Calibration-Free Analysis with Chronoamperometry at Microelectrodes.

Analytical methods are crucial for monitoring and assessing the concentration of important chemicals, and there is now a growing demand for methodologies that allow miniaturization, require lower sample volumes, and enable real-time analysis in the field. Most electroanalytical techniques depend on calibrations or standards, and this has several limitations, ranging from matrix interference, to stability problems, time required, cost and waste. Therefore, strategies that do not require standards or calibration curves greatly interest the analytical chemistry community. Here, we propose a new quantification method that does not rely on calibration and is only based on a single chronoamperometric curve recorded with a microelectrode. We show that satisfactory analytical information is obtained with just one chronoamperometric experiment that only takes a few seconds. We propose different data treatments to determine the unknown concentration, we consider the experimental conditions and instrument parameters, we report how parallel reactions affect the results, and we recommend procedures to implement the method in autonomous sensors. We also show that the concentration of several species can be derived if their E° values are sufficiently far apart or the sum of all concentrations if the E° values are too close. The proposed method was validated with a model redox system then further evaluated by determining ascorbic acid concentrations in standard solutions and food supplements, and paracetamol in a pain killer. The results for ascorbic acid were compared with those obtained by coulometry, and a good agreement was found, with a maximum deviation ca. 10.8%. The approach was also successfully applied to ascorbic acid quantification in solutions with different viscosity using ethylene glycol as a thickener.

Spatio-temporal detachment of homogeneous electron transfer in controlling selectivity in mediated organic electrosynthesis.

In electrosynthesis, electron transfer (ET) mediators are normally chosen such that they are more easily reduced (or oxidised) than the substrate for cathodic (or anodic) processes; setting the electrode potential to the mediator therefore ensures selective heterogeneous ET with the mediator at the electrode, rather than the substrate. The current work investigates the opposite, and counter intuitive, situation for a successful mediated electroreductive process where the mediator (phenanthrene) has a reduction potential that is negative to that of the substrate, and the cathode potential is set negative to both (Eele < EM < Es). Simulations reveal a complex interplay between mass transport, the relative concentrations of the mediator and substrate as well as the heterogeneous and homogeneous rate constants for multiple steps, which under suitable conditions, leads to separation of the homogeneous chemistry in a reaction layer detached from the electrode. Reaction layer detachment is a spatio-temporal effect arising due to opposing fluxes of the mediator radical anion M˙- and the substrate 1, which ultimately prevents 1 from reaching the electrode, thereby affording a different reaction pathway. Simulations representative of unstirred batch (1D) and flow (2D) electrolysis are presented, which qualitatively reproduce the experimental selectivity outcomes for mediated and unmediated electroreductive cyclisation of aryl iodide 1. The potential to use highly reducing homogeneous ET agents, possessing reduction potentials beyond those of the substrates, offers exciting opportunities in mediated electrosynthesis.

Cathodic Radical Cyclisation of Aryl Halides Using a Strongly-Reducing Catalytic Mediator in Flow.

Electro-reductive radical cyclisation of aryl halides affords the corresponding hetero- and carbo-cycles in an undivided flow reactor equipped with steel and carbon electrodes using an organic mediator. A dissolving metal anode is not needed, and the mediator can be employed in a sub-stoichiometric amount (0.05 equiv), increasing the practical utility of cathodic radical cyclisation. The methodology is applied to O-, N-, and C-tethers, yielding tricyclic fused and spiro systems. In the absence of mediator, the major pathway is hydrogenolysis of the C-X bond, a 2 e- process occurring at the cathode. Predominance of the radical pathway in presence of a strongly reducing mediator (M) is consistent with homogeneous electron-transfer in a reaction layer detached from the cathode surface, where the flux of M.- leaving the electrode is such that little aryl halide reaches the cathode.

The in situ electrochemical detection of microbubble oscillations during motion through a channel.

Bubble oscillation has many applications, from driving local fluid motion to cleaning. However, in order to exploit their action, a full understanding of this motion, particularly in confined spaces (such as crevices etc. which are important in ultrasonic decontamination) is important. To this end, here we show how a Coulter counter can be used to characterize microbubbles produced through the ultrasonication of electrolytes. These microbubbles are shown to exist in relatively high concentrations while bubble activity is driven by ultrasound. Detection of these microbubbles, and their oscillatory behaviour, is achieved via translocation through a cylindrical glass microchannel (GMC). The microbubbles oscillate within the 40 µm channel employed and this behaviour is observed to change over the translocation period. This is attributed to the acoustic environment present or changes to the physical conditions in the interior of the chamber compared to the exterior. High-speed imaging confirms the presence of microbubbles as they move or 'skate' across the surface of the structures present before translocating through the channel. The observations are useful as they show that microbubble oscillation occurs within small structures, is preceded by surface confined bubbles and could be enhanced through pressure driven flow through a structure.

Nanostructured Pd hydride microelectrodes: in situ monitoring of pH variations in a porous medium.

In this study we report the exceptional potentiometric properties of pH microprobes made with nanostructured palladium hydride microelectrodes and demonstrate their application by monitoring pH variations resulting from a reaction confined in a porous medium. Their potentiometric response was found to be reproducible and stable over several hours but primarily Nernstian over a remarkably wide pH range, including alkaline conditions up to pH 14. Continuous operation was demonstrated by reloading hydrogen at regular intervals to maintain the correct hydride composition thereby alleviating the need for calibration. These properties were validated by detecting pH transients during the carbonation of Ca(OH)2 within a fibrous mesh. Experimental pHs recorded in situ were in excellent agreement with theoretical calculations for the CO2 partial pressures considered. Results also showed that the electrodes were sufficiently sensitive to differentiate between the formation of vaterite and calcite, two polymorphs of CaCO3. These nanostructured microelectrodes are uniquely suited to the determination of pH in highly alkaline solutions, particularly those arising from interfacial reactions at solid and porous surfaces and are thus highly appropriate as pH sensing tips in scanning electrochemical microscopy.

Sampled-current voltammetry at microdisk electrodes: kinetic information from pseudo steady state voltammograms.

In sampled-current voltammetry (SCV), current transients acquired after stepping the potential along the redox wave of interest are sampled at a fixed time to produce a sigmoidal current-potential curve akin to a pseudo steady state voltammogram. Repeating the sampling for different times yields a family of sampled-current voltammograms, one for each time scale. The concept has been used to describe the current-time-potential relationship at planar electrodes but rarely employed as an electroanalytical method except in normal pulse voltammetry where the chronoamperograms are sampled once to produce a single voltammogram. Here we combine the unique properties of microdisk electrodes with SCV and report a simple protocol to analyze and compare the microdisk sampled-current voltammograms irrespective of sampling time. This is particularly useful for microelectrodes where cyclic voltammograms change shape as the mass transport regime evolves from planar diffusion at short times to hemispherical diffusion at long times. We also combine microdisk sampled-current voltammetry (MSCV) with a conditioning waveform to produce voltammograms where each data point is recorded with the same electrode history and demonstrate that the waveform is crucial to obtaining reliable sampled-current voltammograms below 100 ms. To facilitate qualitative analysis of the voltammograms, we convert the current-potential data recorded at different time scales into a unique sigmoidal curve, which clearly highlights kinetic complications. To quantitatively model the MSCVs, we derive an analytical expression which accounts for the diffusion regime and kinetic parameters. The procedure is validated with the reduction of Ru(NH3)6(3+), a model one electron outer sphere process, and applied to the derivation of the kinetic parameters for the reduction of Fe(3+) on Pt microdisks. The methodology reported here is easily implemented on computer controlled electrochemical workstations as a new electroanalytical method to exploit the unique properties of microelectrodes, in particular at short times.

Film before aggregates: an operando GISAXS study on electrochemically assisted surfactant assembly.

The process of electrochemically assisted surfactant assembly was followed in real time by grazing incidence small angle X-ray scattering with the aim to deconvolute the formation of mesoporous silica film and unwanted porous particles. The X-ray technique proved to be useful for the characterisation of this process, as it takes place at a very dynamic, solid/liquid interface. This paper shows the electrochemically driven onset and evolution of silica/surfactant structures. Additional control experiments indicate the formation of vertically aligned structures without the use of an electric field, although it seems to be beneficial for increased pore ordering.

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

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 ß and α phases (OCP(ß→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(ß→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.

Electrochemical current-sensing atomic force microscopy in conductive solutions.

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.

Gold-gold junction electrodes:the disconnection method.

The formation of gold-gold junction electrodes for application in electroanalysis is described here based on electro-deposition from a non-cyanide gold plating bath. Converging growth of two hemispherical gold deposits on two adjacent platinum microelectrodes (both 100 µm diameter in glass, ca. 45 µm gap) followed by careful etching in aqueous chloride solution was employed. During growth both gold hemispheres "connect" and during etching "disconnection" is evident in a drop in current. Gold-gold junctions with sub-micron gaps are formed and applied for the electroanalytical detection of sub-micromolar concentrations of hydroquinone in 0.1 M phosphate buffer pH 7 (E(rev) = 0.04 V vs. SCE) and sub-micromolar concentration of dopamine in 0.1 M phosphate buffer pH 7 (E(rev) = 0.14 V vs. SCE). The potential future uses in analysis and limitations of gold-gold junction electrodes are discussed.

Atomic force microscopy-scanning electrochemical microscopy: influence of tip geometry and insulation defects on diffusion controlled currents at conical electrodes.

Numerical simulations were performed to predict the amperometric response of conical electrodes used as atomic force microscopy-scanning electrochemical microscopy (AFM-SECM) probes. A simple general expression was derived which predicts their steady state limiting current as a function of their insulation sheath thickness and cone aspect ratio. Simulated currents were successfully compared with experimental currents. Geometrical parameters such as insulation angle and tip bluntness were then studied to determine their effect on the limiting current. Typical tip defects were also modeled using 3D simulations, and their influence on the current was quantified. Although obtained for SECM-AFM probes, these results are directly applicable to conical micro- and nanoelectrodes.

An Analytical Differential Resistance Pulse System Relying on a Time Shift Signal Analysis-Applications in Coulter Counting.

Improving the sensitivity and ultimately the range of particle sizes that can be detected with a single pore extends the versatility of the Coulter counting technique. Here, to enable a pore to have greater sensitivity, we have developed and tested a novel differential resistive pulse sensing (DiS) system for sizing particles. To do this, the response was generated through a time shift approach utilizing a "self-servoing regime" to enable the final signal to operate with a zero background in the absence of particle translocation. The detection and characterization of a series of polystyrene particles, forced to translocate through a cylindrical glass microchannel (GMC) by a suitable static pressure difference using this approach, is demonstrated. An analytical response, which scales with the size of the particles employed, was verified. Parasitic capacitive effects are discussed; however, translocations on the millisecond time scale can be detected with high sensitivity and accuracy using the approach described.

Oxygen as redox mediator in scanning electrochemical microscopy. Application to the study of localised acid attack of marble.

Oxygen from air-saturated aqueous solutions was employed as redox mediator in SECM experiments. Accurate approach curves under negative-feedback conditions were obtained using platinum and gold microelectrodes. Imaging experiments were also carried out, using a 2.5 microns gold microelectrode and oxygen that acted as distance mediator. The topographic images of a glass surface and that of a marble surface prior and after localised acid attack were recorded. High concentrations of hydrogen ions were produced locally, at the microelectrode tip held 3 microns above the marble surface, by applying a large enough positive potential within the oxygen evolution region. Under these conditions, the dissolution of CaCO3 occurred. Pits were produced, and the crater volumes thus obtained were linearly dependent on the electrolysis time.

Scanning electrochemical microscopy: approach curves for sphere-cap scanning electrochemical microscopy tips.

The parameters of functions used to predict diffusion-controlled scanning electrochemical microscopy approach curves under positive and negative (hindered diffusion) feedback for sphere-cap tips are reported. These functions were obtained by fitting approach curves simulated with an error-bounded adaptive finite element algorithm. Several geometries corresponding to different sphere-cap dimensions were considered including the effect of the tip insulating sheath. The simulated approach curves were successfully compared with experimental ones obtained with mercury sphere caps electrodeposited onto platinum microdisk electrodes.

Fabrication and characterization of nanostructured Pd hydride pH microelectrodes.

Novel pH microsensors were made by electrodepositing mesoporous Pd films onto Pt microdisks, electrochemically loading the films with hydrogen to form the alpha+beta Pd hydride phase, and then switching to the potentiometric mode to monitor pH. To create a nanostructure, the films were deposited within a molecular template formed by the self-assembly of surfactant molecules, a technique known as true liquid crystal templating. The films retain the micrometer size of the Pt microdisk but offer electroactive areas up to 900 times larger. Optimum hydrogen loading conditions were determined, and the mesoporous Pd microdisks were found to have excellent potentiometric properties. From pH 2 to 12, their potential was Nernstian, highly reproducible, very stable (+/-1.2 mV over 2 h), and without hysteresis. Their response time was better than 1 s. However, the presence of oxygen reduced their lifetime significantly, thereby requiring frequent reloading. These microelectrodes do not require calibration before and after measurements, a procedure normally essential for potentiometric pH microsensors. To our knowledge, these are the first results where nanostructured materials made by the true liquid crystal templating method have been used in the potentiometric mode; moreover, these are the first results demonstrating the application of nanostructured microdisks in the potentiometric mode.

Mesoporous palladium-the surface electrochemistry of palladium in aqueous sodium hydroxide and the cathodic reduction of nitrite.

The voltammetry of nanostructured palladium layers electrodeposited from a hexagonal liquid crystal phase onto platinum microdiscs show well defined peaks for the adsorption/desorption of hydrogen and surface oxidation/reduction in 2 M NaOH. These peaks are more clearly resolved than at smooth palladium and reveal the complications associated with hydrogen adsorption/desorption on palladium in aqueous alkaline solutions. The reduction of nitrite at the nanostructured palladium is also reported and it is shown that it occurs via a mechanism involving a chemical reaction between adsorbed hydrogen and adsorbed nitrite ion.

Steady-state voltammetry of hydroxide ion oxidation in aqueous solutions containing ammonia.

An oxidation process observed in dilute aqueous solutions of ammonia was investigated under steady-state conditions with gold microelectrodes with radii in the range 2.5-30 microm. Over the ammonia concentration range 0.1-10 mM, a well-defined voltammetric wave was observed at approximately 1.4 V versus Ag/AgCl. It was attributed to the oxidation of hydroxide ions that arise from the dissociation of the weak base. The steady-state limiting current was found to depend on the concentration of supporting electrolyte, and in solution with low electrolyte, it was enhanced by migration contribution, as expected for a negatively charged species that oxidizes on a positively charged electrode. In addition, the steady-state limiting current was proportional to both the ammonia concentration and the electrode radius. The overall electrode process was analyzed in terms of a CE mechanism (homogeneous chemical reaction preceding the heterogeneous electron transfer) with a fast chemical reaction when measurements were carried out in solutions containing NH3 at < or = 5 mM and with electrodes having a radius of > or = 5 microm. This was ascertained by comparing experimental and theoretical data obtained by simulation. The formation of the soluble complex species Au(NH3)2+ was also considered as a possible alternative to explain the presence of the oxidation wave. This process however was ruled out, as the experimental data did not fit theoretical predictions in any of the conditions employed in the investigation. Instead, the direct oxidation of NH3, probably to N2O, was invoked to explain the anomalous currents found when the CE process was strongly kinetically hindered. Throughout this study, a parallel was made between the CE mechanism investigated here and that known to occur during the hydrogen evolution reaction from weak acids.

Detection of hydrogen peroxide at mesoporous platinum microelectrodes.

Mesoporous (H(I)-ePt) platinum microelectrodes electrodeposited from the hexagonal (H(I)) lyotropic liquid crystalline phase are shown to be excellent amperometric sensors for the detection of hydrogen peroxide over a wide range of concentrations. Good reproducibility, high precision, and accuracy of measurements are demonstrated. Mesoporous microelectrodes retain the high rates of mass transport typical of conventional microelectrodes, and their high real surface area greatly enhances their catalytic activity. This unique combination of properties overcomes the limitations of previous amperometric hydrogen peroxide sensors and yields outstanding qualitative and quantitative results.