How changes in interfacial pH lead to new voltammetric features: the case of the electrochemical oxidation of hydrazine.

The electrochemical oxidation of hydrazine was investigated in strongly and weakly pH buffered solutions to reveal the role of buffer capacity in proton-electron transfer redox reactions. In sufficiently buffered solutions, a single voltammetric feature was observed. However, increasing the hydrazine concentration (or, equivalently, moving to an insufficiently buffered solution) gave rise to a second voltammetric feature. These results are rationalised with a conceptually simple model and finite element simulations. We demonstrate that the new voltammetric feature is caused by a large change in the pH at the electrode surface as the reaction proceeds. Importantly, we show that the occurrence of additional voltammetric features are general for proton-electron transfer reactions in insufficiently buffered solutions, and should not be confused with changes in the reaction mechanism.

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

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.

Impact of Surface Chemistry on Nanoparticle-Electrode Interactions in the Electrochemical Detection of Nanoparticle Collisions.

The electrochemical detection of a single nanoparticle (NP) at a support electrode can provide key information on surface chemistry and fundamental electron transfer (ET) properties at the nanoscale. This study employs scanning electrochemical cell microscopy (SECCM) as a fluidic device to both deliver individual citrate-capped gold nanoparticles (AuNPs) and study the interactions between them and a range of alkanethiol-modified Au electrodes with different terminal groups, namely, -COOH, -OH, and -CH3. Single NP collisions were detected through the AuNP-mediated ET reaction of Fe(CN)6(4-/3-) in aqueous solution. The collision frequency, residence time, and current-time characteristics of AuNPs are greatly affected by the terminal groups of the alkanethiol. Methods to determine these parameters, including the effect of the instrument response function, and derive ET kinetics are outlined. To further understand the interactions of AuNPs with these surfaces, atomic force microscopy (AFM) force measurements were performed using citrate-modified Au-coated AFM tips and the same alkanethiol-modified Au substrates in aqueous solution at the same potential bias as for the AuNP collision experiments. Force curves on OH-terminated surfaces showed no repulsion and negligible adhesion force. In contrast, a clear repulsion (on approach) was seen for COOH-terminated surface and adhesion forces (on retract) were observed for both COOH- and CH3-terminated surfaces. These interactions help to explain the residence times and collision frequencies in AuNP collisions. More generally, as the interfacial properties probed by AFM appear to be amplified in NP collision experiments, and new features also become evident, it is suggested that such experiments provide a new means of probing surface chemistry at the nanoscale.

Spatially resolved electrochemistry in ionic liquids: surface structure effects on triiodide reduction at platinum electrodes.

Understanding the relationship between electrochemical activity and electrode structure is vital for improving the efficiency of dye-sensitized solar cells. Here, the reduction of triiodide to iodide in 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF4]) room temperature ionic liquid (RTIL) is investigated on polycrystalline platinum using scanning electrochemical cell microscopy (SECCM) and correlated to the crystallographic orientation from electron backscatter diffraction (EBSD). Although the rate determining step in all grains was the first electron transfer, significant grain-dependent variations in activity were revealed, with grains with a dominant (110) crystallographic character exhibiting higher catalytic activity compared to those with a major (100) orientation. The SECCM technique is demonstrated to resolve heterogeneity in activity, highlighting that methods incorporating polycrystalline electrodes miss vital details for understanding and optimizing electrocatalysts. An additional advantage of the SECCM over single-crystal techniques is its ability to probe high index facets.

High resolution mapping of oxygen reduction reaction kinetics at polycrystalline platinum electrodes.

The scanning droplet-based technique, scanning electrochemical cell microscopy (SECCM), combined with electron backscatter diffraction (EBSD), is demonstrated as a powerful approach for visualizing surface structure effects on the rate of the oxygen reduction reaction (ORR) at polycrystalline platinum electrodes. Elucidating the effect of electrode structure on the ORR is of major interest in connection to electrocatalysis for energy-related applications. The attributes of the approach herein stem from: (i) the ease with which the polycrystalline substrate electrode can be prepared; (ii) the wide range of surface character open to study; (iii) the possibility of mapping reactivity within a particular facet (or grain), in a pseudo-single-crystal approach, and acquiring a high volume of data as a consequence; (iv) the ready ability to measure the activity at grain boundaries; and (v) an experimental arrangement (SECCM) that mimics the three-phase boundary in low temperature fuel cells. The kinetics of the ORR was analyzed and a finite element method model was developed to explore the effect of the three-phase boundary, in particular to examine pH variations in the droplet and the differential transport rates of the reactants and products. We have found a significant variation of activity across the platinum substrate, inherently linked to the crystallographic orientation, but do not detect any enhanced activity at grain boundaries. Grains with (111) and (100) contributions exhibit considerably higher activity than those with (110) and (100) contributions. These results, which can be explained by reference to previous single-crystal measurements, enhance our understanding of ORR structure-activity relationships on complex high-index platinum surfaces, and further demonstrate the power of high resolution flux imaging techniques to visualize and understand complex electrocatalyst materials.

Electrochemistry of nanoparticles.

Metal nanoparticles (NPs) find widespread application as a result of their unique physical and chemical properties. NPs have generated considerable interest in catalysis and electrocatalysis, where they provide a high surface area to mass ratio and can be tailored to promote particular reaction pathways. The activity of NPs can be analyzed especially well using electrochemistry, which probes interfacial chemistry directly. In this Review, we discuss key issues related to the electrochemistry of NPs. We highlight model studies that demonstrate exceptional control over the NP shape and size, or mass-transport conditions, which can provide key insights into the behavior of ensembles of NPs. Particular focus is on the challenge of ultimately measuring reactions at individual NPs, and relating the response to their structure, which is leading to imaginative experiments that have an impact on electrochemistry in general as well as broader surface and colloid science.

Pseudo-single-crystal electrochemistry on polycrystalline electrodes: visualizing activity at grains and grain boundaries on platinum for the Fe2+/Fe3+ redox reaction.

The influence of electrode surface structure on electrochemical reaction rates and mechanisms is a major theme in electrochemical research, especially as electrodes with inherent structural heterogeneities are used ubiquitously. Yet, probing local electrochemistry and surface structure at complex surfaces is challenging. In this paper, high spatial resolution scanning electrochemical cell microscopy (SECCM) complemented with electron backscatter diffraction (EBSD) is demonstrated as a means of performing 'pseudo-single-crystal' electrochemical measurements at individual grains of a polycrystalline platinum electrode, while also allowing grain boundaries to be probed. Using the Fe(2+/3+) couple as an illustrative case, a strong correlation is found between local surface structure and electrochemical activity. Variations in electrochemical activity for individual high index grains, visualized in a weakly adsorbing perchlorate medium, show that there is higher activity on grains with a significant (101) orientation contribution, compared to those with (001) and (111) contribution, consistent with findings on single-crystal electrodes. Interestingly, for Fe(2+) oxidation in a sulfate medium a different pattern of activity emerges. Here, SECCM reveals only minor variations in activity between individual grains, again consistent with single-crystal studies, with a greatly enhanced activity at grain boundaries. This suggests that these sites may contribute significantly to the overall electrochemical behavior measured on the macroscale.

Landing and catalytic characterization of individual nanoparticles on electrode surfaces.

We demonstrate a novel and versatile pipet-based approach to study the landing of individual nanoparticles (NPs) on various electrode materials without any need for encapsulation or fabrication of complex substrate electrode structures, providing great flexibility with respect to electrode materials. Because of the small electrode area defined by the pipet dimensions, the background current is low, allowing for the detection of minute current signals with good time resolution. This approach was used to characterize the potential-dependent activity of Au NPs and to measure the catalytic activity of a single NP on a TEM grid, combining electrochemical and physical characterization at the single NP level for the first time. Such measurements open up the possibility of studying the relation between the size, structure and activity of catalyst particles unambiguously.

Active sites for outer-sphere, inner-sphere, and complex multistage electrochemical reactions at polycrystalline boron-doped diamond electrodes (pBDD) revealed with scanning electrochemical cell microscopy (SECCM).

The local rate of heterogeneous electron transfer (HET) at polycrystalline boron-doped diamond (pBDD) electrodes has been visualized at high spatial resolution for various aqueous electrochemical reactions, using scanning electrochemical cell microscopy (SECCM), which is a technique that uses a mobile pipet-based electrochemical cell as an imaging probe. As exemplar systems, three important classes of electrode reactions have been investigated: outer-sphere (one-electron oxidation of ferrocenylmethyltrimethylammonium (FcTMA(+))), inner-sphere (one-electron oxidation of Fe(2+)), and complex processes with coupled electron transfer and chemical reactions (oxidation of serotonin). In all cases, the pattern of reactivity is similar: the entire pBDD surface is electroactive, but there are variations in activity between different crystal facets which correlate directly with differences in the local dopant level, as visualized qualitatively by field-emission scanning electron microscopy (FE-SEM). No evidence was found for enhanced activity at grain boundaries for any of the reactions. The case of serotonin oxidation is particularly interesting, as this process is known to lead to deterioration of the electrodes, because of blocking by reaction products, and therefore cannot be studied with conventional scanning electrochemical probe microscopy (SEPM) techniques. Yet, we have found this system nonproblematic to study, because the meniscus of the scanning pipet is only in contact with the surface investigated for a brief time and any blocking product is left behind as the pipet moves to a new location. Thus, SECCM opens up the possibility of investigating and visualizing much more complex heterogeneous electrode reactions than possible presently with other SEPM techniques.

Scanning electrochemical cell microscopy: theory and experiment for quantitative high resolution spatially-resolved voltammetry and simultaneous ion-conductance measurements.

Scanning electrochemical cell microscopy (SECCM) is a high resolution electrochemical scanning probe technique that employs a dual-barrel theta pipet probe containing electrolyte solution and quasi-reference counter electrodes (QRCE) in each barrel. A thin layer of electrolyte protruding from the tip of the pipet ensures that a gentle meniscus contact is made with a substrate surface, which defines the active surface area of an electrochemical cell. The substrate can be an electrical conductor, semiconductor, or insulator. The main focus here is on the general case where the substrate is a working electrode, and both ion-conductance measurements between the QRCEs in the two barrels and voltammetric/amperometric measurements at the substrate can be made simultaneously. In usual practice, a small perpendicular oscillation of the probe with respect to the substrate is employed, so that an alternating conductance current (ac) develops, due to the change in the dimensions of the electrolyte contact (and hence resistance), as well as the direct conductance current (dc). It is shown that the dc current can be predicted for a fixed probe by solving the Nernst-Planck equation and that the ac response can also be derived from this response. Both responses are shown to agree well with experiment. It is found that the pipet geometry plays an important role in controlling the dc conductance current and that this is easily measured by microscopy. A key feature of SECCM is that mass transport to the substrate surface is by diffusion and, for charged analytes, ion migration which can be controlled and varied quantifiably via the bias between the two QRCEs. For a working electrode substrate this means that charged redox-active analytes can be transported to the electrode/solution interface in a well-defined and controllable manner and that relatively fast heterogeneous electron transfer kinetics can be studied. The factors controlling the voltammetric response are determined by both simulation and experiment. Experiments demonstrate the realization of simultaneous quantitative voltammetric and ion conductance measurements and also identify a general rule of thumb that the surface contacted by electrolyte is of the order of the pipet probe dimensions.

Visualizing zeptomole (electro)catalysis at single nanoparticles within an ensemble.

The relationship between the structural properties, such as the size and the shape, of a catalytic nanoparticle and its reactivity is a key concept in (electro)catalysis. Current understanding of this relationship is mainly derived from studies involving large ensembles of nanoparticles (NPs). However, the results necessarily reflect the average catalytic behavior of an ensemble, even though the properties of individual particles may vary widely. Here, we demonstrate a novel approach using scanning electrochemical cell microscopy (SECCM) to locate and map the reactivity of individual NPs within an electrocatalytic ensemble, consisting of platinum NPs supported on a single carbon nanotube. Significantly, our studies show that subtle variations in the morphology of NPs lead to dramatic changes in (potential-dependent) reactivity, which has important implications for the design and assessment of NP catalysts. The instrumental approach described is general and opens up new avenues of research in functional imaging, nanoscale electron transfer, and catalysis.

Electrocatalytic oxidation of alcohols on gold in alkaline media: base or gold catalysis?

On the basis of a comparison of the oxidation activity of a series of similar alcohols with varying pK(a) on gold electrodes in alkaline solution, we find that the first deprotonation is base catalyzed, and the second deprotonation is fast but gold catalyzed. The base catalysis follows a Hammett-type correlation with pK(a), and dominates overall reactivity for a series of similar alcohols. The high oxidation activity on gold compared to platinum for some of the alcohols is related to the high resistance of gold toward the formation of poisoning surface oxides. These results indicate that base catalysis is the main driver behind the high oxidation activity of many organic fuels on fuel cell anodes in alkaline media, and not the catalyst interaction with hydroxide.

The influence of solution-phase HNO2 decomposition on the electrocatalytic nitrite reduction at a hemin-pyrolitic graphite electrode.

The mechanism of nitrite electroreduction by hemin adsorbed at pyrolitic graphite is investigated. Two main issues are addressed: the effect of the medium pH and the selectivity of the reaction, which was determined by the combined use of the rotating ring disk electrode (RRDE) and online electrochemical mass spectroscopy (OLEMS). In acidic media, the behavior observed is indicative of the presence of NO, as the main reactant, generated from the solution-phase decomposition of HNO(2). Reduction of the NO-heme complex shows a Tafel slope of 59 mV/dec(-1) and a pH dependence of 42 mV/pH, indicative of a so-called EC mechanism. In acidic media, HNO(2) and NO are reduced to hydroxylamine (NH(2)OH) with almost 100% selectivity at low potentials, nitrous oxide (N(2)O) being only a minor side product. In neutral media, the hemin is largely unresponsive to the presence of nitrite, giving only a very small reduction current. The comparison of our simple heme catalyst to the behavior of the naturally occurring heme-containing nitrite reductases, which operate under biological conditions, suggests that these enzymes dissociate nitrite at neutral pH either via a complexation step favored by a specific ligating environment or by locally regulating the pH to induce HNO(2) dissociation.

Ethanol electro-oxidation on platinum in alkaline media.

The electrochemical oxidation of ethanol as well as its irreversible adsorption on platinum single crystal electrodes has been studied in an alkaline solution. In addition, the adsorbed species in the ethanol oxidation reaction were also studied by means of surface enhanced Raman spectroscopy (SERS) on a platinum film electrode. It was found that the oxidation of ethanol is very sensitive to the electrode surface structure: a higher concentration of low-coordination sites increases the current, lowers the overpotential required and lowers the deactivation rate. Furthermore, the terrace length also affects the amounts and the nature of the adsorbed species: on Pt (110), only CO(ad) was observed, whereas adsorbed CH(x) could only be found on electrode surfaces with (111) terrace sites. Based on the results here, a model for the ethanol electro-oxidation reaction in alkaline media is presented, and the differences with the same reaction in acidic media are pointed out.

Unconventional Electrochemistry in Micro-/Nanofluidic Systems.

Electrochemistry is ideally suited to serve as a detection mechanism in miniaturized analysis systems. A significant hurdle can, however, be the implementation of reliable micrometer-scale reference electrodes. In this tutorial review, we introduce the principal challenges and discuss the approaches that have been employed to build suitable references. We then discuss several alternative strategies aimed at eliminating the reference electrode altogether, in particular two-electrode electrochemical cells, bipolar electrodes and chronopotentiometry.

Deformability Assessment of Waterborne Protozoa Using a Microfluidic-Enabled Force Microscopy Probe.

Many modern filtration technologies are incapable of the complete removal of Cryptosporidium oocysts from drinking-water. Consequently, Cryptosporidium-contaminated drinking-water supplies can severely implicate both water utilities and consumers. Existing methods for the detection of Cryptosporidium in drinking-water do not discern between non-pathogenic and pathogenic species, nor between viable and non-viable oocysts. Using FluidFM, a novel force spectroscopy method employing microchannelled cantilevers for single-cell level manipulation, we assessed the size and deformability properties of two species of Cryptosporidium that pose varying levels of risk to human health. A comparison of such characteristics demonstrated the ability of FluidFM to discern between Cryptosporidium muris and Cryptosporidium parvum with 86% efficiency, whilst using a measurement throughput which exceeded 50 discrete oocysts per hour. In addition, we measured the deformability properties for untreated and temperature-inactivated oocysts of the highly infective, human pathogenic C. parvum to assess whether deformability may be a marker of viability. Our results indicate that untreated and temperature-inactivated C. parvum oocysts had overlapping but significantly different deformability distributions.

Nucleation, aggregative growth and detachment of metal nanoparticles during electrodeposition at electrode surfaces.

The nucleation and growth of metal nanoparticles (NPs) on surfaces is of considerable interest with regard to creating functional interfaces with myriad applications. Yet, key features of these processes remain elusive and are undergoing revision. Here, the mechanism of the electrodeposition of silver on basal plane highly oriented pyrolytic graphite (HOPG) is investigated as a model system at a wide range of length scales, spanning electrochemical measurements from the macroscale to the nanoscale using scanning electrochemical cell microscopy (SECCM), a pipette-based approach. The macroscale measurements show that the nucleation process cannot be modelled as either truly instantaneous or progressive, and that step edge sites of HOPG do not play a dominant role in nucleation events compared to the HOPG basal plane, as has been widely proposed. Moreover, nucleation numbers extracted from electrochemical analysis do not match those determined by atomic force microscopy (AFM). The high time and spatial resolution of the nanoscale pipette set-up reveals individual nucleation and growth events at the graphite basal surface that are resolved and analysed in detail. Based on these results, corroborated with complementary microscopy measurements, we propose that a nucleation-aggregative growth-detachment mechanism is an important feature of the electrodeposition of silver NPs on HOPG. These findings have major implications for NP electrodeposition and for understanding electrochemical processes at graphitic materials generally.

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

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.

Electro-oxidation of ethanol and acetaldehyde on platinum single-crystal electrodes.

The electrochemical oxidation of ethanol and acetaldehyde in sulfuric acid and perchloric acid were studied at Pt (111), Pt (110), and a number of Pt [n(l11)x(111)] single-crystal electrodes. The oxidation of ethanol shows a marked dependence on the surface structure, roughly increasing as the surface step density increases. The oxidation of acetaldehyde shows a reversed correlation, the activity decreasing with increasing step density. Based on the results obtained here and reported earlier in electrochemical and ultrahigh vacuum literature, a detailed reaction scheme for the ethanol oxidation mechanism is suggested.