Electrochemically controlled nanopipettes are becoming increasingly versatile tools for a diverse range of sequencing, sizing, and imaging applications. Herein, the use of nanopipettes to induce and quantitatively monitor crystallization and dissolution in real time is considered, using CaCO₃ in aqueous solution as an exemplar system. The bias between a quasi-reference counter electrode in a nanopipette and one in a bulk solution is used to mix (or de-mix) two different solutions by ion migration and drive either growth or dissolution, depending on the polarity. Furthermore, Raman spectroscopy can be applied simultaneously to identify polymorphs formed in the nanopipette. The technique is supported with a robust finite element method model that allows the extraction of time-dependent saturation levels and mixing characteristics at the nanoscale. The technique shows great promise as a tool for rapidly screening growth additives and inhibitors, allowing eight different additives to be ranked in order of efficacy for crystal growth rate inhibition.

Single nanoparticle (NP) electrochemical impacts is a rapidly expanding field of fundamental electrochemistry, with applications from electrocatalysis to electroanalysis. These studies, which involve monitoring the electrochemical (usually current–time, I–t) response when a NP from solution impacts with a collector electrode, have the scope to provide considerable information on the properties of individual NPs. Taking the widely studied oxidative dissolution of individual silver nanoparticles (Ag NPs) as an important example, we present measurements with unprecedented noise (< 5 pA) and time resolution (time constant 100 μs) that are highly revealing of Ag NP dissolution dynamics. Whereas Ag NPs of diameter, d = 10 nm are mostly dissolved in a single event (on the timescale of the measurements), a wide variety of complex processes operate for NPs of larger diameter (d ≥ 20 nm). Detailed quantitative analysis of the I–t features, consumed charge, event duration and impact frequency leads to a major conclusion: Ag NPs undergo sequential partial stripping (oxidative dissolution) events, where a fraction of a NP is electrochemically oxidized, followed by the NP drifting away and back to the tunnelling region before the next partial stripping event. As a consequence, analysis of the charge consumed by single events (so-called “impact coulometry”) cannot be used as a general method to determine the size of colloidal NPs. However, a proper analysis of the I–t responses provides highly valuable information on the transient physicochemical interactions between NPs and polarized surfaces.

Physicochemical processes that take place at the oil-water interface of an epoxy-amine emulsion polymerisation system influence the properties and structural morphology of the polymeric microparticles formed. Investigating these processes, such as the transport of monomers across the liquid/liquid interface brings new understanding which can be used to tune polymeric morphology. Two different approaches are used to provide new insights on these processes. Microelectrochemical measurements at expanding droplets (MEMED) is used to measure the transfer of amine from an organic phase comprised of epoxide and amine into an aqueous receptor phase. The rate of amine transfer across the liquid/liquid interface is characterised using MEMED and finite element method modelling and kinetic values are reported. Time lapse microscopy of epoxide droplets held in deionised water or an aqueous amine solution heated to different temperatures is further used to characterise epoxide dissolution into the aqueous phase. Mass-transport of epoxide into the aqueous phase is shown to be temperature-dependent. Epoxide homopolymerisation at the droplet-water interface is found to influence the rate of epoxide droplet dissolution. The rate of the epoxy-amine cure reaction is shown to be faster than the rate of the epoxide homopolymerisation reaction. The combination of methods used here is not limited to emulsion polymerisation and should find application in a myriad of processes at liquid/liquid interfaces.

There is great interest in finding and developing new, efficient, and more active electrocatalytic materials. Surface modification of highly oriented pyrolytic graphite, through the introduction of surface “blisters”, is demonstrated to result in an electrode material with greatly enhanced electrochemical activity. The increased electrochemical activity of these blisters, which are produced by electro-oxidation in HClO₄, is revealed through the use of scanning electrochemical cell microscopy (SECCM), coupled with complementary techniques (optical microscopy, field emission-scanning electron microscopy, Raman spectroscopy, and atomic force microscopy). The use of a linear sweep voltammetry (LSV)-SECCM scan regime allows for dynamic electrochemical mapping, where a voltammogram is produced at each pixel, from which movies consisting of spatial electrochemical currents, at a series of applied potentials, are produced. The measurements reveal significantly enhanced electrocatalytic activity at blisters when compared to the basal planes, with a significant cathodic shift in the onset potential of the hydrazine electro-oxidation reaction. The improved electrochemical activity of the hollow structure of blistered graphite could be explained by the increased adsorption of protonated hydrazine at oxygenated defect sites, the ease of ion–solvent intercalation/deintercalation, and the reduced susceptibility to N₂ nanobubble attachment (as a product of the reaction). This study highlights the capability of electrochemistry to tailor the surface structure of graphite and presents a new electrocatalyst for hydrazine electro-oxidation.

The electrochemistry of the Fe3+/2+ redox couple has been studied on highly oriented pyrolytic graphite (HOPG) samples that differ in step edge density by 2 orders of magnitude to elucidate the effect of surface structure on the electron transfer (ET) kinetics. Macroscopic cyclic voltammetry measurements in a droplet-cell arrangement, highlight that the Fe3+/2+ process is characterised by slow ET kinetics on HOPG and that step edge coverage has little effect on the electrochemistry of Fe3+/2+. A standard heterogeneous ET rate constant of ~5 × 10-5 cm s-1 for freshly cleaved HOPG was derived from simulation of the experimental results, which fell into the range of the values reported for metal eletrodes, e.g. platinum and gold, despite the remarkable difference in density of electronic states (DOS) between HOPG and metal electrodes. This provides further evidence that outer-sphere redox processes on metal and sp2 carbon electrodes appear to be adiabatic. Complementary surface electroactivity mapping of HOPG, using scanning electrochemical cell microscopy, reveal the basal plane to be the predominant site for the Fe3+/2+ redox process. It is found that time after cleavage of the HOPG surface has an impact on the surface wettability (and surface contamination), as determined by contact angle measurements, and that this leads to a slow deterioration of the kinetics. These studies further confirm the importance of understanding and evaluating surface structure and history effects in HOPG electrochemistry, and how high resolution measurements, coupled with macroscopic studies provide a holistic view of electrochemical processes.

Surface coverage measurements of electroactive quinone groups present on sp² carbon sites, are used to inform on the sp² surface content of boron doped diamond (BDD) electrodes. Laser micromachining of an electrode surface is used to systematically increase the amount of sp² carbon present by increasing the area machined. A linear relationship between quinone surface coverage and surface area lasered is determined (R² = 0.9999). This approach can also be used for comparative assessment of electrodes containing different amounts of surface sp² carbon.