Scanning Electrochemical Microscopy Tip Research Articles

Scanning electrochemical microscopy for the investigation of corrosion processes: Measurement of Zn 2+ spatial distribution with ion selective microelectrodes

Ion-selective microelectrodes can be employed as tips in scanning electrochemical microscopy (SECM) for chemical imaging of corrosion processes. They present higher chemical selectivity than conventional amperometric microdisks, and may be the only effective option to visualize the dissolution of metals with negative redox potentials in aqueous environments when the use of Pt microelectrodes is limited by the onset of oxygen reduction and hydrogen evolution reactions. A robust micro-sized ion selective electrode has been developed which allows the spatial distribution of Zn 2+ during galvanic corrosion of a model Fe/Zn couple to be investigated using SECM. Owing to the low internal contact potential achieved with the novel design, the resistance of the micropipette electrodes is only fractions of the resistance of conventional micropipette electrodes of the same size. As a result, no special shielding of the microelectrodes is required and higher scanning rate can be used for scanning in the potentiometric modes using these micropipette tips. Concentration profiles over corroding surfaces measured with this technique will be presented.

Visualization of Chlorine Evolution at Dimensionally Stable Anodes by Means of Scanning Electrochemical Microscopy

Scanning electrochemical microscopy (SECM) has been used to detect and visualize the local electrocatalytic activity of dimensionally stable anodes (DSA) for Cl(2) evolution from brine. The sample generation-tip collection (SG-TC) mode of SECM shows limitations arising from complications connected with the reduction of Cl(2) at the SECM tip due to the presence of a significant amount of nondissolved Cl(2) gas. Because only dissolved Cl(2) can be electrochemically reduced at the tip, a large amount of the Cl(2) gas which is produced at active spots of the DSA is not detected. Additionally, a decrease of the cathodic current at the tip may occur owing to the adhesion of gas bubbles and blocking of the electrode surface. To overcome this limitation, the redox competition mode of SECM was extended and applied to the local visualization of Cl(2) evolution from highly concentrated brine solutions. High concentrations of Cl(2) produced at the sample can cause inhibition of the same reaction at the tip by accumulation of Cl(2) in the proximity of the SECM tip. In this way the tip current is decreased, which can be used as a measure for the catalytic activity of the sample underneath the tip.

Surface Reactivity from Electrochemical Lithography: Illustration in the Steady-State Reductive Etching of Perfluorinated Surfaces

The scanning electrochemical microscope (SECM) in the lithographic mode is used to assess quantitatively, from both theoretical and experimental points of view, the kinetics of irreversible transformation of electroactive molecular moieties immobilized on a surface as self-assembled monolayers (SAMs). The SECM tip allows the generation of an etchant that transforms the surface locally and irreversibly. The resulting surface patterning is detectable by different surface analyses. The quantification of the surface transformation kinetics is deduced from the evolution of the pattern dimensions with the etching time. The special case of slow etching kinetics is presented; it is predicted that the pattern evolution follows the expansion of the etchant at the substrate surface. The case of a chemically unstable etchant is considered. The model is then tested by inspecting the slow reductive patterning of a perfluorinated SAM. Good agreement is found with different independent SECM interrogation modes, depending on the insulating or conducting nature of the covered substrate. The surface transformation measurements are also compared to the reduction of solutions of perfluoroalkanes. The three-orders-of-magnitude-slower electron transfer observed at the immobilized molecules likely describes the large reorganization associated with the generation of a perfluoroalkyl-centered radical anion.

A new AC-SECM mode: On the way to high-resolution local impedance measurements in SECM

Scanning electrochemical microscopy (SECM) is frequently employed to detect local chemical activity of inhomogeneous samples. Here, a modified AC-SECM mode is proposed for detecting perturbations of concentration gradients of a redox couple and electric fields imposed by the local electrochemical activity of the sample while simultaneously recording the overall impedance of the sample. The method is based on an alternating current-perturbation of the sample while recording the local alternate potential of the positioned SECM tip. The low frequency part is predominantly determined by the spatial changes in the electrochemical activity of the sample. The proposed method is intrinsically not limited by the tip size and is hence able to substantially increase the resolution of local impedance measurements.

Iodide/triiodide electrochemistry in ionic liquids: Effect of viscosity on mass transport, voltammetry and scanning electrochemical microscopy

The electrochemistry of I −/I 3 − was studied in ionic liquids using a combination of cyclic voltammetry, chronoamperometry and scanning electrochemical microscopy (SECM). The electrolytes were 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide [C n C 1Im][Tf 2N], ionic liquids (where n = 2, 4 and 8) and I − was typically added at a concentration of approximately 11 mM. During cyclic voltammetry, two sets of peaks were observed in each ionic liquid due to oxidation and reduction of the I −/I 3 − redox couple and oxidation/reduction of the I 3 −/I 2 redox couple. The diffusion coefficients of I − and I 3 −, as determined using chronoamperometry, increased with increasing temperature and decreased with increasing ionic liquid viscosity. The effect of ionic liquid viscosity on ultramicroelectrode (UME) voltammetry was also determined using the I −/I 3 − redox couple. Steady-state behaviour was observed at 1.3 μm UMEs at slow voltammetric scan rates and steady-state SECM feedback approach curves were also obtained at a 1.3 μm Pt SECM tips, provided that the tip approach speed was sufficiently low.

On the diffusion of ferrocenemethanol in room-temperature ionic liquids: an electrochemical study

The electrochemical behaviour of ferrocenemethanol (FcMeOH) has been studied in a range of room-temperature ionic liquids (RTILs) using cyclic voltammetry, chronoamperomery and scanning electrochemical microscopy (SECM). The diffusion coefficient of FcMeOH, measured using chronoamperometry, decreased with increasing RTIL viscosity. Analysis of the mass transport properties of the RTILs revealed that the Stokes-Einstein equation did not apply to our data. The "correlation length" was estimated from diffusion coefficient data and corresponded well to the average size of holes (voids) in the liquid, suggesting that a model in which the diffusing species jumps between holes in the liquid is appropriate in these liquids. Cyclic voltammetry at ultramicroelectrodes demonstrated that the ability to record steady-state voltammograms during ferrocenemethanol oxidation depended on the voltammetric scan rate, the electrode dimensions and the RTIL viscosity. Similarly, the ability to record steady-state SECM feedback approach curves depended on the RTIL viscosity, the SECM tip radius and the tip approach speed. Using 1.3 μm Pt SECM tips, steady-state SECM feedback approach curves were obtained in RTILs, provided that the tip approach speed was low enough to maintain steady-state diffusion at the SECM tip. In the case where tip-induced convection contributed significantly to the SECM tip current, this effect could be accounted for theoretically using mass transport equations that include diffusive and convective terms. Finally, the rate of heterogeneous electron transfer across the electrode/RTIL interface during ferrocenemethanol oxidation was estimated using SECM, and k(0) was at least 0.1 cm s(-1) in one of the least viscous RTILs studied.

Uses of scanning electrochemical microscopy for the characterization of thin inhibitor films on reactive metals: The protection of copper surfaces by benzotriazole

Scanning electrochemical microscopy (SECM) was used to study the film formation of benzotriazole towards corrosion of copper. SECM was operated in the feedback mode by using ferrocene–methanol as redox mediator, and the sample was left unbiased at all times to freely attain its open circuit potential in the test environment. Following exposure to aggressive electrolytes the anticorrosion abilities of the layers were characterized by image analysis and by an electrochemical method derived from the experimental approach curves. Changes in the shape of the approach curves were clearly observed during the inhibitor film formation process. They showed the transition from an active conducting behaviour towards ferrocinium reoxidation typical of unprotected copper, to a surface exhibiting insulating characteristics when the metal was covered by a surface film containing the inhibitor. This supports that SECM is a practical technique in the investigation of corrosion inhibitor performance. However, a consistent tendency for the characterization of inhibitor film formation using SECM measurements in the positive feedback mode for the copper-benzotriazole system was only found if the experiments were conducted when the inhibitor molecule was not present in the test solution. That is, inhibitor molecules were found to interact not only with the copper surface during the monitoring process, but with the SECM tip as well, this effect being significantly enhanced when chloride ions were present in the electrolyte. Finally, a procedure to image the chemical activity of copper surfaces partially covered with the inhibitor film with SECM is proposed.

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

We report on the application of scanning electrochemical microscopy (SECM) to 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 the 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.

Pt−Ag Catalysts as Cathode Material for Oxygen-Depolarized Electrodes in Hydrochloric Acid Electrolysis

Pt-Ag nanoparticles were prepared on a glassy carbon (GC) surface by pulsed electrodeposition and tested using cyclic voltammetry and scanning electrochemical microscopy (SECM) with respect to their possible use as catalyst material for oxygen reduction in 400 mM HCl solution. For comparison, a Pt catalyst was investigated under similar conditions. The redox competition mode of scanning electrochemical microscopy (RC-SECM) was adapted to the specific conditions caused by the presence of Cl(-) ions and used to visualize the local catalytic activity of the Pt-Ag deposits. Similarly prepared Pt deposits were shown to dissolve underneath the SECM tip. Pt-Ag composites showed improved long-term stability toward oxygen reduction as compared with Pt even under multiple switching off to open-circuit potential in 400 mM HCl.

Scanning electrochemical microscopy assay of DNA based on hairpin probe and enzymatic amplification biosensor

A novel scheme for scanning electrochemical microscopy (SECM) assay of DNA based on hairpin probe and enzymatic amplification biosensor was described. In this method, streptavidin–horseradish peroxidase (HRP) was captured by double-stranded DNA (ds-DNA) modified gold substrate via biotin–streptavidin interaction after hybridization of target DNA to the immobilized hairpin probe functioned with a biotin at its 3′ end. In the presence of H 2O 2, hydroquinone (H 2Q) was oxidized to benzoquinone (BQ) at the modified substrate surface through the HRP catalytic reaction, and the generated BQ corresponding to the amount of target DNA was reduced in solution by a SECM tip. The resulting reduction current allowed concentration detection of target DNA and SECM imaging of hybridization between the target DNA and the immobilized hairpin probe. The detection limit of this method was as low as 17 pM for complementary target DNA and it had good selectivity to discriminate between the complementary sequence and one containing base mismatches.

Galvanic coupling between copper and aluminium in a thin-layer cell

The Al/Cu coupling was investigated in a thin-layer cell formed by a large Cu electrode and an Al microelectrode embedded in an insulator placed above the Cu electrode. By using a scanning electrochemical microscope (SECM) the thickness of the thin layer was perfectly controlled with a precision in the micrometer range. A copper deposit on an electrochemical quartz crystal microbalance (EQCM) was also used as SECM substrate to quantify the copper dissolution rate. It was shown that such an experimental set-up allows to mimic the galvanic corrosion of intermetallic particles embedded in the aluminium matrix of the 2XXX series aluminium alloys. The combination of the SECM and the EQCM permitted the evaluation of the corrosion rate of copper at the corrosion potential of the 2024 Al alloy, whereas cyclic voltammetry performed on the SECM tip indicated the enrichment in Cu 2+ ions in the thin electrolyte layer.

Characterization of metal-supported Al 2O 3 thin films by scanning electrochemical microscopy

In this paper, physiochemical properties of amorphous alumina thin films, grown by the metal organic chemical vapour deposition process on the surface of platinum (Pt/Al 2O 3) and stainless steel (SS/Al 2O 3), were investigated in aqueous media. The study was performed by the use of scanning electrochemical microscopy (SECM), which allowed obtaining information on uniformity, topography and chemical stability/reactivity of the alumina coatings with high spatial resolution. In particular, the effects due to local acid, base and fluoride ions attack on alumina layers of thickness of about 250 nm (in the Pt/Al 2O 3 sample) and 1000 nm (in the SS/Al 2O 3 sample) were investigated. In the acid and base attack, high concentrations of H 2SO 4 and KOH were electrogenerated locally by the use of a 25 μm diameter platinum microelectrode. The latter was also used as SECM tip to monitor the chemical effect on the alumina layers. It was found that, regardless of the thickness of the film, alumina provided good resistance against local attack of concentrated H 2SO 4; instead, the film dissolved when subjected to KOH attack. The dissolution rate depended on several experimental parameters, such as SECM-tip to substrate distance, electrolysis time and alumina film thickness. The alumina layer proved also relatively poor resistance to etching in 0.1 M NaF solutions.

Adsorbed protein detection by scanning electrochemical microscopy

A scanning electrochemical microscopy (SECM) protein detection methodology has been developed based on the tagging of free cysteines and other nucleophiles in proteins and peptides by benzoquinone. The tagged proteins are detected by the mediated reduction of benzoquinone with a redox species produced electrochemically at the SECM tip. After careful optimization, a sensitivity in the low ng mm −2 range was reached for bovine serum albumin. One of the major advantages of the present technique is that the selectivity of the protein tagging can be tuned by changing the pH of the reaction media. Depending on the requirements, cysteine selective or general detection can therefore be achieved with a high sensitivity. As a proof of concept, this technique was applied to the detection of protein spots and to the imaging of human fingerprints and further compared to the actual SECM state-of-art approach.

Electrocatalytic Activity of Pd−Co Bimetallic Mixtures for Formic Acid Oxidation Studied by Scanning Electrochemical Microscopy

The electrochemical oxidation of formic acid was studied by the tip generation-substrate collection (TG-SC) mode of scanning electrochemical microscopy (SECM), extending the number of applications of SECM in electrocatalysis. Formic acid was generated at a Hg on Au ultramicroelectrode (UME) tip by reduction of CO(2) in a 0.1 M KHCO(3) solution saturated with this gas. The electrocatalytic activity of different Pd-Co bimetallic compositions was evaluated using a Pd-Co electrocatalyst array formed by spots deposited onto glassy carbon (GC) as a SECM substrate. The SECM tip, which generated a constant formic acid flux, was scanned above the array and the oxidation current generated when formic acid was collected by active electrocatalytic spots was displayed as a function of tip position. This generated a SECM image that showed the electrocatalytic activity of each spot. SECM screening identified Pd(50)Co(50) (Pd/Co = 50:50, atomic ratio) as a better electrocatalyst toward the formic acid oxidation than pure Pd or Pt in 0.1 M KHCO(3) solution and this result was confirmed by cyclic voltammetry. Positive feedback was observed for the most active compositions of Pd-Co which suggests fast reaction kinetics and chemical reversibility during the oxidation of formic acid to CO(2). Moreover this feedback increases the contrast between active and non-active spots in this imaging mode.

Spatially Resolved Detection of a Nanometer-Scale Gap by Scanning Electrochemical Microscopy

Nanowires with nanometer-scale gaps are an emerging class of nanomaterials with potential applications in electronics and optics. Here, we demonstrate that the feedback mode of scanning electrochemical microscopy (SECM) allows for spatially resolved detection of a nanogap on the basis of its electrical conductivity. A gapped nanoband is used as a model system to describe a mechanism of a unique feedback effect from a nanogap. Interestingly, both experiments and numerical simulations confirm that a peak current response is obtained when an SECM tip is laterally scanned above an insulating nanogap formed in an unbiased nanoband. On the other hand, no peak current response is expected for a highly conductive nanogap, which must be extremely narrow or filled with highly conductive molecules for efficient electron transport.

Imaging Biocatalytic Activity of Enzyme−Polymer Spots by Means of Combined Scanning Electrochemical Microscopy/Electrogenerated Chemiluminescence

The purpose of this study was to develop a scanning electrochemical microscopy (SECM) and scanning electrogenerated chemiluminescence (SECL) setup to visualize the localized enzymatic activity using glucose oxidase as a model. Combination of SECM and electrogenerated chemiluminescence (ECL) was made possible by integrating a photomultiplier tube (PMT) within a SECM setup which is mounted on top of an inverted microscope. An enzyme-polymer spot formed on a glass slide and placed on top of the entrance window of the PMT was used as a model sample to evaluate the potential of the combined SECM/ECL setup. Hydrogen peroxide, which was locally generated by the glucose oxidase (GOx)-catalyzed reaction, reacted with oxidized luminol which was simultaneously electrochemically generated at the positioned SECM electrode tip. By using the phase-sensitive lock-in amplifier, the potential applied to the SECM tip was sinusoidally swept to invoke an associated oscillation of the ECL. Thus, sensitivity of SECL could be substantially enhanced. Images of the local immobilized enzyme activity obtained both by ECL and generator/collector (GC) mode of SECM were compared to elucidate the pathway in which the SECM and SECL signals are generated.

Local Modulation of the Redox State of p‐Nitrothiophenol Self‐Assembled Monolayers Using the Direct Mode of Scanning Electrochemical Microscopy

Local reduction of the terminating nitro groups of a p-nitrothiophenol self-assembled monolayer (SAM) under formation of either hydroxylamine or amino groups is invoked using the direct mode of scanning electrochemical microscopy (SECM). By choosing the appropriate potential and a potential pulse sequence, the reduction of the SAM end groups to the desired oxidation state can be achieved, locally restricted to the area of the sample surface directly underneath the positioned SECM tip. Following the "writing" of redox microstructures within the SAM end groups, the local modification of the redox states is visualized ("reading") by using the feedback mode of SECM. The current at the Pt tip electrode is determined by the electron-transfer rate for reoxidation of the redox mediator at the sample surface. Thus, heterogeneities in the SAM surface, which are caused by local differences in the redox state of the end groups, are distinguishable due to the different electron-transfer rates governed by the redox state of the SAM end groups. To further unequivocally prove the successful local modification of the redox state of the SAM end groups during the writing process, the micropatterned surface is selectively modified with biotin at areas with reduced SAM end groups for further complementary binding of an avidin-enzyme conjugate. Selective post-functionalization with an avidin-alkaline phosphatase conjugate allows visualization of the microstructure using the generator-collector mode of SECM.

Optimization of an Electrochemical DNA Assay by Using a 48‐Electrode Array and Redox Amplification Studies by Means of Scanning Electrochemical Microscopy

Sensible DNA: An electrochemical DNA assay based on specific Salmonella spp. capture probes and enzyme labeling with alkaline phosphatase was optimized by using a 48-electrode microarray and scanning electrochemical microscopy (SECM). SECM was further used to evaluate potential amplification strategies due to redox cycling. Due to insufficient detection limits and selectivity, electrochemical DNA sensors are not yet used as everyday tools in diagnostics. Here, we present an electrochemical DNA assay that is based on specific Salmonella spp. capture probes. Our optimization strategies and the specific features of related electrochemical DNA sensor arrays, which are comprised of a chip with 48 gold electrodes, are also described. A ssDNA monolayer is formed by chemisorption of the thiol-modified capture strand on the different gold electrodes of the array after spotting with a needle spotter. The assay parameters were optimized for the use of minimum amounts of sample and reagents and short assay times. Scanning electrochemical microscopy (SECM) has been used to visualize the local activity of an enzyme label used for amplified hybridization detection at high lateral resolution. The potential of SECM to further amplify the sensor signal by means of redox cycling is demonstrated by using single-stranded DNA capture probe modified gold microelectrodes as SECM tips. The detection limit of the proposed DNA sensor is shown to be in the femtomolar range without redox cycling amplification.

Detection of DNA π-Stack Lesions Using Scanning Electrochemical Microscopy

The Scanning electrochemical microscopy (SECM) is used to selectively detect intervening mismatches and abasic sites within monolayers of ds-DNA self-assembled onto gold electrodes. The electrocatalytic cycle involving oxidation of leucomethylene blue (LB), an electrochemically reduced form of methylene blue intercalated within the ds-DNA monolayer self-assembled on gold electrode, by the SECM tip-generated ferricyanide allows regeneration of LB via long-range heterogenous electron transfer mediated by the DNA π-stack. Monolayers featuring disruptions in the DNA π-stack via a single-base mismatch or abasic site exhibit strongly attenuated methylene blue electrochemistry within the DNA film leading to a disruption of the catalytic cycle, thereby diminishing the SECM tip current. The inherent differences in catalytic tip currents can be used to distinguish monolayer domains containing native ds-DNA versus ds-DNA containing π-stack lesions within the micron-level lateral spatial resolution of SECM.

Nanoscale Imaging of Surface Topography and Reactivity with the Scanning Electrochemical Microscope

Over the last 2 decades, scanning electrochemical microscopy (SECM) has been extensively employed for topographic imaging and mapping surface reactivity on the micrometer scale. We used flat, polished nanoelectrodes as SECM tips to carry out feedback mode imaging of various substrates with nanoscale resolution. Constant-height and constant-current images of plastic and Au compact disc surfaces and more complicated objects (computer chips and wafers) were obtained. The possibility of simultaneous imaging of surface topography and electrochemical reactivity was demonstrated. Very fast mass transfer at nanoelectrodes allowed us to obtain high-quality electrochemical images in viscous media under steady-state conditions, e.g., in 1-methyl-3-octylimidazolium-bis(tetrafluoromethylsulfonyl)imide (C(8)mimC(1)C(1)N) ionic liquid. Ion-transfer-based imaging was also performed using nanopipets as SECM tips.