, and the standard deviation of the charge density as a function of the plasma species fluxes incident on the surface. It is shown that for normal values of plasma parameters, the Coulomb force repelling a submicron dust particle from a charge spot of somewhat larger size can reach a few tenths of pN, which is comparable to the value of the adhesive van der Waals force that holds dust particles on the surface. The possibility of improving the cleaning efficiency with changes in surface treatment conditions is analyzed as well.

Carrier Density-Dependent Localized Surface Plasmon Resonance and Charge Transfer Observed by Controllable Semiconductor Content

We discuss how the controllable carrier influences the localized surface plasmon resonance (LSPR) and charge transfer (CT) in the same system based on ultraviolet-visible and surface-enhanced Raman scattering (SERS) measurements. The LSPR can be easily tuned from 580 to 743 nm by changing the sputtering power of Cu2S in the Ag and Cu2S composite substrate. During this process, surprisingly, we find that the LSPR is proportional to the sputtering power of Cu2S. This observation indicates that LSPR can be accurately adjusted by changing the content of the semiconductor, or even the carrier density. Moreover, we characterize the carrier density through the detection of the Hall effect to analyze the Raman shift caused by CT and obtain the relationships between them. These fundamental discussions provide a guideline for tunable LSPR and the investigation of CT.

The Resting Potential and K+ Currents in Primary Human Articular Chondrocytes.

Human transplant programs provide significant opportunities for detailed in vitro assessments of physiological properties of selected tissues and cell types. We present a semi-quantitative study of the fundamental electrophysiological/biophysical characteristics of human chondrocytes, focused on K+ transport mechanisms, and their ability to regulate to the resting membrane potential, Em. Patch clamp studies on these enzymatically isolated human chondrocytes reveal consistent expression of at least three functionally distinct K+ currents, as well as transient receptor potential (TRP) currents. The small size of these cells and their exceptionally low current densities present significant technical challenges for electrophysiological recordings. These limitations have been addressed by parallel development of a mathematical model of these K+ and TRP channel ion transfer mechanisms in an attempt to reveal their contributions to Em. In combination, these experimental results and simulations yield new insights into: (i) the ionic basis for Em and its expected range of values; (ii) modulation of Em by the unique articular joint extracellular milieu; (iii) some aspects of TRP channel mediated depolarization-secretion coupling; (iv) some of the essential biophysical principles that regulate K+ channel function in “chondrons.” The chondron denotes the chondrocyte and its immediate extracellular compartment. The presence of discrete localized surface charges and associated zeta potentials at the chondrocyte surface are regulated by cell metabolism and can modulate interactions of chondrocytes with the extracellular matrix. Semi-quantitative analysis of these factors in chondrocyte/chondron function may yield insights into progressive osteoarthritis.

Combined Ion Conductance and Atomic Force Microscope for Fast Simultaneous Topographical and Surface Charge Imaging.

We report here an advanced approach for simultaneous and independent submicroscale imaging of local surface charge and topography using microchanneled cantilevers, also known as FluidFM nanopipette probes. These hollow cantilevers with a 300 nm opening are employed for ion current measurements that provide access to the local properties of the electrical double layer using the phenomenon of ion current rectification, while also taking advantage of the force sensing capabilities for accurate probe vertical positioning and topography imaging. The independent nature of this atomic force microscope (AFM) feedback opens up a possibility to significantly increase the sensitivity for probing local surface charges in a wider range of salt concentrations, especially in electrolytes of low ionic strength (below 10 mM), where classical local ion conductance measurements with glass nanopipettes would suffer from inaccuracies and instabilities, but where the electrical double layer extends further into the liquid medium and has stronger effect on the measured ion currents for charge imaging. We demonstrate that the measurements with FluidFM do not compromise the positioning accuracy and enable accurate and simultaneous topographical and charge imaging in contact mode (similar to AFM) at high scanning rates, approaching thousands of pixels per second, therefore overtaking state-of-the-art techniques for charge mapping by at least 2 orders of magnitude (the probes reach translation rates of 120 μm s-1 equating to 2 ms per image pixel). We also reveal experimentally the physical limit of this high speed scanning, constrained by the rate of ion redistribution in surface-induced rectification required for double layer sensing and charge mapping.

Reverse electrodialysis through nanochannels with inhomogeneously charged surfaces and overlapped electric double layers

Modeling of electro-chemo-mechanical transport phenomena in simple (nanochannel) or complex (nanoporous media) geometries with inhomogeneous surface charge and overlapped electric double layers remains challenging. This bottleneck originates from lack of a comprehensive model to predict the local surface charge density based on the variable local solution properties. This work aims to propose a model, so-called representative bulk layer (RBL), which makes the chemically non-isolated solid-liquid interfaces (due to the electric double layers interaction) as isolated interfaces by introducing a local effective bulk ion concentration. Using RBL together with the electrical triple layer model to provide boundary conditions for the multi-physio-chemical transport equations (PNP + NS), we investigate the reverse electrodialysis (RED) in nanochannels. Our modeling results indicate that the length of an ion-selective membrane not only influences the ionic current but also the logarithm of the slope of current-voltage curve increases linearly with the ratio of nanochannel length to height. This interesting finding inspires us to propose a dimensionless relation for the current-voltage curve that is independent of the nanochannel dimensions. The present contribution numerical framework could shed light on the electro-chemo-mechanical transport mechanism through nanofluidic devices and membranes.

Controlling the Local Electronic Properties of Si(553)-Au through Hydrogen Doping.

We propose a quantitative and reversible method for tuning the charge localization of Au-stabilized stepped Si surfaces by site-specific hydrogenation. This is demonstrated for Si(553)-Au as a model system by combining density functional theory simulations and reflectance anisotropy spectroscopy experiments. We find that controlled H passivation is a two-step process: step-edge adsorption drives excess charge into the conducting metal chain "reservoir" and renders it insulating, while surplus H recovers metallic behavior. Our approach illustrates a route towards microscopic manipulation of the local surface charge distribution and establishes a reversible switch of site-specific chemical reactivity and magnetic properties on vicinal surfaces.

Propagation of atmospheric-pressure ionization waves along the tapered tube

Gas discharge in a small radius dielectric tube may result in atmospheric pressure plasma jets with high energy and density of electrons. In this study, the atmospheric pressure ionization waves (IWs) were generated inside a tapered tube. The propagation behaviors of IWs inside the tube were studied by using a spatially and temporally resolved optical detection system. Our measurements show that both the intensity and velocity of the IWs decrease dramatically when they propagate to the tapered region. After the taper, the velocity, intensity, and electron density of the IWs are improved with the tube inner diameter decreasing from 4.0 to 0.5 mm. Our analysis indicates that the local gas conductivity and surface charges may play a role in the propagation of the IWs under such a geometrical constraint, and the difference in the dynamics of the IWs after the taper can be related to the restriction in the size of IWs.

Direct measurement of surface charge distribution in phase separating supported lipid bilayers.

The local surface charge density of the cell membrane influences regulation and localization of membrane proteins. The local surface charge density could, until recently, not be measured directly under physiological conditions, and it was largely a hypothetical yet very important parameter. Here we use unsaturated lipids of a distinct charge (DOTAP, DOPC, and DOPG) and a neutral fully saturated lipid (DPPC) to create model membranes with phase separating domains of a defined charge. We then apply quantitative surface charge microscopy (QSCM) to investigate the local surface charge density; this is a technique based on a scanning ion conductance microscope (SICM) capable of measuring surface charge density with nanoscale lateral resolution. We are able to clearly distinguish lipid domains from charge and topography in all three model membranes. The measured surface charge densities furthermore reveal that disordered domains formed by charged lipids are in fact not only impure, but also incorporate uncharged saturated lipids. We estimate that at least 30% of disordered domains in DOPG : DPPC and DOTAP : DPPC will be DPPC. These ratios could present a limit for the formation of charged domains in lipid membranes.

Probing Homogeneous Line Broadening in CdSe Nanocrystals Using Multidimensional Electronic Spectroscopy.

The finite spectral line width of an ensemble of CdSe nanocrystals arises from size and shape inhomogeneity and the single-nanocrystal spectrum itself. This line width directly limits the performance of nanocrystal-based devices, yet most optical measurements cannot resolve the underlying contributions. We use two-dimensional electronic spectroscopy (2D ES) to measure the line width of the band-edge exciton of CdSe nanocrystals as a function of radii and surface chemistry. We find that the homogeneous width decreases for increasing nanocrystal radius and that surface chemistry plays a critical role in controlling this line width. To explore the hypothesis that unpassivated trap states serve to broaden the homogeneous line width and to explain its size-dependence, we use 3D ES to identify the spectral signatures of exciton-phonon coupling to optical and acoustic phonons. We find enhanced coupling to optical phonon modes for nanocrystals that lack electron-passivating ligands, suggesting that localized surface charges enhance exciton-phonon coupling via the Fröhlich interaction. Lastly, the data reveal that spectral diffusion contributes negligibly to the homogeneous line width on subnanosecond time scales.

Back Cover: Direct simulation of electroosmosis around a spherical particle with inhomogeneously acquired surface charge

ELECTROPHORESISVolume 38, Issue 5 Back CoverFree Access Back Cover: Direct simulation of electroosmosis around a spherical particle with inhomogeneously acquired surface charge First published: 03 March 2017 https://doi.org/10.1002/elps.201770036AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat Graphical Abstract Amer Alizadeh and Moran Wang Electrophoresis 2017, 38, 580–595. DOI: 10.1002/elps.201600378 The back cover picture shows the surface charge acquiring of a spherical particle within a tube due to the chemical interaction with the solution around the particle. The particle surface-solution electric charge determines based on the counter-ions concentration and solution pH. Whilst a homogeneously polarized electric cloud covers the particle, applying an external electric field could be induced inhomogeneous ionic concentrations within the cloud. To uncover the near-to-reality mechanism of the surface charge distribution, we proposed a robust model which could consider the thoroughly coupled electro-chemo-mechanical transport phenomena. Our model could predict the local surface charge density based on the local solution properties. The theoretical analysis showed that not only the solution pH significantly influenced the surface charge distribution on the particle surface but also the particle size could affect the surface charge amount. Volume38, Issue5Special Issue: Fundamentals of ElectrophoresisMarch 2017 RelatedInformation

Cation Dependent Surface Charge Regulation in Gated Nanofluidic Devices.

Surface charge governs nanoscale aqueous electrolyte transport, both in engineered analytical systems and in biological entities such as ion channels and ion pumps as a function of ion type and concentration. Embedded electrodes in a nanofluidic channel, isolated from the fluid in the channel by a dielectric layer, act as active, tunable gates to systematically modify local surface charge density at the interface between the nanochannel surface and the aqueous electrolyte solution, causing significant changes in measured nanochannel conductance. A systematic comparison of transport of monovalent electrolytes [potassium chloride (KCl), sodium chloride (NaCl)], 2:1 electrolytes [magnesium chloride (MgCl2), calcium chloride (CaCl2)], and electrolyte mixtures (KCl + CaCl2) through a gated nanofluidic device was performed. Ion-surface interactions between divalent Ca2+ and Mg2+ ions and the nanochannel walls reduced the native surface charge density by up to ∼4-5 times compared to the monovalent cations. In electrolyte mixtures, Ca2+ was the dominating cation with nanochannel conductance independent of KCl concentration. Systematic changes in local electrostatic surface state induced by the gate electrode are impacted by the divalent cation-surface interactions, limiting modulation of the local surface potential by the gate electrode and resulting in cation dependent nanoscale ion transport as seen through conductance measurements and numerical models.

Fast Nanoscale Surface Charge Mapping with Pulsed-Potential Scanning Ion Conductance Microscopy.

A vast range of interfacial systems exhibit charge heterogeneities on the nanoscale. These differences in local surface charge density are challenging to visualize, but recent work has shown the scanning ion conductance microscope (SICM) to be a very promising tool to spatially resolve and map surface charge and topography via a hopping potential sweep technique with a single nanopipette probe, with harmonic modulation of a bias applied between quasi-reference counter electrodes in the nanopipette and bulk solution, coupled with lock-in detection. Although powerful, this is a relatively slow process, with limitations on resolution and the size of the images that can be collected. Herein, we demonstrate a new scanning routine for mapping surface charge and topography with SICM, which increases the data acquisition rate by an order of magnitude and with the potential for further gains. Furthermore, the method is simplified, eliminating the need for bias modulation lock-in detection, by utilizing a potential-pulse, chronoamperometric approach, with self-referencing calibration of the response at each pixel in the image. We demonstrate the application of this new method to both a model substrate and living PC-12 cells under physiological (high ionic strength) conditions, where charge mapping is most challenging (small Debye length). This work contributes significantly to the emergence of SICM as a multifunctional technique for simultaneously probing interfacial structure and function with nanometer resolution.

Experimental Evidence and Theoretical Analysis of Nanobubble Stability Within Graphene Nanoscrolls.

In this study direct observation and dynamics of nanoscale water and nanobubbles within graphene nanoscrolls were reported. The life time of these nanobubbles is much higher than expected, which we propose is due to the combination of several factors including localized heating and surface charge. The stability of the nanobubbles within graphene nanoscrolls has been theoretically analyzed. The nanobubbles inside these nanoscrolls reveal a wide distribution of graphene-water contact angles. Bubble dynamics within these graphene nanochannels was directly observed and recorded.