Science.gov

Sample records for electrochemical microscopy rc-secm

  1. Scanning Electrochemical Microscopy

    NASA Astrophysics Data System (ADS)

    Amemiya, Shigeru; Bard, Allen J.; Fan, Fu-Ren F.; Mirkin, Michael V.; Unwin, Patrick R.

    2008-07-01

    This review describes work done in scanning electrochemical microscopy (SECM) since 2000 with an emphasis on new applications and important trends, such as nanometer-sized tips. SECM has been adapted to investigate charge transport across liquid/liquid interfaces and to probe charge transport in thin films and membranes. It has been used in biological systems like single cells to study ion transport in channels, as well as cellular and enzyme activity. It is also a powerful and useful tool for the evaluation of the electrocatalytic activities of different materials for useful reactions, such as oxygen reduction and hydrogen oxidation. SECM has also been used as an electrochemical tool for studies of the local properties and reactivity of a wide variety of materials, including metals, insulators, and semiconductors. Finally, SECM has been combined with several other nonelectrochemical techniques, such as atomic force microscopy, to enhance and complement the information available from SECM alone.

  2. Scanning Electrochemical Microscopy in Neuroscience

    NASA Astrophysics Data System (ADS)

    Schulte, Albert; Nebel, Michaela; Schuhmann, Wolfgang

    2010-07-01

    This article reviews recent work involving the application of scanning electrochemical microscopy (SECM) to the study of individual cultured living cells, with an emphasis on topographical and functional imaging of neuronal and secretory cells of the nervous and endocrine system. The basic principles of biological SECM and associated negative amperometric-feedback and generator/collector-mode SECM imaging are discussed, and successful use of the methodology for screening soft and fragile membranous objects is outlined. The drawbacks of the constant-height mode of probe movement and the benefits of the constant-distance mode of SECM operation are described. Finally, representative examples of constant-height and constant-distance mode SECM on a variety of live cells are highlighted to demonstrate the current status of single-cell SECM in general and of SECM in neuroscience in particular.

  3. Kelvin Probe Force Microscopy in liquid using Electrochemical Force Microscopy

    SciTech Connect

    Collins, Liam; Jesse, Stephen; Kilpatrick, J.; Tselev, Alexander; Okatan, Mahmut Baris; Kalinin, Sergei V.; Rodriguez, Brian

    2015-01-01

    Conventional closed loop-Kelvin probe force microscopy (KPFM) has emerged as a powerful technique for probing electric and transport phenomena at the solid-gas interface. The extension of KPFM capabilities to probe electrostatic and electrochemical phenomena at the solid–liquid interface is of interest for a broad range of applications from energy storage to biological systems. However, the operation of KPFM implicitly relies on the presence of a linear lossless dielectric in the probe-sample gap, a condition which is violated for ionically-active liquids (e.g., when diffuse charge dynamics are present). Here, electrostatic and electrochemical measurements are demonstrated in ionically-active (polar isopropanol, milli-Q water and aqueous NaCl) and ionically-inactive (non-polar decane) liquids by electrochemical force microscopy (EcFM), a multidimensional (i.e., bias- and time-resolved) spectroscopy method. In the absence of mobile charges (ambient and non-polar liquids), KPFM and EcFM are both feasible, yielding comparable contact potential difference (CPD) values. In ionically-active liquids, KPFM is not possible and EcFM can be used to measure the dynamic CPD and a rich spectrum of information pertaining to charge screening, ion diffusion, and electrochemical processes (e.g., Faradaic reactions). EcFM measurements conducted in isopropanol and milli-Q water over Au and highly ordered pyrolytic graphite electrodes demonstrate both sample- and solvent-dependent features. Finally, the feasibility of using EcFM as a local force-based mapping technique of material-dependent electrostatic and electrochemical response is investigated. The resultant high dimensional dataset is visualized using a purely statistical approach that does not require a priori physical models, allowing for qualitative mapping of electrostatic and electrochemical material properties at the solid–liquid interface.

  4. Kelvin probe force microscopy in liquid using electrochemical force microscopy.

    PubMed

    Collins, Liam; Jesse, Stephen; Kilpatrick, Jason I; Tselev, Alexander; Okatan, M Baris; Kalinin, Sergei V; Rodriguez, Brian J

    2015-01-01

    Conventional closed loop-Kelvin probe force microscopy (KPFM) has emerged as a powerful technique for probing electric and transport phenomena at the solid-gas interface. The extension of KPFM capabilities to probe electrostatic and electrochemical phenomena at the solid-liquid interface is of interest for a broad range of applications from energy storage to biological systems. However, the operation of KPFM implicitly relies on the presence of a linear lossless dielectric in the probe-sample gap, a condition which is violated for ionically-active liquids (e.g., when diffuse charge dynamics are present). Here, electrostatic and electrochemical measurements are demonstrated in ionically-active (polar isopropanol, milli-Q water and aqueous NaCl) and ionically-inactive (non-polar decane) liquids by electrochemical force microscopy (EcFM), a multidimensional (i.e., bias- and time-resolved) spectroscopy method. In the absence of mobile charges (ambient and non-polar liquids), KPFM and EcFM are both feasible, yielding comparable contact potential difference (CPD) values. In ionically-active liquids, KPFM is not possible and EcFM can be used to measure the dynamic CPD and a rich spectrum of information pertaining to charge screening, ion diffusion, and electrochemical processes (e.g., Faradaic reactions). EcFM measurements conducted in isopropanol and milli-Q water over Au and highly ordered pyrolytic graphite electrodes demonstrate both sample- and solvent-dependent features. Finally, the feasibility of using EcFM as a local force-based mapping technique of material-dependent electrostatic and electrochemical response is investigated. The resultant high dimensional dataset is visualized using a purely statistical approach that does not require a priori physical models, allowing for qualitative mapping of electrostatic and electrochemical material properties at the solid-liquid interface. PMID:25671164

  5. Kelvin Probe Force Microscopy in liquid using Electrochemical Force Microscopy

    DOE PAGESBeta

    Collins, Liam; Jesse, Stephen; Kilpatrick, J.; Tselev, Alexander; Okatan, Mahmut Baris; Kalinin, Sergei V.; Rodriguez, Brian

    2015-01-01

    Conventional closed loop-Kelvin probe force microscopy (KPFM) has emerged as a powerful technique for probing electric and transport phenomena at the solid-gas interface. The extension of KPFM capabilities to probe electrostatic and electrochemical phenomena at the solid–liquid interface is of interest for a broad range of applications from energy storage to biological systems. However, the operation of KPFM implicitly relies on the presence of a linear lossless dielectric in the probe-sample gap, a condition which is violated for ionically-active liquids (e.g., when diffuse charge dynamics are present). Here, electrostatic and electrochemical measurements are demonstrated in ionically-active (polar isopropanol, milli-Q watermore » and aqueous NaCl) and ionically-inactive (non-polar decane) liquids by electrochemical force microscopy (EcFM), a multidimensional (i.e., bias- and time-resolved) spectroscopy method. In the absence of mobile charges (ambient and non-polar liquids), KPFM and EcFM are both feasible, yielding comparable contact potential difference (CPD) values. In ionically-active liquids, KPFM is not possible and EcFM can be used to measure the dynamic CPD and a rich spectrum of information pertaining to charge screening, ion diffusion, and electrochemical processes (e.g., Faradaic reactions). EcFM measurements conducted in isopropanol and milli-Q water over Au and highly ordered pyrolytic graphite electrodes demonstrate both sample- and solvent-dependent features. Finally, the feasibility of using EcFM as a local force-based mapping technique of material-dependent electrostatic and electrochemical response is investigated. The resultant high dimensional dataset is visualized using a purely statistical approach that does not require a priori physical models, allowing for qualitative mapping of electrostatic and electrochemical material properties at the solid–liquid interface.« less

  6. Soft stylus probes for scanning electrochemical microscopy.

    PubMed

    Cortés-Salazar, Fernando; Träuble, Markus; Li, Fei; Busnel, Jean-Marc; Gassner, Anne-Laure; Hojeij, Mohamad; Wittstock, Gunther; Girault, Hubert H

    2009-08-15

    A soft stylus microelectrode probe has been developed to carry out scanning electrochemical microscopy (SECM) of rough, tilted, and large substrates in contact mode. It is fabricated by first ablating a microchannel in a polyethylene terephthalate thin film and filling it with a conductive carbon ink. After curing the carbon track and lamination with a polymer film, the V-shaped stylus was cut thereby forming a probe, with the cross section of the carbon track at the tip being exposed either by UV-photoablation machining or by blade cutting followed by polishing to produce a crescent moon-shaped carbon microelectrode. The probe properties have been assessed by cyclic voltammetry, approach curves, and line scans over electrochemically active and inactive substrates of different roughness. The influence of probe bending on contact mode imaging was then characterized using simple patterns. Boundary element method simulations were employed to rationalize the distance-dependent electrochemical response of the soft stylus probes. PMID:19630394

  7. Electrochemical strain microscopy of silica glasses

    NASA Astrophysics Data System (ADS)

    Proksch, R.

    2014-08-01

    Piezoresponse Force Microscopy and Electrochemical Strain Microscopy (ESM) are two related techniques that have had considerable success in nano-scale probing of functional material properties. Both measure the strain of the sample in response to a localized electric field beneath a sharp conductive tip. In this work, a collection of commercially available glass samples were measured with a variety of Si cantilevers coated with different conductive metals. In some cases, these glasses showed significant hysteresis loops, similar in appearance to those measured on ferroelectric materials with spontaneous permanent electric dipoles. The magnitude of the electrochemical strain and hysteresis correlated well with the molar percentage of sodium in the glass material, with high sodium (soda-lime) glass showing large hysteresis and fused silica (pure SiO2) showing essentially no hysteresis. The "elephant-ear" shape of the hysteresis loops correlated well with it originating from relaxation behavior—an interpretation verified by observing the temperature dependent relaxation of the ESM response. Cation mobility in a disordered glass should have a low diffusion constant. To evaluate this diffusion constant, the temperature of the glass was varied between room temperature to ˜200 °C. Vanishing hysteresis as the temperature increased was associated with a decrease in the relaxation time of the electrochemical response. The hysteretic behavior changed drastically in this temperature range, consistent with bound surface water playing a large role in the relaxation. This demonstrates the ability of ESM to differentiate cationic concentrations in a range of silica glasses. In addition, since glass is a common sample substrate for, this provides some clear guidance for avoiding unwanted substrate crosstalk effects in piezoresponse and electrochemical strain response measurements.

  8. Simultaneous Nanomechanical and Electrochemical Mapping: Combining Peak Force Tapping Atomic Force Microscopy with Scanning Electrochemical Microscopy.

    PubMed

    Knittel, Peter; Mizaikoff, Boris; Kranz, Christine

    2016-06-21

    Soft electronic devices play a crucial role in, e.g., neural implants as stimulating electrodes, transducers for biosensors, or selective drug-delivery. Because of their elasticity, they can easily adapt to their environment and prevent immunoreactions leading to an overall improved long-term performance. In addition, flexible electronic devices such as stretchable displays will be increasingly used in everyday life, e.g., for so-called electronic wearables. Atomic force microscopy (AFM) is a versatile tool to characterize these micro- and nanostructured devices in terms of their topography. Using advanced imaging techniques such as peak force tapping (PFT), nanomechanical properties including adhesion, deformation, and Young's modulus can be simultaneously mapped along with surface features. However, conventional AFM provides limited laterally resolved information on electrical or electrochemical properties such as the activity of an electrode array. In this study, we present the first combination of AFM with scanning electrochemical microscopy (SECM) in PFT mode, thereby offering spatially correlated electrochemical and nanomechanical information paired with high-resolution topographical data under force control (QNM-AFM-SECM). The versatility of this combined scanning probe approach is demonstrated by mapping topographical, electrochemical, and nanomechanical properties of gold microelectrodes and of gold electrodes patterned onto polydimethylsiloxane. PMID:27203837

  9. Electrochemical current-sensing atomic force microscopy in conductive solutions

    NASA Astrophysics Data System (ADS)

    Pobelov, Ilya V.; Mohos, Miklós; Yoshida, Koji; Kolivoska, Viliam; Avdic, Amra; Lugstein, Alois; Bertagnolli, Emmerich; Leonhardt, Kelly; Denuault, Guy; Gollas, Bernhard; Wandlowski, Thomas

    2013-03-01

    Insulated atomic force microscopy probes carrying gold conductive tips were fabricated and employed as bifunctional force and current sensors in electrolyte solutions under electrochemical potential control. The application of the probes for current-sensing imaging, force and current-distance spectroscopy as well as scanning electrochemical microscopy experiments was demonstrated.

  10. Variable temperature electrochemical strain microscopy of Sm-doped ceria

    SciTech Connect

    Jesse, Stephen; Morozovska, A. N.; Kalinin, Sergei V; Eliseev, E. A.; Yang, Nan; Doria, Sandra; Tebano, Antonello

    2013-01-01

    Variable temperature electrochemical strain microscopy has been used to study the electrochemical activity of Sm-doped ceria as a function of temperature and bias. The electrochemical strain microscopy hysteresis loops have been collected across the surface at different temperatures and the relative activity at different temperatures has been compared. The relaxation behavior of the signal at different temperatures has been also evaluated to relate kinetic process during bias induced electrochemical reactions with temperature and two different kinetic regimes have been identified. The strongly non-monotonic dependence of relaxation behavior on temperature is interpreted as evidence for water-mediated mechanisms.

  11. Menadione metabolism to thiodione in hepatoblastoma by scanning electrochemical microscopy

    PubMed Central

    Mauzeroll, Janine; Bard, Allen J.; Owhadian, Omeed; Monks, Terrence J.

    2004-01-01

    The cytotoxicity of menadione on hepatocytes was studied by using the substrate generation/tip collection mode of scanning electrochemical microscopy by exposing the cells to menadione and detecting the menadione-S-glutathione conjugate (thiodione) that is formed during the cellular detoxication process and is exported from the cell by an ATP-dependent pump. This efflux was electrochemically detected and allowed scanning electrochemical microscopy monitoring and imaging of single cells and groups of highly confluent live cells. Based on a constant flux model, ≈6 × 106 molecules of thiodione per cell per second are exported from monolayer cultures of Hep G2 cells. PMID:15601769

  12. Combined scanning electrochemical-atomic force microscopy.

    PubMed

    Macpherson, J V; Unwin, P R

    2000-01-15

    A combined scanning electrochemical microscope (SECM)-atomic force microscope (AFM) is described. The instrument permits the first simultaneous topographical and electrochemical measurements at surfaces, under fluid, with high spatial resolution. Simple probe tips suitable for SECM-AFM, have been fabricated by coating flattened and etched Pt microwires with insulating, electrophoretically deposited paint. The flattened portion of the probe provides a flexible cantilever (force sensor), while the coating insulates the probe such that only the tip end (electrode) is exposed to the solution. The SECM-AFM technique is illustrated with simultaneous electrochemical-probe deflection approach curves, simultaneous topographical and electrochemical imaging studies of track-etched polycarbonate ultrafiltration membranes, and etching studies of crystal surfaces. PMID:10658320

  13. Combined scanning electrochemical atomic force microscopy for tapping mode imaging

    NASA Astrophysics Data System (ADS)

    Kueng, A.; Kranz, C.; Mizaikoff, B.; Lugstein, A.; Bertagnolli, E.

    2003-03-01

    With the integration of submicro- and nanoelectrodes into atomic force microscopy (AFM) tips using microfabrication techniques, an elegant approach combining scanning electrochemical microscopy (SECM) with atomic force microscopy has recently been demonstrated. Simultaneous imaging of topography and electrochemistry at a sample surface in AFM tapping mode with integrated SECM-AFM cantilevers oscillated at or near their resonance frequency is shown. In contrast to contact mode AFM imaging frictional forces at the sample surface are minimized. Hence, topographical and electrochemical information of soft surfaces (e.g., biological species) can be obtained.

  14. Scanning electrochemical microscopy of individual catalytic nanoparticles.

    PubMed

    Sun, Tong; Yu, Yun; Zacher, Brian J; Mirkin, Michael V

    2014-12-15

    Electrochemistry at individual metal nanoparticles (NPs) can provide new insights into their electrocatalytic behavior. Herein, the electrochemical activity of single AuNPs attached to the catalytically inert carbon surface is mapped by using extremely small (≥3 nm radius) polished nanoelectrodes as tips in the scanning electrochemical microscope (SECM). The use of such small probes resulted in the spatial resolution significantly higher than in previously reported electrochemical images. The currents produced by either rapid electron transfer or the electrocatalytic hydrogen evolution reaction at a single 10 or 20 nm NP were measured and quantitatively analyzed. The developed methodology should be useful for studying the effects of nanoparticle size, geometry, and surface attachment on electrocatalytic activity in real-world application environment. PMID:25332196

  15. Impedance feedback control for scanning electrochemical microscopy.

    PubMed

    Alpuche-Aviles, M A; Wipf, D O

    2001-10-15

    A new constant-distance imaging method based on the relationship between tip impedance and tip-substrate separation has been developed for the scanning electrochemical microscope. The tip impedance is monitored by application of a high-frequency ac voltage bias between the tip and auxiliary electrode. The high-frequency ac current is easily separated from the dc-level faradaic electrochemistry with a simple RC filter, which allows impedance measurements during feedback or generation/collection experiments. By employing a piezo-based feedback controller, we are able to maintain the impedance at a constant value and, thus, maintain a constant tip-substrate separation. Application of the method to feedback and generation/collection experiments with tip electrodes as small as 2 microm is presented. PMID:11681463

  16. Visualization of ion transport in Nafion using electrochemical strain microscopy

    SciTech Connect

    Kim, Suran; No, Kwangsoo; Hong, Seungbum

    2015-12-24

    The electromechanical response of a Nafion membrane immersed in water was probed using electrochemical strain microscopy (ESM) to redistribute protons and measure the resulting local strain that is caused by the movement of protons. We also measured the relaxation of protons from the surface resulting from proton diffusion. Using this technique, we can visualize and analyze the local strain change resulting from the redistribution and relaxation of hydrated protons.

  17. Playing peekaboo with graphene oxide: a scanning electrochemical microscopy investigation.

    PubMed

    Rapino, Stefania; Treossi, Emanuele; Palermo, Vincenzo; Marcaccio, Massimo; Paolucci, Francesco; Zerbetto, Francesco

    2014-11-01

    Scanning electrochemical microscopy (SECM) can image graphene oxide (GO) flakes on insulating and conducting substrates. The contrast between GO and the substrate is controlled by the electrostatic interactions that are established between the charges of the molecular redox mediator and the charges present in the sheet/substrate. SECM also allows quantitative measurement - at the nano/microscale - of the charge transfer kinetics between single monolayer sheets and agent molecules. PMID:25224581

  18. Ultramicrosensors based on transition metal hexacyanoferrates for scanning electrochemical microscopy.

    PubMed

    Komkova, Maria A; Holzinger, Angelika; Hartmann, Andreas; Khokhlov, Alexei R; Kranz, Christine; Karyakin, Arkady A; Voronin, Oleg G

    2013-01-01

    We report here a way for improving the stability of ultramicroelectrodes (UME) based on hexacyanoferrate-modified metals for the detection of hydrogen peroxide. The most stable sensors were obtained by electrochemical deposition of six layers of hexacyanoferrates (HCF), more specifically, an alternating pattern of three layers of Prussian Blue and three layers of Ni-HCF. The microelectrodes modified with mixed layers were continuously monitored in 1 mM hydrogen peroxide and proved to be stable for more than 5 h under these conditions. The mixed layer microelectrodes exhibited a stability which is five times as high as the stability of conventional Prussian Blue-modified UMEs. The sensitivity of the mixed layer sensor was 0.32 A·M(-1)·cm(-2), and the detection limit was 10 µM. The mixed layer-based UMEs were used as sensors in scanning electrochemical microscopy (SECM) experiments for imaging of hydrogen peroxide evolution. PMID:24205459

  19. Scanning electrochemical microscopy of Li-ion batteries.

    PubMed

    Ventosa, E; Schuhmann, W

    2015-11-21

    Li-ion batteries (LIBs) are receiving increasing attention over the past decade due to their high energy density. This energy storage technology is expected to continue improving the performance, especially for its large-scale deployment in plug-in hybrid electric vehicles (PHEVs) and full electric vehicles (EVs). Such improvement requires having a large variety of analytical techniques at scientists' disposal in order to understand and address the multiple mechanisms and processes occurring simultaneously in this complex system. This perspective article aims to highlight the strength and potential of scanning electrochemical microscopy (SECM) in this field. After a brief description of a LIB system and the most commonly used techniques in this field, the unique information provided by SECM is illustrated by discussing several recent examples from the literature. PMID:26076998

  20. Topographical and electrochemical nanoscale imaging of living cells using voltage-switching mode scanning electrochemical microscopy

    PubMed Central

    Takahashi, Yasufumi; Shevchuk, Andrew I.; Novak, Pavel; Babakinejad, Babak; Macpherson, Julie; Unwin, Patrick R.; Shiku, Hitoshi; Gorelik, Julia; Klenerman, David; Korchev, Yuri E.; Matsue, Tomokazu

    2012-01-01

    We describe voltage-switching mode scanning electrochemical microscopy (VSM-SECM), in which a single SECM tip electrode was used to acquire high-quality topographical and electrochemical images of living cells simultaneously. This was achieved by switching the applied voltage so as to change the faradaic current from a hindered diffusion feedback signal (for distance control and topographical imaging) to the electrochemical flux measurement of interest. This imaging method is robust, and a single nanoscale SECM electrode, which is simple to produce, is used for both topography and activity measurements. In order to minimize the delay at voltage switching, we used pyrolytic carbon nanoelectrodes with 6.5–100 nm radii that rapidly reached a steady-state current, typically in less than 20 ms for the largest electrodes and faster for smaller electrodes. In addition, these carbon nanoelectrodes are suitable for convoluted cell topography imaging because the RG value (ratio of overall probe diameter to active electrode diameter) is typically in the range of 1.5–3.0. We first evaluated the resolution of constant-current mode topography imaging using carbon nanoelectrodes. Next, we performed VSM-SECM measurements to visualize membrane proteins on A431 cells and to detect neurotransmitters from a PC12 cells. We also combined VSM-SECM with surface confocal microscopy to allow simultaneous fluorescence and topographical imaging. VSM-SECM opens up new opportunities in nanoscale chemical mapping at interfaces, and should find wide application in the physical and biological sciences. PMID:22611191

  1. Scanning Electrochemical Microscopy of DNA Monolayers Modified with Nile Blue

    PubMed Central

    Gorodetsky, Alon A.; Hammond, William J.; Hill, Michael G.; Slowinski, Krzysztof; Barton, Jacqueline K.

    2009-01-01

    Scanning electrochemical microscopy (SECM) is used to probe long-range charge transport (CT) through DNA monolayers containing the redox-active Nile Blue (NB) intercalator covalently affixed at a specific location in the DNA film. At substrate potentials negative of the formal potential of covalently attached NB, the electrocatalytic reduction of Fe(CN)63− generated at the SECM tip is observed only when NB is located at the DNA/solution interface; for DNA films containing NB in close proximity to the DNA/electrode interface, the electrocatalytic effect is absent. This behavior is consistent with both rapid DNA-mediated CT between the NB intercalator and the gold electrode as well as a rate-limiting electron transfer between NB and the solution phase Fe(CN)63−. The DNA-mediated nature of the catalytic cycle is confirmed through sequence-specific and localized detection of attomoles of TATA-binding protein, a transcription factor that severely distorts DNA upon binding. Importantly, the strategy outlined here is general and allows for the local investigation of the surface characteristics of DNA monolayers both in the absence and in the presence of DNA binding proteins. These experiments highlight the utility of DNA-modified electrodes as versatile platforms for SECM detection schemes that take advantage of CT mediated by the DNA base pair stack. PMID:19053641

  2. Scanning Electrochemical Microscopy Imaging during Respiratory Burst in Human Cell

    PubMed Central

    Kikuchi, Hiroyuki; Prasad, Ankush; Matsuoka, Ryo; Aoyagi, Shigeo; Matsue, Tomokazu; Kasai, Shigenobu

    2016-01-01

    Phagocytic cells, such as neutrophils and monocytes, consume oxygen and generate reactive oxygen species (ROS) in response to external stimuli. Among the various ROS, the superoxide anion radical is known to be primarily produced by nicotinamide adenine dinucleotide phosphate hydrogen (NADPH) oxidase. In the current study, we attempt to evaluate the respiratory burst by monitoring the rapid consumption of oxygen by using scanning electrochemical microscopy (SECM) imaging. The respiratory burst was measured in a human monocytic cell line (THP-1 cells) derived from an acute monocytic leukemia patient under the effect of the exogenous addition of phorbol 12-myristate 13-acetate, which acts as a differentiation inducer. SECM imaging composed of a microelectrode was used to compare oxygen consumption between normal cellular respiration and during respiratory burst in THP-1 cells. Two-dimensional respiratory activity imaging was performed using XY-scan. In addition, the quantitative evaluation of oxygen consumption in THP-1 cells was performed using a Z-scan. The results obtained show higher consumption of oxygen in cells undergoing respiratory burst. SECM imaging is thus claimed to be a highly sensitive and appropriate technique compared to other existing techniques available for evaluating oxidative stress in human cells, making it potentially useful for widespread applications in biomedical research and clinical trials. PMID:26903876

  3. In-situ electrochemical transmission electron microscopy for battery research.

    PubMed

    Mehdi, B Layla; Gu, Meng; Parent, Lucas R; Xu, Wu; Nasybulin, Eduard N; Chen, Xilin; Unocic, Raymond R; Xu, Pinghong; Welch, David A; Abellan, Patricia; Zhang, Ji-Guang; Liu, Jun; Wang, Chong-Min; Arslan, Ilke; Evans, James; Browning, Nigel D

    2014-04-01

    The recent development of in-situ liquid stages for (scanning) transmission electron microscopes now makes it possible for us to study the details of electrochemical processes under operando conditions. As electrochemical processes are complex, care must be taken to calibrate the system before any in-situ/operando observations. In addition, as the electron beam can cause effects that look similar to electrochemical processes at the electrolyte/electrode interface, an understanding of the role of the electron beam in modifying the operando observations must also be understood. In this paper we describe the design, assembly, and operation of an in-situ electrochemical cell, paying particular attention to the method for controlling and quantifying the experimental parameters. The use of this system is then demonstrated for the lithiation/delithiation of silicon nanowires. PMID:24755142

  4. In-Situ Electrochemical Transmission Electron Microscopy for Battery Research

    SciTech Connect

    Mehdi, Beata L; Gu, Meng; Parent, Lucas; Xu, WU; Nasybulin, Eduard; Chen, Xilin; Unocic, Raymond R; Xu, Pinghong; Welch, David; Abellan, Patricia; Zhang, Ji-Guang; Liu, Jun; Wang, Chongmin; Arslan, Ilke; Evans, James E; Browning, Nigel

    2014-01-01

    The recent development of in-situ liquid stages for (scanning) transmission electron microscopes now makes it possible for us to study the details of electrochemical processes under operando conditions. As electrochemical processes are complex, care must be taken to calibrate the system before any in-situ/operando observations. In addition, as the electron beam can cause effects that look similar to electrochemical processes at the electrolyte/electrode interface, an understanding of the role of the electron beam in modifying the operando observations must also be understood. In this paper we describe the design, assembly, and operation of an in-situ electrochemical cell, paying particular attention to the method for controlling and quantifying the experimental parameters. The use of this system is then demonstrated for the lithiation/delithiation of silicon nanowires.

  5. In Situ Electrochemical Transmission Electron Microscopy for Battery Research

    SciTech Connect

    Mehdi, Beata L.; Gu, Meng; Parent, Lucas R.; Xu, Wu; Nasybulin, Eduard N.; Chen, Xilin; Unocic, Raymond R.; Xu, Pinghong; Welch, David A.; Abellan, Patricia; Zhang, Jiguang; Liu, Jun; Wang, Chong M.; Arslan, Ilke; Evans, James E.; Browning, Nigel D.

    2014-04-01

    The recent development of in situ liquid stages for (scanning) transmission electron microscopes now makes it possible for us to study the details of electrochemical processes under operando conditions. As electrochemical processes are complex, care must be taken to calibrate the system before any in situ/operando observations. In addition, as the electron beam can cause effects that look similar to electrochemical processes at the electrolyte/electrode interface, an understanding of the role of the electron beam in modifying the operando observations must also be understood. In this paper we describe the design, assembly, and operation of an in situ electrochemical cell, paying particular attention to the method for controlling and quantifying the experimental parameters. The use of this system is then demonstrated for the lithiation/delithiation of silicon nanowires.

  6. Detection of hydrogen peroxide produced during electrochemical oxygen reduction using scanning electrochemical microscopy.

    PubMed

    Shen, Yan; Träuble, Markus; Wittstock, Gunther

    2008-02-01

    The substrate-generation/tip-collection mode of scanning electrochemical microscopy was used to detect hydrogen peroxide formed as an intermediate during oxygen reduction at various electrodes. The experiment is conceptually similar to rotating ring-disk experiments but does not require the production of a ring-disk assembly for the specific electrode material in question. In order to limit the extension of the diffusion layer above the sample, the sample electrode potential is pulsed while the Pt ultramicroelectrode probe (UME) is held at a constant potential for oxidative amperometric detection of hydrogen peroxide. The signal at UME is influenced by the sample region within the diffusion length of hydrogen peroxide during the pulse of 2.5 s. The method is tested with three model electrodes showing different behavior with respect to the oxygen reduction reaction (ORR) in acidic solution. Simple analytical models were used to extract effective rate constants for the most important reaction paths of ORR at gold and palladium-cobalt samples from the chronoamperometric response of the UME to a reduction pulse at the sample electrode. PMID:18179180

  7. Electro-deposition of Cu studied with in situ electrochemical scanning transmission x-ray microscopy

    NASA Astrophysics Data System (ADS)

    Hitchcock, A. P.; Qin, Z.; Rosendahl, S. M.; Lee, V.; Reynolds, M.; Hosseinkhannazer, H.

    2016-01-01

    Soft X-ray scanning transmission X-ray microscopy (STXM) was used to investigate Cu deposition onto, and stripping from a Au surface. Cu 2p spectromicroscopy was used to analyze initial and final states (ex situ processing) and follow the processes in situ. The in situ experiments were carried out using a static electrochemical cell with an electrolyte layer thickness of ˜1 μm. A new apparatus for in situ electrochemical STXM is described.

  8. Scanning electrochemical microscopy of living cells. 3. Rhodobacter sphaeroides.

    PubMed

    Cai, Chenxin; Liu, Biao; Mirkin, Michael V; Frank, Harry A; Rusling, James F

    2002-01-01

    The scanning electrochemical microscope (SECM) was used to probe the redox activity of individual purple bacteria (Rhodobacter sphaeroides). The approaches developed in our previous studies of mammalian cells were expanded to measure the rates and investigate the pathway of transmembrane charge transfer in bacteria. The two groups of redox mediators (i.e., hydrophilic and hydrophobic redox species) were used to shuttle the electrons between the SECM tip electrode in solution and the redox centers inside the cell. The analysis of the dependencies of the measured rate constant on formal potential and concentration of mediator species in solution yielded information about the permeability of the outer cell membrane to different ionic species and intracellular redox properties. The maps of redox reactivity of the cell surface were obtained with a micrometer or submicrometer spatial resolution. PMID:11795778

  9. Application of scanning electrochemical microscopy to biological samples.

    PubMed

    Lee, C; Kwak, J; Bard, A J

    1990-03-01

    The scanning electrochemical microscope can be used in the feedback mode in two-dimensional scans over biological substrates to obtain topographic information at the micrometer level. In this mode, the effect of distance between a substrate (either conductive or insulating) and a scanning ultramicroelectrode tip on the electrolytic current flowing at the tip is recorded as a function of the tip x-y position. Scans of the upper surface of a grass leaf and the lower surface of a Ligustrum sinensis leaf (which show open stomata structures) immersed in aqueous solution are shown. Scans of the upper surface of an elodea leaf in the dark and under irradiation, where the tip reaction is the reduction of oxygen produced by photosynthesis, demonstrate the possibility of obtaining information about the distribution of reaction sites on the substrate surface. PMID:2308933

  10. Application of scanning electrochemical microscopy to biological samples.

    PubMed Central

    Lee, C; Kwak, J; Bard, A J

    1990-01-01

    The scanning electrochemical microscope can be used in the feedback mode in two-dimensional scans over biological substrates to obtain topographic information at the micrometer level. In this mode, the effect of distance between a substrate (either conductive or insulating) and a scanning ultramicroelectrode tip on the electrolytic current flowing at the tip is recorded as a function of the tip x-y position. Scans of the upper surface of a grass leaf and the lower surface of a Ligustrum sinensis leaf (which show open stomata structures) immersed in aqueous solution are shown. Scans of the upper surface of an elodea leaf in the dark and under irradiation, where the tip reaction is the reduction of oxygen produced by photosynthesis, demonstrate the possibility of obtaining information about the distribution of reaction sites on the substrate surface. Images PMID:2308933

  11. Application of Scanning Electrochemical Microscopy to Biological Samples

    NASA Astrophysics Data System (ADS)

    Lee, Chongmok; Kwak, Juhyoun; Bard, Allen J.

    1990-03-01

    The scanning electrochemical microscope can be used in the feedback mode in two-dimensional scans over biological substrates to obtain topographic information at the micrometer level. In this mode, the effect of distance between a substrate (either conductive or insulating) and a scanning ultramicroelectrode tip on the electrolytic current flowing at the tip is recorded as a function of the tip x-y position. Scans of the upper surface of a grass leaf and the lower surface of a Ligustrum sinensis leaf (which show open stomata structures) immersed in aqueous solution are shown. Scans of the upper surface of an elodea leaf in the dark and under irradiation, where the tip reaction is the reduction of oxygen produced by photosynthesis, demonstrate the possibility of obtaining information about the distribution of reaction sites on the substrate surface.

  12. Mapping Ionic Currents and Reactivity on the Nanoscale: Electrochemical Strain Microscopy

    SciTech Connect

    Kalinin, S.V.

    2010-10-19

    Solid-state electrochemical processes in oxides underpin a broad spectrum of energy and information storage devices, ranging from Li-ion and Li-air batteries, to solid oxide fuel cells (SOFC) to electroresistive and memristive systems. These functionalities are controlled by the bias-driven diffusive and electromigration transport of mobile ionic species, as well as intricate a set of electrochemical and defect-controlled reactions at interfaces and in bulk. Despite the wealth of device-level and atomistic studies, little is known on the mesoscopic mechanisms of ion diffusion and electronic transport on the level of grain clusters, individual grains, and extended defects. The development of the capability for probing ion transport on the nanometer scale is a key to deciphering complex interplay between structure, functionality, and performance in these systems. Here we introduce Electrochemical Strain Microscopy, a scanning probe microscopy technique based on strong strain-bias coupling in the systems in which local ion concentrations are changed by electrical fields. The imaging capability, as well as time- and voltage spectroscopies analogous to traditional current based electrochemical characterization methods are developed. The reversible intercalation of Li and mapping electrochemical activity in LiCoO2 is demonstrated, illustrating higher Li diffusivity at non-basal planes and grain boundaries. In Si-anode device structure, the direct mapping of Li diffusion at extended defects and evolution of Li-activity with charge state is explored. The electrical field-dependence of Li mobility is studied to determine the critical bias required for the onset of electrochemical transformation, allowing reaction and diffusion processes in the battery system to be separated at each location. Finally, the applicability of ESM for probing oxygen vacancy diffusion and oxygen reduction/evolution reactions is illustrated, and the high resolution ESM maps are correlated with

  13. Voltammetric Scanning Electrochemical Cell Microscopy: Dynamic Imaging of Hydrazine Electro-oxidation on Platinum Electrodes.

    PubMed

    Chen, Chang-Hui; Jacobse, Leon; McKelvey, Kim; Lai, Stanley C S; Koper, Marc T M; Unwin, Patrick R

    2015-06-01

    Voltammetric scanning electrochemical cell microscopy (SECCM) incorporates cyclic voltammetry measurements in the SECCM imaging protocol, by recording electrochemical currents in a wide potential window at each pixel in a map. This provides much more information compared to traditional fixed potential imaging. Data can be represented as movies (hundreds of frames) of current (over a surface region) at a series of potentials and are highly revealing of subtle variations in electrode activity. Furthermore, by combining SECCM data with other forms of microscopy, e.g. scanning electron microscopy and electron backscatter diffraction data, it is possible to directly relate the current-voltage characteristics to spatial position and surface structure. In this work we use a "hopping mode", where the SECCM pipet probe is translated toward the surface at a series of positions until meniscus contact. Small amounts of residue left on the surface, upon probe retraction, demark the precise area of each measurement. We use these techniques to study hydrazine oxidation on a polycrystalline platinum substrate both in air and in a deaerated environment. In both cases, the detected faradaic current shows a structural dependence on the surface crystallographic orientation. Significantly, in the presence of oxygen (aerated solution) the electrochemical current decreases strongly for almost all grains (crystallographic orientations). The results highlight the flexibility of voltammetric SECCM for electrochemical imaging and present important implications for hydrazine electroanalysis. PMID:25942527

  14. Selective insulation with poly(tetrafluoroethylene) of substrate electrodes for electrochemical background reduction in scanning electrochemical microscopy.

    PubMed

    Rodriguez-Lopez, Joaquin; Alpuche-Aviles, Mario A; Bard, Allen J

    2008-03-01

    We describe a wet process for the fabrication of poly(tetrafluoroethylene) (PTFE)-covered electrodes in which arrays of holes ( approximately 200 microm) are formed. The PTFE coating provides electrical insulation of most of the electrode surface with selected regions exposed for electrochemical experiments. The arrays of microholes can be controllably patterned and filled with precursor solutions using a piezoelectric dispenser. A micrometer spot of electrocatalyst is produced after reduction of the precursor. The application is tested for scanning electrochemical microscopy (SECM) in the tip generation-substrate collection (TG-SC) studies of electrocatalysts. The method is shown to reduce the substrate background currents that are included in the electrochemical signal read from the local perturbation induced with the SECM tip to the substrate in the TG-SC mode of SECM. This background current reduction is consistent with the decrease in the exposed area of the electrode. The general methodology for the fabrication of the substrate electrodes and two proof-of-concept applications in the TG-SC SECM modality are described. PMID:18251520

  15. Topographic, electrochemical, and optical images captured using standing approach mode scanning electrochemical/optical microscopy.

    PubMed

    Takahashi, Yasufumi; Hirano, Yu; Yasukawa, Tomoyuki; Shiku, Hitoshi; Yamada, Hiroshi; Matsue, Tomokazu

    2006-12-01

    We developed a high-resolution scanning electrochemical microscope (SECM) for the characterization of various biological materials. Electrode probes were fabricated by Ti/Pt sputtering followed by parylene C-vapor deposition polymerization on the pulled optical fiber or glass capillary. The effective electrode radius estimated from the cyclic voltammogram of ferrocyanide was found to be 35 nm. The optical aperture size was less than 170 nm, which was confirmed from the cross section of the near-field scanning optical microscope (NSOM) image of the quantum dot (QD) particles with diameters in the range of 10-15 nm. The feedback mechanism controlling the probe-sample distance was improved by vertically moving the probe by 0.1-3 microm to reduce the damage to the samples. This feedback mode, defined as "standing approach (STA) mode" (Yamada, H.; Fukumoto, H.; Yokoyama, T.; Koike, T. Anal. Chem. 2005, 77, 1785-1790), has allowed the simultaneous electrochemical and topographic imaging of the axons and cell body of a single PC12 cell under physiological conditions for the first time. STA-mode feedback imaging functions better than tip-sample regulation by the conventionally available AFM. For example, polystyrene beads (diameter approximately 6 microm) was imaged using the STA-mode SECM, whereas imaging was not possible using a conventional AFM instrument. PMID:17128996

  16. Towards quantitative electrochemical measurements on the nanoscale by scanning probe microscopy: environmental and current spreading effects

    SciTech Connect

    Arruda, Thomas M; Kumar, Amit; Veith, Gabriel M; Jesse, Stephen; Tselev, Alexander; Baddorf, Arthur P; Balke, Nina; Kalinin, Sergei V

    2013-01-01

    The application of electric bias across tip-surface junctions in scanning probe microscopy can readily induce surface and bulk electrochemical processes that can be further detected though changes in surface topography, Faradaic or conductive currents, or electromechanical strain responses. However, the basic factors controlling tip-induced electrochemical processes, including the relationship between applied tip bias and the thermodynamics of local processes remains largely unexplored. Using the model Li-ion reduction reaction on the surface in Li-ion conducting glass ceramic, we explore the factors controlling Li-metal formation and find surprisingly strong effects of atmosphere and back electrode composition on the process. These studies suggest the feasibility of SPM-based quantitative electrochemical studies under proper environmental controls, extending the concepts of ultramicroelectrodes to the single-digit nanometer scale.

  17. Scanning Electrochemical Cell Microscopy: A Versatile Technique for Nanoscale Electrochemistry and Functional Imaging

    NASA Astrophysics Data System (ADS)

    Ebejer, Neil; Güell, Aleix G.; Lai, Stanley C. S.; McKelvey, Kim; Snowden, Michael E.; Unwin, Patrick R.

    2013-06-01

    Scanning electrochemical cell microscopy (SECCM) is a new pipette-based imaging technique purposely designed to allow simultaneous electrochemical, conductance, and topographical visualization of surfaces and interfaces. SECCM uses a tiny meniscus or droplet, at the end of a double-barreled (theta) pipette, for high-resolution functional imaging and nanoscale electrochemical measurements. Here we introduce this technique and provide an overview of its principles, instrumentation, and theory. We discuss the power of SECCM in resolving complex structure-activity problems and provide considerable new information on electrode processes by referring to key example systems, including graphene, graphite, carbon nanotubes, nanoparticles, and conducting diamond. The many longstanding questions that SECCM has been able to answer during its short existence demonstrate its potential to become a major technique in electrochemistry and interfacial science.

  18. Individual Detection and Electrochemically Assisted Identification of Adsorbed Nanoparticles by Using Surface Plasmon Microscopy.

    PubMed

    Nizamov, Shavkat; Kasian, Olga; Mirsky, Vladimir M

    2016-06-13

    The increasing production and application of nanoparticles necessitates a highly sensitive analytical method for the quantification and identification of these potentially hazardous materials. We describe here an application of surface plasmon microscopy for the individual detection of each adsorbed nanoparticle and for visualization of its electrochemical conversion. Whereas the adsorption rate characterizes the number concentration of nanoparticles, the potential at which the adsorbed nanoparticles disappear during an anodic potential sweep characterizes the type of material. All the adsorbed nanoparticles are subjected to the potential sweep simultaneously; nevertheless, each of the up to a million adsorbed nanoparticles is identified individually by its electrochemical dissolution potential. The technique has been tested with silver and copper nanoparticles, but can be extended to many other electrochemically active nanomaterials. PMID:27139913

  19. Scanning electrochemical cell microscopy: a versatile technique for nanoscale electrochemistry and functional imaging.

    PubMed

    Ebejer, Neil; Güell, Aleix G; Lai, Stanley C S; McKelvey, Kim; Snowden, Michael E; Unwin, Patrick R

    2013-01-01

    Scanning electrochemical cell microscopy (SECCM) is a new pipette-based imaging technique purposely designed to allow simultaneous electrochemical, conductance, and topographical visualization of surfaces and interfaces. SECCM uses a tiny meniscus or droplet, at the end of a double-barreled (theta) pipette, for high-resolution functional imaging and nanoscale electrochemical measurements. Here we introduce this technique and provide an overview of its principles, instrumentation, and theory. We discuss the power of SECCM in resolving complex structure-activity problems and provide considerable new information on electrode processes by referring to key example systems, including graphene, graphite, carbon nanotubes, nanoparticles, and conducting diamond. The many longstanding questions that SECCM has been able to answer during its short existence demonstrate its potential to become a major technique in electrochemistry and interfacial science. PMID:23560932

  20. In situ electrochemical studies of lithium-ion battery cathodes using atomic force microscopy

    NASA Astrophysics Data System (ADS)

    Ramdon, Sanjay; Bhushan, Bharat; Nagpure, Shrikant C.

    2014-03-01

    Lithium-ion (Li-ion) batteries have been implemented for numerous applications, including plug-in hybrid electric vehicles (PHEV) and pure electric vehicles (EV). In an effort to prolong battery life, it is important to understand the mechanisms that cause reduced battery capacity with aging. Past studies have shown that morphological changes occur in aged cathodes. In situ electrochemical studies using atomic force microscopy allow for the direct observation of the morphology of the Li-ion battery cathode, at a nanometer scale resolution, during the cycling of an electrochemical cell. A simple electrochemical cell designed for in situ characterization is introduced. Charge/discharge curves and morphology data obtained during charging and discharging of cells are presented, and relevant mechanisms are discussed.

  1. Characterization of LiMn2O4 cathodes by electrochemical strain microscopy

    DOE PAGESBeta

    Alikin, D. O.; Ievlev, A. V.; Luchkin, S. Yu.; Turygin, A. P.; Shur, V. Ya.; Kalinin, S. V.; Kholkin, A. L.

    2016-03-15

    Electrochemical strain microscopy (ESM) is a scanning probe microscopy(SPM) method in which the local electrodiffusion is probed via application of AC voltage to the SPM tip and registration of resulting electrochemical strain. In this study, we implemented ESM to measure local strain in bulk LiMn2O4 cathodes of a commercial Li-battery in different states of charge to investigate distribution of Li-ion mobility and concentration. Ramped AC ESM imaging and voltage spectroscopy were used to find the most reliable regime of measurements allowing separating and diminishing different contributions to ESM. This is not a trivial task due to complex geometry of themore » sample and various obstacles resulting in less predictable contributions of different origins into ESM response: electrostatic tip–surface interactions, charge injection, electrostriction, and flexoelectricity. Finally, understanding and control of these contributions is an important step towards quantitative interpretation of ESM data.« less

  2. Characterization of LiMn2O4 cathodes by electrochemical strain microscopy

    NASA Astrophysics Data System (ADS)

    Alikin, D. O.; Ievlev, A. V.; Luchkin, S. Yu.; Turygin, A. P.; Shur, V. Ya.; Kalinin, S. V.; Kholkin, A. L.

    2016-03-01

    Electrochemical strain microscopy (ESM) is a scanning probe microscopy (SPM) method in which the local electrodiffusion is probed via application of AC voltage to the SPM tip and registration of resulting electrochemical strain. Here, we implemented ESM to measure local strain in bulk LiMn2O4 cathodes of a commercial Li-battery in different states of charge to investigate distribution of Li-ion mobility and concentration. Ramped AC ESM imaging and voltage spectroscopy were used to find the most reliable regime of measurements allowing separating and diminishing different contributions to ESM. This is not a trivial task due to complex geometry of the sample and various obstacles resulting in less predictable contributions of different origins into ESM response: electrostatic tip-surface interactions, charge injection, electrostriction, and flexoelectricity. Understanding and control of these contributions is an important step towards quantitative interpretation of ESM data.

  3. Local electrochemical functionality in energy storage materials and devices by scanning probe microscopies: status and perspectives.

    PubMed

    Kalinin, Sergei V; Balke, Nina

    2010-09-15

    Energy storage and conversion systems are an integral component of emerging green technologies, including mobile electronic devices, automotive, and storage components of solar and wind energy economics. Despite the rapidly expanding manufacturing capabilities and wealth of phenomenological information on the macroscopic device behaviors, the microscopic mechanisms underpinning battery and fuel cell operations in the nanometer-micrometer range are virtually unknown. This lack of information is due to the dearth of experimental techniques capable of addressing elementary mechanisms involved in battery operation, including electronic and ion transport, vacancy injection, and interfacial reactions, on the nanometer scale. In this article, a brief overview of scanning probe microscopy (SPM) methods addressing nanoscale electrochemical functionalities is provided and compared with macroscopic electrochemical methods. Future applications of emergent SPM methods, including near field optical, electromechanical, microwave, and thermal probes and combined SPM-(S)TEM (scanning transmission electron microscopy) methods in energy storage and conversion materials are discussed. PMID:20730814

  4. Direct electrochemical measurements inside a 2000 angstrom thick polymer film by scanning electrochemical microscopy.

    PubMed

    Mirkin, M V; Fan, F R; Bard, A J

    1992-07-17

    An extremely small, conically shaped Pt microelectrode tip (with a radius of 30 nanometers) and the precise positioning capabilities of the scanning electrochemical microscope were used to penetrate a thin (200 nanometers) polymer film and obtain directly the standard potential and kinetic parameters of an electrode reaction within the film. The thickness of the film was determined while it was immersed in and swollen by an electrolyte solution. The film studied was the perfluorosulfonate Nafion containing Os(bpy)(3)(2+) (bpy, 2,2'-bipyridine) cast on an indium tin oxide surface. The steady-state response at the ultramicroelectrode allowed direct determination of the rate constant for heterogeneous electron transfer K(o) and the diffusion coefficient D without complications caused by transport in the liquid phase, charge exchange at the liquid-polymer interface, and resistive drop. PMID:17832832

  5. In Situ Characterization of Ultrathin Films by Scanning Electrochemical Impedance Microscopy.

    PubMed

    Estrada-Vargas, Arturo; Bandarenka, Aliaksandr; Kuznetsov, Volodymyr; Schuhmann, Wolfgang

    2016-03-15

    Control over the properties of ultrathin films plays a crucial role in many fields of science and technology. Although nondestructive optical and electrical methods have multiple advantages for local surface characterization, their applicability is very limited if the surface is in contact with an electrolyte solution. Local electrochemical methods, e.g., scanning electrochemical microscopy (SECM), cannot be used as a robust alternative yet because their methodological aspects are not sufficiently developed with respect to these systems. The recently proposed scanning electrochemical impedance microscopy (SEIM) can efficiently elucidate many key properties of the solid/liquid interface such as charge transfer resistance or interfacial capacitance. However, many fundamental aspects related to SEIM application still remain unclear. In this work, a methodology for the interpretation of SEIM data of "charge blocking systems" has been elaborated with the help of finite element simulations in combination with experimental results. As a proof of concept, the local film thickness has been visualized using model systems at various tip-to-sample separations. Namely, anodized aluminum oxide (Al2O3, 2-20 nm) and self-assembled monolayers based on 11-mercapto-1-undecanol and 16-mercapto-1-hexadecanethiol (2.1 and 2.9 nm, respectively) were used as model systems. PMID:26871004

  6. Focused-Ion-Beam-Milled Carbon Nanoelectrodes for Scanning Electrochemical Microscopy

    PubMed Central

    Chen, Ran; Hu, Keke; Yu, Yun; Mirkin, Michael V.; Amemiya, Shigeru

    2016-01-01

    Nanoscale scanning electrochemical microscopy (SECM) has emerged as a powerful electrochemical method that enables the study of interfacial reactions with unprecedentedly high spatial and kinetic resolution. In this work, we develop carbon nanoprobes with high electrochemical reactivity and well-controlled size and geometry based on chemical vapor deposition of carbon in quartz nanopipets. Carbon-filled nanopipets are milled by focused ion beam (FIB) technology to yield a flat disk tip with a thin quartz sheath as confirmed by transmission electron microscopy. The extremely high electroactivity of FIB-milled carbon nanotips is quantified by enormously high standard electron-transfer rate constants of ≥10 cm/s for Ru(NH3)63+. The tip size and geometry are characterized in electrolyte solutions by SECM approach curve measurements not only to determine inner and outer tip radii of down to ~27 and ~38 nm, respectively, but also to ensure the absence of a conductive carbon layer on the outer wall. In addition, FIB-milled carbon nanotips reveal the limited conductivity of ~100 nm-thick gold films under nanoscale mass-transport conditions. Importantly, carbon nanotips must be protected from electrostatic damage to enable reliable and quantitative nanoelectrochemical measurements.

  7. Electrochemical characterization of sub-micro-gram amounts of organic semiconductors using scanning droplet cell microscopy

    PubMed Central

    Gasiorowski, Jacek; Mardare, Andrei I.; Sariciftci, Niyazi S.; Hassel, Achim Walter

    2013-01-01

    Scanning droplet cell microscopy (SDCM) uses a very small electrolyte droplet at the tip of a capillary which comes in contact with the working electrode. This method is particularly interesting for studies on organic semiconductors since it provides localized electrochemical investigations with high reproducibility. One clear advantage of applying SDCM is represented by the very small amounts of material necessary (less than 1 mg). Organic materials can be investigated quickly and inexpensively in electrochemical studies with a high throughput. In the present study, thin layers of poly(3-hexylthiophene) (P3HT), which is one of the most often used material for organic solar cells, were deposited on ITO/glass as working electrodes in SDCM studies. The redox reactions in 0.1 M tetra(n-butyl)ammonium hexafluorophosphate (TBAPF6) dissolved in propylene carbonate were studied by cyclic voltammetry and by electrochemical impedance spectroscopy. Two reversible, distinct oxidation steps of the P3HT were detected and their kinetics were studied in detail. The doping of P3HT increased due to the electrochemical oxidation and had resulted in a decrease of the film resistance by a few orders of magnitude. Due to localization on the sample various parameter combinations can be studied quantitatively and reproducibly. PMID:24926226

  8. Electrochemical characterization of sub-micro-gram amounts of organic semiconductors using scanning droplet cell microscopy.

    PubMed

    Gasiorowski, Jacek; Mardare, Andrei I; Sariciftci, Niyazi S; Hassel, Achim Walter

    2013-02-15

    Scanning droplet cell microscopy (SDCM) uses a very small electrolyte droplet at the tip of a capillary which comes in contact with the working electrode. This method is particularly interesting for studies on organic semiconductors since it provides localized electrochemical investigations with high reproducibility. One clear advantage of applying SDCM is represented by the very small amounts of material necessary (less than 1 mg). Organic materials can be investigated quickly and inexpensively in electrochemical studies with a high throughput. In the present study, thin layers of poly(3-hexylthiophene) (P3HT), which is one of the most often used material for organic solar cells, were deposited on ITO/glass as working electrodes in SDCM studies. The redox reactions in 0.1 M tetra(n-butyl)ammonium hexafluorophosphate (TBAPF6) dissolved in propylene carbonate were studied by cyclic voltammetry and by electrochemical impedance spectroscopy. Two reversible, distinct oxidation steps of the P3HT were detected and their kinetics were studied in detail. The doping of P3HT increased due to the electrochemical oxidation and had resulted in a decrease of the film resistance by a few orders of magnitude. Due to localization on the sample various parameter combinations can be studied quantitatively and reproducibly. PMID:24926226

  9. Mapping fluxes of radicals from the combination of electrochemical activation and optical microscopy.

    PubMed

    Munteanu, Sorin; Roger, Jean Paul; Fedala, Yasmina; Amiot, Fabien; Combellas, Catherine; Tessier, Gilles; Kanoufi, Frédéric

    2013-01-01

    The coating of gold (Au) electrode surfaces with nitrophenyl (NP) layers is studied by combination of electrochemical actuation and optical detection. The electrochemical actuation of the reduction of the nitrobenzenediazonium (NBD) precursor is used to generate NP radicals and therefore initiate the electrografting. The electrografting process is followed in situ and in real time by light reflectivity microscopy imaging, allowing for spatio-temporal imaging with sub-micrometer lateral resolution and sub-nanometer thickness sensitivity of the local growth of a transparent organic coating onto a reflecting Au electrode. The interest of the electrochemical actuation resides in its ability to finely control the grafting rate of the NP layer through the electrode potential. Coupling the electrochemical actuation with microscopic imaging of the electrode surface allows quantitative estimates of the local grafting rates and subsequently a real time and in situ mapping of the reacting fluxes of NP radicals on the surface. Over the 2 orders of magnitude range of grafting rates (from 0.04 to 4 nm s(-1)), it is demonstrated that the edge of Au electrodes are grafted -1.3 times more quickly than their centre, illustrating the manifestation of edge-effects on flux distribution at an electrode. A model is proposed to explain the observed edge-effect, it relies on the short lifetime of the intermediate NP radical species. PMID:24466667

  10. Scanning electrochemical microscopy for study of aptamer-thrombin interfacial interactions on gold disk microelectrodes.

    PubMed

    Bai, Huei-Yu; del Campo, F Javier; Tsai, Yu-Chen

    2014-03-01

    A feasibility for the determination of thrombin on gold disk microelectrodes (GDMs) using scanning electrochemical microscopy (SECM) is reported. The assembly process step-by-step of thrombin aptasensor on GDMs is monitored by SECM. SECM analysis reveals the immobilization of thrombin aptamers on GDMs. The interaction between thrombin aptamers and thrombin on GDMs is imaged by SECM with feedback mode using ferrocenemethanol as an electrochemical mediator. The formation of thrombin/thrombin aptamer complex on GDMs results in a decrease in the tip peak current on spatial SECM images. This method is able to linearly and selectively detect thrombin over a linear range from 10(-12) to 10(-5)M with a detection limit of 6.07 fM. PMID:24407695

  11. Imaging of Biological Macromolecules on Mica in Humid Air by Scanning Electrochemical Microscopy

    NASA Astrophysics Data System (ADS)

    Fan, Fu-Ren F.; Bard, Allen J.

    1999-12-01

    Imaging of DNA, keyhole limpet hemocyanin, mouse monoclonal IgG, and glucose oxidase on a mica substrate has been accomplished by scanning electrochemical microscopy with a tungsten tip. The technique requires the use of a high relative humidity to form a thin film of water on the mica surface that allows electrochemical reactions to take place at the tip and produce a faradaic current (≈ 1\\ pA) that can be used to control tip position. The effect of relative humidity and surface pretreatment with buffer solutions on the ionic conductivity of a mica surface was investigated to find appropriate conditions for imaging. Resolution of the order of 1 nm was obtained.

  12. Imaging of biological macromolecules on mica in humid air by scanning electrochemical microscopy

    PubMed Central

    Fan, Fu-Ren F.; Bard, Allen J.

    1999-01-01

    Imaging of DNA, keyhole limpet hemocyanin, mouse monoclonal IgG, and glucose oxidase on a mica substrate has been accomplished by scanning electrochemical microscopy with a tungsten tip. The technique requires the use of a high relative humidity to form a thin film of water on the mica surface that allows electrochemical reactions to take place at the tip and produce a faradaic current (≈1 pA) that can be used to control tip position. The effect of relative humidity and surface pretreatment with buffer solutions on the ionic conductivity of a mica surface was investigated to find appropriate conditions for imaging. Resolution of the order of 1 nm was obtained. PMID:10588687

  13. Scanning electrochemical microscopy of genomic DNA microarrays--study of adsorption and subsequent interactions.

    PubMed

    Roberts, William S; Davis, Frank; Higson, Séamus P J

    2009-07-01

    The adsorption of genomic DNA and subsequent interactions between adsorbed and solvated DNA have been studied using scanning electrochemical microscopy (SECM). Microarrays of polyethylenimine (PEI) films could be deposited on screen-printed carbon substrates using the SECM. Single stranded herring DNA was electrostatically adsorbed at the surface of the polyethylenimine. The further adsorption of complementary single stranded DNA on the surface was observed to give rise to substantial decreases in interfacial impedance at the surface as measured by increases of tip current of the order of 1-2 nA (6%). Conversely adsorption of DNA from alternate species, i.e. salmon ssDNA on herring ssDNA, yielded much smaller changes in tip current of 0.2 nA. The significance of this work is that the approach opens up the possibility for direct label-free electrochemical interrogation of DNA microarrays as an alternative to other existing optical techniques. PMID:19562194

  14. A leveling method based on current feedback mode of scanning electrochemical microscopy.

    PubMed

    Han, Lianhuan; Yuan, Ye; Zhang, Jie; Zhao, Xuesen; Cao, Yongzhi; Hu, Zhenjiang; Yan, Yongda; Dong, Shen; Tian, Zhong-Qun; Tian, Zhao-Wu; Zhan, Dongping

    2013-02-01

    Substrate leveling is an essential but neglected instrumental technique of scanning electrochemical microscopy (SECM). In this technical note, we provide an effective substrate leveling method based on the current feedback mode of SECM. By using an air-bearing rotary stage as the supporter of an electrolytic cell, the current feedback presents a periodic waveform signal, which can be used to characterize the levelness of the substrate. Tuning the adjusting screws of the tilt stage, substrate leveling can be completed in minutes by observing the decreased current amplitude. The obtained high-quality SECM feedback curves and images prove that this leveling technique is valuable in not only SECM studies but also electrochemical machining. PMID:23289726

  15. In situ electrochemical digital holographic microscopy; a study of metal electrodeposition in deep eutectic solvents.

    PubMed

    Abbott, Andrew P; Azam, Muhammad; Ryder, Karl S; Saleem, Saima

    2013-07-16

    This study has shown for the first time that digital holographic microscopy (DHM) can be used as a new analytical tool in analysis of kinetic mechanism and growth during electrolytic deposition processes. Unlike many alternative established electrochemical microscopy methods such as probe microscopy, DHM is both the noninvasive and noncontact, the unique holographic imaging allows the observations and measurement to be made remotely. DHM also provides interferometric resolution (nanometer vertical scale) with a very short acquisition time. It is a surface metrology technique that enables the retrieval of information about a 3D structure from the phase contrast of a single hologram acquired using a conventional digital camera. Here DHM has been applied to investigate directly the electro-crystallization of a metal on a substrate in real time (in situ) from two deep eutectic solvent (DES) systems based on mixture of choline chloride and either urea or ethylene glycol. We show, using electrochemical DHM that the nucleation and growth of silver deposits in these systems are quite distinct and influenced strongly by the hydrogen bond donor of the DES. PMID:23751128

  16. X-Ray Photoelectron Spectroscopy and Scanning Electrochemical Microscopy Studies of Branched Multiwalled Carbon Nanotube Paper Modified by Electrochemical Grafting and Click Chemistry

    NASA Astrophysics Data System (ADS)

    Coates, Megan; Nyokong, Tebello

    2013-06-01

    Modification of nanomaterials through electrochemical grafting is a useful approach to introduce linking groups on to the surface of these structures. This work shows the possibility of applying electrochemical grafting to branched multiwalled carbon nanotube paper with an electrical resistance of 0.1 ohm-cm, and subsequent reaction of the grafted 4-azidobenzenediazonium with ethynylferrocene through the Sharpless click chemistry reaction. A comparison is made between this paper electrode and adsorbed single-walled carbon nanotubes on a glassy carbon electrode, with electrochemistry, X-ray photoelectron spectroscopy and scanning electrochemical microscopy used for characterization.

  17. In Situ Characterization of Pitting Corrosion of Stainless Steel by a Scanning Electrochemical Microscopy

    NASA Astrophysics Data System (ADS)

    Dong, C. F.; Luo, H.; Xiao, K.; Li, X. G.; Cheng, Y. F.

    2012-03-01

    In this work, a scanning electrochemical microscopy (SECM) was used to characterize in situ the metastable and stable pitting processes occurring on a stainless steel in the chloride solution. It was found that metastable pitting would occur on the steel that was at corrosion potential and passive potential. The positive shift of potential would enhance the metastable pitting current. On application of a potential exceeding pitting potential, the pit became stabilized and maintained a continuous growth. The SECM is capable of detecting the microdissolution event and provides a "visual" observation of the pitting processes.

  18. Design and fabrication of nanoelectrodes for applications with scanning electrochemical microscopy

    NASA Astrophysics Data System (ADS)

    Thakar, Rahul

    Scanning electrochemical microscope (SECM) was introduced two decades ago and has since emerged as a powerful research tool to investigate localized electrochemical reactions at the surface of material and biological samples. The ability to obtain chemical information at a surface differentiates SECM from competing scanning probe microscopy (SPM) techniques. Although, chemical specificity is a unique advantage offered by SECM, inherent limitations due to a slow feedback response, and challenges associated with production of smaller electrodes have remained major drawbacks. Initially in this research, SECM was utilized as a characterization and investigative tool. Later, advances in SECM imaging were achieved with design and production of multifunctional nanoelectrodes. At first, platinum based nanoelectrodes were fabricated for use as electrochemical probes to investigate local electron transfer at chemically-modified surfaces. Further, micron and sub-micron platinum electrodes with chemically modified shrouds were prepared and characterized with voltammetric measurements. Studies reveal experimental evidence for the presence of edge-effects that are typically associated with submicron electrodes. Interestingly, we observed selectivity of these electrodes based on hydrophobic/ hydrophilic character. Through vapor deposition of parylene over microstructured material, single-pore membranes and porous membrane arrays were produced. Pore size characterization within porous membranes was performed with templated growth of micro/nanostructures. Characterization of transport properties of ions and redox-active molecules through hydrophobic parylene membranes was investigated with ion conductance microscopy and SECM, individually. Parylene is an insulative material that is chemically resistant, deposits conformally over high-aspect ratio objects and also converts into conductive carbon at high-temperature pyrolysis. Motivated by these results we identified a unique

  19. Second harmonic detection in the electrochemical strain microscopy of Ag-ion conducting glass

    SciTech Connect

    Yang, Sangmo; Okatan, Mahmut Baris; Paranthaman, Mariappan Parans; Jesse, Stephen; Noh, Tae Won; Kalinin, Sergei V.

    2014-11-14

    The first and second harmonic electromechanical responses and their cross-correlation in Ag-ion conducting glass were investigated using band-excitation electrochemical strain microscopy (ESM). Consecutive ESM images with increasing magnitudes of the applied AC voltage allowed observation of not only reversible surface displacement but also irreversible silver nanoparticle formation above a certain threshold voltage. The second harmonic ESM response was anticorrelated with the first harmonic response in many local regions. Furthermore, the nucleation sites of silver nanoparticles were closely related to the anti-correlated regions, specifically, with low second harmonic and high first harmonic ESM responses. The possible origins of the second harmonic ESM response are discussed.

  20. Scanning electrochemical microscopy of menadione-glutathione conjugate export from yeast cells.

    PubMed

    Mauzeroll, Janine; Bard, Allen J

    2004-05-25

    The uptake of menadione (2-methyl-1,4-naphthoquinone), which is toxic to yeast cells, and its expulsion as a glutathione complex were studied by scanning electrochemical microscopy. The progression of the in vitro reaction between menadione and glutathione was monitored electrochemically by cyclic voltammetry and correlated with the spectroscopic (UV-visible) behavior. By observing the scanning electrochemical microscope tip current of yeast cells suspended in a menadione-containing solution, the export of the conjugate from the cells with time could be measured. Similar experiments were performed on immobilized yeast cell aggregates stressed by a menadione solution. From the export of the menadione-glutathione conjugate detected at a 1-microm-diameter electrode situated 10 microm from the cells, a flux of about 30,000 thiodione molecules per second per cell was extracted. Numerical simulations based on an explicit finite difference method further revealed that the observation of a constant efflux of thiodione from the cells suggested the rate was limited by the uptake of menadione and that the efflux through the glutathione-conjugate pump was at least an order of magnitude faster. PMID:15148374

  1. Scanning electrochemical microscopy of menadione-glutathione conjugate export from yeast cells

    PubMed Central

    Mauzeroll, Janine; Bard, Allen J.

    2004-01-01

    The uptake of menadione (2-methyl-1,4-naphthoquinone), which is toxic to yeast cells, and its expulsion as a glutathione complex were studied by scanning electrochemical microscopy. The progression of the in vitro reaction between menadione and glutathione was monitored electrochemically by cyclic voltammetry and correlated with the spectroscopic (UV–visible) behavior. By observing the scanning electrochemical microscope tip current of yeast cells suspended in a menadione-containing solution, the export of the conjugate from the cells with time could be measured. Similar experiments were performed on immobilized yeast cell aggregates stressed by a menadione solution. From the export of the menadione-glutathione conjugate detected at a 1-μm-diameter electrode situated 10 μm from the cells, a flux of about 30,000 thiodione molecules per second per cell was extracted. Numerical simulations based on an explicit finite difference method further revealed that the observation of a constant efflux of thiodione from the cells suggested the rate was limited by the uptake of menadione and that the efflux through the glutathione-conjugate pump was at least an order of magnitude faster. PMID:15148374

  2. Carbon nanofiber electrodes and controlled nanogaps for scanning electrochemical microscopy experiments.

    PubMed

    Tel-Vered, Ran; Walsh, Darren A; Mehrgardi, Masoud A; Bard, Allen J

    2006-10-01

    The electrochemical behavior of electrodes made by sealing carbon nanofibers in glass or with electrophoretic paint has been studied by scanning electrochemical microscopy (SECM). Because of their small electroactive surface area, conical geometry with a low aspect ratio and high overpotential for proton and oxygen reduction, carbon nanofiber (CNF) electrodes are promising candidates for producing electrode nanogaps, imaging with high spatial resolution and for the electrodeposition of single metal nanoparticles (e.g., Pt, Pd) for studies as electrocatalysts. By using the feedback mode of the SECM, a CNF tip can produce a gap that is smaller than 20 nm from a platinum disk. Similarly, the SECM used in a tip-collection substrate-generation mode, which subsequently shows a feedback interaction at short distances, makes it possible to detect a single CNF by another CNF and then to form a nanometer gap between the two electrodes. This approach was used to image vertically aligned CNF arrays. This method is useful in the detection in a homogeneous solution of short-lifetime intermediates, which can be electrochemically generated at one electrode and collected at the second at distances that are equivalent to a nanosecond time scale. PMID:17007521

  3. Electrochemomechanics with flexoelectricity and modelling of electrochemical strain microscopy in mixed ionic-electronic conductors

    NASA Astrophysics Data System (ADS)

    Yu, Pengfei; Hu, Shuling; Shen, Shengping

    2016-08-01

    Recently, a new scanning probe microscopy approach, referred to as electrochemical strain microscopy (ESM), for probing local ionic flows and electrochemical reactions in solids based on the bias-strain coupling was proposed by Morozovska et al. Then, a series of theoretical papers for analyzing the image formation and spectroscopic mechanism of ESM were published within the framework of Fermi-Dirac statistics, the Vegard law, the direct flexoelectric coupling effect, the electrostriction effect, and so on. However, most of the models in these papers are limited to the partial coupling or particular process, and numerically solved by using decoupling approximation. In this paper, to model the ESM measurement with the coupling electrical-chemical-mechanical process, the chemical Gibbs function variational principle for the thermal electrical chemical mechanical fully coupling problem is proposed. The fully coupling governing equations are derived from the variational principle. When the tip concentrates the electric field within a small volume of the material, the inhomogeneous electric field is induced. So, both direct and inverse flexoelectric effects should be taken into account. Here, the bulk defect electrochemical reactions are also taken into account, which are usually omitted in the existing works. This theory can be used to deal with coupling problems in solids, including conductors, semiconductors, and piezoelectric and non-piezoelectric dielectrics. As an application of this work, a developed initial-boundary value problem is solved numerically in a mixed ion-electronic conductor. Numerical results show that it is meaningful and necessary to consider the bulk defect chemical reaction. Besides, the chemical reaction and the flexoelectric effect have an interactive influence on each other. This work can provide theoretical basis for the ESM as well as investigating the bulk chemical reaction process in solids.

  4. Second harmonic detection in the electrochemical strain microscopy of Ag-ion conducting glass

    DOE PAGESBeta

    Yang, Sangmo; Okatan, Mahmut Baris; Paranthaman, Mariappan Parans; Jesse, Stephen; Noh, Tae Won; Kalinin, Sergei V.

    2014-11-14

    The first and second harmonic electromechanical responses and their cross-correlation in Ag-ion conducting glass were investigated using band-excitation electrochemical strain microscopy (ESM). Consecutive ESM images with increasing magnitudes of the applied AC voltage allowed observation of not only reversible surface displacement but also irreversible silver nanoparticle formation above a certain threshold voltage. The second harmonic ESM response was anticorrelated with the first harmonic response in many local regions. Furthermore, the nucleation sites of silver nanoparticles were closely related to the anti-correlated regions, specifically, with low second harmonic and high first harmonic ESM responses. The possible origins of the second harmonicmore » ESM response are discussed.« less

  5. Imaging space charge regions in Sm-doped ceria using electrochemical strain microscopy

    SciTech Connect

    Chen, Qian Nataly; Li, Jiangyu; Adler, Stuart B.

    2014-11-17

    Nanocrystalline ceria exhibits a total conductivity several orders of magnitude higher than microcrystalline ceria in air at high temperature. The most widely accepted theory for this enhancement (based on fitting of conductivity data to various transport and kinetic models) is that relatively immobile positively charged defects and/or impurities accumulate at the grain boundary core, leading to a counterbalancing increase in the number of mobile electrons (small polarons) within a diffuse space charge region adjacent to each grain boundary. In an effort to validate this model, we have applied electrochemical strain microscopy to image the location and relative population of mobile electrons near grain boundaries in polycrystalline Sm-doped ceria in air at 20–200 °C. Our results show the first direct (spatially resolved) evidence that such a diffuse space charge region does exist in ceria, and is localized to both grain boundaries and the gas-exposed surface.

  6. Analysis of beat fluctuations and oxygen consumption in cardiomyocytes by scanning electrochemical microscopy.

    PubMed

    Hirano, Yu; Kodama, Mikie; Shibuya, Masahiro; Maki, Yoshiyuki; Komatsu, Yasuo

    2014-02-15

    The contractile behavior of cardiomyocytes can be monitored by measuring their action potentials, and the analysis is essential for screening the safety of potential drugs. However, immobilizing cardiac cells on a specific electrode is considerably complicated. In this study, we demonstrate that scanning electrochemical microscopy (SECM) can be used to analyze rapid topographic changes in beating cardiomyocytes in a standard culture dish. Various cardiomyocyte contraction parameters and oxygen consumption based on cell respiration could be determined from SECM data. We also confirmed that cellular changes induced by adding the cardiotonic agent digoxin were conveniently monitored by this SECM system. These results show that SECM can be a potentially powerful tool for use in drug development for cardiovascular diseases. PMID:24252541

  7. Finger probe array for topography-tolerant scanning electrochemical microscopy of extended samples.

    PubMed

    Lesch, Andreas; Chen, Po-Chung; Roelfs, Folkert; Dosche, Carsten; Momotenko, Dmitry; Cortés-Salazar, Fernando; Girault, Hubert H; Wittstock, Gunther

    2014-01-01

    Scanning electrochemical microscopy with soft microelectrode array probes has recently been used to enable reactivity imaging of extended areas and to compensate sample corrugation perpendicular to the scanning direction. Here, the use of a new type of microelectrode arrays is described in which each individual microelectrode can independently compensate corrugations of the sample surface. It consists of conventional Pt microelectrodes enclosed in an insulating glass sheath. The microelectrodes are individually fixed to a new holder system by magnetic forces. The concept was tested using a large 3D sample with heights up to 12 μm specially prepared by inkjet printing. The microelectrodes follow the topography in a constant working distance independently from each other while exerting low pressure on the surface. PMID:24328212

  8. Feedback Effects in Combined Fast-Scan Cyclic Voltammetry-Scanning Electrochemical Microscopy

    PubMed Central

    Schrock, Daniel S.; Wipf, David O.; Baur, John E.

    2008-01-01

    Fast-scan cyclic voltammetry at scan rates between 5 and 1000 Vs−1 was performed at the tip of a scanning electrochemical microscope immersed in a solution of redox mediator. The effect of conducting and insulating substrates on the voltammetric signal was investigated as a function of scan rate and tip-substrate distance. It was found that diffusional interactions between the tip and the substrate are greatest at lower scan rates and on the reverse sweep of the voltammogram. At the fastest scan rates used, the tip could be brought to with 1 μm of the substrate without appreciable perturbation of the voltammogram. By selecting scan rates and tip-substrate distances such that feedback effects were negligible, it was possible to image the diffusion layer of a 10 μm Pt substrate electrode. With the tip placed 1 μm above a biological cell, tip-substrate diffusional interactions were greatly diminished at a scan rate of 100 Vs−1, and absent at a scan rate of 1000 Vs−1. These results suggest conditions can be selected that allow chemical imaging of substrates without the feedback interactions typically encountered in scanning electrochemical microscopy. PMID:17550230

  9. Feedback effects in combined fast-scan cyclic voltammetry-scanning electrochemical microscopy.

    PubMed

    Schrock, Daniel S; Wipf, David O; Baur, John E

    2007-07-01

    Fast-scan cyclic voltammetry at scan rates between 5 and 1000 V s(-1) was performed at the tip of a scanning electrochemical microscope immersed in a solution of redox mediator. The effect of conducting and insulating substrates on the voltammetric signal was investigated as a function of scan rate and tip-substrate distance. It was found that diffusional interactions between the tip and the substrate are greatest at lower scan rates and on the reverse sweep of the voltammogram. At the fastest scan rates used, the tip could be brought to with 1 microm of the substrate without appreciable perturbation of the voltammogram. By selecting scan rates and tip-substrate distances such that feedback effects were negligible, it was possible to image the diffusion layer of a 10 microm Pt substrate electrode. With the tip placed 1 microm above a biological cell, tip-substrate diffusional interactions were greatly diminished at a scan rate of 100 V s(-1) and absent at a scan rate of 1000 V s(-1). These results suggest conditions can be selected that allow chemical imaging of substrates without the feedback interactions typically encountered in scanning electrochemical microscopy. PMID:17550230

  10. Assessment of multidrug resistance on cell coculture patterns using scanning electrochemical microscopy

    PubMed Central

    Kuss, Sabine; Polcari, David; Geissler, Matthias; Brassard, Daniel; Mauzeroll, Janine

    2013-01-01

    The emergence of resistance to multiple unrelated chemotherapeutic drugs impedes the treatment of several cancers. Although the involvement of ATP-binding cassette transporters has long been known, there is no in situ method capable of tracking this transporter-related resistance at the single-cell level without interfering with the cell’s environment or metabolism. Here, we demonstrate that scanning electrochemical microscopy (SECM) can quantitatively and noninvasively track multidrug resistance-related protein 1–dependent multidrug resistance in patterned adenocarcinoma cervical cancer cells. Nonresistant human cancer cells and their multidrug resistant variants are arranged in a side-by-side format using a stencil-based patterning scheme, allowing for precise positioning of target cells underneath the SECM sensor. SECM measurements of the patterned cells, performed with ferrocenemethanol and [Ru(NH3)6]3+ serving as electrochemical indicators, are used to establish a kinetic “map” of constant-height SECM scans, free of topography contributions. The concept underlying the work described herein may help evaluate the effectiveness of treatment administration strategies targeting reduced drug efflux. PMID:23686580

  11. Electrodeposition and Screening of Photoelectrochemical Activity in Conjugated Polymers Using Scanning Electrochemical Cell Microscopy.

    PubMed

    Aaronson, Barak D B; Garoz-Ruiz, Jesus; Byers, Joshua C; Colina, Alvaro; Unwin, Patrick R

    2015-11-24

    A number of renewable energy systems require an understanding and correlation of material properties and photoelectrochemical activity on the micro to nanoscale. Among these, conducting polymer electrodes continue to be important materials. In this contribution, an ultrasensitive scanning electrochemical cell microscopy (SECCM) platform is used to electrodeposit microscale thin films of poly(3-hexylthiophene) (P3HT) on an optically transparent gold electrode and to correlate the morphology (film thickness and structural order) with photoactivity. The electrochemical growth of P3HT begins with a thin ordered film up to 10 nm thick, after which a second more disordered film is deposited, as revealed by micro-Raman spectroscopy. A decrease in photoactivity for the thicker films, measured in situ immediately following film deposition, is attributed to an increase in bulk film disorder that limits charge transport. Higher resolution ex situ SECCM phototransient measurements, using a smaller diameter probe, show local variations in photoactivity within a given deposit. Even after aging, thinner, more ordered regions within a deposit exhibit sustained enhanced photocurrent densities compared to areas where the film is thicker and more disordered. The platform opens up new possibilities for high-throughput combinatorial correlation studies, by allowing materials fabrication and high spatial resolution probing of processes in photoelectrochemical materials. PMID:26502089

  12. Assessment of multidrug resistance on cell coculture patterns using scanning electrochemical microscopy.

    PubMed

    Kuss, Sabine; Polcari, David; Geissler, Matthias; Brassard, Daniel; Mauzeroll, Janine

    2013-06-01

    The emergence of resistance to multiple unrelated chemotherapeutic drugs impedes the treatment of several cancers. Although the involvement of ATP-binding cassette transporters has long been known, there is no in situ method capable of tracking this transporter-related resistance at the single-cell level without interfering with the cell's environment or metabolism. Here, we demonstrate that scanning electrochemical microscopy (SECM) can quantitatively and noninvasively track multidrug resistance-related protein 1-dependent multidrug resistance in patterned adenocarcinoma cervical cancer cells. Nonresistant human cancer cells and their multidrug resistant variants are arranged in a side-by-side format using a stencil-based patterning scheme, allowing for precise positioning of target cells underneath the SECM sensor. SECM measurements of the patterned cells, performed with ferrocenemethanol and [Ru(NH3)6](3+) serving as electrochemical indicators, are used to establish a kinetic "map" of constant-height SECM scans, free of topography contributions. The concept underlying the work described herein may help evaluate the effectiveness of treatment administration strategies targeting reduced drug efflux. PMID:23686580

  13. High-speed scanning electrochemical microscopy method for substrate kinetic determination: application to live cell imaging in human cancer.

    PubMed

    Kuss, Sabine; Trinh, Dao; Mauzeroll, Janine

    2015-08-18

    Scanning electrochemical microscopy (SECM) is increasingly applied to study and image live cells. Quantitative analyses of biological systems, however, still remain challenging. In the presented study, single human adenocarcinoma cervical cancer cells are electrochemically investigated by means of SECM. The target cell's electrochemical response is observed over time under the influence of green tea catechins (GTC), which are suggested to offer chemopreventive and therapeutic effects on cancer. The electrochemical response of living target cells is measured experimentally and quantified in an apparent heterogeneous rate constant by using a numerical model, based on forced convection during high speed SECM imaging. The beneficial effect of GTC on cancer cells could be confirmed by SECM, and the presented study shows an alternative approach toward unraveling the mechanisms involved during inhibition of carcinogenesis. PMID:26167832

  14. Direct Visualization of Solid Electrolyte Interphase Formation in Lithium-Ion Batteries with In Situ Electrochemical Transmission Electron Microscopy

    SciTech Connect

    Unocic, Raymond R.; Sun, Xiao-Guang; Sacci, Robert L.; Adamczyk, Leslie A.; Alsem, Daan Hein; Dai, Sheng; Dudney, Nancy J.; More, Karren Leslie

    2014-08-01

    Complex, electrochemically driven transport processes form the basis of electrochemical energy storage devices. The direct imaging of electrochemical processes at high spatial resolution and within their native liquid electrolyte would significantly enhance our understanding of device functionality, but has remained elusive. In this work we use a recently developed liquid cell for in situ electrochemical transmission electron microscopy to obtain insight into the electrolyte decomposition mechanisms and kinetics in lithium-ion (Li-ion) batteries by characterizing the dynamics of solid electrolyte interphase (SEI) formation and evolution. Here we are able to visualize the detailed structure of the SEI that forms locally at the electrode/electrolyte interface during lithium intercalation into natural graphite from an organic Li-ion battery electrolyte. We quantify the SEI growth kinetics and observe the dynamic self-healing nature of the SEI with changes in cell potential.

  15. Photosynthetic Electron Transport in Single Guard Cells as Measured by Scanning Electrochemical Microscopy.

    PubMed Central

    Tsionsky, M.; Cardon, Z. G.; Bard, A. J.; Jackson, R. B.

    1997-01-01

    Scanning electrochemical microscopy (SECM) is a powerful new tool for studying chemical and biological processes. It records changes in faradaic current as a microelectrode ([less than equal]7 [mu]m in diameter) is moved across the surface of a sample. The current varies as a function of both distance from the surface and the surface's chemical and electrical properties. We used SECM to examine in vivo topography and photosynthetic electron transport of individual guard cells in Tradescantia fluminensis, to our knowledge the first such analysis for an intact plant. We measured surface topography at the micrometer level and concentration profiles of O2 evolved in photosynthetic electron transport. Comparison of topography and oxygen profiles above single stomatal complexes clearly showed photosynthetic electron transport in guard cells, as indicated by induction of O2 evolution by photosynthetically active radiation. SECM is unique in its ability to measure topography and chemical fluxes, combining some of the attributes of patch clamping with scanning tunneling microscopy. In this paper we suggest several questions in plant physiology that it might address. PMID:12223651

  16. Non-destructive Patterning of Carbon Electrodes by Using the Direct Mode of Scanning Electrochemical Microscopy.

    PubMed

    Stratmann, Lutz; Clausmeyer, Jan; Schuhmann, Wolfgang

    2015-11-16

    Patterning of glassy carbon surfaces grafted with a layer of nitrophenyl moieties was achieved by using the direct mode of scanning electrochemical microscopy (SECM) to locally reduce the nitro groups to hydroxylamine and amino functionalities. SECM and atomic force microscopy (AFM) revealed that potentiostatic pulses applied to the working electrode lead to local destruction of the glassy carbon surface, most likely caused by etchants generated at the positioned SECM tip used as the counter electrode. By applying galvanostatic pulses, and thus, limiting the current during structuring, corrosion of the carbon surface was substantially suppressed. After galvanostatic patterning, unambiguous proof of the formation of the anticipated amino moieties was possible by modulation of the pH value during the feedback mode of SECM imaging. This patterning strategy is suitable for the further bio-modification of microstructured surfaces. Alkaline phosphatase, as a model enzyme, was locally bound to the modified areas, thus showing that the technique can be used for the development of protein microarrays. PMID:26316379

  17. Self-consistent modeling of electrochemical strain microscopy of solid electrolytes

    DOE PAGESBeta

    Tselev, Alexander; Morozovska, Anna N.; Udod, Alexei; Eliseev, Eugene A.; Kalinin, Sergei V.

    2014-10-10

    Electrochemical strain microscopy (ESM) employs a strong electromechanical coupling in solid ionic conductors to map ionic transport and electrochemical processes with nanometer-scale spatial resolution. To elucidate the mechanisms of the ESM image formation, we performed self-consistent numerical modeling of the electromechanical response in solid electrolytes under the probe tip in a linear, small-signal regime using the Boltzmann–Planck–Nernst–Einstein theory and Vegard's law while taking account of the electromigration and diffusion. We identified the characteristic time scales involved in the formation of the ESM response and found that the dynamics of the charge carriers in the tip-electrolyte system with blocking interfaces canmore » be described as charging of the diffuse layer at the tip-electrolyte interface through the tip contact spreading resistance. At the high frequencies used in the detection regime, the distribution of the charge carriers under the tip is governed by evanescent concentration waves generated at the tip-electrolyte interface. The ion drift length in the electric field produced by the tip determines the ESM response at high frequencies, which follows a 1/f asymptotic law. The electronic conductivity, as well as the electron transport through the electrode-electrolyte interface, do not have a significant effect on the ESM signal in the detection regime. The results indicate, however, that for typical solid electrolytes at room temperature, the ESM response originates at and contains information about the very surface layer of a sample, and the properties of the one-unit-cell-thick surface layer may significantly contribute to the ESM response, implying a high surface sensitivity and a high lateral resolution of the technique. On the other hand, it follows that a rigorous analysis of the ESM signals requires techniques that account for the discrete nature of a solid.« less

  18. Nanogap-enabled study of electrode reactions by scanning electrochemical microscopy

    NASA Astrophysics Data System (ADS)

    Nioradze, Nikoloz

    The nanogap quasi-steady-state voltammetry, developed in my work, presents the way to monitor and study rapid electron transfer reactions on macroscopic substrates of scanning electrochemical microscopy (SECM). It combines the cyclic voltammetry and SECM and monitors substrate reaction as a tip current. The resulting plot of iT versus ES features the retraceable sigmoidal shape of a quasi-steady state voltammogram although a transient peak-shape voltammogram is obtained simultaneously at the macroscopic substrate. This simplifies measurement and analysis of a quasi-steady-state voltammogram and gives information about thermodynamic as well as kinetic parameters of the reaction taking place at the interface. No charging current at the amperometric tip, high and adjustable mass transport under the tip and high spatial resolution are all advantages of quasi-steady-state voltammetry. I also introduced generalized theory for nanoscale iT-ES voltammetry of substrate reactions with arbitrary reversibility and mechanism under comprehensive experimental conditions including any substrate potential and both SECM modes (feedback and substrate generation tip collection, SG/TC). I nanofabricated submicrometer size highly reliable Pt SECM tips and found the way of protection of these tiny electrodes from the damage caused either by electrostatic discharge or electrochemical etching. Subsequent application of quasi-steady-state voltammetry and reliable nanofabricated SECM probes enabled sensitive detection of adsorption of organic impurities from air and ultrapure water to the HOPG surface as evidenced by redox reaction of ferrocenylmethyl)trimethyl ammonium (FcTMA +). Study revealed that hydrophobic contaminant layer slows down the access of hydrophilic aqueous redox species to the underlying HOPG surface, thereby yielding a lower standard rate constant, k 0. Moreover, this barrier effects stronger to a more charged form (FcTMA2+) of a redox couple so that the electron

  19. Self-consistent modeling of electrochemical strain microscopy of solid electrolytes.

    PubMed

    Tselev, Alexander; Morozovska, Anna N; Udod, Alexei; Eliseev, Eugene A; Kalinin, Sergei V

    2014-11-01

    Electrochemical strain microscopy (ESM) employs a strong electromechanical coupling in solid ionic conductors to map ionic transport and electrochemical processes with nanometer-scale spatial resolution. To elucidate the mechanisms of the ESM image formation, we performed self-consistent numerical modeling of the electromechanical response in solid electrolytes under the probe tip in a linear, small-signal regime using the Boltzmann-Planck-Nernst-Einstein theory and Vegard's law while taking account of the electromigration and diffusion. The characteristic time scales involved in the formation of the ESM response were identified. It was found that the dynamics of the charge carriers in the tip-electrolyte system with blocking interfaces can be described as charging of the diffuse layer at the tip-electrolyte interface through the tip contact spreading resistance. At the high frequencies used in the detection regime, the distribution of the charge carriers under the tip is governed by evanescent concentration waves generated at the tip-electrolyte interface. The ion drift length in the electric field produced by the tip determines the ESM response at high frequencies, which follows a 1/f asymptotic law. The electronic conductivity, as well as the electron transport through the electrode-electrolyte interface, do not have a significant effect on the ESM signal in the detection regime. The results indicate, however, that for typical solid electrolytes at room temperature, the ESM response originates at and contains information about the very surface layer of a sample, and the properties of the one-unit-cell-thick surface layer may significantly contribute to the ESM response, implying a high surface sensitivity and a high lateral resolution of the technique. On the other hand, it follows that a rigorous analysis of the ESM signals requires techniques that account for the discrete nature of a solid. PMID:25302673

  20. Self-consistent modeling of electrochemical strain microscopy of solid electrolytes

    SciTech Connect

    Tselev, Alexander; Morozovska, Anna N.; Udod, Alexei; Eliseev, Eugene A.; Kalinin, Sergei V.

    2014-10-10

    Electrochemical strain microscopy (ESM) employs a strong electromechanical coupling in solid ionic conductors to map ionic transport and electrochemical processes with nanometer-scale spatial resolution. To elucidate the mechanisms of the ESM image formation, we performed self-consistent numerical modeling of the electromechanical response in solid electrolytes under the probe tip in a linear, small-signal regime using the Boltzmann–Planck–Nernst–Einstein theory and Vegard's law while taking account of the electromigration and diffusion. We identified the characteristic time scales involved in the formation of the ESM response and found that the dynamics of the charge carriers in the tip-electrolyte system with blocking interfaces can be described as charging of the diffuse layer at the tip-electrolyte interface through the tip contact spreading resistance. At the high frequencies used in the detection regime, the distribution of the charge carriers under the tip is governed by evanescent concentration waves generated at the tip-electrolyte interface. The ion drift length in the electric field produced by the tip determines the ESM response at high frequencies, which follows a 1/f asymptotic law. The electronic conductivity, as well as the electron transport through the electrode-electrolyte interface, do not have a significant effect on the ESM signal in the detection regime. The results indicate, however, that for typical solid electrolytes at room temperature, the ESM response originates at and contains information about the very surface layer of a sample, and the properties of the one-unit-cell-thick surface layer may significantly contribute to the ESM response, implying a high surface sensitivity and a high lateral resolution of the technique. On the other hand, it follows that a rigorous analysis of the ESM signals requires techniques that account for the discrete nature of a solid.

  1. Effect of tribolayer formation on corrosion of CoCrMo alloys investigated using scanning electrochemical microscopy.

    PubMed

    Meyer, Joshua N; Mathew, Mathew T; Wimmer, Markus A; LeSuer, Robert J

    2013-08-01

    Scanning electrochemical microscopy was used to probe the topography and electrochemical activity of CoCrMo alloys mechanically polished in the presence of bovine calf serum (BCS) in a hip simulator. These substrates are made of the same alloy used in metal-on-metal bearings for artificial hip joints. The BCS serves as an in vitro substitute for the synovial fluid which forms a lubricant in the actual orthopedic device. Chemical and mechanical processes result in the formation of a tribolayer which passivates the alloy surface. Our studies of the heterogeneous electron transfer between ferrocenemethanol and the alloy indicate that the tribolayer formed on both high- and low-carbon substrates is highly heterogeneous with regions of high electrochemical activity. Whereas pits in the samples polished in the absence of BCS show the regions of highest electrochemical activity, the tribolayer-coated samples have electrochemical hot spots in topographically smooth regions of the surface. The tribolayer provides some attenuation of the electrochemical activity of the alloy but does not prevent the possibility of corrosion from occurring. PMID:23848566

  2. Scanning Electrochemical Microscopy as a Novel Proximity Sensor for Atraumatic Cochlear Implant Insertion

    PubMed Central

    Velmurugan, J.; Mirkin, M. V.; Svirsky, M. A.; Lalwani, A. K.; Llinas, R. R.

    2014-01-01

    A growing number of minimally invasive surgical and diagnostic procedures require the insertion of an optical, mechanical, or electronic device in narrow spaces inside a human body. In such procedures, precise motion control is essential to avoid damage to the patient’s tissues and/or the device itself. A typical example is the insertion of a cochlear implant which should ideally be done with minimum physical contact between the moving device and the cochlear canal walls or the basilar membrane. Because optical monitoring is not possible, alternative techniques for sub millimeter-scale distance control can be very useful for such procedures. The first requirement for distance control is distance sensing. We developed a novel approach to distance sensing based on the principles of scanning electrochemical microscopy (SECM). The SECM signal, i.e., the diffusion current to a microelectrode, is very sensitive to the distance between the probe surface and any electrically insulating object present in its proximity. With several amperometric microprobes fabricated on the surface of an insertable device, one can monitor the distances between different parts of the moving implant and the surrounding tissues. Unlike typical SECM experiments, in which a disk-shaped tip approaches a relatively smooth sample, complex geometries of the mobile device and its surroundings make distance sensing challenging. Additional issues include the possibility of electrode surface contamination in biological fluids and the requirement for a biologically compatible redox mediator. PMID:24845292

  3. Scanning electrochemical microscopy of model neurons: imaging and real-time detection of morphological changes.

    PubMed

    Liebetrau, Johanna M; Miller, Heather M; Baur, John E; Takacs, Sara A; Anupunpisit, Vipavee; Garris, Paul A; Wipf, David O

    2003-02-01

    Living PC12 cells, a model cell type for studying neuronal function, were imaged using the negative feedback mode of a scanning electrochemical microscope (SECM). Six biocompatible redox mediators were successfully identified from a large pool of candidates and were then used for imaging PC12 cells before and after exposure to nerve growth factor (NGF). When exposed to NGF, cells differentiate into a neuron phenotype by growing narrow neurites (1-2 microm wide) that can extend > 100 microm from the cell proper. We demonstrate that carbon fiber electrodes with reduced tip diameters can be used for imaging both the cell proper and these neurites. Regions of decreased current, possibly resulting from raised features not identifiable by light microscopy, are clearly evident in the SECM images. Changes in the morphology of undifferentiated PC12 cells could be detected in real time with the SECM. After exposure to hypotonic and hypertonic solutions, reversible changes in cell height of <2 microm were measured. PMID:12585485

  4. Imaging of ATP membrane transport with dual micro-disk electrodes and scanning electrochemical microscopy.

    PubMed

    Kueng, Angelika; Kranz, Christine; Mizaikoff, Boris

    2005-08-15

    Extracellular adenosine-5'-triphosphate (ATP) is involved in a variety of relevant regulatory mechanisms at a cellular level and has therefore been focus of extensive research. One of the major challenges associated with measuring this key regulatory analyte is the ability to detect and localize extracellular ATP with sufficient spatial and temporal resolution in physiological environments. In this study, scanning electrochemical microscopy (SECM) utilizing an amperometric micro-biosensor based on co-immobilization of the enzymes glucose oxidase and hexokinase is applied for imaging ATP transport through a porous polycarbonate membrane under physiologically relevant conditions. The enzymatic biosensor operates on competitive consumption of the substrate glucose between the immobilized enzymes glucose oxidase and hexokinase involving ATP as a co-substrate. Quantitative determination of the ATP concentration is based on a linear correlation between the glucose consumption and the ATP level. Integration of the amperometric ATP micro-biosensor into a dual micro-disk electrode configuration is achieved by immobilizing the enzymes at one of the micro-disk electrodes while the second disk serves as an unmodified amperometric probe for controlled positioning of the micro-biosensor in close proximity to the sample surface enabling quantification of the obtained current signal. PMID:16023962

  5. Impact of Adsorption on Scanning Electrochemical Microscopy Voltammetry and Implications for Nanogap Measurements.

    PubMed

    Tan, Sze-yin; Zhang, Jie; Bond, Alan M; Macpherson, Julie V; Unwin, Patrick R

    2016-03-15

    Scanning electrochemical microscopy (SECM) is a powerful tool that enables quantitative measurements of fast electron transfer (ET) kinetics when coupled with modeling predictions from finite-element simulations. However, the advent of nanoscale and nanogap electrode geometries that have an intrinsically high surface area-to-solution volume ratio realizes the need for more rigorous data analysis procedures, as surface effects such as adsorption may play an important role. The oxidation of ferrocenylmethyl trimethylammonium (FcTMA(+)) at highly oriented pyrolytic graphite (HOPG) is used as a model system to demonstrate the effects of reversible reactant adsorption on the SECM response. Furthermore, the adsorption of FcTMA(2+) species onto glass, which is often used to encapsulate ultramicroelectrodes employed in SECM, is also found to be important and affects the voltammetric tip response in a nanogap geometry. If a researcher is unaware of such effects (which may not be readily apparent in slow to moderate scan voltammetry) and analyzes SECM data assuming simple ET kinetics at the substrate and an inert insulator support around the tip, the result is the incorrect assignment of tip-substrate heights, kinetics, and thermodynamic parameters. Thus, SECM kinetic measurements, particularly in a nanogap configuration where the ET kinetics are often very fast (only just distinguishable from reversible), require that such effects are fully characterized. This is possible by expanding the number of experimental variables, including the voltammetric scan rate and concentration of redox species, among others. PMID:26877069

  6. Electrochemical strain microscopy time spectroscopy: Model and experiment on LiMn2O4

    NASA Astrophysics Data System (ADS)

    Amanieu, Hugues-Yanis; Thai, Huy N. M.; Luchkin, Sergey Yu.; Rosato, Daniele; Lupascu, Doru C.; Keip, Marc-André; Schröder, Jörg; Kholkin, Andrei L.

    2015-08-01

    Electrochemical Strain Microscopy (ESM) can provide useful information on ionic diffusion in solids at the local scale. In this work, a finite element model of ESM measurements was developed and applied to commercial lithium manganese (III,IV) oxide (LiMn2O4) particles. ESM time spectroscopy was used, where a direct current (DC) voltage pulse locally disturbs the spatial distribution of mobile ions. After the pulse is off, the ions return to equilibrium at a rate which depends on the Li diffusivity in the material. At each stage, Li diffusivity is monitored by measuring the ESM response to a small alternative current (AC) voltage simultaneously applied to the tip. The model separates two different mechanisms, one linked to the response to DC bias and another one related to the AC excitation. It is argued that the second one is not diffusion-driven but is rather a contribution of the sum of several mechanisms with at least one depending on the lithium ion concentration explaining the relaxation process. With proper fitting of this decay, diffusion coefficients of lithium hosts could be extracted. Additionally, the effect of phase transition in LiMn2O4 is taken into account, explaining some experimental observations.

  7. Measurement of stress and strain applied to electrochemically aligned collagen fibres by second-harmonic generation microscopy

    NASA Astrophysics Data System (ADS)

    Goami, Nobutaka; Yoshiki, Keisuke; Namazu, Takahiro; Inoue, Shozo

    2011-10-01

    In this study, we developed a novel strain measurement technique for electrochemically aligned collagen (ELAC) fibres using second harmonic generation (SHG) microscopy. The ELAC fibres were prepared by a typical electrochemical method and were subjected to cross-linking. For comparison with natural collagen fibres, polarization dependency of the prepared ELAC fibres and that of a human Achilles' tendon were evaluated. The results showed that, because of crosslinking, the ELAC fibres exhibit polarization dependency similar to that of the tendon but only in a region close to the tendon. The relationship between SHG and the applied strain was determined by a combination of SHG microscopy and tensile tests. The SHG from the ELAC fibres changed in the high strain region because of the applied stress.

  8. Virtual Electrochemical Strain Microscopy of Polycrystalline LiCoO2 Films

    SciTech Connect

    Chung, Ding-wen; Balke, Nina; Kalinin, Sergei V; Garcia, R. Edwin

    2011-01-01

    A recently developed technique, electrochemical strain microscopy (ESM), utilizes the strong coupling between ionic current and anisotropic volumetric chemical expansion of lithium-ion electrode materials to dynamically probe the sub-one-hundred? nm inter-facial kinetic intercalation properties. A numerical technique based on the finite element method was developed to analyze the underlying physics that govern the ESM signal generation and establish relations to battery performance. The performed analysis demonstrates that the diffusion path within a thin film is tortuous and the extent of lithium diffusion into the electrode is dependent on the SPM-tip-imposed overpotential frequency. The detected surface actuation gives rise to the development of an electromechanical hysteresis loop whose shape is dependent on grain size and overpotential frequency. Shape and tilting angle of the loop are classified into low and high frequency regimes, separated by a transition frequency which is also a function of lithium diffusivity and grain size, f{sub T} = D//{sup 2}. Research shows that the crystallographic orientation of the surface actuated grain has a significant impact on the shape of the loop. The polycrystalline crystallographic orientation of the grains induces a diffusion path network in the electrode which impacts on the mechanical reliability of the battery. Simulations demonstrate that continuous battery cycling results in a cumulative capacity loss as a result of the hysteric non-reversible lithium intercalation. Furthermore, results suggest that ESM has the capability to infer the local out-of-plane lithium diffusivity and the out-of-plane contribution to Vegard tensor.

  9. Virtual Electrochemical Strain Microscopy of Polycrystalline LiCoO2 Films

    SciTech Connect

    Chung, Ding-Wen; Balke, Nina; Kalinin, Sergei V.; Edwin Garcia, R.

    2011-08-03

    A recently developed technique, electrochemical strain microscopy (ESM), utilizes the strong coupling between ionic current and anisotropic volumetric chemical expansion of lithium-ion electrode materials to dynamically probe the sub-one-hundred? nm inter-facial kinetic intercalation properties. A numerical technique based on the finite element method was developed to analyze the underlying physics that govern the ESM signal generation and establish relations to battery performance. The performed analysis demonstrates that the diffusion path within a thin film is tortuous and the extent of lithium diffusion into the electrode is dependent on the SPM-tip-imposed overpotential frequency. The detected surface actuation gives rise to the development of an electromechanical hysteresis loop whose shape is dependent on grain size and overpotential frequency. Shape and tilting angle of the loop are classified into low and high frequency regimes, separated by a transition frequency which is also a function of lithium diffusivity and grain size, fT = D/l₂. Research shows that the crystallographic orientation of the surface actuated grain has a significant impact on the shape of the loop. The polycrystalline crystallographic orientation of the grains induces a diffusion path network in the electrode which impacts on the mechanical reliability of the battery. Simulations demonstrate that continuous battery cycling results in a cumulative capacity loss as a result of the hysteric non-reversible lithium intercalation. Furthermore, results suggest that ESM has the capability to infer the local out-of-plane lithium diffusivity and the out-of-plane contribution to Vegard tensor.

  10. Microstamped Petri Dishes for Scanning Electrochemical Microscopy Analysis of Arrays of Microtissues

    PubMed Central

    Sridhar, Adithya; de Boer, Hans L.; van den Berg, Albert; Le Gac, Séverine

    2014-01-01

    While scanning electrochemical microscopy (SECM) is a powerful technique for non-invasive analysis of cells, SECM-based assays remain scarce and have been mainly limited so far to single cells, which is mostly due to the absence of suitable platform for experimentation on 3D cellular aggregates or microtissues. Here, we report stamping of a Petri dish with a microwell array for large-scale production of microtissues followed by their in situ analysis using SECM. The platform is realized by hot embossing arrays of microwells (200 μm depth; 400 μm diameter) in commercially available Petri dishes, using a PDMS stamp. Microtissues form spontaneously in the microwells, which is demonstrated here using various cell lines (e.g., HeLa, C2C12, HepG2 and MCF-7). Next, the respiratory activity of live HeLa microtissues is assessed by monitoring the oxygen reduction current in constant height mode and at various distances above the platform surface. Typically, at a 40 μm distance from the microtissue, a 30% decrease in the oxygen reduction current is measured, while above 250 μm, no influence of the presence of the microtissues is detected. After exposure to a model drug (50% ethanol), no such changes in oxygen concentration are found at any height in solution, which reflects that microtissues are not viable anymore. This is furthermore confirmed using conventional live/dead fluorescent stains. This live/dead assay demonstrates the capability of the proposed approach combining SECM and microtissue arrays formed in a stamped Petri dish for conducting cellular assays in a non-invasive way on 3D cellular models. PMID:24690887

  11. Noninvasively measuring respiratory activity of rat primary hepatocyte spheroids by scanning electrochemical microscopy.

    PubMed

    Takahashi, Ryosuke; Zhou, Yuanshu; Horiguchi, Yoshiko; Shiku, Hitoshi; Sonoda, Hiroshi; Itabashi, Naoshi; Yamamoto, Jiro; Saito, Taku; Matsue, Tomokazu; Hisada, Akiko

    2014-01-01

    Construction of an in vitro drug screening method for evaluating drug metabolism and toxicity by using cells is required instead of the conventional in vivo one that uses animals. In order to realize the in vitro study, analyzing the cellular activity or viability noninvasively in advance of the screening is essential. The aim of the current study is to establish a method that can evaluate the cellular activity depending on spheroid sizes by means of oxygen consumption and to determine the valid diameter of hepatocyte spheroids. To measure the respiratory activity of the spheroids, which were formed on a nanopillar sheet, we applied scanning electrochemical microscopy (SECM). From the viewpoint of high respiratory activity and its small variation, we determined that spheroids with 70 μm in diameter were adequate. We then performed a gene expression analysis by using a real-time PCR to evaluate the correlation with respiratory activity. As a result, a higher expression level of Hnf4α, which is essential for hepatocytes to fulfill many liver functions and is the indicator of well-differentiated hepatocytes, showed relatively higher respiratory activity. We concluded that the noninvasive SECM technique could evaluate the cellular activity of a single spheroid. Noninvasively measuring cellular activity by SECM makes it possible to evaluate the cellular activity prior to a nonclinical test and enables the continued monitoring of the drug response by using single spheroid. SECM becomes a powerful tool to satisfying the increasing demand for an in vitro system in the course of new drug development. PMID:23890543

  12. Origin of Asymmetry of Paired Nanogap Voltammograms Based on Scanning Electrochemical Microscopy: Contamination Not Adsorption.

    PubMed

    Chen, Ran; Balla, Ryan J; Li, Zhiting; Liu, Haitao; Amemiya, Shigeru

    2016-08-16

    Formation of a nanometer-wide gap between tip and substrate electrodes by scanning electrochemical microscopy (SECM) enables voltammetric measurement of ultrafast electron-transfer kinetics. Herein, we demonstrate the advantage of SECM-based nanogap voltammetry to assess the cleanness of the substrate surface in solution by confirming that airborne contamination of highly oriented pyrolytic graphite (HOPG) causes the nonideal asymmetry of paired nanogap voltammograms of (ferrocenylmethyl)trimethylammonium (Fc(+)). We hypothesize that the amperometric response of a 1 μm-diameter Pt tip is less enhanced in the feedback mode, where more hydrophilic Fc(2+) is generated from Fc(+) at the tip and reduced voltammetrically at the HOPG surface covered with airborne hydrophobic contaminants. The tip current is more enhanced in the substrate generation/tip collection mode, where less charged Fc(+) is oxidized at the contaminated HOPG surface. In fact, symmetric pairs of nanogap voltammograms are obtained with the cleaner HOPG surface that is exfoliated in humidified air and covered with a nanometer-thick water adlayer to suppress airborne contamination. This result disproves a misconception that the asymmetry of paired nanogap voltammograms is due to electron exchange mediated by Fc(2+) adsorbed on the glass sheath of the tip. Moreover, weak Fc(+) adsorption on the HOPG surface causes only the small hysteresis of each voltammogram upon forward and reverse sweeps of the HOPG potential. Significantly, no Fc(2+) adsorption on the HOPG surface ensures that the simple outer-sphere pathway mediates ultrafast electron transfer of the Fc(2+/+) couple with standard rate constants of ≥12 cm/s as estimated from symmetric pairs of reversible nanogap voltammograms. PMID:27426255

  13. Direct evidence of arsenic(III)-carbonate complexes obtained using electrochemical scanning tunneling microscopy.

    PubMed

    Han, Mei-Juan; Hao, Jumin; Christodoulatos, Christos; Korfiatis, George P; Wan, Li-Jun; Meng, Xiaoguang

    2007-05-15

    Electrochemical scanning tunneling microscopy (ECSTM), ion chromatography (IC), and electrospray ionization-mass spectrometry/mass spectrometry were applied to investigate the interactions between arsenite [As(III)] and carbonate and arsenate [As(V)] and carbonate. The chemical species in the single and binary component solutions of As(III), As(V), and carbonate were attached to a Au(111) surface and then imaged in a 0.1 M NaClO4 solution at the molecular level by ECSTM. The molecules formed highly ordered adlayers on the Au(111) surface. High-resolution STM images revealed the orientation and packing arrangement of the molecular adlayers. Matching the STM images with the molecular models constructed using the Hyperchem software package indicated that As(III) formed two types of complexes with carbonate, including As(OH)2CO3- and As(OH)3(HCO3-)2. No complexes were formed between As(V) and carbonate. IC chromatograms of the solutions revealed the emergence of the new peak only in the aged As(III)-carbonate solution. MS spectra showed the presence of a new peak at m/z 187 in the aged As(III)-carbonate solution. The results obtained with the three independent methods confirmed the formation of As(OH)2CO3-. The results also indicated that As(OH)3 could be associated with HCO3- through a hydrogen bond. The knowledge of the formation of the As(III) and carbonate complexes will improve the understanding of As(III) mobility in the environment and removal of As(III) in water treatment systems. PMID:17441685

  14. Scanning electrochemical microscopy of graphene/polymer hybrid thin films as supercapacitors: Physical-chemical interfacial processes

    NASA Astrophysics Data System (ADS)

    Gupta, Sanju; Price, Carson

    2015-10-01

    Hybrid electrode comprising an electric double-layer capacitor of graphene nanosheets and a pseudocapacitor of the electrically conducting polymers namely, polyaniline; PAni and polypyrrole; PPy are constructed that exhibited synergistic effect with excellent electrochemical performance as thin film supercapacitors for alternative energy. The hybrid supercapacitors were prepared by layer-by-layer (LbL) assembly based on controlled electrochemical polymerization followed by reduction of graphene oxide electrochemically producing ErGO, for establishing intimate electronic contact through nanoscale architecture and chemical stability, producing a single bilayer of (PAni/ErGO)1, (PPy/ErGO)1, (PAni/GO)1 and (PPy/GO)1. The rationale design is to create thin films that possess interconnected graphene nanosheets (GNS) with polymer nanostructures forming well-defined tailored interfaces allowing sufficient surface adsorption and faster ion transport due to short diffusion distances. We investigated their electrochemical properties and performance in terms of gravimetric specific capacitance, Cs, from cyclic voltammograms. The LbL-assembled bilayer films exhibited an excellent Cs of ≥350 F g-1 as compared with constituents (˜70 F g-1) at discharge current density of 0.3 A g-1 that outperformed many other hybrid supercapacitors. To gain deeper insights into the physical-chemical interfacial processes occurring at the electrode/electrolyte interface that govern their operation, we have used scanning electrochemical microscopy (SECM) technique in feedback and probe approach modes. We present our findings from viewpoint of reinforcing the role played by heterogeneous electrode surface composed of nanoscale graphene sheets (conducting) and conducting polymers (semiconducting) backbone with ordered polymer chains via higher/lower probe current distribution maps. Also targeted is SECM imaging that allowed to determine electrochemical (re)activity of surface ion adsorption sites

  15. Scanning electrochemical microscopy of graphene/polymer hybrid thin films as supercapacitors: Physical-chemical interfacial processes

    SciTech Connect

    Gupta, Sanju Price, Carson

    2015-10-15

    Hybrid electrode comprising an electric double-layer capacitor of graphene nanosheets and a pseudocapacitor of the electrically conducting polymers namely, polyaniline; PAni and polypyrrole; PPy are constructed that exhibited synergistic effect with excellent electrochemical performance as thin film supercapacitors for alternative energy. The hybrid supercapacitors were prepared by layer-by-layer (LbL) assembly based on controlled electrochemical polymerization followed by reduction of graphene oxide electrochemically producing ErGO, for establishing intimate electronic contact through nanoscale architecture and chemical stability, producing a single bilayer of (PAni/ErGO){sub 1}, (PPy/ErGO){sub 1}, (PAni/GO){sub 1} and (PPy/GO){sub 1}. The rationale design is to create thin films that possess interconnected graphene nanosheets (GNS) with polymer nanostructures forming well-defined tailored interfaces allowing sufficient surface adsorption and faster ion transport due to short diffusion distances. We investigated their electrochemical properties and performance in terms of gravimetric specific capacitance, C{sub s}, from cyclic voltammograms. The LbL-assembled bilayer films exhibited an excellent C{sub s} of ≥350 F g{sup −1} as compared with constituents (∼70 F g{sup −1}) at discharge current density of 0.3 A g{sup −1} that outperformed many other hybrid supercapacitors. To gain deeper insights into the physical-chemical interfacial processes occurring at the electrode/electrolyte interface that govern their operation, we have used scanning electrochemical microscopy (SECM) technique in feedback and probe approach modes. We present our findings from viewpoint of reinforcing the role played by heterogeneous electrode surface composed of nanoscale graphene sheets (conducting) and conducting polymers (semiconducting) backbone with ordered polymer chains via higher/lower probe current distribution maps. Also targeted is SECM imaging that allowed to determine

  16. Characterization of microfabricated probes for combined atomic force and high-resolution scanning electrochemical microscopy.

    PubMed

    Gullo, Maurizio R; Frederix, Patrick L T M; Akiyama, Terunobu; Engel, Andreas; deRooij, Nico F; Staufer, Urs

    2006-08-01

    A combined atomic force and scanning electrochemical microscope probe is presented. The probe is electrically insulated except at the very apex of the tip, which has a radius of curvature in the range of 10-15 nm. Steady-state cyclic voltammetry measurements for the reduction of Ru(NH3)6Cl3 and feedback experiments showed a distinct and reproducible response of the electrode. These experimental results agreed with finite element simulations for the corresponding diffusion process. Sequentially topographical and electrochemical studies of Pt lines deposited onto Si3N4 and spaced 100 nm apart (edge to edge) showed a lateral electrochemical resolution of 10 nm. PMID:16878880

  17. Stress-modified electrochemical reactivity of metallic surfaces: atomic force microscopy imaging studies of nickel and alloyed aluminum

    NASA Astrophysics Data System (ADS)

    Hahm, J.; Sibener, S. J.

    2000-07-01

    In this paper, we demonstrate that externally applied tensile and compressive stresses can systematically modify the electrochemical surface reactivity of pure and alloyed metals. Atomic force microscopy (AFM) is used to statistically characterize the extent and nature of interface change for nickel and aluminum alloy 2024-T3 subjected to electrochemical conditions under various levels of stress. Statistical analysis of AFM images reveals that the extent of electrochemical reactivity is significantly enhanced when subjecting the sample to tensile as opposed to compressive stress; this enhancement increases monotonically as the level of applied stress is systematically increased. Surface morphologies differ on the pure nickel and alloyed aluminum samples, with the nickel interfaces exhibiting facetted features which are aligned 120° from one another while the surface features on aluminum alloy 2024-T3 are circular pores. These results unambiguously indicate that the kinetics for electrochemical metallic processes, which nucleate at surface defects and grain boundaries, can be significantly modified by the presence of external stress fields.

  18. Frequency-dependent alternating-current scanning electrochemical microscopy (4D AC-SECM) for local visualisation of corrosion sites.

    PubMed

    Eckhard, Kathrin; Erichsen, Thomas; Stratmann, Martin; Schuhmann, Wolfgang

    2008-01-01

    For a better understanding of the initiation of localised corrosion, there is a need for analytical tools that are capable of imaging corrosion pits and precursor sites with high spatial resolution and sensitivity. The lateral electrochemical contrast in alternating-current scanning electrochemical microscopy (AC-SECM) has been found to be highly dependent on the frequency of the applied alternating voltage. In order to be able to obtain data with optimum contrast and high resolution, the AC frequency is swept in a full spectrum at each point in space instead of performing spatially resolved measurements at one fixed perturbation frequency. In doing so, four-dimensional data sets are acquired (4D AC-SECM). Here, we describe the instrument set-up and modus operandi, along with the first results from the imaging of corroding surfaces. Corrosion precursor sites and local defects in protective organic coatings, as well as an actively corroding pit on 304 stainless steel, have been successfully visualised. Since the lateral electrochemical contrast in these images varies with the perturbation frequency, the proposed approach constitutes an indispensable tool for obtaining optimum electrochemical contrast. PMID:18351698

  19. Coupling Electrochemistry with Fluorescence Confocal Microscopy To Investigate Electrochemical Reactivity: A Case Study with the Resazurin-Resorufin Fluorogenic Couple.

    PubMed

    Doneux, Thomas; Bouffier, Laurent; Goudeau, Bertrand; Arbault, Stéphane

    2016-06-21

    The redox couple resazurin-resorufin exhibits electrofluorochromic properties which are investigated herein by absorption and fluorescence spectroelectrochemistry and by electrochemically coupled-fluorescence confocal laser scanning microscopy (EC-CLSM). At pH 10, the highly fluorescent resorufin dye is generated at the electrode surface by the electrochemical reduction of the poorly fluorescent resazurin. Performing EC-CLSM at electrode surfaces allows to monitor spatially resolved electrochemical processes in situ and in real time. Using a small (315 μm diameter) cylindrical electrode, a steady-state diffusion layer builds up under potentiostatic conditions at -0.45 V vs Ag|AgCl. Mapping the fluorescence intensity in 3D by CLSM enables us to reconstruct the relative concentration profile of resorufin around the electrode. The comparison of the experimental diffusion-profile with theoretical predictions demonstrates that spontaneous convection has a direct influence on the actual thickness of the diffusion layer, which is smaller than the value predicted for a purely diffusional transport. This study shows that combining fluorescence CLSM with electrochemistry is a powerful tool to study electrochemical reactivity at a spatially resolved level. PMID:27247989

  20. Scanning electrochemical microscopy. 36. A combined scanning electrochemical microscope-quartz crystal microbalance instrument for studying thin films.

    PubMed

    Cliffel, D E; Bard, A J

    1998-05-01

    The design of a combined scanning electrochemical microscope-quartz crystal microbalance (SECM-QCM) with separate potential control of the tip and substrate is described. Both lateral and vertical tip movements near the substrate affect the QCM resonant frequency because of perturbations of the longitudinal and shear waves of the quartz crystal (QC) acoustic wave sensor. The SECM-QCM was used to study etching of a thin Ag layer deposited on the QC contact by generating an etchant, iron(III) tris(bipyridine), at the tip near the surface. The SECM-QCM was also used to monitor film mass and surrounding electrolyte composition during potential cycling of a film of C(60) on an electrode. PMID:21651290

  1. Investigation of the interactions between silver nanoparticles and Hela cells by scanning electrochemical microscopy.

    PubMed

    Chen, Zhong; Xie, Shubao; Shen, Li; Du, Yu; He, Shali; Li, Qing; Liang, Zhongwei; Meng, Xin; Li, Bo; Xu, Xiaodong; Ma, Hongwei; Huang, Yanyi; Shao, Yuanhua

    2008-09-01

    The interactions between Hela cells and silver nanoparticles (AgNPs) have been studied by scanning electrochemical microscopy (SECM) with both IrCl(6)(2-/3-) and Fe(CN)(6)(3-/4-) as the dual mediators. IrCl(6)(2-), which can be produced in situ and react with AgNPs, is used as the mediator between the AgNPs on the cells and the SECM tip. Another redox couple, Fe(CN)(6)(3-/4-), which has a similar hydrophilicity to IrCl(6)(2-/3-), but cannot react with AgNPs, is also employed for the contrast experiments. The cell array is cultured successfully onto a Petri dish by microcontact printing (muCP) technique, which can provide a basic platform for studying of single cells. The approach curve and line scan are the two methods of SECM employed here to study the Hela cells. The former can provide the information about the interaction between Hela cells and AgNPs whereas the later gives the cell imaging. The permeability of cell membranes and morphology are two main factors which have effects on the feedback mode signals when K(3)Fe(CN)(6) is used as the mediator. The permeability of the cell membranes can be ignored after interaction with high concentration of AgNP solution and the height of the Hela cells is slightly decreased in this process. The kinetic rate constants (k(0)) between IrCl(6)(2-) and Ag on the Hela cell can be evaluated using K(3)IrCl(6) as the mediator, and they are increased with the higher concentrations of the AgNP solutions. The k(0) is changed about 10 times from 0.43 +/- 0.04 x 10(-4) to 1.25 +/- 0.07 x 10(-4) and to 3.93 +/- 1.9 x 10(-4) cm s(-1) corresponding to 0, 1 and 5 mM of AgNO(3) solution. The experimental results demonstrate that the AgNPs can be adsorbed on the cell surface and detected by SECM. Thus, the amount of AgNPs adsorbed on cell membranes and the permeability or morphology changes can be investigated simultaneously using this approach. The dual mediator system and cell array fabricated by muCP technique can provide better

  2. Real-time mapping of salt glands on the leaf surface of Cynodon dactylon L. using scanning electrochemical microscopy.

    PubMed

    Parthasarathy, Meera; Pemaiah, Brindha; Natesan, Ravichandran; Padmavathy, Saralla R; Pachiappan, Jayaraman

    2015-02-01

    Salt glands are specialized organelles present in the leaf tissues of halophytes, which impart salt-tolerance capability to the plant species. These glands are usually identified only by their morphology using conventional staining procedures coupled with optical microscopy. In this work, we have employed scanning electrochemical microscopy to identify the salt glands not only by their morphology but also by their salt excretion behavior. Bermuda grass (Cynodon dactylon L.) species was chosen for the study as they are known to be salt-tolerant and contain salt glands on leaf surfaces. Scanning electrochemical microscopy performed in sodium chloride medium in the presence and absence of potassium ferrocyanide as redox mediator, reveals the identity of salt glands. More insight into the ion expulsion behavior of these glands was obtained by mapping lateral and vertical variations in ion concentrations using surface impedance measurements which indicated five times higher resistance over the salt glands compared to the surrounding tissues and bulk solution. The protocol could be used to understand the developmental processes in plants grown in different soil/water conditions in order to improve salt tolerance of food crops by genetic engineering and hence improve their agricultural productivity. PMID:25460612

  3. Evaluation of the chemical reactions from two electrogenerated species in picoliter volumes by scanning electrochemical microscopy.

    PubMed

    Wang, Qian; Rodríguez-López, Joaquín; Bard, Allen J

    2010-09-10

    The volume created by the positioning of two scanning electrochemical microscope (SECM) probes (tip and substrate) at a micrometric distance defines a "picoliter beaker" where homogeneous electron-transfer reactions are studied. The SECM is used to concurrently electrogenerate in situ two reactive species and to evaluate the possibility of detecting their reactivity. Two reaction cases are studied: the first, called the "reversible case", occurs when the electrochemically generated species at the substrate electrode can also react at the tip to yield the same product as the reaction in the gap. The second case, named the "irreversible case", occurs when the electrochemically generated species at the substrate are not able to react at the tip. Digital simulations are performed and compared to experimental studies. These show that an unusual compensation between collection and feedback effects render the analysis inapplicable in the "reversible case". The "irreversible case" is shown experimentally. PMID:20687152

  4. Scanning Electrochemical Microscopy of Single Spherical Nanoparticles: Theory and Particle Size Evaluation.

    PubMed

    Yu, Yun; Sun, Tong; Mirkin, Michael V

    2015-07-21

    Experiments at individual metal nanoparticles (NPs) can provide important information about their electrochemical and catalytic properties. The scanning electrochemical microscope (SECM) equipped with a nanometer-sized tip was recently used to image single 10 or 20 nm gold particles and quantitatively investigate electrochemical reactions occurring at their surfaces. In this Article, the theory is developed for SECM current vs distance curves obtained with a disk-shaped tip approaching a comparably sized, surface-bound conductive or insulating spherical NP. The possibility of evaluating the size of a surface-bound particle by fitting the experimental current-distance curve to the theory is shown for NPs and tips of different radii. The effects of the NP being partially buried into an insulating layer and the imperfect positioning of the tip with respect to the NP center are considered. The collection efficiency is calculated for redox species generated at the nanoparticle surface and collected at the tip. PMID:26151412

  5. Alternating current measurements in scanning electrochemical microscopy, part 2: detection of adsorbates.

    PubMed

    Trinh, Dao; Keddam, Michel; Novoa, Xosé Ramón; Vivier, Vincent

    2011-08-01

    A scanning electrochemical microscope (SECM) in ac mode is used for the characterisation of the adsorption process during the hydrogen evolution reaction (HER) in sulfuric acid solution. It is shown that this technique allows quantitative analysis of the adsorption process, and measurements of the differential capacitance with the frequency as parameter are obtained. The time constant for relaxation of adsorbed hydrogen (H(ads)) is approximately 2 Hz, and analysis of the Nyquist plot allows direct evaluation of the charge involved. In addition, the direct comparison of the usual electrochemical impedance data and ac-SECM results obtained simultaneously permits characterisation of processes occurring at the surface and in solution. PMID:21630411

  6. Integrated scanning Kelvin probe-scanning electrochemical microscope system: development and first applications.

    PubMed

    Maljusch, Artjom; Schönberger, Bernd; Lindner, Armin; Stratmann, Martin; Rohwerder, Michael; Schuhmann, Wolfgang

    2011-08-01

    The integration of a scanning Kelvin probe (SKP) and a scanning electrochemical microscope (SECM) into a single SKP-SECM setup, the concept of the proposed system, its technical realization, and first applications are presented and discussed in detail. A preloaded piezo actuator placed in a grounded stainless steel case was used as the driving mechanism for oscillation of a Pt disk electrode as conventionally used in SECM when the system was operated in the SKP mode. Thus, the same tip is recording the contact potential difference (CPD) during SKP scanning and is used as a working electrode for SECM imaging in the redox-competition mode (RC-SECM). The detection of the local CPD is established by amplification of the displacement current at an ultralow noise operational amplifier and its compensation by application of a variable backing potential (V(b)) in the external circuit. The control of the tip-to-sample distance is performed by applying an additional alternating voltage with a much lower frequency than the oscillation frequency of the Kelvin probe. The main advantage of the SKP-SECM system is that it allows constant distance measurements of the CPD in air under ambient conditions and in the redox-competition mode of the SECM in the electrolyte of choice over the same sample area without replacement of the sample or exchange of the working electrode. The performance of the system was evaluated using a test sample made by sputtering thin Pt and W films on an oxidized silicon wafer. The obtained values of the CPD correlate well with known data, and the electrochemical activity for oxygen reduction is as expected higher over Pt than W. PMID:21675763

  7. Single cells and intracellular processes studied by a plasmonic-based electrochemical impedance microscopy

    NASA Astrophysics Data System (ADS)

    Wang, Wei; Foley, Kyle; Shan, Xiaonan; Wang, Shaopeng; Eaton, Seron; Nagaraj, Vinay J.; Wiktor, Peter; Patel, Urmez; Tao, Nongjian

    2011-03-01

    Electrochemical impedance spectroscopy is a crucial tool for the detection and study of various biological substances, from DNA and proteins to viruses and bacteria. It does not require any labelling species, and methods based on it have been developed to study cellular processes (such as cell spreading, adhesion, invasion, toxicology and mobility). However, data have so far lacked spatial information, which is essential for investigating heterogeneous processes and imaging high-throughput microarrays. Here, we report an electrochemical impedance microscope based on surface plasmon resonance that resolves local impedance with submicrometre spatial resolution. We have used an electrochemical impedance microscope to monitor the dynamics of cellular processes (apoptosis and electroporation of individual cells) with millisecond time resolution. The high spatial and temporal resolution makes it possible to study individual cells, but also resolve subcellular structures and processes without labels, and with excellent detection sensitivity (~2 pS). We also describe a model that simulates cellular and electrochemical impedance microscope images based on local dielectric constant and conductivity.

  8. Scanning electrochemical microscopy of living cells: different redox activities of nonmetastatic and metastatic human breast cells.

    PubMed

    Liu, B; Rotenberg, S A; Mirkin, M V

    2000-08-29

    Electrochemical methods have been widely used to monitor physiologically important molecules in biological systems. This report describes the first application of the scanning electrochemical microscope (SECM) to probe the redox activity of individual living cells. The possibilities of measuring the rate and investigating the pathway of transmembrane charge transfer are demonstrated. By this approach, significant differences are detected in the redox responses given by nonmotile, nontransformed human breast epithelial cells, breast cells with a high level of motility (engendered by overexpression of protein kinase Calpha), and highly metastatic breast cancer cells. SECM analysis of the three cell lines reveals reproducible differences with respect to the kinetics of charge transfer by several redox mediators. PMID:10963658

  9. Scanning electrochemical microscopy of living cells: Different redox activities of nonmetastatic and metastatic human breast cells

    PubMed Central

    Liu, Biao; Rotenberg, Susan A.; Mirkin, Michael V.

    2000-01-01

    Electrochemical methods have been widely used to monitor physiologically important molecules in biological systems. This report describes the first application of the scanning electrochemical microscope (SECM) to probe the redox activity of individual living cells. The possibilities of measuring the rate and investigating the pathway of transmembrane charge transfer are demonstrated. By this approach, significant differences are detected in the redox responses given by nonmotile, nontransformed human breast epithelial cells, breast cells with a high level of motility (engendered by overexpression of protein kinase Cα), and highly metastatic breast cancer cells. SECM analysis of the three cell lines reveals reproducible differences with respect to the kinetics of charge transfer by several redox mediators. PMID:10963658

  10. Scanning electrochemical microscopy: theory and application of the transient (chronoamperometric) SECM response.

    PubMed

    Bard, A J; Denuault, G; Friesner, R A; Dornblaser, B C; Tuckerman, L S

    1991-07-01

    A study of the transient (chronoamperometric) response of the scanning electrochemical microscope (SECM) is presented. SECM transients were simulated digitally with a novel integrator based on a Krylov algorithm. The transients observed with planar electrodes (PE), microdisks (MD), and thin-layer cells (TLC) are shown to be limiting cases that fit the simulated SECM transients at very short, intermediate, and long times, respectively. A procedure is established that, provided the tip radius is known, allows the determination of the diffusion coefficient of the species in solution independent of its concentration and the number of electrons transferred in the electrode reaction. Experimental SECM transients are reported for the electrochemical oxidation of Fe(CN)6(4-) in KCl; the diffusion coefficient of Fe(CN)6(4-) was found to agree very well with the literature value. PMID:1897720

  11. Electron transport in two-dimensional arrays of gold nanocrystals investigated by scanning electrochemical microscopy.

    PubMed

    Liljeroth, Peter; Vanmaekelbergh, Daniël; Ruiz, Virginia; Kontturi, Kyösti; Jiang, Hua; Kauppinen, Esko; Quinn, Bernadette M

    2004-06-01

    This article reports the use of the scanning electrochemical microscope (SECM) to investigate the electronic properties of Langmuir monolayers of alkane thiol protected gold nanocrystals (NCs). A substantial increase in monolayer conductivity upon mechanical compression of the Au NC monolayer is reported for the first time. This may be the room temperature signature of the insulator to metal transition previously reported for comparable silver NC monolayers. Factors influencing the conductivity of the monolayer NC array are discussed. PMID:15174884

  12. Scanning electrochemical microscopy. 23. Reaction localization of artificially patterned and tissue-bound enzymes.

    PubMed

    Pierce, D T; Bard, A J

    1993-12-15

    The scanning electrochemical microscope (SECM), operating in the feedback mode, was used to image localized surface reactions of redox enzymes at the micrometer level. Surfaces imaged with the SECM included glucose oxidase immobilized within 8-microns-diameter pores of a filtration membrane and individual whole mitochondria with active NADH cytochrome reductase enzymes in their outer membranes. Factors influencing enzyme image resolution and specificity are discussed. PMID:8311246

  13. Alternating-current measurements in scanning electrochemical microscopy, part 1: principle and theory.

    PubMed

    Trinh, Dao; Keddam, Michel; Novoa, Xosé R; Vivier, Vincent

    2011-08-01

    The development of the scanning electrochemical microscope in ac mode is presented from both experimental and theoretical point of views. The experiments are performed with the ferri/ferrocyanide redox mediator as model system. Based on analysis of the frequency-dependent collection efficiency, diffusion between the probe and the substrate is investigated, and analysis of time constants allows evaluation of the size of the sensing area under investigation. The experimental results are in good agreement with numerical simulations. PMID:21633998

  14. Note: Circuit design for direct current and alternating current electrochemical etching of scanning probe microscopy tips

    NASA Astrophysics Data System (ADS)

    Jobbins, Matthew M.; Raigoza, Annette F.; Kandel, S. Alex

    2012-03-01

    We present control circuits designed for electrochemically etching, reproducibly sharp STM probes. The design uses an Arduino UNO microcontroller to allow for both ac and dc operation, as well as a comparator driven shut-off that allows for etching to be stopped in 0.5-1 μs. The Arduino allows the instrument to be customized to suit a wide variety of potential applications without significant changes to hardware. Data is presented for coarse chemical etching of 80:20 platinum-iridium, tungsten, and nickel tips.

  15. Note: Circuit design for direct current and alternating current electrochemical etching of scanning probe microscopy tips.

    PubMed

    Jobbins, Matthew M; Raigoza, Annette F; Kandel, S Alex

    2012-03-01

    We present control circuits designed for electrochemically etching, reproducibly sharp STM probes. The design uses an Arduino UNO microcontroller to allow for both ac and dc operation, as well as a comparator driven shut-off that allows for etching to be stopped in 0.5-1 μs. The Arduino allows the instrument to be customized to suit a wide variety of potential applications without significant changes to hardware. Data is presented for coarse chemical etching of 80:20 platinum-iridium, tungsten, and nickel tips. PMID:22462971

  16. Scanning electrochemical microscopy: surface interrogation of adsorbed hydrogen and the open circuit catalytic decomposition of formic acid at platinum.

    PubMed

    Rodríguez-López, Joaquín; Bard, Allen J

    2010-04-14

    The surface interrogation mode of scanning electrochemical microscopy (SECM) is extended to the in situ quantification of adsorbed hydrogen, H(ads), at polycrystalline platinum. The methodology consists of the production, at an interrogator electrode, of an oxidized species that is able to react with H(ads) on the Pt surface and report the amounts of this adsorbate through the SECM feedback response. The technique is validated by comparison to the electrochemical underpotential deposition (UPD) of hydrogen on Pt. We include an evaluation of electrochemical mediators for their use as oxidizing reporters for adsorbed species at platinum; a notable finding is the ability of tetramethyl-p-phenylenediamine (TMPD) to oxidize (interrogate) H(ads) on Pt at low pH (0.5 M H(2)SO(4) or 1 M HClO(4)) and with minimal background effects. As a case study, the decomposition of formic acid (HCOOH) in acidic media at open circuit on Pt was investigated. Our results suggest that formic acid decomposes at the surface of unbiased Pt through a dehydrogenation route to yield H(ads) at the Pt surface. The amount of H(ads) depended on the open circuit potential (OCP) of the Pt electrode at the time of interrogation; at a fixed concentration of HCOOH, a more negative OCP yielded larger amounts of H(ads) until reaching a coulomb limiting coverage close to 1 UPD monolayer of H(ads). The introduction of oxygen into the cell shifted the OCP to more positive potentials and reduced the quantified H(ads); furthermore, the system was shown to be chemically reversible, as several interrogations could be run consecutively and reproducibly regardless of the path taken to reach a given OCP. PMID:20225806

  17. A positionable microcell for electrochemistry and scanning electrochemical microscopy in subnanoliter volumes.

    PubMed

    Spaine, T W; Baur, J E

    2001-03-01

    Positionable voltammetric cells with tip diameters of < 50 microm were constructed from theta glass capillaries. One channel of the pulled glass capillary contains a carbon fiber microelectrode sealed in epoxy while the other houses a Ag/AgCl reference electrode that makes electrical contact to the analyte solution via a salt bridge at the tip. The device can be operated as a two-electrode cell and can therefore make measurements in droplets of solution that are similar in size to the tip. Alternatively, if the droplet of solution is larger than the tip, spatially resolved measurements of a substrate in solution can be made. Voltammetric experiments and feedback imaging with the scanning electrochemical microscope (SECM) were accomplished in microdroplets with solution volumes of less than 1 nL. pH images of a substrate immersed in 70-microL-thick films of solution were obtained in the generator-collector mode of SECM using an iridium oxide-modified microcell. This type of microcell is particularly useful for making electrochemical measurements in very small droplets of solution where a mobile working electrode could easily collide with a separately positioned reference electrode. PMID:11289438

  18. High-Resolution Electrochemical Scanning Tunneling Microscopy (EC-STM) Flow-Cell Studies.

    PubMed

    Lay, Marcus D; Sorenson, Thomas A; Stickney, John L

    2003-09-25

    Atomic-level studies involving an electrochemical scanning tunneling microscope (EC-STM) flow-cell are presented. Multiple electrochemical atomic layer epitaxy (EC-ALE) cycles of CdTe formation were observed. For a binary compound (i.e., CdTe), an EC-ALE cycle involves exposure of the substrate to a solution of the first precursor (CdSO4), followed by exposure to the second precursor (TeO2), while maintaining potential control. Interleaving blank rinses may also be used, but were omitted in the present studies. To allow the exchange of solutions, the EC-STM cell was modified to allow solution exchange via a single peristaltic pump. A selection valve was used to choose the solution to be introduced into the cell. There is evidence that the growth of the initial layer of CdTe on Au(111), the (√7 × √7)-CdTe monolayer, can be improved in homogeneity and morphology by repeatedly depositing and stripping the Cd atomic layer. Therefore, a new starting cycle, which should improve the quality of deposits formed via EC-ALE, has been developed. PMID:26317446

  19. Novel Protein Crystal Growth Electrochemical Cell For Applications in X-ray Diffraction and Atomic Force Microscopy

    SciTech Connect

    G Gil-Alvaradejo; R Ruiz-Arellano; C Owen; A Rodriguez-Romero; E Rudino-Pinera; M Antwi; V Stojanoff; A Moreno

    2011-12-31

    A new crystal growth cell based on transparent indium tin oxide (ITO) glass-electrodes for electrochemically assisted protein crystallization allows for reduced nucleation and crystal quality enhancement. The crystallization behavior of lysozyme and ferritin was monitored as a function of the electric current applied to the growth cell. The X-ray diffraction analysis showed that for specific currents, the crystal quality is substantially improved. No conformational changes were observed in the 3D crystallographic structures determined for crystals grown under different electric current regimes. Finally, the strong crystal adhesion on the surface of ITO electrode because of the electroadhesion allows a sufficiently strong fixing of the protein crystals, to undergo atomic force microscopy investigations in a fluid cell.

  20. Self-consistent modelling of electrochemical strain microscopy in mixed ionic-electronic conductors: Nonlinear and dynamic regimes

    NASA Astrophysics Data System (ADS)

    Varenyk, O. V.; Silibin, M. V.; Kiselev, D. A.; Eliseev, E. A.; Kalinin, S. V.; Morozovska, A. N.

    2015-08-01

    The frequency dependent Electrochemical Strain Microscopy (ESM) response of mixed ionic-electronic conductors is analyzed within the framework of Fermi-Dirac statistics and the Vegard law, accounting for steric effects from mobile donors. The emergence of dynamic charge waves and nonlinear deformation of the surface in response to bias applied to the tip-surface junction is numerically explored. The 2D maps of the strain and concentration distributions across the mixed ionic-electronic conductor and bias-induced surface displacements are calculated. The obtained numerical results can be applied to quantify the ESM response of Li-based solid electrolytes, materials with resistive switching, and electroactive ferroelectric polymers, which are of potential interest for flexible and high-density non-volatile memory devices.

  1. Identical Location Transmission Electron Microscopy Imaging of Site-Selective Pt Nanocatalysts: Electrochemical Activation and Surface Disordering.

    PubMed

    Arán-Ais, Rosa M; Yu, Yingchao; Hovden, Robert; Solla-Gullón, Jose; Herrero, Enrique; Feliu, Juan M; Abruña, Héctor D

    2015-12-01

    We have employed identical location transmission electron microscopy (IL-TEM) to study changes in the shape and morphology of faceted Pt nanoparticles as a result of electrochemical cycling; a procedure typically employed for activating platinum surfaces. We find that the shape and morphology of the as-prepared hexagonal nanoparticles are rapidly degraded as a result of potential cycling up to +1.3 V. As few as 25 potential cycles are sufficient to cause significant degradation, and after about 500-1000 cycles the particles are dramatically degraded. We also see clear evidence of particle migration during potential cycling. These finding suggest that great care must be exercised in the use and study of shaped Pt nanoparticles (and related systems) as electrocatlysts, especially for the oxygen reduction reaction where high positive potentials are typically employed. PMID:26524187

  2. Atomic force microscopy and electrochemical investigation on the corrosion behavior of carbon steel passivated by molybdate and chromate.

    PubMed

    Chen, Zhenyu; Zhang, Xiulan; Huang, Ling; Guo, Xingpeng

    2013-02-01

    The effects of CrO(4)(2-) and MoO(4)(2-) ions on the corrosion behavior of carbon steel in 0.5 M NaCl solution have been studied using electrochemical measurements and atomic force microscopy. The results suggest that both ions have good inhibition effects on the general and pitting corrosion of carbon steel. At the same concentration, the inhibition efficiency of CrO(4)(2-) is higher than that of MoO(4)(2-). The passive film formed by CrO(4)(2-) is also much harder than that formed by MoO(4)(2-). The passive films formed by both ions are nonconductive. PMID:23180386

  3. Electrochemical atomic force microscopy imaging of redox-immunomarked proteins on native potyviruses: from subparticle to single-protein resolution.

    PubMed

    Nault, Laurent; Taofifenua, Cécilia; Anne, Agnès; Chovin, Arnaud; Demaille, Christophe; Besong-Ndika, Jane; Cardinale, Daniela; Carette, Noëlle; Michon, Thierry; Walter, Jocelyne

    2015-05-26

    We show herein that electrochemical atomic force microscopy (AFM-SECM), operated in molecule touching (Mt) mode and combined with redox immunomarking, enables the in situ mapping of the distribution of proteins on individual virus particles and makes localization of individual viral proteins possible. Acquisition of a topography image allows isolated virus particles to be identified and structurally characterized, while simultaneous acquisition of a current image allows the sought after protein, marked by redox antibodies, to be selectively located. We concomitantly show that Mt/AFM-SECM, due to its single-particle resolution, can also uniquely reveal the way redox functionalization endowed to viral particles is distributed both statistically among the viruses and spatially over individual virus particles. This possibility makes Mt/AFM-SECM a unique tool for viral nanotechnology. PMID:25905663

  4. Self-consistent modelling of electrochemical strain microscopy in mixed ionic-electronic conductors: Nonlinear and dynamic regimes

    SciTech Connect

    Varenyk, O. V.; Morozovska, A. N. E-mail: anna.n.morozovska@gmail.com; Silibin, M. V.; Kiselev, D. A.; Eliseev, E. A.; Kalinin, S. V. E-mail: anna.n.morozovska@gmail.com

    2015-08-21

    The frequency dependent Electrochemical Strain Microscopy (ESM) response of mixed ionic-electronic conductors is analyzed within the framework of Fermi-Dirac statistics and the Vegard law, accounting for steric effects from mobile donors. The emergence of dynamic charge waves and nonlinear deformation of the surface in response to bias applied to the tip-surface junction is numerically explored. The 2D maps of the strain and concentration distributions across the mixed ionic-electronic conductor and bias-induced surface displacements are calculated. The obtained numerical results can be applied to quantify the ESM response of Li-based solid electrolytes, materials with resistive switching, and electroactive ferroelectric polymers, which are of potential interest for flexible and high-density non-volatile memory devices.

  5. Study on the Electrochemical Reaction Mechanism of ZnFe2O4 by In Situ Transmission Electron Microscopy

    PubMed Central

    Su, Qingmei; Wang, Shixin; Yao, Libing; Li, Haojie; Du, Gaohui; Ye, Huiqun; Fang, Yunzhang

    2016-01-01

    A family of mixed transition–metal oxides (MTMOs) has great potential for applications as anodes for lithium ion batteries (LIBs). However, the reaction mechanism of MTMOs anodes during lithiation/delithiation is remain unclear. Here, the lithiation/delithiation processes of ZnFe2O4 nanoparticles are observed dynamically using in situ transmission electron microscopy (TEM). Our results suggest that during the first lithiation process the ZnFe2O4 nanoparticles undergo a conversion process and generate a composite structure of 1–3 nm Fe and Zn nanograins within Li2O matrix. During the delithiation process, volume contraction and the conversion of Zn and Fe take place with the disappearance of Li2O, followed by the complete conversion to Fe2O3 and ZnO not the original phase ZnFe2O4. The following cycles are dominated by the full reversible phase conversion between Zn, Fe and ZnO, Fe2O3. The Fe valence evolution during cycles evidenced by electron energy–loss spectroscopy (EELS) techniques also exhibit the reversible conversion between Fe and Fe2O3 after the first lithiation, agreeing well with the in situ TEM results. Such in situ TEM observations provide valuable phenomenological insights into electrochemical reaction of MTMOs, which may help to optimize the composition of anode materials for further improved electrochemical performance. PMID:27306189

  6. Study on the Electrochemical Reaction Mechanism of ZnFe2O4 by In Situ Transmission Electron Microscopy

    NASA Astrophysics Data System (ADS)

    Su, Qingmei; Wang, Shixin; Yao, Libing; Li, Haojie; Du, Gaohui; Ye, Huiqun; Fang, Yunzhang

    2016-06-01

    A family of mixed transition–metal oxides (MTMOs) has great potential for applications as anodes for lithium ion batteries (LIBs). However, the reaction mechanism of MTMOs anodes during lithiation/delithiation is remain unclear. Here, the lithiation/delithiation processes of ZnFe2O4 nanoparticles are observed dynamically using in situ transmission electron microscopy (TEM). Our results suggest that during the first lithiation process the ZnFe2O4 nanoparticles undergo a conversion process and generate a composite structure of 1–3 nm Fe and Zn nanograins within Li2O matrix. During the delithiation process, volume contraction and the conversion of Zn and Fe take place with the disappearance of Li2O, followed by the complete conversion to Fe2O3 and ZnO not the original phase ZnFe2O4. The following cycles are dominated by the full reversible phase conversion between Zn, Fe and ZnO, Fe2O3. The Fe valence evolution during cycles evidenced by electron energy–loss spectroscopy (EELS) techniques also exhibit the reversible conversion between Fe and Fe2O3 after the first lithiation, agreeing well with the in situ TEM results. Such in situ TEM observations provide valuable phenomenological insights into electrochemical reaction of MTMOs, which may help to optimize the composition of anode materials for further improved electrochemical performance.

  7. Study on the Electrochemical Reaction Mechanism of ZnFe2O4 by In Situ Transmission Electron Microscopy.

    PubMed

    Su, Qingmei; Wang, Shixin; Yao, Libing; Li, Haojie; Du, Gaohui; Ye, Huiqun; Fang, Yunzhang

    2016-01-01

    A family of mixed transition-metal oxides (MTMOs) has great potential for applications as anodes for lithium ion batteries (LIBs). However, the reaction mechanism of MTMOs anodes during lithiation/delithiation is remain unclear. Here, the lithiation/delithiation processes of ZnFe2O4 nanoparticles are observed dynamically using in situ transmission electron microscopy (TEM). Our results suggest that during the first lithiation process the ZnFe2O4 nanoparticles undergo a conversion process and generate a composite structure of 1-3 nm Fe and Zn nanograins within Li2O matrix. During the delithiation process, volume contraction and the conversion of Zn and Fe take place with the disappearance of Li2O, followed by the complete conversion to Fe2O3 and ZnO not the original phase ZnFe2O4. The following cycles are dominated by the full reversible phase conversion between Zn, Fe and ZnO, Fe2O3. The Fe valence evolution during cycles evidenced by electron energy-loss spectroscopy (EELS) techniques also exhibit the reversible conversion between Fe and Fe2O3 after the first lithiation, agreeing well with the in situ TEM results. Such in situ TEM observations provide valuable phenomenological insights into electrochemical reaction of MTMOs, which may help to optimize the composition of anode materials for further improved electrochemical performance. PMID:27306189

  8. Scanning electrochemical microscopy. 46. Shielding effects on reversible and quasireversible reactions.

    PubMed

    Zoski, Cynthia G; Aguilar, Julio C; Bard, Allen J

    2003-07-01

    An approximate theory for the feedback mode of the scanning electrochemical microscope (SECM) is developed to interpret the effects of substrate shielding on an ultramicroelectrode tip during a recording of iT versus d curves (approach curves) for reversible and quasireversible kinetics at a substrate surface. The resulting expressions for the tip current, iT, show a good fit to more accurate SECM simulations as well as to the experimental response of a reversible and quasireversible reaction. SECM shielding experiments thus give an interesting new insight into SECM approach curves over electrodes at different potentials, which suggest possible applications to measuring heterogeneous kinetics for fast reactions and diffusion coefficient determination. PMID:12964739

  9. Monitoring of glucose and glutamate using enzyme microstructures and scanning electrochemical microscopy.

    PubMed

    Mureşan, Laura; Nistor, Mihaela; Gáspár, Szilveszter; Popescu, Ionel Cătălin; Csöregi, Elisabeth

    2009-09-01

    Glucose oxidase and glutamate oxidase lines, with typical width of 100 microm, were patterned on gold surfaces using a micro-dispensing system, by shooting 100 pl droplets of the corresponding enzyme solutions. The probe of a scanning electrochemical microscope (SECM) was then carefully positioned in the close proximity of the enzyme microstructure and poised to +600 mV vs. Ag/AgCl, KCl 0.1 M. The H(2)O(2), generated by the enzyme lines at different concentrations of glucose and glutamate in the surrounding solution, was sequentially monitored. Reproducible calibration curves for glucose and glutamate were obtained in one single experiment, proving that the combination of enzyme microstructures with SECM can provide a new way of achieving multianalyte detection. PMID:19520620

  10. Chemical imaging with combined fast-scan cyclic voltammetry-scanning electrochemical microscopy.

    PubMed

    Schrock, Daniel S; Baur, John E

    2007-09-15

    Fast-scan cyclic voltammetry (FSCV) is applied to the tip of a scanning electrochemical microscope (SECM) for imaging the distribution of chemical species near a substrate. This approach was used to image the diffusion layer of both a large substrate electrode (3-mm-diameter glassy carbon) and a microelectrode substrate (10-microm-diameter Pt). Additionally, oxygen depletion near living cells was measured and correlated to respiratory activity. Finally, oxygen and hydrogen peroxide were simultaneously detected during the oxidative burst of a zymosan-stimulated macrophage cell. These results demonstrate the utility of FSCV-SECM for chemical imaging when conditions are chosen such that feedback interactions with the substrate are minimal. PMID:17705555

  11. Scanning electrochemical microscopy investigations of monolayers bound to p-type silicon substrates.

    PubMed

    Ghilane, Jalal; Hauquier, Fanny; Fabre, Bruno; Hapiot, Philippe

    2006-09-01

    p-Si type electrodes modified with different organic monolayers were investigated by reaction with radical anion and cation electrogenerated at a microelectrode operating in the configuration of a scanning electrochemical microscope. The method proves to be a convenient tool for investigating both the quality and the redox properties of the layer as previously demonstrated on metallic electrodes especially when the sample cannot be electrically connected. Approach curves recorded with the different mediators were used to investigate the electron-transfer rates across alkyl monolayers bound to p-type silicon substrates. Preliminary results indicate that the interfacial electron transfer occurs via electron tunneling through the organic layer as generally described for SAMs grafted on gold electrodes. PMID:16944879

  12. Patterning of polystyrene by scanning electrochemical microscopy. Biological applications to cell adhesion.

    PubMed

    Ktari, N; Poncet, P; Sénéchal, H; Malaquin, L; Kanoufi, F; Combellas, C

    2010-11-16

    Polystyrene surfaces may be patterned by Ag(II), NO(3)(•), and OH(•) electrogenerated at the tip of a scanning electrochemical microscope. These electrogenerated reagents lead to local surface oxidation of the polymer. The most efficient surface treatment is obtained with Ag(II). The patterns are evidenced by XPS and IR and also by the surface wettability contrast between the hydrophobic virgin surface and the hydrophilic pattern. Such Ag(II) treatment of a polystyrene Petri dish generates discriminative surfaces able to promote or disfavor the adhesion of proteins and also the adhesion and growth of adherent cells. The process is also successfully applied to a cyclo-olefin copolymer and should be suitable to pattern any hydrogenated polymer. PMID:20945917

  13. Scanning electrochemical microscopy of metallic biomaterials: reaction rate and ion release imaging modes.

    PubMed

    Gilbert, J L; Smith, S M; Lautenschlager, E P

    1993-11-01

    The Scanning Electrochemical Microscope (SECM) is a nonoptical scanning microscopic instrument capable of imaging highly localized electrical currents associated with charge transfer reactions on metallic biomaterials surfaces. The SECM operates as an aqueous electrochemical cell under bipotentiostatic control with a microelectrode and sample independently biased as working electrodes. Microelectrode current and position is recorded as it is scanned very near a metallurgically polished planar sample surface. To date, the SECM has imaged metallic biomaterials surfaces in oxygen reaction rate imaging (ORRI) and ion release and deposition imaging (IRDI) modes. In ORRI, sample and microelectrode are biased at sufficiently negative potentials to reduce absorbed oxygen. As the microelectrode scans areas of active oxygen reduction, localized diffusion fields with decreased oxygen solution concentrations are encountered and resultant decrements in microelectrode current are observed. In IRDI mode the sample is positively biased and the microelectrode is negatively biased. The microelectrode detects anodic dissolution products with highest currents being observed over the most active areas. Performance of the SECM has been evaluated on Ni minigrids, gamma-1 Hg-Ag dental amalgam crystals, and sintered beads of Co-Cr-Mo alloy which represent significantly different geometries and corrosion processes to help demonstrate the potential of this instrument. The SECM is a valuable tool for imaging microelectrochemical processes on the surfaces of metallurgically polished metallic biomaterials samples and a wide variety of other surfaces of biological interest where charge transfer reactions occur. The SECM allows selective biasing of metallic biomaterials surfaces and Faradaic reactions can be selectively imaged while the surface is in the active, passive, or transpassive state. PMID:8262998

  14. Quantitative analysis and application of tip position modulation-scanning electrochemical microscopy.

    PubMed

    Edwards, Martin A; Whitworth, Anna L; Unwin, Patrick R

    2011-03-15

    Tip position modulation (TPM) involves moving the ultramicroelectrode (UME) tip of a scanning electrochemical microscope (SECM) perpendicular to the substrate in a sinusoidal fashion with a small amplitude compared to the tip/sample separation. The UME, which serves as the working electrode in a conventional voltammetric setup, is held at a potential to detect a species in solution at a transport-limited rate and the resulting current (ac and dc) is measured. This paper shows that tip-induced convection is an important factor in TPM. A model has been developed that describes the TPM response for the most challenging case of an inert substrate, where tip-induced convective effects compared to diffusion are greatest. The model provides an improved description of the ac response compared to existing treatment, as evidenced by the analysis of TPM-SECM approach curves (current-distance characteristics). The extension of the model to SECM-induced transfer is considered and it is shown that one can extract highly precise information on the permeability of a sample from such measurements, for which experiments and theory are compared. The prospects for using the technique more widely are highlighted and routes to improving the theoretical analysis further are briefly discussed. PMID:21322581

  15. Fabricating and imaging carbon-fiber immobilized enzyme ultramicroelectrodes with scanning electrochemical microscopy.

    PubMed

    Ge, F; Tenent, R C; Wipf, D O

    2001-01-01

    The scanning electrochemical microscope (SECM) is used to image the activity of enzymes immobilized on the surfaces of disk-shaped carbon-fiber electrodes. SECM was used to map the concentration of enzymatically produced hydroquinone or hydrogen peroxide at the surface of a 33-microm diameter disk-shaped carbon-fiber electrode modified by an immobilized glucose-oxidase layer. Sub-monolayer coverage of the enzyme at the electrode surface could be detected with micrometer resolution. The SECM was also employed as a surface modification tool to produce microscopic regions of enzyme activity by using a variety of methods. One method is a gold-masking process in which microscopic gold patterns act as mask for producing patterns of chemical modification. The gold masks allow operation in both a positive or negative process for patterning enzyme activity. A second method uses the direct mode of the SECM to produce covalently attached amine groups on the carbon surface. The amine groups are anchors for attachment of glucose oxidase by use of a biotin/avidin process. The effect of non-uniform enzyme activity was investigated by using the SECM tip to temporarily damage an immobilized enzyme surface. SECM imaging can observe the spatial extent and time-course of the enzyme recovery process. PMID:11993673

  16. Spatial distributions of copper in microbial biofilms by scanning electrochemical microscopy.

    PubMed

    Hu, Zhiqiang; Jin, Jing; Abruña, Héctor D; Houston, Paul L; Hay, Anthony G; Ghiorse, William C; Shuler, Michael L; Hidalgo, Gabriela; Lion, Leonard W

    2007-02-01

    The spatial distribution of Cu was determined in Escherichia coli PHL628 biofilms using a scanning electrochemical microscope (SECM) consisting of a microelectrode in conjunction with a piezoelectric micropositioning system. Aqueous labile copper species were determined using voltametric stripping after reductive deposition of Cu for 4 min on the microelectrode at -0.7 V (vs Ag/AgCl). The position of the bulk solution-biofilm interface was determined from the change in current produced by 0.4 mM hydroxymethyl ferrocene that was added as a redox indicator. After a 2 h exposure to 0.2 mM copper, Cu was located in the upper region of the biofilm with a penetration depth less than 150 microm. A one-dimensional diffusive transport model adequately described the spatial distribution of copper in the biofilm, but the Cu retardation factor in the biofilm was more than 6-fold larger than that calculated from the isotherm for Cu binding to suspensions of E. coli PHL628 cells. There are several possible reasons for this difference, including an increase in the amount of extracellular polymer per cell within the biofilm and/or tortuosity that might hinder Cu transport into biofilms. The SECM technique in combination with model calculations provides direct evidence in support of the concept that formation of a biofilm may confer resistance to transient spikes in the bulk solution concentration of toxic metal species by retarding metal diffusion and reducing the metal exposure of cells within the biofilm. PMID:17328206

  17. Using scanning electrochemical microscopy to probe chemistry at the solid-liquid interface in chemically amplified immersion lithography

    NASA Astrophysics Data System (ADS)

    LeSuer, Robert J.; Fan, Fu-Ren F.; Bard, Allen J.; Taylor, J. Christopher; Tsiartas, Pavlos; Willson, Grant; Conley, Willard E.; Feit, Gene; Kunz, Roderick R.

    2004-05-01

    Three modes of scanning electrochemical microscopy (SECM) - voltammetry, pH, and conductivity - have been used to better understand the chemistry at, and diffusion through, the solid/liquid interface formed between a resist film and water in 193 nm immersion lithography. Emphasis has been placed on investigating the photoacid generator (PAG), triphenylsulfonium perfluorobutanesulfonate, and the corresponding photoacid. The reduction of triphenylsulfonium at a hemispherical Hg microelectrode was monitored using square wave voltammetry to detect trace amounts of the PAG leaching from the surface. pH measurements at a 100 μm diameter Sb microelectrode show the formation of acid in the water layer above a resist upon exposure with UV irradiation. Bipolar conductance measurements at a 100 μm Pt tip positioned 100 μm from the surface indicate that the conductivity of the solution during illumination is dependent upon the percentage of PAG in the film. Liquid chromatography mass spectrometric analysis of water samples in contact with resist films has been used to quantify the amounts (< 10 ng/cm2) of PAG leaching from the film in the dark which occurs within the first 30 seconds of contact time. Washing the film removes approximately 80% of the total leachable PAG.

  18. Microscopy Study of Structural Evolution in Epitaxial LiCoO2 Positive Electrode Films during Electrochemical Cycling.

    PubMed

    Tan, Haiyan; Takeuchi, Saya; Bharathi, K Kamala; Takeuchi, Ichiro; Bendersky, Leonid A

    2016-03-01

    The evolution of interface between the epitaxial thin film LiCoO2 (LCO) electrode and liquid electrolyte and inside the LCO film during electrochemical cycling has been analyzed by high resolution scanning transmission electron microscopy. Relaxation of sharp translational domain boundaries with mismatched layers of CoO2 octahedra occurs during cycling and results in formation of continuous CoO2 layers across the boundaries. The original trigonal layered structure of LiCoO2 tends to change into a spinel structure at the electrode/electrolyte interface after significant extraction of Li from LCO. This change is more pronounced at 4.2 V peak of CV, indicating lower stability of the layered LCO structure near its surface after Li is extracted above 60%. The transformed structure is identified to be close to Co3O4, with Co both on tetrahedral and octahedral sites, rather than to LiCo2O4 as it was suggested in earlier publications. Electron energy-loss spectroscopy measurements also show that Co ions oxidation state is reduced to mixed valence state Co(2+)/Co(3+) during the structure changes to spinel rather than oxidized. PMID:26911456

  19. Giant Electric-Field-Induced Strain in PVDF-Based Battery Separator Membranes Probed by Electrochemical Strain Microscopy.

    PubMed

    Romanyuk, Konstantin; Costa, Carlos M; Luchkin, Sergey Yu; Kholkin, Andrei L; Lanceros-Méndez, Senentxu

    2016-05-31

    Efficiency of lithium-ion batteries largely relies on the performance of battery separator membrane as it controls the mobility and concentration of Li-ions between the anode and cathode electrodes. Recent advances in electrochemical strain microscopy (ESM) prompted the study of Li diffusion and transport at the nanoscale via electromechanical strain developed under an application of inhomogeneous electric field applied via the sharp ESM tip. In this work, we observed unexpectedly high electromechanical strain developed in polymer membranes based on porous poly(vinylidene fluoride) (PVDF) and poly(vinylidene fluoride-co-chlorotrifluoroethylene) (PVDF-CTFE) and, using it, could study a dynamics of electroosmotic flow of electrolyte inside the pores. We show that, independently of the separator membrane, electric field-induced deformation observed by ESM on wetted membrane surfaces can reach up to 10 nm under a moderate bias of 1 V (i.e., more than an order of magnitude higher than that in best piezoceramics). Such a high strain is explained by the electroosmotic flow in a porous media composed of PVDF. It is shown that the strain-based ESM method can be used to extract valuable information such as average pore size, porosity, elasticity of membrane in electrolyte solvent, and membrane-electrolyte affinity expressed in terms of zeta potential. Besides, such systems can, in principle, serve as actuators even in the absence of apparent piezoelectricity in amorphous PVDF. PMID:27142946

  20. Electrochemical strain microscopy time spectroscopy: Model and experiment on LiMn{sub 2}O{sub 4}

    SciTech Connect

    Amanieu, Hugues-Yanis; Thai, Huy N. M. Schröder, Jörg; Luchkin, Sergey Yu.; Rosato, Daniele; Lupascu, Doru C.; Keip, Marc-André; Kholkin, Andrei L.

    2015-08-07

    Electrochemical Strain Microscopy (ESM) can provide useful information on ionic diffusion in solids at the local scale. In this work, a finite element model of ESM measurements was developed and applied to commercial lithium manganese (III,IV) oxide (LiMn{sub 2}O{sub 4}) particles. ESM time spectroscopy was used, where a direct current (DC) voltage pulse locally disturbs the spatial distribution of mobile ions. After the pulse is off, the ions return to equilibrium at a rate which depends on the Li diffusivity in the material. At each stage, Li diffusivity is monitored by measuring the ESM response to a small alternative current (AC) voltage simultaneously applied to the tip. The model separates two different mechanisms, one linked to the response to DC bias and another one related to the AC excitation. It is argued that the second one is not diffusion-driven but is rather a contribution of the sum of several mechanisms with at least one depending on the lithium ion concentration explaining the relaxation process. With proper fitting of this decay, diffusion coefficients of lithium hosts could be extracted. Additionally, the effect of phase transition in LiMn{sub 2}O{sub 4} is taken into account, explaining some experimental observations.

  1. Real-time dynamic adsorption processes of cytochrome c on an electrode observed through electrochemical high-speed atomic force microscopy.

    PubMed

    Takeda, Kouta; Uchihashi, Takayuki; Watanabe, Hiroki; Ishida, Takuya; Igarashi, Kiyohiko; Nakamura, Nobuhumi; Ohno, Hiroyuki

    2015-01-01

    An understanding of dynamic processes of proteins on the electrode surface could enhance the efficiency of bioelectronics development and therefore it is crucial to gain information regarding both physical adsorption of proteins onto the electrode and its electrochemical property in real-time. We combined high-speed atomic force microscopy (HS-AFM) with electrochemical device for simultaneous observation of the surface topography and electron transfer of redox proteins on an electrode. Direct electron transfer of cytochrome c (cyt c) adsorbed on a self-assembled monolayers (SAMs) formed electrode is very attractive subject in bioelectrochemistry. This paper reports a real-time visualization of cyt c adsorption processes on an 11-mercaptoundecanoic acid-modified Au electrode together with simultaneous electrochemical measurements. Adsorbing cyt c molecules were observed on a subsecond time resolution simultaneously with increasing redox currents from cyt c using EC-HS-AFM. The root mean square roughness (RRMS) from the AFM images and the number of the electrochemically active cyt c molecules adsorbed onto the electrode (Γ) simultaneously increased in positive cooperativity. Cyt c molecules were fully adsorbed on the electrode in the AFM images when the peak currents were steady. This use of electrochemical HS-AFM significantly facilitates understanding of dynamic behavior of biomolecules on the electrode interface and contributes to the further development of bioelectronics. PMID:25671430

  2. Real-Time Dynamic Adsorption Processes of Cytochrome c on an Electrode Observed through Electrochemical High-Speed Atomic Force Microscopy

    PubMed Central

    Takeda, Kouta; Uchihashi, Takayuki; Watanabe, Hiroki; Ishida, Takuya; Igarashi, Kiyohiko; Nakamura, Nobuhumi; Ohno, Hiroyuki

    2015-01-01

    An understanding of dynamic processes of proteins on the electrode surface could enhance the efficiency of bioelectronics development and therefore it is crucial to gain information regarding both physical adsorption of proteins onto the electrode and its electrochemical property in real-time. We combined high-speed atomic force microscopy (HS-AFM) with electrochemical device for simultaneous observation of the surface topography and electron transfer of redox proteins on an electrode. Direct electron transfer of cytochrome c (cyt c) adsorbed on a self-assembled monolayers (SAMs) formed electrode is very attractive subject in bioelectrochemistry. This paper reports a real-time visualization of cyt c adsorption processes on an 11-mercaptoundecanoic acid-modified Au electrode together with simultaneous electrochemical measurements. Adsorbing cyt c molecules were observed on a subsecond time resolution simultaneously with increasing redox currents from cyt c using EC-HS-AFM. The root mean square roughness (RRMS) from the AFM images and the number of the electrochemically active cyt c molecules adsorbed onto the electrode (Γ) simultaneously increased in positive cooperativity. Cyt c molecules were fully adsorbed on the electrode in the AFM images when the peak currents were steady. This use of electrochemical HS-AFM significantly facilitates understanding of dynamic behavior of biomolecules on the electrode interface and contributes to the further development of bioelectronics. PMID:25671430

  3. Mapping Cd²⁺-induced membrane permeability changes of single live cells by means of scanning electrochemical microscopy.

    PubMed

    Filice, Fraser P; Li, Michelle S M; Henderson, Jeffrey D; Ding, Zhifeng

    2016-02-18

    Scanning Electrochemical Microscopy (SECM) is a powerful, non-invasive, analytical methodology that can be used to investigate live cell membrane permeability. Depth scan SECM imaging allowed for the generation of 2D current maps of live cells relative to electrode position in the x-z or y-z plane. Depending on resolution, one depth scan image can contain hundreds of probe approach curves (PACs). Individual PACs were obtained by simply extracting vertical cross-sections from the 2D image. These experimental PACs were overlaid onto theoretically generated PACs simulated at specific geometry conditions. Simulations were carried out using 3D models in COMSOL Multiphysics to determine the cell membrane permeability coefficients at different locations on the surface of the cells. Common in literature, theoretical PACs are generated using a 2D axially symmetric geometry. This saves on both compute time and memory utilization. However, due to symmetry limitations of the model, only one experimental PAC right above the cell can be matched with simulated PAC data. Full 3D models in this article were developed for the SECM system of live cells, allowing all experimental PACs over the entire cell to become usable. Cd(2+)-induced membrane permeability changes of single human bladder (T24) cells were investigated at several positions above the cell, displaced from the central axis. The experimental T24 cells under study were incubated with Cd(2+) in varying concentrations. It is experimentally observed that 50 and 100 μM Cd(2+) caused a decrease in membrane permeability, which was uniform across all locations over the cell regardless of Cd(2+) concentration. The Cd(2+) was found to have detrimental effects on the cell, with cells shrinking in size and volume, and the membrane permeability decreasing. A mapping technique for the analysis of the cell membrane permeability under the Cd(2+) stress is realized by the methodology presented. PMID:26826690

  4. Impact of electrolyte composition on the reactivity of a redox active polymer studied through surface interrogation and ion-sensitive scanning electrochemical microscopy.

    PubMed

    Burgess, Mark; Hernández-Burgos, Kenneth; Cheng, Kevin J; Moore, Jeffrey S; Rodríguez-López, Joaquín

    2016-06-21

    Elucidating the impact of interactions between the electrolyte and electroactive species in redox active polymers is key to designing better-performing electrodes for electrochemical energy storage and conversion. Here, we present on the improvement of the electrochemical activity of poly(para-nitrostyrene) (PNS) in solution and as a film by exploiting the ionic interactions between reduced PNS and K(+), which showed increased reactivity when compared to tetrabutylammonium (TBA(+))- and Li(+)-containing electrolytes. While cyclic voltammetry enabled the study of the effects of cations on the electrochemical reversibility and the reduction potential of PNS, scanning electrochemical microscopy (SECM) provided new tools to probe the ionic and redox reactivity of this system. Using an ion-sensitive Hg SECM tip allowed to probe the ingress of ions into PNS redox active films, while surface interrogation SECM (SI-SECM) measured the specific kinetics of PNS and a solution phase mediator in the presence of the tested electrolytes. SI-SECM measurements illustrated that the interrogation kinetics of PNS in the presence of K(+) compared to TBA(+) and Li(+) are greatly enhanced under the same surface concentration of adsorbed radical anion, exhibiting up to a 40-fold change in redox kinetics. We foresee using this new application of SECM methods for elucidating optimal interactions that enhance polymer reactivity for applications in redox flow batteries. PMID:27064026

  5. Detection of heavy metals released at the sediment/water interface by combining Anodic Stripping Voltammetry (ASV) and Scanning Electrochemical Microscopy (SECM) measurements

    NASA Astrophysics Data System (ADS)

    Daniele, S.; Ciani, I.; Bragato, C.; Baldo, M. A.

    2003-05-01

    Hemisphere mercury microelectrodes are investigated in combine anodic stripping voltammetry (ASV) and scanning electrochemical microscopy (SECM) experiments for the detection of heavy metal ions at the solid/solution interface of a sediment sample. Relatively large anodic stripping peaks due to lead are monitored at μm distances from the solid particles, while, under the same experimental conditions, no or lower ASV peaks are found in the bulk solution. This suggests that diffusion gradients at sediment/water interface is monitored. This method, therefore, offers a new possibility for investigating on spatial differences of immobilization and remobilization processes of heavy metals at sediment/water interfaces.

  6. Photoelectrochemical and Electrochemical Characterization of Sub-Micro-Gram Amounts of Organic Semiconductors Using Scanning Droplet Cell Microscopy.

    PubMed

    Kollender, Jan Philipp; Gasiorowski, Jacek; Sariciftci, Niyazi S; Mardare, Andrei I; Hassel, Achim Walter

    2014-07-31

    A model organic semiconductor (MDMO-PPV) was used for testing a modified version of a photoelectrochemical scanning droplet cell microscope (PE-SDCM) adapted for use with nonaqueous electrolytes and containing an optical fiber for localized illumination. The most attractive features of the PE-SDCM are represented by the possibility of addressing small areas on the investigated substrate and the need of small amounts of electrolyte. A very small amount (ng) of the material under study is sufficient for a complete electrochemical and photoelectrochemical characterization due to the scanning capability of the cell. The electrochemical behavior of the polymer was studied in detail using potentiostatic and potentiodynamic investigations as well as electrochemical impedance spectroscopy. Additionally, the photoelectrochemical properties were investigated under illumination conditions, and the photocurrents found were at least 3 orders of magnitude higher than the dark (background) current, revealing the usefulness of this compact microcell for photovoltaic characterizations. PMID:25101149

  7. Photoelectrochemical and Electrochemical Characterization of Sub-Micro-Gram Amounts of Organic Semiconductors Using Scanning Droplet Cell Microscopy

    PubMed Central

    2014-01-01

    A model organic semiconductor (MDMO-PPV) was used for testing a modified version of a photoelectrochemical scanning droplet cell microscope (PE-SDCM) adapted for use with nonaqueous electrolytes and containing an optical fiber for localized illumination. The most attractive features of the PE-SDCM are represented by the possibility of addressing small areas on the investigated substrate and the need of small amounts of electrolyte. A very small amount (ng) of the material under study is sufficient for a complete electrochemical and photoelectrochemical characterization due to the scanning capability of the cell. The electrochemical behavior of the polymer was studied in detail using potentiostatic and potentiodynamic investigations as well as electrochemical impedance spectroscopy. Additionally, the photoelectrochemical properties were investigated under illumination conditions, and the photocurrents found were at least 3 orders of magnitude higher than the dark (background) current, revealing the usefulness of this compact microcell for photovoltaic characterizations. PMID:25101149

  8. Scanning Electrochemical Microscopy for the Investigation of Galvanic Corrosion of Iron with Zinc in 0.1 M NaCl Solution

    NASA Astrophysics Data System (ADS)

    Joseph Raj, X.; Nishimura, T.

    2016-02-01

    Scanning electrochemical microscopy was used to monitor microscopic aspects of the electrochemical processes at the iron-zinc couple immersed in 0.1 M NaCl aqueous solution. The SECM measured the concentration of chemical species relevant to the corrosion processes. The electrochemical behavior of galvanic Fe/Zn coupling was investigated as a function of time using SECM microelectrode both as Fe/Zn joined together as well as away from each other. SECM amperometric line scan curves were obtained over the Fe/Zn at a constant distance. In the first case, the chemical species participating in the corrosion reactions at the sample are detected at the SECM tip by applying appropriate potential values to the microelectrode. The release of Zn2+ ionic species into the solution phase from local anodic sites, as well as the consumption of dissolved oxygen at the corresponding cathodic locations, was successfully monitored. The results revealed that the galvanic couple where Fe/Zn is close to each other will show higher corrosion rate of zinc than that of galvanic couple away from each other. The Fe/Zn couple away from each other showed a decrease in current values with time. This is due to the formation of oxide layer of Zn over the Fe followed by the protection of the corrosion products with further exposure times.

  9. Electrochemical etching of metal wires in low-stress electric contact using a liquid metal electrode to fabricate tips for scanning tunneling microscopy

    NASA Astrophysics Data System (ADS)

    Nishimura, Takashi; Hassan, Amer Mahmoud Amer; Tomitori, Masahiko

    2013-11-01

    A liquid metal electrode of Ga was used to reproducibly fabricate a sharpened metal tip with an elongated shank by electrochemical etching for scanning tunneling microscopy (STM). The electrode was in contact with the wire for the tip in low stress; it was prevented that the tip end from being rugged owing to mechanical tear-off on splitting into two pieces by etching. The wire was vertically penetrated down through a film of an electrolyte solution held in meniscus onto a platinum (Pt) ring, and the lower part of the wire under the film was softly in contact with an electrode of the liquid metal having high wettability and viscosity, resulting in a good electric contact. A tip with a radius less than 20 nm and an elongated tip length of order of 1 μm was obtained, which was preferable for the build-up process in a thermal-field treatment. The tip was evaluated by scanning electron microscopy and field emission microscopy, and used in STM observation.

  10. Structural characterization by confocal laser scanning microscopy and electrochemical study of multi-walled carbon nanotube tyrosinase matrix for phenol detection.

    PubMed

    Guix, Maria; Pérez-López, Briza; Sahin, Melike; Roldán, Mònica; Ambrosi, Adriano; Merkoçi, Arben

    2010-08-01

    A novel visualization methodology based on the use of immunofluorescence and Confocal Laser Scanning Microscopy (CLSM) was used to quantify and visualize tyrosinase enzyme within a MWCNTs matrix immobilized onto carbon based screen-printed electrodes. CLSM was shown to be an extremely powerful technique which allowed a clear visualization of the distribution of the enzyme within both the MWCNTs and carbon based layers and provided additional and useful morphological data for a better understanding of the interaction between biomolecules and electrode materials. Transmission Electron Microscopy (TEM) and Scanning Electron Microscopy (SEM) were also employed to fully characterize the system components. The proposed MWCNT/Tyrosinase matrix was applied to the detection of phenol, as an alternative biosensor material. Electrochemical analytical performances of the biosensor were investigated in order to determine the optimal fabrication design along with the enzyme stability. The biosensor based on the developed biomaterial matrix proved promising results in terms of cost, simplicity and analytical performance. A detection limit of 1.35 microM and a sensitivity of 47.4 microA mM(-1) within a linear response range of 2.5 to 75 microM phenol were obtained. The biosensor performed well as a disposable device and could be stored in a refrigerator (-18 degrees C) without loss of activity for up to 2 months. PMID:20532304

  11. Scanning electrochemical microscopy. 38. Application of SECM to the study of charge transfer through bilayer lipid membranes.

    PubMed

    Tsionsky, M; Zhou, J; Amemiya, S; Fan, F R; Bard, A J; Dryfe, R A

    1999-10-01

    The use of the scanning electrochemical microscope (SECM) to probe the kinetics of charge-transfer processes at bilayer lipid membranes (BLM) is presented. Analysis of the SECM tip response demonstrates that an unmodified BLM behaves as an insulator, whereas a BLM doped with iodine shows some positive feedback. The SECM technique thus allows one to probe processes at a BLM and determine the kinetics of the charge-transfer process. The SECM can also be used to determine the shape of the BLM. PMID:10660439

  12. Shearforce-based constant-distance scanning electrochemical microscopy as fabrication tool for needle-type carbon-fiber nanoelectrodes.

    PubMed

    Hussien, Emad Mohamed; Schuhmann, Wolfgang; Schulte, Albert

    2010-07-01

    Carbon fiber nanoelectrodes with nanometer radii tip curvatures were fabricated using a shearforce-based constant-distance scanning electrochemical microscope and electrochemically induced polymer deposition. A simple DC etching procedure in alkaline solution provided conically sharpened single carbon fibers with well-formed nanocones at their bottom. Coating the stems but not the end of the tips of the tapered structures with anodic electrodeposition paint was the strategy for limiting the bare carbon to the foremost end and restricting a feasible voltammetry current response to exactly this section. The electrodeposition of the polymer was prevented at the foremost end of the tip using a shearforce-based tip-to-sample distance control that allowed approaching the etched tips carefully in just touching distance to a film of a silicone elastomer. Analysis of the steady-state cyclic voltammograms in presence of a reversible redox compound revealed effective radii for the obtained needle-type carbon-fiber nanoelectrodes down to as small as 46 nm. The method offers an alternative pathway toward the fabrication of highly miniaturized carbon electrodes. PMID:20533837

  13. Analysis of diffusion-controlled stochastic events of iridium oxide single nanoparticle collisions by scanning electrochemical microscopy.

    PubMed

    Kwon, Seong Jung; Bard, Allen J

    2012-04-25

    We investigated the electrochemical detection of single iridium oxide nanoparticle (IrO(x) NP) collisions at the NaBH(4)-treated Pt ultramicroelectrode (UME) in a scanning electrochemical microscope (SECM) over an insulating surface. The NP collision events were monitored by observing the electrocatalytic water oxidation reaction at potentials where it does not take place on the Pt UME. These collisions occurred stochastically, resulting in a transient response ("blip") for each collision. The frequency of the collisions is proportional to the flux of NPs to the UME tip, and thus equivalent to the SECM current. A plot of collision frequency versus distance followed the theoretical approach curve behavior for negative feedback for a high concentration of mediator, demonstrating that the collisions were diffusion-controlled and that single-particle measurements of mass transport are equivalent to ensemble ones. When the SECM was operated with a Pt substrate at the same potential as the tip, the behavior followed that expected of the shielding mode. These studies and additional ones result in a model where the IrO(x) NP collision on the Pt UME is adsorptive, with oxygen produced by the catalyzed water oxidation causing a current decay. This results in a blip current response, with the current decay diminished in the presence of the oxygen scavenger, sulfite ion. Random walk and theoretical bulk simulations agreed with the proposed mechanism of IrO(x) NP collision, adsorption, and subsequent deactivation. PMID:22452267

  14. Electropolishing of stainless steels in a choline chloride based ionic liquid: an electrochemical study with surface characterisation using SEM and atomic force microscopy.

    PubMed

    Abbott, Andrew P; Capper, Glen; McKenzie, Katy J; Glidle, Andrew; Ryder, Karl S

    2006-09-28

    We have studied the anodic dissolution (electropolishing) of various stainless steel alloys in an ionic liquid comprising a 2 : 1 stoichiometric mix of ethylene glycol (EG) and choline chloride. We have used a combination of electrochemical and spectroscopic methods together with in situ liquid probe microscopy. We discuss the role and influence of the surface oxide passivation layer, characterized here by X-ray photoelectron spectroscopy (XPS) and linear sweep voltammetry, on the polishing process. We address the question of dealloying during the polish in order to contribute to our understanding of the viability of the ionic liquid as a replacement industrial electropolishing medium; the current commercial process uses a corrosive mixture of phosphoric and sulfuric acids. Also, we present data from ex situ and in situ liquid AFM studies giving both a qualitative and quantitative insight into the nature and scale of morphological changes at the steel surface during the polishing process. PMID:16971989

  15. Scanning photo-electrochemical microscopy as a versatile tool to investigate dye-sensitized nano-crystalline surfaces for solar cells

    NASA Astrophysics Data System (ADS)

    Figgemeier, Egbert; Kylberg, William H.; Bozic, Biljana

    2006-04-01

    Self-assembled monolayers (SAMs) of metal complexes are a central component of functional chemical systems for energy conversion like in e.g. the dye-sensitized photoelectrochemical solar cells or photocatalytic processes at semiconductor surfaces. In this context, scanning electrochemical microscopy (SECM) under illumination is a most valuable tool for the understanding of elementary processes of such systems. SECM comprises an ultra-microelectrode (UME), which is incorporated into a 3- or 4-electrode, respectively, electrochemical setup and which can be positioned with sub-micrometer resolution in 3 dimensions relative to a substrate. In our system, we used Pt-UMEs and dye-sensitized nano-structured electrodes as substrates. The substrate can be illuminated from the backside, which resembles working conditions of solar cell arrangements. The electrolyte consists of 2-methoxypropionitrile in conjunction with redox couples as they are used in dye-sensitized nano-structured solar cell. With this setup the photoelectrochemistry in close contact to the substrate surface initiated by the injection of electrons from the dye into the conduction band of the TiO II due to illumination at working conditions has been investigated. In this contribution we present the general principle of the method as well as an initial validation by relating photocurrents measured with the SECM and solar cell performances.

  16. Electron beam lithographically-defined scanning electrochemical-atomic force microscopy probes: fabrication method and application to high resolution imaging on heterogeneously active surfaces.

    PubMed

    Dobson, Phillip S; Weaver, John M R; Burt, David P; Holder, Mark N; Wilson, Neil R; Unwin, Patrick R; Macpherson, Julie V

    2006-09-01

    This paper describes in detail the use of electron beam lithography (EBL) to successfully batch microfabricate combined scanning electrochemical-atomic force microscopy (SECM-AFM) probes. At present, the process produces sixty probes at a time, on a 1/4 of a three-inch wafer. Using EBL, gold triangular-shaped electrodes can be defined at the tip apex, with plasma enhanced chemical vapor deposited silicon nitride serving as an effective insulating layer, at a thickness of 75 nm. The key features of the fabrication technique and the critical steps are discussed. The capability of these probes for SECM-AFM imaging in both tapping and constant distance mode is illustrated with dual topographical-electrochemical scans over an array of closely-spaced 1 microm diameter Pt disc electrodes, held at a suitable potential to generate an electroactive species at a transport-limited rate. As highlighted herein, understanding diffusion to heterogeneous electrode surfaces, including array electrodes, is currently topical and we present preliminary data highlighting the use of SECM-AFM as a valuable tool for the investigation of diffusion and reactivity at high spatial resolution. PMID:19817052

  17. Scanning electrochemical microscopy. Theory of the feedback mode for hemispherical ultramicroelectrodes: steady-state and transient behavior

    PubMed

    Selzer; Mandler

    2000-06-01

    This contribution represents the first comprehensive attempt to treat complex geometry configurations of the scanning electrochemical microscope (SECM) using the alternating direction implicit finite difference method (ADIFDM). Specifically, ADIFDM is used to simulate the steady-state as well as the transient (chronoamperometric) behavior of a hemispherical ultramicroelectrode (UME) tip of the SECM. The feedback effect in this configuration is less pronounced as compared with a disk-shaped UME system. The differences between the two systems are discussed. Analytical approximations for the steady-state behavior and for characteristic features of the transient behavior are suggested. Finally, experimental feedback currents measured above a conductor and an insulator are in excellent agreement with the theory. PMID:10857609

  18. The Kv channel blocker 4-aminopyridine enhances Ag+ uptake: A scanning electrochemical microscopy study of single living cells

    PubMed Central

    Zhan, Dongping; Fan, Fu-Ren F.; Bard, Allen. J.

    2008-01-01

    We report that silver ion (Ag+) uptake is enhanced by 4-aminopyridine (4-AP), a well known voltage-sensitive potassium ion channel (Kv) blocker. Both bacterial (Escherichia coli) and mammalian (3T3 fibroblast) cells were used as model systems. Ag+ uptake was monitored with a scanning electrochemical microscope with an amperometric Ag+ ion-selective electrode (Ag+-ISE) and the respiration rates of E. coli cells were measured by oxygen reduction at an ultramicroelectrode. The results showed that not only the amount but also the rate of silver uptake by the cells increased significantly when 4-AP was added to the solution. For fibroblasts, the Ag+ uptake rate was 4.8 × 107 ions per cell per sec without 4-AP compared with 1.0 × 108 ions per cell per sec with 0.2 mM 4-AP. For E. coli cells, the uptake rate was 1.5 × 104 ions per cell per sec without 4-AP vs. 3.5 × 104 ions per cell per sec with 0.5 mM 4-AP and 5.9 × 104 ions per cell per sec with 1 mM 4-AP. Thus, 4-AP might be useful where silver is used as antimicrobial agent to speed its uptake. PMID:18719098

  19. The Kv channel blocker 4-aminopyridine enhances Ag+ uptake: a scanning electrochemical microscopy study of single living cells.

    PubMed

    Zhan, Dongping; Fan, Fu-Ren F; Bard, Allen J

    2008-08-26

    We report that silver ion (Ag(+)) uptake is enhanced by 4-aminopyridine (4-AP), a well known voltage-sensitive potassium ion channel (K(v)) blocker. Both bacterial (Escherichia coli) and mammalian (3T3 fibroblast) cells were used as model systems. Ag(+) uptake was monitored with a scanning electrochemical microscope with an amperometric Ag(+) ion-selective electrode (Ag(+)-ISE) and the respiration rates of E. coli cells were measured by oxygen reduction at an ultramicroelectrode. The results showed that not only the amount but also the rate of silver uptake by the cells increased significantly when 4-AP was added to the solution. For fibroblasts, the Ag(+) uptake rate was 4.8 x 10(7) ions per cell per sec without 4-AP compared with 1.0 x 10(8) ions per cell per sec with 0.2 mM 4-AP. For E. coli cells, the uptake rate was 1.5 x 10(4) ions per cell per sec without 4-AP vs. 3.5 x 10(4) ions per cell per sec with 0.5 mM 4-AP and 5.9 x 10(4) ions per cell per sec with 1 mM 4-AP. Thus, 4-AP might be useful where silver is used as antimicrobial agent to speed its uptake. PMID:18719098

  20. Electrophoretic capture and detection of nanoparticles at the opening of a membrane pore using scanning electrochemical microscopy.

    PubMed

    Lee, Sungwon; Zhang, Yanhui; White, Henry S; Harrell, C Chad; Martin, Charles R

    2004-10-15

    Stochastic electrophoretic capture of individual nanometer-scale particles at the small opening of a conically shaped nanopore in a synthetic membrane is described. Particle capture is sensed using a scanning electrochemical microscope (SECM) to measure the decrease in the transport rate of a redox-active molecule through the pore. The SECM tip is positioned at the larger backside opening of pore and used to amperometrically monitor the transport rate prior, during, and after particle capture. Following capture, the particle is released by electrophoretically driving it out of the pore opening and back into the solution. The capture and release method is demonstrated by detection of charged polystyrene spheres (43-150-nm diameter) using a polycarbonate membrane with conically shaped pores, the small opening of the pore having a diameter of 60 nm. The inverse of the time to capture polystyrene spheres increases with particle concentration over the range 10(8)-10(10) particles/mL. Selective detection based on nanoparticle charge and size is also demonstrated. A quantitative theoretical description of the rate of particle capture is presented, and the physical mechanism of particle capture, based on the balance of electrostatic and entropic forces, is considered. PMID:15481960

  1. Lipid Peroxides Promote Large Rafts: Effects of Excitation of Probes in Fluorescence Microscopy and Electrochemical Reactions during Vesicle Formation

    PubMed Central

    Ayuyan, Artem G.; Cohen, Fredric S.

    2006-01-01

    Raft formation and enlargement was investigated in liposomes and supported bilayers prepared from sphingomyelin (SM), cholesterol, and unsaturated phospholipids; NBD-DPPE and rhodamine-(DOPE) were employed as fluorescent probes. Rafts were created by lowering temperature. Maintaining 20 mol % SM, fluorescence microscopy showed that, in the absence of photooxidation, large rafts did not form in giant unilamellar vesicles (GUVs) containing 20 or more mol % cholesterol. But if photooxidation was allowed to proceed, large rafts were readily observed. In population, cuvette experiments, small rafts formed without photooxidation at high cholesterol concentrations. Thus, photooxidation was the cause of raft enlargement during microscopy experiments. Because photooxidation results in peroxidation at lipid double bonds, photosensitization experiments were performed to explicitly produce peroxides of SM and an unsaturated phospholipid. GUVs of high cholesterol content containing the breakdown products of SM-peroxide, but not phospholipid-peroxide, resulted in large rafts after lowering temperature. In addition, GUV production by electroswelling can result in peroxides that cause large raft formation. The use of titanium electrodes eliminates this problem. In conclusion, lipid peroxides and their breakdown products are the cause of large raft formation in GUVs containing biological levels of cholesterol. It is critical that experiments investigating rafts in bilayer membranes avoid the production of peroxides. PMID:16815906

  2. Scanning electrochemical microscopy: using the potentiometric mode of SECM to study the mixed potential arising from two independent redox processes.

    PubMed

    Serrapede, Mara; Denuault, Guy; Sosna, Maciej; Pesce, Giovanni Luca; Ball, Richard J

    2013-09-01

    This study demonstrates how the potentiometric mode of the scanning electrochemical microscope (SECM) can be used to sensitively probe and alter the mixed potential due to two independent redox processes provided that the transport of one of the species involved is controlled by diffusion. This is illustrated with the discharge of hydrogen from nanostructured Pd hydride films deposited on the SECM tip. In deareated buffered solutions the open circuit potential of the PdH in equilibrium between its β and α phases (OCP(β→α)) does not depend on the tip-substrate distance while in aerated conditions it is found to be controlled by hindered diffusion of oxygen. Chronopotentiometric and amperometric measurements at several tip-substrate distances reveal how the flux of oxygen toward the Pd hydride film determines its potential. Linear sweep voltammetry shows that the polarization resistance increases when the tip approaches an inert substrate. The SECM methodology also demonstrates how dissolved oxygen affects the rate of hydrogen extraction from the Pd lattice. Over a wide potential window, the highly reactive nanostructure promotes the reduction of oxygen which rapidly discharges hydrogen from the PdH. The flux of oxygen toward the tip can be adjusted via hindered diffusion. Approaching the substrate decreases the flux of oxygen, lengthens the hydrogen discharge, and shifts OCP(β→α) negatively. The results are consistent with a mixed potential due to the rate of oxygen reduction balancing that of the hydride oxidation. The methodology is generic and applicable to other mixed potential processes in corrosion or catalysis. PMID:23919805

  3. In situ transmission electron microscopy study of electrochemical lithiation and delithiation cycling of the conversion anode RuO2.

    PubMed

    Gregorczyk, Keith E; Liu, Yang; Sullivan, John P; Rubloff, Gary W

    2013-07-23

    Conversion-type electrodes represent a broad class of materials with a new Li(+) reactivity concept. Of these materials, RuO2 can be considered a model material due to its metallic-like conductivity and its high theoretical capacity of 806 mAh/g. In this paper, we use in situ transmission electron microscopy to study the reaction between single-crystal RuO2 nanowires and Li(+). We show that a large volume expansion of 95% occurs after lithiation, 26% of which is irreversible after delithiation. Significant surface roughening and lithium embrittlement are also present. Furthermore, we show that the initial reaction from crystalline RuO2 to the fully lithiated mixed phase of Ru/Li2O is not fully reversible, passing through an intermediate phase of LixRuO2. In subsequent cycles, the phase transitions are between amorphous RuO2 in the delithiated state and a nanostructured network of Ru/Li2O in the fully lithiated phase. PMID:23782274

  4. Demonstration of an Electrochemical Liquid Cell for Operando Transmission Electron Microscopy Observation of the Lithiation/Delithiation Behavior of Si Nanowire Battery Anodes

    SciTech Connect

    Gu, Meng; Parent, Lucas R.; Mehdi, Beata L.; Unocic, Raymond R.; McDowell, Matthew T.; Sacci, Robert L.; Xu, Wu; Connell, Justin G.; Xu, Pinghong; Abellan Baeza, Patricia; Chen, Xilin; Zhang, Yaohui; Perea, Daniel E.; Evans, James E.; Lauhon, Lincoln; Zhang, Jiguang; Liu, Jun; Browning, Nigel D.; Cui, Yi; Arslan, Ilke; Wang, Chong M.

    2013-11-13

    Over the last few years, in-situ transmission electron microscopy (TEM) studies of lithium ion batteries using an open-cell configuration have helped us to gain fundamental insights into the structural and chemical evolution of the electrode materials in real time. In the standard open-cell configuration, the electrolyte is either solid lithium oxide or an ionic liquid, which is point-contacted with the electrode. This cell design is inherently different from a real battery, where liquid electrolyte forms conformal contact with electrode materials. The knowledge learnt from open cells can deviate significantly from the real battery, calling for operando TEM technique with conformal liquid electrolyte contact. In this paper, we developed an operando TEM electrochemical liquid cell to meet this need, providing the configuration of a real battery and in a relevant liquid electrolyte. To demonstrate this novel technique, we studied the lithiation/delithiation behavior of single Si nanowires. Some of lithiation/delithation behaviors of Si obtained using the liquid-cell are consistent with the results from the open-cell studies. However, we also discovered new insights different from the open cell configuration - the dynamics of the electrolyte and, potentially, a future quantitative characterization of the SEI layer formation and structural and chemical evolution.

  5. Investigation of carboxylic-functionalized and n-alkanethiol self-assembled monolayers on gold and their application as pH-sensitive probes using scanning electrochemical microscopy

    NASA Astrophysics Data System (ADS)

    Boldt, Frank-Mario; Baltes, Norman; Borgwarth, Kai; Heinze, Jürgen

    2005-12-01

    We investigated the insulating properties of n-alkanethiol self-assembled monolayers (SAMs) of varying chain lengths [CH 3(CH 2) nSH; n = 7, 9, 11, 15] on polycrystalline gold electrodes using scanning electrochemical microscopy (SECM) and cyclic voltammetry. On the basis of SECM approach curves we examined the local ET through monolayers with increasing chain length in different redox mediators. We were able to distinguish the monolayers because of their different insulating properties and in addition, the status of SAM formation after immersion times of 2 h and 24 h, respectively, could be observed. Cyclic voltammetric measurements confirmed the SECM results and were in good agreement with other experimental data in the literature. High-resolution SECM images of hexadecanethiol SAM micropatterns down to 4 μm in diameter formed by microcontact printing (μCP) were obtained in the feedback mode. Furthermore, we studied the ET and the pH-dependent behavior of mercaptoundecanoic acid monolayers on gold at varying pH and in different redox mediator solutions to test their application as pH-sensors. An additional influence on the ET could be established based on Coulomb/ionic interactions between the charged monolayer and the redox mediator at changing pH. Therefore, we present a new approach for designing pH-sensitive SECM probes using 11-mercaptoundecanoic acid-coated 10 μm-diameter gold ultramicroelectrodes (HOOC-C 11SH/Au UMEs) in aqueous solutions containing hexacyanoferrate. Voltammetric measurements at HOOC-C 11SH/Au UMEs at different pH values enabled us to estimate the degree of dissociation of the carboxylic-terminated monolayers.

  6. In Situ Scanning Tunneling Microscopy Topography Changes of Gold (111) in Aqueous Sulfuric Acid Produced by Electrochemical Surface Oxidation and Reduction and Relaxation Phenomena

    NASA Astrophysics Data System (ADS)

    Pasquale, M. A.; Nieto, F. J. Rodríguez; Arvia, A. J.

    The electrochemical formation and reduction of O-layers on gold (111) films in 1 m sulfuric acid under different potentiodynamic routines are investigated utilizing in situ scanning tunneling microscopy. The surface dynamics is interpreted considering the anodic and cathodic reaction pathways recently proposed complemented with concurrent relaxation phenomena occurring after gold (111) lattice mild disruption (one gold atom deep) and moderate disruption (several atoms deep). The dynamics of both oxidized and reduced gold topographies depends on the potentiodynamic routine utilized to form OH/O surface species. The topography resulting from a mild oxidative disruption is dominated by quasi-2D holes and hillocks of the order of 5 nm, involving about 500-600 gold atoms each, and their coalescence. A cooperative turnover process at the O-layer, in which the anion ad-layer and interfacial water play a key role, determines the oxidized surface topography. The reduction of these O-layers results in gold clusters, their features depending on the applied potential routine. A moderate oxidative disruption produces a surface topography of hillocks and holes several gold atoms high and deep, respectively. The subsequent reduction leads to a spinodal gold pattern. Concurrent coalescence appears to be the result of an Ostwald ripening that involves the surface diffusion of both gold atoms and clusters. These processes produce an increase in surface roughness and an incipient gold faceting. The dynamics of different topographies can be qualitatively explained employing the arguments from colloidal science theory. For 1.1 V ≤ E ≅ Epzc weak electrostatic repulsions favor gold atom/cluster coalescence, whereas for E < Epzc the attenuated electrostatic repulsions among gold surfaces stabilize small clusters over the substrate producing string-like patterns.

  7. Ion-Selective Permeability of Ultrathin Nanoporous Silicon Membrane as Probed by Scanning Electrochemical Microscopy Using Micropipet-Supported ITIES Tips

    PubMed Central

    Ishimatsu, Ryoichi; Kim, Jiyeon; Jing, Ping; Striemer, Christopher C.; Fang, David Z.; Fauchet, Philippe M.; McGrath, James L.; Amemiya, Shigeru

    2010-01-01

    We report on the application of scanning electrochemical microscopy (SECM) for the measurement of the ion-selective permeability of porous nanocrystalline silicon membrane as a new type of nanoporous material with potential applications in analytical, biomedical, and biotechnology device development. The reliable measurement of high permeability in the molecularly thin nanoporous membrane to various ions is important for greater understanding of its structure–permeability relationship and also for its successful applications. In this work, this challenging measurement is enabled by introducing two novel features into amperometric SECM tips based on the micropipet-supported interface between two immiscible electrolyte solutions (ITIES) to reveal the important ion-transport properties of the ultrathin nanopore membrane. The tip of a conventional heat-pulled micropipet is milled using focused ion beam (FIB) technique to be smoother, better aligned, and subsequently, approach closer to the membrane surface, which allows for more precise and accurate permeability measurement. The high membrane permeability to small monovalent ions is determined using FIB-milled micropipet tips to establish a theoretical formula for the membrane permeability that is controlled by free ion diffusion across water-filled nanopores. Moreover, the ITIES tips are rendered selective for larger polyions with biomedical importance, i.e., polyanionic pentasaccharide Arixtra and polycationic peptide protamine, to yield the membrane permeability that is lower than the corresponding diffusion-limited permeability. The hindered transport of the respective polyions is unequivocally ascribed to electrostatic and steric repulsions from the wall of the nanopores, i.e., the charge and size effects. PMID:20690617

  8. Continuous nanoflow-scanning electrochemical microscopy: voltammetric characterization and application for accurate and reproducible imaging of enzyme-labeled protein microarrays.

    PubMed

    Kai, Tianhan; Chen, Shu; Monterroso, Estuardo; Zhou, Feimeng

    2015-04-21

    The coupling of scanning electrochemical microscopy (SECM) to a continuous nanoflow (CNF) system is accomplished with the use of a microconcentric ring electrode/injector probe. The gold microring electrode encapsulated by a glass sheath is robust and can be beveled and polished. The CNF system, comprising a precision gas displacement pump and a rotary valve, is capable of delivering solution to the center of the SECM probe in the range of 1-150 nL/min. Major advantages of the CNF-SECM imaging mode over the conventional SECM generation/collection (G/C) mode include higher imaging resolution, immunity from interferences by species in the bulk solution or at other sites of the substrate, elimination of the feedback current that could interfere with the G/C data interpretation, and versatility of initiating surface reactions/processes via introducing different reactants into the flowing stream. Parameters such as flow rates, probe/substrate separations, and collection efficiencies are examined and optimized. Higher resolution, reproducibility, and accuracy are demonstrated through the application of CNF-SECM to horseradish peroxidase (HRP)-amplified imaging of protein microarrays. By flowing H2O2 and ferrocenemethanol through the injector and detecting the surface-generated ferriceniummethanol, human IgG spots covered with HPR-labeled antihuman IgG can be detected in the range of 13 nM-1.333 μM with a detection limit of 3.0 nM. In addition, consistent images of microarray spots for selective and high-density detection of analytes can be attained. PMID:25831146

  9. The geometry of nanometer-sized electrodes and its influence on electrolytic currents and metal deposition processes in scanning tunneling and scanning electrochemical microscopy

    NASA Astrophysics Data System (ADS)

    Sklyar, Oleg; Treutler, Thomas H.; Vlachopoulos, Nikolaos; Wittstock, Gunther

    2005-12-01

    Electrodes with an effective radius of about 10 nm have been produced by a combination of electrochemical etching, electrophoretic deposition of polymer, and heat curing. Their size and stability were characterized by cyclic voltammetry. They were then used in combined electrochemical scanning tunneling microscopic (ECSTM) and scanning electrochemical microscopic (SECM) experiments. In an extension of an earlier report, electrochemical surface modification approaches are reported here. They comprise the local electrochemical removal of a self-assembled monolayer (SAM) of dodecanethiol on flame-annealed gold by an electrochemical desorption procedure. The possibility of local electrochemical deposition is demonstrated by positioning a nanoelectrode 0.5 nm above a surface and switching off the distance regulation while performing an electrodeposition of Pt at the tip. The growing deposit bridges the tip-sample gap. If the distance regulation is switched on after 1 ms, the Pt junction is disrupted leaving a Pt nanodot at the sample surface. The dot was characterized by ECSTM experiments after solution exchange. Digital simulations by the boundary element method (BEM) provide a quantitative description of Faraday currents in nanoelectrochemical assemblies. A software tool was created that can accept arbitrary geometries as input data sets. The flexibility of the simulation strategy was demonstrated by the calculation of local current densities during electrochemical copper deposition on a smooth electrode in the presence of an ECSTM tip close to the surface. The current densities deviate less than 1% from those in the absence of tip if the average current density is kept below 1 μA cm -2. SECM approach curves for nanoelectrodes were also calculated.

  10. Microwave sintering and in-situ transmission electron microscopy heating study of Li1·2(Mn0·53Co0.27)O2 with improved electrochemical performance

    NASA Astrophysics Data System (ADS)

    Wu, Jingjing; Liu, Xialin; Bi, Han; Song, Yuanzhe; Wang, Chao; Cao, Qi; Liu, Zhengwang; Wang, Min; Che, Renchao

    2016-09-01

    Li1·2(Mn0·53Co0.27)O2 cathode material was successfully synthesized using a microwave sintering method. The as-prepared material remained in an octahedral shape after sintering at 800 °C with a rapid heating rate of 35 °C min-1. The as-prepared sample was demonstrated to have better electrochemical performance than that synthesized using a conventional method. The enhanced electrochemical performance can be ascribed to the minor change in material morphology and less particle agglomeration in the macroscopic scale, which depends on the rapid-sintering mechanism provided by microwave sintering. The rapid-sintering mechanism was studied in an in-situ transmission electron microscopy (TEM) heating experiment, which directly presented the crystal growth process and the evidence for the morphological damage of Li1·2(Mn0·53Co0.27)O2 materials at approximately 830 °C.

  11. New Insights into Electrochemical Lithiation/Delithiation Mechanism of α-MoO3 Nanobelt by in Situ Transmission Electron Microscopy.

    PubMed

    Xia, Weiwei; Zhang, Qiubo; Xu, Feng; Sun, Litao

    2016-04-13

    The α-MoO3 nanobelt has great potential for application as anode of lithium ion batteries (LIBs) because of its high capacity and unique one-dimensional layer structure. However, its fundmental electrochemical failure mechanism during first lithiation/delithiation process is still unclear. Here, we constructed an electrochemical setup within α-MoO3 nanobelt anode inside a transmission electron microscope to observe in situ the mircostructure evolution during cycles. Upon first lithiation, the α-MoO3 nanobelt converted into numerous Mo nanograins within the Li2O matrix, with an obvious size expansion. Interestingly, α-MoO3 nanobelt was found to undergo a two-stage delithiation process. Mo nanograins were first transformed into crystalline Li1.66Mo0.66O2 along with the disappearance of Li2O and size shrink, followed by the conversion to amorphous Li2MoO3. This irreversible phase conversion should be responsible for the large capacity loss in first cycle. In addition, a fully reversile phase conversion between crystalline Mo and amorphous Li2MoO3 was revealed accompanying the formation and disapperance of the Li2O layer during the subsequent cycles. Our experiments provide direct evidence to deeply understand the distinctive electrochemical lithiation/delithiation behaviors of α-MoO3 nanobelt, shedding light onto the development of α-MoO3 anode for LIBs. PMID:27008317

  12. Electrochemical attosyringe

    PubMed Central

    Laforge, François O.; Carpino, James; Rotenberg, Susan A.; Mirkin, Michael V.

    2007-01-01

    The ability to manipulate ultrasmall volumes of liquids is essential in such diverse fields as cell biology, microfluidics, capillary chromatography, and nanolithography. In cell biology, it is often necessary to inject material of high molecular weight (e.g., DNA, proteins) into living cells because their membranes are impermeable to such molecules. All techniques currently used for microinjection are plagued by two common problems: the relatively large injector size and volume of injected fluid, and poor control of the amount of injected material. Here we demonstrate the possibility of electrochemical control of the fluid motion that allows one to sample and dispense attoliter-to-picoliter (10−18 to 10−12 liter) volumes of either aqueous or nonaqueous solutions. By changing the voltage applied across the liquid/liquid interface, one can produce a sufficient force to draw solution inside a nanopipette and then inject it into an immobilized biological cell. A high success rate was achieved in injections of fluorescent dyes into cultured human breast cells. The injection of femtoliter-range volumes can be monitored by video microscopy, and current/resistance-based approaches can be used to control injections from very small pipettes. Other potential applications of the electrochemical syringe include fluid dispensing in nanolithography and pumping in microfluidic systems. PMID:17620612

  13. Analytical and mineralogical studies of ore and impurities from a chromite mineral using X-ray analysis, electrochemical and microscopy techniques.

    PubMed

    Sánchez-Ramos, S; Doménech-Carbó, A; Gimeno-Adelantado, J V; Peris-Vicente, J

    2008-02-15

    A wide analytical study of South African chromite ore, material with high interest in ceramic industry, has been carried out. With this purpose, an accurate chemical identification and mineralogical characterization of the mineral and the gangue have been performed using X-ray fluorescence (XRF), voltammetry, X-ray diffraction (XRD), light microscopy (LM), and scanning electron microscopy (SEM/EDX). The elemental composition of the sample (ore and gangue) has been obtained by XRF. The voltammetric analysis has allowed to demonstrate that iron in the sample was as Fe(II). The main compound of the chromite ore was a spinel (magnesiochromite ferroan), identified by XRD from the sample, which constitutes the chromite ore. This technique has also been useful to characterize some silicates as impurities in the chromite ore sample. Light microscopy has allowed the detection of the spinel and the identification of a silicate impurity (chrome chlorite), by means of their colouration. On the other hand, the other silicate impurity was identified as labradorite by means of X-ray microscopy by SEM/EDX. Finally, a strategy was developed to calculate the composition of each mineral in the unknown sample. The obtained results were: chromite spinel 82.89%, chlorite 12.79% and labradorite 4.32%. PMID:18371822

  14. High-Speed Electrochemical Imaging.

    PubMed

    Momotenko, Dmitry; Byers, Joshua C; McKelvey, Kim; Kang, Minkyung; Unwin, Patrick R

    2015-09-22

    The design, development, and application of high-speed scanning electrochemical probe microscopy is reported. The approach allows the acquisition of a series of high-resolution images (typically 1000 pixels μm(-2)) at rates approaching 4 seconds per frame, while collecting up to 8000 image pixels per second, about 1000 times faster than typical imaging speeds used up to now. The focus is on scanning electrochemical cell microscopy (SECCM), but the principles and practicalities are applicable to many electrochemical imaging methods. The versatility of the high-speed scan concept is demonstrated at a variety of substrates, including imaging the electroactivity of a patterned self-assembled monolayer on gold, visualization of chemical reactions occurring at single wall carbon nanotubes, and probing nanoscale electrocatalysts for water splitting. These studies provide movies of spatial variations of electrochemical fluxes as a function of potential and a platform for the further development of high speed scanning with other electrochemical imaging techniques. PMID:26267455

  15. Electrochemical Techniques

    SciTech Connect

    Chen, Gang; Lin, Yuehe

    2008-07-20

    Sensitive and selective detection techniques are of crucial importance for capillary electrophoresis (CE), microfluidic chips, and other microfluidic systems. Electrochemical detectors have attracted considerable interest for microfluidic systems with features that include high sensitivity, inherent miniaturization of both the detection and control instrumentation, low cost and power demands, and high compatibility with microfabrication technology. The commonly used electrochemical detectors can be classified into three general modes: conductimetry, potentiometry, and amperometry.

  16. Electron microscopy investigation and electrochemical performance of carbon-coated LiFe0.7Mn0.2Ni0.1PO4 for lithium ion battery

    NASA Astrophysics Data System (ADS)

    Rohman, Fadli; Suwandi, Endang; Majid, Nurhalis; Subhan, Achmad

    2016-02-01

    The carbon-coated LiFe0.7Mn0.2Ni0.1PO4 was synthesized using solid state reaction method and sintering process. The carbon was coated on the surface of the LiFe0.7Mn0.2Ni0.1PO4 particle using citric acid as the carbon source. the crystal phase and diffraction peak of the particle was shown from X-Ray Diffraction characterization. The particle morphology and size distribution of this material was investigated using Scanning Electron Microscopy (SEM). The thickness of the carbon coating and the crystal lattice spacing was investigated using Transmission Electron Microscopy (TEM). The particle size, carbon coating thickness, and crystal lattice spacing were found to be 10 - 50 µm, 4 nm, and Å, respectively. The effect of the carbon layer on the surface of the LiFe0.7Mn0.2Ni0.1PO4 particle as a cathode material in lithium-ion battery exhibited in the electrochemical performance test as shown in cyclic voltammetry and charge-discharge measurement test. According to the cyclic voltammetry test, it was shown that the redox peaks of the carbon-coated LiFe0.7Mn0.2Ni0.1PO4 from Fe2+ to Fe3+ were at 3.579 V and 2.96 V, but there was lower peak at 3.52 V. This phenomenon indicated the presence of doped Mn and Ni. The specific capacity of carbon coated LiFe0.7Mn0.2Ni0.1PO4 was 49 mAh/g, which was higher than uncoated LiFe0.7Mn0.2Ni0.1PO4, 30 mAh/g. On the other hand, after 40 cycles the specific capacity of carbon-coated LiFe0.7Mn0.2Ni0.1PO4 was decreasing to 10%, while the specific capacity of uncoated LiFe0.7Mn0.2Ni0.1PO4 remained almost similar before and after 40 cycles. In term of columbic efficiency, carbon-coated LiFe0.7Mn0.2Ni0.1PO4 was more stable, better than uncoated LiFe0.7Mn0.2Ni0.1PO4. Moreover, all samples were in close proximity to 100% efficiency. The C-rates test result showed that the discharge C-rates ability of the carbon coated LiFe0.7Mn0.2Ni0.1PO4 had been better than uncoated LiFe0.7Mn0.2Ni0.1PO4. At 1.5 C rate, the capacity loss of carbon-coated LiFe0

  17. Fluorescence Microscopy

    PubMed Central

    Sanderson, Michael J.; Smith, Ian; Parker, Ian; Bootman, Martin D.

    2016-01-01

    Fluorescence microscopy is a major tool with which to monitor cell physiology. Although the concepts of fluorescence and its optical separation using filters remain similar, microscope design varies with the aim of increasing image contrast and spatial resolution. The basics of wide-field microscopy are outlined to emphasize the selection, advantages, and correct use of laser scanning confocal microscopy, two-photon microscopy, scanning disk confocal microscopy, total internal reflection, and super-resolution microscopy. In addition, the principles of how these microscopes form images are reviewed to appreciate their capabilities, limitations, and constraints for operation. PMID:25275114

  18. Electron Microscopy.

    ERIC Educational Resources Information Center

    Beer, Michael

    1980-01-01

    Reviews technical aspects of structure determination in biological electron microscopy (EM). Discusses low dose EM, low temperature microscopy, electron energy loss spectra, determination of mass or molecular weight, and EM of labeled systems. Cites 34 references. (CS)

  19. Electrochemical cell

    DOEpatents

    Redey, L.I.; Vissers, D.R.; Prakash, J.

    1996-07-16

    An electrochemical cell is described having a bimodal positive electrode, a negative electrode of an alkali metal, and a compatible electrolyte including an alkali metal salt molten at the cell operating temperature. The positive electrode has an electrochemically active layer of at least one transition metal chloride at least partially present as a charging product, and additives of bromide and/or iodide and sulfur in the positive electrode or the electrolyte. Electrode volumetric capacity is in excess of 400 Ah/cm{sup 3}; the cell can be 90% recharged in three hours and can operate at temperatures below 160 C. There is also disclosed a method of reducing the operating temperature and improving the overall volumetric capacity of an electrochemical cell and for producing a positive electrode having a BET area greater than 6{times}10{sup 4}cm{sup 2}/g of Ni. 6 figs.

  20. Electrochemical cell

    DOEpatents

    Redey, Laszlo I.; Vissers, Donald R.; Prakash, Jai

    1994-01-01

    An electrochemical cell having a bimodal positive electrode, a negative electrode of an alkali metal, and a compatible electrolyte including an alkali metal salt molten at the cell operating temperature. The positive electrode has an electrochemically active layer of at least one transition metal chloride at least partially present as a charging product, and additives of bromide and/or iodide and sulfur in the positive electrode or the electrolyte. Electrode volumetric capacity is in excess of 400 Ah/cm.sup.3 ; the cell can be 90% recharged in three hours and can operate at temperatures below 160.degree. C. There is also disclosed a method of reducing the operating temperature and improving the overall volumetric capacity of an electrochemical cell and for producing a positive electrode having a BET area greater than 6.times.10.sup.4 cm.sup.2 /g of Ni.

  1. Electrochemical cell

    DOEpatents

    Redey, Laszlo I.; Vissers, Donald R.; Prakash, Jai

    1996-01-01

    An electrochemical cell having a bimodal positive electrode, a negative electrode of an alkali metal, and a compatible electrolyte including an alkali metal salt molten at the cell operating temperature. The positive electrode has an electrochemically active layer of at least one transition metal chloride at least partially present as a charging product, and additives of bromide and/or iodide and sulfur in the positive electrode or the electrolyte. Electrode volumetric capacity is in excess of 400 Ah/cm.sup.3 ; the cell can be 90% recharged in three hours and can operate at temperatures below 160.degree. C. There is also disclosed a method of reducing the operating temperature and improving the overall volumetric capacity of an electrochemical cell and for producing a positive electrode having a BET area greater than 6.times.10.sup.4 cm.sup.2 /g of Ni.

  2. Electrochemical cell

    DOEpatents

    Redey, L.I.; Vissers, D.R.; Prakash, J.

    1994-02-01

    An electrochemical cell is described having a bimodal positive electrode, a negative electrode of an alkali metal, and a compatible electrolyte including an alkali metal salt molten at the cell operating temperature. The positive electrode has an electrochemically active layer of at least one transition metal chloride at least partially present as a charging product, and additives of bromide and/or iodide and sulfur in the positive electrode or the electrolyte. Electrode volumetric capacity is in excess of 400 Ah/cm[sup 3]; the cell can be 90% recharged in three hours and can operate at temperatures below 160 C. There is also disclosed a method of reducing the operating temperature and improving the overall volumetric capacity of an electrochemical cell and for producing a positive electrode having a BET area greater than 6[times]10[sup 4] cm[sup 2]/g of Ni. 8 figures.

  3. Electrochemical storage

    NASA Technical Reports Server (NTRS)

    Thaller, L. H.

    1984-01-01

    The source of the problem within the individual single cell which is related to the stochastic properties of cell populations and to the actual electrochemistry and chemistry taking place is described. The complications which arise in multicell batteries to show how different electrochemistries might alleviate or accentuate these problems is described. The concept of the electrochemical system is introduced to show how certain shortcomings of the single cell/battery string concept can be circumvented. Some of these electrochemical systems permit performance characteristics that are impossible by using conventional battery design philosophies. Projections for energy density and performance characteristics of the concepts are addressed.

  4. Electrochemical micromachining

    PubMed

    Schuster; Kirchner; Allongue; Ertl

    2000-07-01

    The application of ultrashort voltage pulses between a tool electrode and a workpiece in an electrochemical environment allows the three-dimensional machining of conducting materials with submicrometer precision. The principle is based on the finite time constant for double-layer charging, which varies linearly with the local separation between the electrodes. During nanosecond pulses, the electrochemical reactions are confined to electrode regions in close proximity. This technique was used for local etching of copper and silicon as well as for local copper deposition. PMID:10884233

  5. Electrochemical Deburring

    NASA Technical Reports Server (NTRS)

    Burley, R. K.

    1983-01-01

    Electrochemical deburring removes burrs from assembled injector tubes. Since process uses liquid anodic dissolution in liquid electrolyte to proide deburring action, smoothes surfaces and edges in otherwise inaccessible areas. Tool consists of sleeve that contains metallic ring cathode. Sleeve is placed over tube, and electrolytic solution is forced to flow between tube and sleeve. The workpiece serves an anode.

  6. Electrochemical Engineering.

    ERIC Educational Resources Information Center

    Alkire, Richard C.

    1983-01-01

    Discusses engineering ramifications of electrochemistry, focusing on current/potential distribution, evaluation of trade-offs between influences of different phenomena, use of dimensionless numbers to assist in scale-over to new operating conditions, and economics. Also provides examples of electrochemical engineering education content related to…

  7. Electrochemical construction

    DOEpatents

    Einstein, Harry; Grimes, Patrick G.

    1983-08-23

    An electrochemical cell construction features a novel co-extruded plastic electrode in an interleaved construction with a novel integral separator-spacer. Also featured is a leak and impact resistant construction for preventing the spill of corrosive materials in the event of rupture.

  8. Electrochemical device

    DOEpatents

    Grimes, Patrick G.; Einstein, Harry; Bellows, Richard J.

    1988-01-12

    A tunnel protected electrochemical device features channels fluidically communicating between manifold, tunnels and cells. The channels are designed to provide the most efficient use of auxiliary power. The channels have a greater hydraulic pressure drop and electrical resistance than the manifold. This will provide a design with the optimum auxiliary energy requirements.

  9. Electrochemical capacitor

    DOEpatents

    Anderson, Marc A.; Liu, Kuo -Chuan; Mohr, Charles M.

    1999-10-05

    An inexpensive porous metal oxide material having high surface area, good conductivity and high specific capacitance is advantageously used in an electrochemical capacitor. The materials are formed in a sol-gel process which affords control over the properties of the resultant metal oxide materials.

  10. Analytical Microscopy

    SciTech Connect

    Not Available

    2006-06-01

    In the Analytical Microscopy group, within the National Center for Photovoltaic's Measurements and Characterization Division, we combine two complementary areas of analytical microscopy--electron microscopy and proximal-probe techniques--and use a variety of state-of-the-art imaging and analytical tools. We also design and build custom instrumentation and develop novel techniques that provide unique capabilities for studying materials and devices. In our work, we collaborate with you to solve materials- and device-related R&D problems. This sheet summarizes the uses and features of four major tools: transmission electron microscopy, scanning electron microscopy, the dual-beam focused-ion-beam workstation, and scanning probe microscopy.

  11. Electrochemical cell

    DOEpatents

    Redey, Laszlo I.; Vissers, Donald R.; Prakash, Jai

    1994-01-01

    An electrochemical cell having an alkali metal negative electrode such as sodium and a positive electrode including Ni or transition metals, separated by a .beta." alumina electrolyte and NaAlCl.sub.4 or other compatible material. Various concentrations of a bromine, iodine and/or sulfur containing additive and pore formers are disclosed, which enhance cell capacity and power. The pore formers may be the ammonium salts of carbonic acid or a weak organic acid or oxamide or methylcellulose.

  12. Electrochemical cell

    DOEpatents

    Nagy, Zoltan; Yonco, Robert M.; You, Hoydoo; Melendres, Carlos A.

    1992-01-01

    An electrochemical cell has a layer-type or sandwich configuration with a Teflon center section that houses working, reference and counter electrodes and defines a relatively narrow electrolyte cavity. The center section is surrounded on both sides with thin Teflon membranes. The membranes are pressed in place by a pair of Teflon inner frames which are in turn supported by a pair of outer metal frames. The pair of inner and outer frames are provided with corresponding, appropriately shaped slits that are in plane generally transverse to the plane of the working electrode and permit X-ray beams to enter and exit the cell through the Teflon membranes that cover the slits so that the interface between the working electrode and the electrolyte within the cell may be analyzed by transmission geometry. In one embodiment, the center section consists of two parts, one on top of the other. Alternatively, the center section of the electrochemical cell may consist of two intersliding pieces or may be made of a single piece of Teflon sheet material. The electrolyte cavity is shaped so that the electrochemical cell can be rotated 90.degree. in either direction while maintaining the working and counter electrodes submerged in the electrolyte.

  13. Electrochemical cell

    DOEpatents

    Nagy, Z.; Yonco, R.M.; You, H.; Melendres, C.A.

    1992-08-25

    An electrochemical cell has a layer-type or sandwich configuration with a Teflon center section that houses working, reference and counter electrodes and defines a relatively narrow electrolyte cavity. The center section is surrounded on both sides with thin Teflon membranes. The membranes are pressed in place by a pair of Teflon inner frames which are in turn supported by a pair of outer metal frames. The pair of inner and outer frames are provided with corresponding, appropriately shaped slits that are in plane generally transverse to the plane of the working electrode and permit X-ray beams to enter and exit the cell through the Teflon membranes that cover the slits so that the interface between the working electrode and the electrolyte within the cell may be analyzed by transmission geometry. In one embodiment, the center section consists of two parts, one on top of the other. Alternatively, the center section of the electrochemical cell may consist of two intersliding pieces or may be made of a single piece of Teflon sheet material. The electrolyte cavity is shaped so that the electrochemical cell can be rotated 90[degree] in either direction while maintaining the working and counter electrodes submerged in the electrolyte. 5 figs.

  14. Electrochemical cell

    DOEpatents

    Redey, Laszlo I.; Myles, Kevin M.; Vissers, Donald R.; Prakash, Jai

    1996-01-01

    An electrochemical cell with a positive electrode having an electrochemically active layer of at least one transition metal chloride. A negative electrode of an alkali metal and a compatible electrolyte including an alkali metal salt molten at cell operating temperature is included in the cell. The electrolyte is present at least partially as a corrugated .beta." alumina tube surrounding the negative electrode interior to the positive electrode. The ratio of the volume of liquid electrolyte to the volume of the positive electrode is in the range of from about 0.1 to about 3. A plurality of stacked electrochemical cells is disclosed each having a positive electrode, a negative electrode of an alkali metal molten at cell operating temperature, and a compatible electrolyte. The electrolyte is at least partially present as a corrugated .beta." alumina sheet separating the negative electrode and interior to the positive electrodes. The alkali metal is retained in a porous electrically conductive ceramic, and seals for sealing the junctures of the electrolyte and the adjacent electrodes at the peripheries thereof.

  15. Electrochemical cell

    DOEpatents

    Redey, L.I.; Myles, K.M.; Vissers, D.R.; Prakash, J.

    1996-07-02

    An electrochemical cell is described with a positive electrode having an electrochemically active layer of at least one transition metal chloride. A negative electrode of an alkali metal and a compatible electrolyte including an alkali metal salt molten at cell operating temperature is included in the cell. The electrolyte is present at least partially as a corrugated {beta}{double_prime} alumina tube surrounding the negative electrode interior to the positive electrode. The ratio of the volume of liquid electrolyte to the volume of the positive electrode is in the range of from about 0.1 to about 3. A plurality of stacked electrochemical cells is disclosed each having a positive electrode, a negative electrode of an alkali metal molten at cell operating temperature, and a compatible electrolyte. The electrolyte is at least partially present as a corrugated {beta}{double_prime} alumina sheet separating the negative electrode and interior to the positive electrodes. The alkali metal is retained in a porous electrically conductive ceramic, and seals for sealing the junctures of the electrolyte and the adjacent electrodes at the peripheries thereof. 8 figs.

  16. Correlative Microscopy

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Microscopy and Imaging offers many opportunities to collaborate and cooperate with scientists in many different fields nationally and internationally. Images have proven to be very important components in basic research, product development and understanding structure/function relationships in addit...

  17. Electrochemical cell

    DOEpatents

    Redey, L.I.; Vissers, D.R.; Prakash, J.

    1994-08-23

    An electrochemical cell is described having an alkali metal negative electrode such as sodium and a positive electrode including Ni or transition metals, separated by a [beta] alumina electrolyte and NaAlCl[sub 4] or other compatible material. Various concentrations of a bromine, iodine and/or sulfur containing additive and pore formers are disclosed, which enhance cell capacity and power. The pore formers may be the ammonium salts of carbonic acid or a weak organic acid or oxamide or methylcellulose. 6 figs.

  18. Electrochemical cell

    DOEpatents

    Kaun, Thomas D.

    1984-01-01

    An improved secondary electrochemical cell is disclosed having a negative electrode of lithium aluminum, a positive electrode of iron sulfide, a molten electrolyte of lithium chloride and potassium chloride, and the combination that the fully charged theoretical capacity of the negative electrode is in the range of 0.5-1.0 that of the positive electrode. The cell thus is negative electrode limiting during discharge cycling. Preferably, the negative electrode contains therein, in the approximate range of 1-10 volume % of the electrode, an additive from the materials of graphitized carbon, aluminum-iron alloy, and/or magnesium oxide.

  19. Electrochemical cell

    DOEpatents

    Kaun, T.D.

    An improved secondary electrochemical cell is disclosed having a negative electrode of lithium aluminum, a positive electrode of iron sulfide, a molten electrolyte of lithium chloride and potassium chloride, and the combination that the fully charged theoretical capacity of the negative electrode is in the range of 0.5 to 1.0 that of the positive electrode. The cell thus is negative electrode limiting during discharge cycling. Preferably, the negative electrode contains therein, in the approximate range of 1 to 10 volume % of the electrode, an additive from the materials of graphitized carbon, aluminum-iron alloy, and/or magnesium oxide.

  20. Correlative microscopy.

    PubMed

    Loussert Fonta, Céline; Humbel, Bruno M

    2015-09-01

    In recent years correlative microscopy, combining the power and advantages of different imaging system, e.g., light, electrons, X-ray, NMR, etc., has become an important tool for biomedical research. Among all the possible combinations of techniques, light and electron microscopy, have made an especially big step forward and are being implemented in more and more research labs. Electron microscopy profits from the high spatial resolution, the direct recognition of the cellular ultrastructure and identification of the organelles. It, however, has two severe limitations: the restricted field of view and the fact that no live imaging can be done. On the other hand light microscopy has the advantage of live imaging, following a fluorescently tagged molecule in real time and at lower magnifications the large field of view facilitates the identification and location of sparse individual cells in a large context, e.g., tissue. The combination of these two imaging techniques appears to be a valuable approach to dissect biological events at a submicrometer level. Light microscopy can be used to follow a labelled protein of interest, or a visible organelle such as mitochondria, in time, then the sample is fixed and the exactly same region is investigated by electron microscopy. The time resolution is dependent on the speed of penetration and fixation when chemical fixatives are used and on the reaction time of the operator for cryo-fixation. Light microscopy can also be used to identify cells of interest, e.g., a special cell type in tissue or cells that have been modified by either transfections or RNAi, in a large population of non-modified cells. A further application is to find fluorescence labels in cells on a large section to reduce searching time in the electron microscope. Multiple fluorescence labelling of a series of sections can be correlated with the ultrastructure of the individual sections to get 3D information of the distribution of the marked proteins: array

  1. Expansion Microscopy

    PubMed Central

    Chen, Fei; Tillberg, Paul W.; Boyden, Edward S.

    2014-01-01

    In optical microscopy, fine structural details are resolved by using refraction to magnify images of a specimen. Here we report the discovery that, by synthesizing a swellable polymer network within a specimen, it can be physically expanded, resulting in physical magnification. By covalently anchoring specific labels located within the specimen directly to the polymer network, labels spaced closer than the optical diffraction limit can be isotropically separated and optically resolved, a process we call expansion microscopy (ExM). Thus, this process can be used to perform scalable super-resolution microscopy with diffraction-limited microscopes. We demonstrate ExM with effective ~70 nm lateral resolution in both cultured cells and brain tissue, performing three-color super-resolution imaging of ~107 μm3 of the mouse hippocampus with a conventional confocal microscope. PMID:25592419

  2. Photoacoustic Microscopy

    PubMed Central

    Yao, Junjie; Wang, Lihong V.

    2012-01-01

    Photoacoustic microscopy (PAM) is a hybrid in vivo imaging technique that acoustically detects optical contrast via the photoacoustic effect. Unlike pure optical microscopic techniques, PAM takes advantage of the weak acoustic scattering in tissue and thus breaks through the optical diffusion limit (~1 mm in soft tissue). With its excellent scalability, PAM can provide high-resolution images at desired maximum imaging depths up to a few millimeters. Compared with backscattering-based confocal microscopy and optical coherence tomography, PAM provides absorption contrast instead of scattering contrast. Furthermore, PAM can image more molecules, endogenous or exogenous, at their absorbing wavelengths than fluorescence-based methods, such as wide-field, confocal, and multi-photon microscopy. Most importantly, PAM can simultaneously image anatomical, functional, molecular, flow dynamic and metabolic contrasts in vivo. Focusing on state-of-the-art developments in PAM, this Review discusses the key features of PAM implementations and their applications in biomedical studies. PMID:24416085

  3. Intravital microscopy

    PubMed Central

    Masedunskas, Andrius; Milberg, Oleg; Porat-Shliom, Natalie; Sramkova, Monika; Wigand, Tim; Amornphimoltham, Panomwat; Weigert, Roberto

    2012-01-01

    Intravital microscopy is an extremely powerful tool that enables imaging several biological processes in live animals. Recently, the ability to image subcellular structures in several organs combined with the development of sophisticated genetic tools has made possible extending this approach to investigate several aspects of cell biology. Here we provide a general overview of intravital microscopy with the goal of highlighting its potential and challenges. Specifically, this review is geared toward researchers that are new to intravital microscopy and focuses on practical aspects of carrying out imaging in live animals. Here we share the know-how that comes from first-hand experience, including topics such as choosing the right imaging platform and modality, surgery and stabilization techniques, anesthesia and temperature control. Moreover, we highlight some of the approaches that facilitate subcellular imaging in live animals by providing numerous examples of imaging selected organelles and the actin cytoskeleton in multiple organs. PMID:22992750

  4. Electrochemical supercapacitors

    DOEpatents

    Rudge, Andrew J.; Ferraris, John P.; Gottesfeld, Shimshon

    1996-01-01

    A new class of electrochemical capacitors provides in its charged state a positive electrode including an active material of a p-doped material and a negative electrode including an active material of an n-doped conducting polymer, where the p-doped and n-doped materials are separated by an electrolyte. In a preferred embodiment, the positive and negative electrode active materials are selected from conducting polymers consisting of polythiophene, polymers having an aryl group attached in the 3-position, polymers having aryl and alkyl groups independently attached in the 3- and 4-positions, and polymers synthesized from bridged dimers having polythiophene as the backbone. A preferred electrolyte is a tetraalykyl ammonium salt, such as tetramethylammonium trifluoromethane sulphonate (TMATFMS), that provides small ions that are mobile through the active material, is soluble in acetonitrile, and can be used in a variety of capacitor configurations.

  5. Local probing of electrochemically induced negative differential resistance in TiO2 memristive materials

    NASA Astrophysics Data System (ADS)

    Kim, Yunseok; Hyuck Jang, Jae; Park, Sang-Joon; Jesse, Stephen; Donovan, Leonard; Y Borisevich, Albina; Lee, Woo; Kalinin, Sergei V.

    2013-03-01

    The early stages of electroforming in TiO2 were explored using a combination of electrochemical strain microscopy and local I-V curve measurements. Negative differential resistance and corresponding surface deformation were observed below the electroforming voltages. Electrochemical strain microscopy allowed probing of the changes in local electrochemical activity during the pre-forming and forming stages. The associated structural changes were visualized by transmission electron microscopy. The results allowed an understanding of the electrochemical processes in the early stages of electroforming, and provide a comprehensive approach for exploring irreversible and partially reversible bias-induced transformations in solids.

  6. Local Probing of Electrochemically Induced Negative Differential Resistance in TiO2 Memristive Materials

    SciTech Connect

    Kim, Yunseok; Jesse, Stephen; Kalinin, Sergei V

    2013-01-01

    Early stage of electroforming in TiO2 was observed by deliberately combining conductive atomic force microscopy and electrochemical strain microscopy. The negative differential resistance and the corresponding surface deformation were observed below electroforming voltages. The surface deformations induced by surface oxidation are thermodynamically stable, reversibly controlled by applying voltage bias of different polarities, and electrochemically less active.

  7. Localized electrografting of vinylic monomers on a conducting substrate by means of an integrated electrochemical AFM probe.

    PubMed

    Ghorbal, Achraf; Grisotto, Federico; Charlier, Julienne; Palacin, Serge; Goyer, Cédric; Demaille, Christophe

    2009-05-11

    Combinations of scanning electrochemical microscopy (SECM) with other scanning probe microscopy techniques, such as atomic force microscopy (AFM), show great promise for directing localized modification, which is of great interest for chemical, biochemical and technical applications. Herein, an atomic force scanning electrochemical microscope is used as a new electrochemical lithographic tool (L-AFM-SECM) to locally electrograft, with submicrometer resolution, a non-conducting organic coating on a conducting substrate. PMID:19308970

  8. Positron microscopy

    SciTech Connect

    Hulett, L.D. Jr.; Xu, J.

    1995-02-01

    The negative work function property that some materials have for positrons make possible the development of positron reemission microscopy (PRM). Because of the low energies with which the positrons are emitted, some unique applications, such as the imaging of defects, can be made. The history of the concept of PRM, and its present state of development will be reviewed. The potential of positron microprobe techniques will be discussed also.

  9. Endoscopic Microscopy

    PubMed Central

    Sokolov, Konstantin; Sung, Kung-Bin; Collier, Tom; Clark, Anne; Arifler, Dizem; Lacy, Alicia; Descour, Michael; Richards-Kortum, Rebecca

    2002-01-01

    In vivo endoscopic optical microscopy provides a tool to assess tissue architecture and morphology with contrast and resolution similar to that provided by standard histopathology – without need for physical tissue removal. In this article, we focus on optical imaging technologies that have the potential to dramatically improve the detection, prevention, and therapy of epithelial cancers. Epithelial pre-cancers and cancers are associated with a variety of morphologic, architectural, and molecular changes, which currently can be assessed only through invasive, painful biopsy. Optical imaging is ideally suited to detecting cancer-related alterations because it can detect biochemical and morphologic alterations with sub-cellular resolution throughout the entire epithelial thickness. Optical techniques can be implemented non-invasively, in real time, and at low cost to survey the tissue surface at risk. Our manuscript focuses primarily on modalities that currently are the most developed: reflectance confocal microscopy (RCM) and optical coherence tomography (OCT). However, recent advances in fluorescence-based endoscopic microscopy also are reviewed briefly. We discuss the basic principles of these emerging technologies and their current and potential applications in early cancer detection. We also present research activities focused on development of exogenous contrast agents that can enhance the morphological features important for cancer detection and that have the potential to allow vital molecular imaging of cancer-related biomarkers. In conclusion, we discuss future improvements to the technology needed to develop robust clinical devices. PMID:14646041

  10. Microfluidic electrochemical reactors

    DOEpatents

    Nuzzo, Ralph G.; Mitrovski, Svetlana M.

    2011-03-22

    A microfluidic electrochemical reactor includes an electrode and one or more microfluidic channels on the electrode, where the microfluidic channels are covered with a membrane containing a gas permeable polymer. The distance between the electrode and the membrane is less than 500 micrometers. The microfluidic electrochemical reactor can provide for increased reaction rates in electrochemical reactions using a gaseous reactant, as compared to conventional electrochemical cells. Microfluidic electrochemical reactors can be incorporated into devices for applications such as fuel cells, electrochemical analysis, microfluidic actuation, pH gradient formation.

  11. Carbon-Based Solid-State Calcium Ion-Selective Microelectrode and Scanning Electrochemical Microscopy: A Quantitative Study of pH-Dependent Release of Calcium Ions from Bioactive Glass.

    PubMed

    Ummadi, Jyothir Ganesh; Downs, Corey J; Joshi, Vrushali S; Ferracane, Jack L; Koley, Dipankar

    2016-03-15

    Solid-state ion-selective electrodes are used as scanning electrochemical microscope (SECM) probes because of their inherent fast response time and ease of miniaturization. In this study, we report the development of a solid-state, low-poly(vinyl chloride), carbon-based calcium ion-selective microelectrode (Ca(2+)-ISME), 25 μm in diameter, capable of performing an amperometric approach curve and serving as a potentiometric sensor. The Ca(2+)-ISME has a broad linear response range of 5 μM to 200 mM with a near Nernstian slope of 28 mV/log[a(Ca(2+))]. The calculated detection limit for Ca(2+)-ISME is 1 μM. The selectivity coefficients of this Ca(2+)-ISME are log K(Ca(2+),A) = -5.88, -5.54, and -6.31 for Mg(2+), Na(+), and K(+), respectively. We used this new type of Ca(2+)-ISME as an SECM probe to quantitatively map the chemical microenvironment produced by a model substrate, bioactive glass (BAG). In acidic conditions (pH 4.5), BAG was found to increase the calcium ion concentration from 0.7 mM ([Ca(2+)] in artificial saliva) to 1.4 mM at 20 μm above the surface. In addition, a solid-state dual SECM pH probe was used to correlate the release of calcium ions with the change in local pH. Three-dimensional pH and calcium ion distribution mapping were also obtained by using these solid-state probes. The quantitative mapping of pH and Ca(2+) above the BAG elucidates the effectiveness of BAG in neutralizing and releasing calcium ions in acidic conditions. PMID:26861499

  12. Electrochemical methane sensor

    DOEpatents

    Zaromb, S.; Otagawa, T.; Stetter, J.R.

    1984-08-27

    A method and instrument including an electrochemical cell for the detection and measurement of methane in a gas by the oxidation of methane electrochemically at a working electrode in a nonaqueous electrolyte at a voltage about 1.4 volts vs R.H.E. (the reversible hydrogen electrode potential in the same electrolyte), and the measurement of the electrical signal resulting from the electrochemical oxidation.

  13. Electrochemical oxidation of cholesterol

    PubMed Central

    2015-01-01

    Summary Indirect cholesterol electrochemical oxidation in the presence of various mediators leads to electrophilic addition to the double bond, oxidation at the allylic position, oxidation of the hydroxy group, or functionalization of the side chain. Recent studies have proven that direct electrochemical oxidation of cholesterol is also possible and affords different products depending on the reaction conditions. PMID:25977713

  14. Electrochemical cell stack assembly

    DOEpatents

    Jacobson, Craig P.; Visco, Steven J.; De Jonghe, Lutgard C.

    2010-06-22

    Multiple stacks of tubular electrochemical cells having a dense electrolyte disposed between an anode and a cathode preferably deposited as thin films arranged in parallel on stamped conductive interconnect sheets or ferrules. The stack allows one or more electrochemical cell to malfunction without disabling the entire stack. Stack efficiency is enhanced through simplified gas manifolding, gas recycling, reduced operating temperature and improved heat distribution.

  15. Electrochemical thermodynamic measurement system

    DOEpatents

    Reynier, Yvan; Yazami, Rachid; Fultz, Brent T.

    2009-09-29

    The present invention provides systems and methods for accurately characterizing thermodynamic and materials properties of electrodes and electrochemical energy storage and conversion systems. Systems and methods of the present invention are configured for simultaneously collecting a suite of measurements characterizing a plurality of interconnected electrochemical and thermodynamic parameters relating to the electrode reaction state of advancement, voltage and temperature. Enhanced sensitivity provided by the present methods and systems combined with measurement conditions that reflect thermodynamically stabilized electrode conditions allow very accurate measurement of thermodynamic parameters, including state functions such as the Gibbs free energy, enthalpy and entropy of electrode/electrochemical cell reactions, that enable prediction of important performance attributes of electrode materials and electrochemical systems, such as the energy, power density, current rate and the cycle life of an electrochemical cell.

  16. Planar electrochemical device assembly

    DOEpatents

    Jacobson; Craig P. , Visco; Steven J. , De Jonghe; Lutgard C.

    2010-11-09

    A pre-fabricated electrochemical device having a dense electrolyte disposed between an anode and a cathode preferably deposited as thin films is bonded to a porous electrically conductive support. A second porous electrically conductive support may be bonded to a counter electrode of the electrochemical device. Multiple electrochemical devices may be bonded in parallel to a single porous support, such as a perforated sheet to provide a planar array. Planar arrays may be arranged in a stacked interconnected array. A method of making a supported electrochemical device is disclosed wherein the method includes a step of bonding a pre-fabricated electrochemical device layer to an existing porous metal or porous metal alloy layer.

  17. Planar electrochemical device assembly

    DOEpatents

    Jacobson, Craig P.; Visco, Steven J.; De Jonghe, Lutgard C.

    2007-06-19

    A pre-fabricated electrochemical device having a dense electrolyte disposed between an anode and a cathode preferably deposited as thin films is bonded to a porous electrically conductive support. A second porous electrically conductive support may be bonded to a counter electrode of the electrochemical device. Multiple electrochemical devices may be bonded in parallel to a single porous support, such as a perforated sheet to provide a planar array. Planar arrays may be arranged in a stacked interconnected array. A method of making a supported electrochemical device is disclosed wherein the method includes a step of bonding a pre-fabricated electrochemical device layer to an existing porous metal or porous metal alloy layer.

  18. Preparation of Chemically Etched Tips for Ambient Instructional Scanning Tunneling Microscopy

    ERIC Educational Resources Information Center

    Zaccardi, Margot J.; Winkelmann, Kurt; Olson, Joel A.

    2010-01-01

    A first-year laboratory experiment that utilizes concepts of electrochemical tip etching for scanning tunneling microscopy (STM) is described. This experiment can be used in conjunction with any STM experiment. Students electrochemically etch gold STM tips using a time-efficient method, which can then be used in an instructional grade STM that…

  19. Frontiers in Nanoscale Electrochemical Imaging: Faster, Multifunctional, and Ultrasensitive.

    PubMed

    Kang, Minkyung; Momotenko, Dmitry; Page, Ashley; Perry, David; Unwin, Patrick R

    2016-08-16

    A wide range of interfacial physicochemical processes, from electrochemistry to the functioning of living cells, involve spatially localized chemical fluxes that are associated with specific features of the interface. Scanning electrochemical probe microscopes (SEPMs) represent a powerful means of visualizing interfacial fluxes, and this Feature Article highlights recent developments that have radically advanced the speed, spatial resolution, functionality, and sensitivity of SEPMs. A major trend has been a coming together of SEPMs that developed independently and the use of established SEPMs in completely new ways, greatly expanding their scope and impact. The focus is on nanopipette-based SEPMs, including scanning ion conductance microscopy (SICM), scanning electrochemical cell microscopy (SECCM), and hybrid techniques thereof, particularly with scanning electrochemical microscopy (SECM). Nanopipette-based probes are made easily, quickly, and cheaply with tunable characteristics. They are reproducible and can be fully characterized. Their response can be modeled in considerable detail so that quantitative maps of chemical fluxes and other properties (e.g., local charge) can be obtained and analyzed. This article provides an overview of the use of these probes for high-speed imaging, to create movies of electrochemical processes in action, to carry out multifunctional mapping such as simultaneous topography-charge and topography-activity, and to create nanoscale electrochemical cells for the detection, trapping, and analysis of single entities, particularly individual molecules and nanoparticles (NPs). These studies provide a platform for the further application and diversification of SEPMs across a wide range of interfacial science. PMID:27396415

  20. Investigation of atomic layer deposition for the synthesis of electrochemical electrodes

    NASA Astrophysics Data System (ADS)

    Comstock, David John

    Electrochemical processes dominate a wide range of applications, including sensing, catalysis, and energy storage. Critical to these applications is the electrochemical electrode at which the electrochemical processes are conducted. In this dissertation, atomic layer deposition (ALD) is demonstrated for the controlled synthesis of electrochemical electrodes. ALD is a thin film deposition technique that provides for highly conformal, pinhole-free films with precisely controlled thickness and composition. In particular, the deposition of thin insulating films by ALD is exploited to fabricate ultramicroelectrode (UME) probes for electrochemical imaging applications, and the conformal deposition of thin metal films within nanoporous templates is exploited to synthesize nanostructured, high surface area electrodes. UME probes are commonly used for spatially resolved electrochemical imaging via scanning electrochemical microscopy (SECM) techniques. One of the challenges in UME probe fabrication is the deposition of thin, high quality insulating films to define the conductive electrode solely at the probe tip. This work demonstrates the application of ALD Al2O3 as a high quality, insulating thin film that enables the fabrication of novel UME probes for SECM. In particular, ALD Al2O3 is utilized to prepare integrated probes, in which a UME is integrated into an atomic force microscopy tip and cantilever for scanning electrochemical microscopy-atomic force microscopy and into a nanopipette probe for scanning electrochemical microscopyscanning ion conductance microscopy. High surface area electrodes are also valuable in a range of electrochemical applications. The conformality of ALD is ideally-suited to the synthesis of these electrodes via the deposition of metal films within nanoporous templates. The combination of ALD and nanoporous templates provides for the synthesis of electrodes with precisely controlled morphologies and compositions. To this end, nanostructured Pt

  1. Electrochemical synthesis of cyclopropanes

    NASA Astrophysics Data System (ADS)

    Elinson, M. N.; Dorofeeva, E. O.; Vereshchagin, A. N.; Nikishin, G. I.

    2015-05-01

    Data on methods of electrochemical synthesis of cyclopropanes are summarized and described systematically. Direct electrochemical methods to afford cyclopropanes in both cathodic and anodic processes are considered. Among indirect electrochemical methods such as the processes employing electrogenerated bases and also those involving electrogenerated metal complexes, attention is focused on the most promising methods for the synthesis of functionally substituted cyclopropanes, namely, the electrocatalytic cascade and multicomponent transformations of CH acids and also the joint electrolysis of CH acids and activated alkenes or carbonyl compounds in the presence of alkali metal halides as mediators. The bibliography includes 62 references.

  2. Synthesis and electrochemical performance of polyaniline @MnO2/graphene ternary composites for electrochemical supercapacitors

    NASA Astrophysics Data System (ADS)

    Pan, Chao; Gu, Haiteng; Dong, Li

    2016-01-01

    We introduce a facile method to construct new ternary hierarchical nanocomposites by combining MnO2 coated one dimensional (1D) conducting polyaniline (PANI) nanowires with 2D graphene sheets (GNs). The hierarchical nanocomposite structures of PANI@MnO2/GNs (PMGNs) are further proved by X-ray diffraction (XRD), FT-IR, field emission scanning electron microscopy (FESEM), transmission electron microscope (TEM), thermogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS). The electrochemical characteristics of the electrodes made of the hierarchical structured PMGNs materials are determined by the CV and galvanostatic measurements. These electrochemical tests indicate that electrodes made of the nanostructured PMGNs exhibit an improved reversible capacitance of 695 F g-1 after 1000 cycles at a high current density of 4 A g-1. The ternary composites possess higher electrochemical capacitance than each individual component as supercapacitor electrode materials. Such intriguing electrochemical performance is mainly attributed to the synergistic effects of MnO2, PANI and graphene. The hierarchical ternary nanocomposites show excellent electrochemical properties for energy storage applications, which evidence their potential application as supercapacitors.

  3. Microstructure and electrochemical properties of boron-doped mesocarbon microbeads

    SciTech Connect

    Kim, C.; Fujino, T.; Miyashita, K.; Hayashi, T.; Endo, M.; Dresselhaus, M.S.

    2000-04-01

    The microstructure and electrochemical properties of pristine and boron-doped mesocarbon microbeads (MCMBs) were comparatively studied by X-ray diffraction, field-emission scanning electron microscopy, Raman spectroscopy, and electrochemical measurements. The authors examined the correlation between the boron-doping effect and the electrochemical properties of boron-doped MCMBs prepared at different heat-treatment temperatures. It was found that boron doping in MCMBs starts above 1,800 C, and then the substitution reaction proceeds with increasing heat-treatment temperature. The effect of boron doping is to accelerate graphitization of MCMBs for heat-treatment temperatures in the range from 1,800 to 2,500 C. Electrochemical lithium intercalation takes place at a higher potential in boron-doped MCMBs than in undoped MCMBs, presumably because the substitutional boron acts as an electron acceptor in the MCMBs.

  4. Analysis of machining characteristics in electrochemical etching using laser masking

    NASA Astrophysics Data System (ADS)

    Shin, Hong Shik; Chung, Do Kwan; Park, Min Soo; Chu, Chong Nam

    2011-12-01

    Electrochemical etching using laser masking (EELM), which is a combination of laser beam irradiation for masking and electrochemical etching, allows the micro fabrication of stainless steel without photolithography technology. The EELM process can produce various micro patterns and multilayered structures. In this study, the machining characteristics of EELM were investigated. Changes in characteristics of recast layer formation and the protective effect of the recast layer according to the laser masking conditions and electrochemical etching conditions were investigated by field emission scanning electron microscopy (FE-SEM), focused ion beam (FIB) and X-ray photoelectron spectroscopy (XPS). The oxidized recast layer with a thickness of 500 nm was verified to yield a superior protective effect during electrochemical etching and good form accuracy. Finally, micro patterns and structures were fabricated by EELM.

  5. Chemical imaging of biological systems with the scanning electrochemical microscope.

    PubMed

    Gyurcsányi, Róbert E; Jágerszki, Gyula; Kiss, Gergely; Tóth, Klára

    2004-06-01

    A brief overview on recent advances in the application of scanning electrochemical microscopy (SECM) to the investigation of biological systems is presented. Special emphasis is given to the mapping of local enzyme activity by SECM, which is exemplified by relevant original systems. PMID:15110274

  6. Handbook of Electrochemical Nanotechnology

    SciTech Connect

    Lin, Yuehe; Nalwa, H. S.

    2009-02-12

    This 2-volume handbook provides an overview of recent advances in the field of electrochemical nanotechnology. It will be of great interst to graduate students, scientists, and engineering professionals whose research is at the interface of electrochemistry and nanotechnology.

  7. Electrochemical heat engine

    DOEpatents

    Elliott, Guy R. B.; Holley, Charles E.; Houseman, Barton L.; Sibbitt, Jr., Wilmer L.

    1978-01-01

    Electrochemical heat engines produce electrochemical work, and mechanical motion is limited to valve and switching actions as the heat-to-work cycles are performed. The electrochemical cells of said heat engines use molten or solid electrolytes at high temperatures. One or more reactions in the cycle will generate a gas at high temperature which can be condensed at a lower temperature with later return of the condensate to electrochemical cells. Sodium, potassium, and cesium are used as the working gases for high temperature cells (above 600 K) with halogen gases or volatile halides being used at lower temperature. Carbonates and halides are used as molten electrolytes and the solid electrolyte in these melts can also be used as a cell separator.

  8. Electrochemical Analysis of Neurotransmitters

    PubMed Central

    Bucher, Elizabeth S.; Wightman, R. Mark

    2016-01-01

    Chemical signaling through the release of neurotransmitters into the extracellular space is the primary means of communication between neurons. More than four decades ago, Ralph Adams and his colleagues realized the utility of electrochemical methods for the study of easily oxidizable neurotransmitters, such as dopamine, norepinephrine, and serotonin and their metabolites. Today, electrochemical techniques are frequently coupled to microelectrodes to enable spatially resolved recordings of rapid neurotransmitter dynamics in a variety of biological preparations spanning from single cells to the intact brain of behaving animals. In this review, we provide a basic overview of the principles underlying constant-potential amperometry and fast-scan cyclic voltammetry, the most commonly employed electrochemical techniques, and the general application of these methods to the study of neurotransmission. We thereafter discuss several recent developments in sensor design and experimental methodology that are challenging the current limitations defining the application of electrochemical methods to neurotransmitter measurements. PMID:25939038

  9. Electrochemical Analysis of Neurotransmitters

    NASA Astrophysics Data System (ADS)

    Bucher, Elizabeth S.; Wightman, R. Mark

    2015-07-01

    Chemical signaling through the release of neurotransmitters into the extracellular space is the primary means of communication between neurons. More than four decades ago, Ralph Adams and his colleagues realized the utility of electrochemical methods for the study of easily oxidizable neurotransmitters, such as dopamine, norepinephrine, and serotonin and their metabolites. Today, electrochemical techniques are frequently coupled to microelectrodes to enable spatially resolved recordings of rapid neurotransmitter dynamics in a variety of biological preparations spanning from single cells to the intact brain of behaving animals. In this review, we provide a basic overview of the principles underlying constant-potential amperometry and fast-scan cyclic voltammetry, the most commonly employed electrochemical techniques, and the general application of these methods to the study of neurotransmission. We thereafter discuss several recent developments in sensor design and experimental methodology that are challenging the current limitations defining the application of electrochemical methods to neurotransmitter measurements.

  10. ELECTROCHEMICAL DEGRADATION OF POLYCHLOROBIPHENYLS

    EPA Science Inventory

    Granular graphite is an ideal conductive material for electrochemical reduction technology applications in the field. Granular graphite was used to enhance the transfer of chlorinated aliphatic compounds in saturated, low permeability soils by electroosmosis. It was also used to ...

  11. Solid state electrochemical composite

    SciTech Connect

    Visco, Steven J.; Jacobson, Craig P.; DeJonghe, Lutgard C.

    2009-06-30

    Provided is a composite electrochemical device fabricated from highly electronically conductive materials such as metals, metal alloys, or electronically conductive ceramics. The electronic conductivity of the electrode substrate is maximized. The invention allows for an electrode with high electronic conductivity and sufficient catalytic activity to achieve high power density in ionic (electrochemical) devices such as fuel cells and electrolytic gas separation systems including oxygen generation system.

  12. Scanning electron microscopy analysis of corrosion degradation on tinplate substrates.

    PubMed

    Zumelzu, E; Cabezas, C; Vera, A

    2003-01-01

    The degradation of electrolytic tinplate used in food containers was analysed and evaluated, using scanning electron microscopy and electrochemical measurements of microcorrosion and ion dissolution by atomic absorption to prevent food contamination caused by metal traces and to increase the durability of such tinplates. PMID:12627896

  13. Genomagnetic Electrochemical Biosensors

    NASA Astrophysics Data System (ADS)

    Wang, Joseph; Erdem, Arzum

    The use of nucleic acid technologies has significantly improved preparation and diagnostic procedures in life sciences. Nucleic acid layers combined with electrochemical or optical transducers produce a new kind of affinity biosensors as DNA Biosensor for small molecular weight molecules. Electrochemical DNA biosensors are attractive devices for converting the hybridization event into an analytical signal for obtaining sequence-specific information in connection with clinical, environmental or forensic investigations. DNA hybridization biosensors, based on electrochemical transduction of hybridization, couple the high specificity of hybridization reactions with the excellent sensitivity and portability of electrochemical transducers. The main goal in all researches is to design DNA biosensors for preparing a basis for the future DNA microarray system. DNA chip has now become a powerful tool in biological research, however the real clinic assay is still under development. Recently, there has been a great interest to the magnetic beads and/or nanoparticles labelled with metals such as gold, cadmium, silver, etc. for designing of novel electrochemical DNA biosensor approaches resulting in efficient separation. The attractive features of this technology include simple approach, rapid results, multi-analyte detection, low-cost per measurument, stable, and non-hazardous reagents, and reduced waste handling. Some of these new approaches and applications of the electrochemical DNA biosensors based on magnetic beads and its combining with nanoparticles labelled with metals are described and discussed.

  14. In situ monitoring of the Li-O2 electrochemical reaction on nanoporous gold using electrochemical AFM.

    PubMed

    Wen, Rui; Byon, Hye Ryung

    2014-03-11

    The lithium-oxygen (Li-O2) electrochemical reaction on nanoporous gold (NPG) is observed using in situ atomic force microscopy (AFM) imaging coupled with potentiostatic measurement. Dense Li2O2 nanoparticles form a film at 2.5 V, which is decomposed at 3.8-4.0 V in an ether-based electrolyte. PMID:24469227

  15. The influence of catalyst layer morphology on the electrochemical performance of DMFC anode

    NASA Astrophysics Data System (ADS)

    Wang, Zhanliang; Liu, Yang; Linkov, Vladimir M.

    The anodes with different morphology for DMFC were prepared, and the influences of the microstructure of anode catalyst layer on their electrochemical performance were investigated by scanning electrochemical microscopy (SECM), scanning electron microscopy (SEM), proton induced X-ray emission (PIXE) and electrochemical methods, respectively. The surface morphology of catalyst layer was observed by SEM, and the elements dispersion status and its distribution of activity intensity on electrode catalyst layer were mapped by PIXE and SECM, respectively. Electrochemical impedance spectroscopy (EIS) and anode polarization experiment were employed to analyze the electrochemical properties of anode. The results reveal that the anode with a relative smooth surface of catalyst layer and less cracks shows good interfacial properties and the lower resistance on the electrode reaction of methanol, and its maximum power of MEA as a single cell was about 178 mW cm -2 at 70 °C.

  16. Reclamation of niobium compounds from ionic liquid electrochemical polishing of superconducting radio frequency cavities

    SciTech Connect

    Wixtrom, Alex I.; Buhler, Jessica E.; Reece, Charles E.; Abdel-Fattah, Tarek M.

    2013-06-01

    Recent research has shown that choline chloride (vitamin B4)-based solutions can be used as a greener alternative to acid-based electrochemical polishing solutions. This study demonstrated a successful method for electrochemical deposition of niobium compounds onto the surface of copper substrates using a novel choline chloride-based ionic liquid. Niobium ions present in the ionic liquid solution were dissolved into the solution prior to deposition via electrochemical polishing of solid niobium. A black coating was clearly visible on the surface of the Cu following deposition. This coating was analyzed using scanning electron microscopy (SEM), electron dispersive X-ray spectroscopy (EDX), atomic force microscopy (AFM), and X-ray fluorescence spectroscopy (XRF). This ionic liquid-based electrochemical deposition method effectively recycles previously dissolved niobium from electrochemical polishing of superconducting radio frequency (SRF) cavities.

  17. Facile and controllable electrochemical reduction of graphene oxide and its applications

    SciTech Connect

    Shao, Yuyan; Wang, Jun; Engelhard, Mark H.; Wang, Chong M.; Lin, Yuehe

    2010-01-01

    Graphene oxide is electrochemically reduced which is called electrochemically reduced graphene oxide (ER-G). ER-G is characterized with scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and X-ray diffraction. The oxygen content is significantly decreased and the sp 2 carbon is restored after electrochemical reduction. ER-G exhibits much higher electrochemical capacitance and cycling durability than carbon nanotubes (CNTs) and chemically reduced graphene; the specific capacitance measured with cyclic voltammetry (20 mV/s) is ~165 F/g, ~86 F/g, and ~100 F/g for ER-G, CNTs, and chemically reduced graphene,1 respectively. The electrochemical reduction of oxygen and hydrogen peroxide was greatly enhanced on ER-G electrodes as compared with CNTs. ER-G has shown a good potential for applications in energy storage, biosensors, and electrocatalysis.

  18. Electrochemical Biosensors - Sensor Principles and Architectures

    PubMed Central

    Grieshaber, Dorothee; MacKenzie, Robert; Vörös, Janos; Reimhult, Erik

    2008-01-01

    Quantification of biological or biochemical processes are of utmost importance for medical, biological and biotechnological applications. However, converting the biological information to an easily processed electronic signal is challenging due to the complexity of connecting an electronic device directly to a biological environment. Electrochemical biosensors provide an attractive means to analyze the content of a biological sample due to the direct conversion of a biological event to an electronic signal. Over the past decades several sensing concepts and related devices have been developed. In this review, the most common traditional techniques, such as cyclic voltammetry, chronoamperometry, chronopotentiometry, impedance spectroscopy, and various field-effect transistor based methods are presented along with selected promising novel approaches, such as nanowire or magnetic nanoparticle-based biosensing. Additional measurement techniques, which have been shown useful in combination with electrochemical detection, are also summarized, such as the electrochemical versions of surface plasmon resonance, optical waveguide lightmode spectroscopy, ellipsometry, quartz crystal microbalance, and scanning probe microscopy. The signal transduction and the general performance of electrochemical sensors are often determined by the surface architectures that connect the sensing element to the biological sample at the nanometer scale. The most common surface modification techniques, the various electrochemical transduction mechanisms, and the choice of the recognition receptor molecules all influence the ultimate sensitivity of the sensor. New nanotechnology-based approaches, such as the use of engineered ion-channels in lipid bilayers, the encapsulation of enzymes into vesicles, polymersomes, or polyelectrolyte capsules provide additional possibilities for signal amplification. In particular, this review highlights the importance of the precise control over the delicate

  19. Materials for electrochemical capacitors.

    PubMed

    Simon, Patrice; Gogotsi, Yury

    2008-11-01

    Electrochemical capacitors, also called supercapacitors, store energy using either ion adsorption (electrochemical double layer capacitors) or fast surface redox reactions (pseudo-capacitors). They can complement or replace batteries in electrical energy storage and harvesting applications, when high power delivery or uptake is needed. A notable improvement in performance has been achieved through recent advances in understanding charge storage mechanisms and the development of advanced nanostructured materials. The discovery that ion desolvation occurs in pores smaller than the solvated ions has led to higher capacitance for electrochemical double layer capacitors using carbon electrodes with subnanometre pores, and opened the door to designing high-energy density devices using a variety of electrolytes. Combination of pseudo-capacitive nanomaterials, including oxides, nitrides and polymers, with the latest generation of nanostructured lithium electrodes has brought the energy density of electrochemical capacitors closer to that of batteries. The use of carbon nanotubes has further advanced micro-electrochemical capacitors, enabling flexible and adaptable devices to be made. Mathematical modelling and simulation will be the key to success in designing tomorrow's high-energy and high-power devices. PMID:18956000

  20. Materials for electrochemical capacitors

    NASA Astrophysics Data System (ADS)

    Simon, Patrice; Gogotsi, Yury

    2008-11-01

    Electrochemical capacitors, also called supercapacitors, store energy using either ion adsorption (electrochemical double layer capacitors) or fast surface redox reactions (pseudo-capacitors). They can complement or replace batteries in electrical energy storage and harvesting applications, when high power delivery or uptake is needed. A notable improvement in performance has been achieved through recent advances in understanding charge storage mechanisms and the development of advanced nanostructured materials. The discovery that ion desolvation occurs in pores smaller than the solvated ions has led to higher capacitance for electrochemical double layer capacitors using carbon electrodes with subnanometre pores, and opened the door to designing high-energy density devices using a variety of electrolytes. Combination of pseudo-capacitive nanomaterials, including oxides, nitrides and polymers, with the latest generation of nanostructured lithium electrodes has brought the energy density of electrochemical capacitors closer to that of batteries. The use of carbon nanotubes has further advanced micro-electrochemical capacitors, enabling flexible and adaptable devices to be made. Mathematical modelling and simulation will be the key to success in designing tomorrow's high-energy and high-power devices.

  1. Pulse electrochemical meso/micro/nano ultraprecision machining technology.

    PubMed

    Lee, Jeong Min; Kim, Young Bin; Park, Jeong Woo

    2013-11-01

    This study demonstrated meso/micro/nano-ultraprecision machining through electrochemical reactions using intermittent DC pulses. The experiment focused on two machining methods: (1) pulse electrochemical polishing (PECP) of stainless steel, and (2) pulse electrochemical nano-patterning (PECNP) on a silicon (Si) surface, using atomic force microscopy (AFM) for fabrication. The dissolution reaction at the stainless steel surface following PECP produced a very clean, smooth workpiece. The advantages of the PECP process included improvements in corrosion resistance, deburring of the sample surface, and removal of hydrogen from the stainless steel surface as verified by time-of-flight secondary-ion mass spectrometry (TOF-SIMS). In PECNP, the electrochemical reaction generated within water molecules produced nanoscale oxide textures on a Si surface. Scanning probe microscopy (SPM) was used to evaluate nanoscale-pattern processing on a Si wafer surface produced by AFM-PECNP For both processes using pulse electrochemical reactions, three-dimensional (3-D) measurements and AFM were used to investigate the changes on the machined surfaces. Preliminary results indicated the potential for advancing surface polishing techniques and localized micro/nano-texturing technology using PECP and PECNP processes. PMID:24245325

  2. Morphology dependent electrochemical performance of sputter deposited Sn thin films

    SciTech Connect

    Nimisha, C.S.; Venkatesh, G.; Rao, K. Yellareswara; Rao, G. Mohan; Munichandraiah, N.

    2012-08-15

    Graphical abstract: Smooth homogenous anode surface results in better electrochemical performance in terms of capacity and cycle life. Highlights: ► Controlling rate of deposition of Sn thin films for different surface morphology. ► Higher deposition rate results in poor capacity retention. ► Lower deposition rate of 0.25 nm s{sup −1} helps in higher capacity retention. ► Electrochemical performance correlated homogeneity and interparticle contact area. -- Abstract: This study deals with tailoring of the surface morphology, microstructure, and electrochemical properties of Sn thin films deposited by magnetron sputtering with different deposition rates. Scanning electron microscopy and atomic force microscopy are used to characterize the film surface morphology. Electrochemical properties of Sn thin film are measured and compared by cyclic voltammetry and charge–discharge cycle data at a constant current density. Sn thin film fabricated with a higher deposition rate exhibited an initial discharge capacity of 798 mAh g{sup −1} but reduced to 94 mAh g{sup −1} at 30th cycle. Film deposited with lower deposition rate delivered 770 mAh g{sup −1} during 1st cycle with improved capacity retention of 521 mAh g{sup −1} on 30th cycle. Comparison of electrochemical performances of these films has revealed important distinctions, which are associated with the surface morphology and hence on rate of deposition.

  3. A Comprehensive Pitting Study of High Velocity Oxygen Fuel Inconel 625 Coating by Using Electrochemical Testing Techniques

    NASA Astrophysics Data System (ADS)

    Niaz, Akbar; Khan, Sajid Ullah

    2016-01-01

    In the present work, Inconel 625 was coated on a mild steel substrate using a high velocity oxygen fuel coating process. The pitting propensity of the coating was tested by using open circuit potential versus time, potentiodynamic polarization, electrochemical potentiokinetic reactivation, and scanning electrochemical microscopy. The pitting propensity of the coating was compared with bulk Inconel 625 alloy. The results confirmed that there were regions of different electrochemical activities on the coating which have caused pitting corrosion.

  4. Separators for electrochemical cells

    SciTech Connect

    Carlson, Steven Allen; Anakor, Ifenna Kingsley

    2014-11-11

    Provided are separators for use in an electrochemical cell comprising (a) an inorganic oxide and (b) an organic polymer, wherein the inorganic oxide comprises organic substituents. Preferably, the inorganic oxide comprises an hydrated aluminum oxide of the formula Al.sub.2O.sub.3.xH.sub.2O, wherein x is less than 1.0, and wherein the hydrated aluminum oxide comprises organic substituents, preferably comprising a reaction product of a multifunctional monomer and/or organic carbonate with an aluminum oxide, such as pseudo-boehmite and an aluminum oxide. Also provided are electrochemical cells comprising such separators.

  5. Electrochemical micro sensor

    DOEpatents

    Setter, Joseph R.; Maclay, G. Jordan

    1989-09-12

    A micro-amperometric electrochemical sensor for detecting the presence of a pre-determined species in a fluid material is disclosed. The sensor includes a smooth substrate having a thin coating of solid electrolytic material deposited thereon. The working and counter electrodes are deposited on the surface of the solid electrolytic material and adhere thereto. Electrical leads connect the working and counter electrodes to a potential source and an apparatus for measuring the change in an electrical signal caused by the electrochemical oxidation or reduction of the species. Alternatively, the sensor may be fabricated in a sandwich structure and also may be cylindrical, spherical or other shapes.

  6. Electrochemical Membrane Incinerator

    SciTech Connect

    Johnson, Dennis C.; Houk, Linda L.; Feng, Jianren

    1998-12-08

    Electrochemical incineration of benzoquinone was evaluated as a model for the mineralization of carbon in toxic aromatic compounds. A Ti or Pt anode was coated with a film of the oxides of Ti, Ru, Sn and Sb. This quaternary metal oxide film was stable; elemental analysis of the electrolyzed solution indicated the concentration of these metal ions to be 3 {micro}g/L or less. The anode showed good reactivity for the electrochemical incineration of benzoquinone. The use of a dissolved salt matrix as the so-called ''supporting electrolyte'' was eliminated in favor of a solid-state electrolyte sandwiched between the anode and cathode.

  7. Electrochemical membrane incinerator

    DOEpatents

    Johnson, Dennis C.; Houk, Linda L.; Feng, Jianren

    2001-03-20

    Electrochemical incineration of p-benzoquinone was evaluated as a model for the mineralization of carbon in toxic aromatic compounds. A Ti or Pt anode was coated with a film of the oxides of Ti, Ru, Sn and Sb. This quaternary metal oxide film was stable; elemental analysis of the electrolyzed solution indicated the concentration of these metal ions to be 3 .mu.g/L or less. The anode showed good reactivity for the electrochemical incineration of benzoquinone. The use of a dissolved salt matrix as the so-called "supporting electrolyte" was eliminated in favor of a solid-state electrolyte sandwiched between the anode and cathode.

  8. Engineering electrochemical capacitor applications

    NASA Astrophysics Data System (ADS)

    Miller, John R.

    2016-09-01

    Electrochemical capacitor (EC) applications have broadened tremendously since EC energy storage devices were introduced in 1978. Then typical applications operated below 10 V at power levels below 1 W. Today many EC applications operate at voltages approaching 1000 V at power levels above 100 kW. This paper briefly reviews EC energy storage technology, shows representative applications using EC storage, and describes engineering approaches to design EC storage systems. Comparisons are made among storage systems designed to meet the same application power requirement but using different commercial electrochemical capacitor products.

  9. Electrochemical fabrication of capacitors

    DOEpatents

    Mansour, Azzam N.; Melendres, Carlos A.

    1999-01-01

    A film of nickel oxide is anodically deposited on a graphite sheet held in osition on an electrochemical cell during application of a positive electrode voltage to the graphite sheet while exposed to an electrolytic nickel oxide solution within a volumetrically variable chamber of the cell. An angularly orientated x-ray beam is admitted into the cell for transmission through the deposited nickel oxide film in order to obtain structural information while the film is subject to electrochemical and in-situ x-ray spectroscopy from which optimum film thickness, may be determined by comparative analysis for capacitor fabrication purposes.

  10. Electrochemical fabrication of capacitors

    SciTech Connect

    Mansour, A.N.; Melendres, C.A.

    1999-12-14

    A film of nickel oxide is anodically deposited on a graphite sheet held in position on an electrochemical cell during application of a positive electrode voltage to the graphite sheet while exposed to an electrolytic nickel oxide solution within a volumetrically variable chamber of the cell. An angularly orientated x-ray beam is admitted into the cell for transmission through the deposited nickel oxide film in order to obtain structural information while the film is subject to electrochemical and in-situ x-ray spectroscopy from which optimum film thickness, may be determined by comparative analysis for capacitor fabrication purposes.