Investigation of the Electrocatalytic Reduction of Peroxydisulfate Using Scanning Electrochemical Microscopy.

The elementary steps of the electrocatalytic reduction of S2O82- using the Ru(NH3)63+/2+ redox couple were investigated using scanning electrochemical microscopy (SECM) and steady-state voltammetry (SSV). SECM investigations were carried out in a 0.1 M KCl solution using a 3.5 µm radius carbon ultramicroelectrode (UME) as the SECM tip and a 25 µm radius platinum UME as the substrate electrode. Approach curves were recorded in the positive feedback mode of SECM by reducing Ru(NH3)63+ at the tip electrode and oxidizing Ru(NH3)62+ at the substrate electrode, as a function of the tip-substrate separation and S2O82- concentration. The one-electron reaction between electrogenerated Ru(NH3)62+ and S2O82- yields the unstable S2O83•-, which rapidly dissociates to produce highly oxidizing SO4•-. Because SO4•- is such a strongly oxidizing species, it can be further reduced at both the tip and the substrate, or it can react with Ru(NH3)62+ to regenerate Ru(NH3)63+. SECM approach curves display a complex dependence on the tip-substrate distance, d, due to redox mediation reactions at both the tip and the substrate. Finite element method (FEM) simulations of both SECM approach curves and SSV confirm a previously proposed mechanism for the mediated reduction of S2O82- using the Ru(NH3)63+/2+ redox couple. Our results provide a lower limit for dissociation rate constant of S2O83•- (∼1 × 106 s-1), as well as the rate constants for electron transfer between SO4•- and Ru(NH3)62+ (∼1 × 109 M-1 s-1) and between S2O82- and Ru(NH3)62+ (∼7 × 105 M-1 s-1).

Simultaneous Multipass Resistive-Pulse Sensing and Fluorescence Imaging of Liposomes.

Simultaneous multipass resistive-pulse sensing and fluorescence imaging have been used to correlate the size and fluorescence intensity of individual E. coli lipid liposomes composed of E. coli polar lipid extracts labeled with membrane-bound 3,3-dioctadecyloxacarbocyanine (DiO) fluorescent molecules. Here, a nanopipet serves as a waveguide to direct excitation light to the resistive-pulse sensing zone at the end of the nanopipet tip. Individual DiO-labeled liposomes (>50 nm radius) were multipassed back and forth through the orifices of glass nanopipets' 110-150 nm radius via potential switching to obtain subnanometer sizing precision, while recording the fluorescence intensity of the membrane-bound DiO molecules. Fluorescence was measured as a function of liposome radius and found to be approximately proportional to the total membrane surface area. The observed relationship between liposome size and fluorescence intensity suggests that multivesicle liposomes emit greater fluorescence compared to unilamellar liposomes, consistent with all lipid membranes of the multivesicle liposomes containing DiO. Fluorescent and nonfluorescent liposomes are readily distinguished from each other in the same solution using simultaneous multipass resistive-pulse sensing and fluorescence imaging. A fluorescence "dead zone" of ∼1 µm thickness just outside of the nanopipet orifice was observed during resistive-pulse sensing, resulting in "on/off" fluorescent behavior during liposome multipassing.

Electrocatalytic Reduction of Benzyl Bromide during Single Ag Nanoparticle Collisions.

Previous reports of the electrocatalytic activity of Ag nanoparticles (AgNPs) toward the reduction of organic halides have been limited to measurements of immobilized nanoparticle ensembles. Here, we have investigated the electrochemical reduction of benzyl bromide (PhCH2Br) occurring at single AgNPs (4.2 to 37 nm radius) in methanol, where the effects of nanoparticle size on catalytic behavior can be more thoroughly examined and rigorously quantified. AgNP collisions at a 6.3 µm radius Au ultramicroelectrode (UME) result in measurable electrocatalytic amplification currents from the reduction of PhCH2Br, where collision events are indicated by a sudden step increase in the reduction current recorded in the current-time trace. The dependence of the height of these steps on the applied potential allowed for an analysis of reaction kinetics based on the Butler-Volmer model, resulting in an estimation of the standard rate constant (k0) as a function of AgNP size. Measured values of k0 range from 4.0 × 10-4 to 8.0 × 10-4 cm/s on AgNPs with radii of 14, 29, and 37 nm, whereas k0 was found to be 6.2 × 10-4 cm/s at a 12.3 µm radius Ag disk UME. The results indicate that the kinetics of PhCH2Br reduction are independent of AgNP size and are similar to the reaction kinetics observed at a Ag UME. The frequency of observed particle collisions was found to be dependent on particle size, where 14 nm radius AgNPs resulted in the highest-frequency collisions. The potential- and size-dependent interactions of AgNPs with the Au UME are discussed in terms of the DLVO theory.

Unraveling Hydrogen Atom Transfer Mechanisms with Voltammetry: Oxidative Formation and Reactivity of Cobalt Hydride.

The utility of transition metal hydride catalyzed hydrogen atom transfer (MHAT) has been widely demonstrated in organic transformations such as alkene isomerization and hydrofunctionalization reactions. However, the highly reactive nature of the hydride and radical intermediates has hindered mechanistic insight into this pivotal reaction. Recent advances in electrochemical MHAT have opened up the possibility for new analytical approaches for mechanistic diagnosis. Here, we report a voltammetric interrogation of Co-based MHAT reactivity, describing in detail the oxidative formation and reactivity of the key Co-H intermediate and its reaction with aryl alkenes. Insights from cyclic voltammetry and finite element simulations help elucidate the rate-limiting step as metal hydride formation, which we show to be widely tunable based on ligand design. Voltammetry is also suggestive of the formation of Co-alkyl intermediates and a dynamic equilibrium with the reactive neutral radical. These mechanistic studies provide information for the design of future hydrofunctionalization reactions, such as catalyst and silane choice, the relative stability of metal-alkyl species, and how hydrofunctionalization reactions utilize Co-alkyl intermediates. In summary, these studies establish an important template for studying MHAT reactions from the perspective of electrochemical kinetic frameworks.

Electroorganic synthesis in aqueous solution via generation of strongly oxidizing and reducing intermediates.

Water is the ideal green solvent for organic electrosynthesis. However, a majority of electroorganic processes require potentials that lie beyond the electrochemical window for water. In general, water oxidation and reduction lead to poor synthetic yields and selectivity or altogether prohibit carrying out a desired reaction. Herein, we report several electroorganic reactions in water using synthetic strategies referred to as reductive oxidation and oxidative reduction. Reductive oxidation involves the homogeneous reduction of peroxydisulfate (S2O82-) via electrogenerated Ru(NH3)62+ at potential of -0.2 V vs. Ag/AgCl (3.5 M KCl) to form the highly oxidizing sulfate radical anion (E0' (SO4˙-/SO42-) = 2.21 V vs. Ag/AgCl), which is capable of oxidizing species beyond the water oxidation potential. Electrochemically generated SO4˙- then efficiently abstracts a hydrogen atom from a variety of organic compounds such as benzyl alcohol and toluene to yield product in water. The reverse analogue of reductive oxidation is oxidative reduction. In this case, the homogeneous oxidation of oxalate (C2O42-) by electrochemically generated Ru(bpy)33+ produces the strongly reducing carbon dioxide radical anion (E0' (CO2˙-/CO2) = -2.1 V vs. Ag/AgCl), which can reduce species at potential beyond the water or proton reduction potential. In preliminary studies, the CO2˙- has been used to homogeneously reduce the C-Br moiety belonging to benzyl bromide at an oxidizing potential in aqueous solution.

Single-Molecule Electrical Currents Associated with Valinomycin Transport of K.

A quantitative description of ionophore-mediated ion transport is important in understanding ionophore activity in biological systems and developing ionophore applications. Herein, we describe the direct measurement of the electrical current resulting from K+ transport mediated by individual valinomycin (val) ionophores. Step fluctuations in current measured across a 1,2-diphytanoyl-sn-glycero-3-phosphocholine (DPhPC) bilayer suspended over a ∼400 nm radius glass nanopore result from dynamic partitioning of val between the bilayer and torus region, effectively increasing or decreasing the total number of val present in the membrane. In our studies, approximately 30 val are present in the membrane on average with a val entering or leaving the bilayer approximately every 50 s, allowing measurement of changes in electrical current associated with individual val. The single-molecule val(K+) transport current at 0.1 V applied potential is (1.3 ± 0.6) × 10-15 A, consistent with estimates of the transport kinetics based on large val ensembles. This methodology for analyzing single ionophore transport is general and can be applied to other carrier-type ionophores.

Electrocatalytic Hydrogen Evolution at Full Atomic Utilization over ITO-Supported Sub-nano-Ptn Clusters: High, Size-Dependent Activity Controlled by Fluxional Pt Hydride Species.

A combination of density functional theory (DFT) and experiments with atomically size-selected Ptn clusters deposited on indium-tin oxide (ITO) electrodes was used to examine the effects of applied potential and Ptn size on the electrocatalytic activity of Ptn (n = 1, 4, 7, and 8) for the hydrogen evolution reaction (HER). Activity is found to be negligible for isolated Pt atoms on ITO, increasing rapidly with Ptn size such that Pt7/ITO and Pt8/ITO have roughly double the activity per Pt atom compared to atoms in the surface layer of polycrystalline Pt. Both the DFT and experiment find that hydrogen under-potential deposition (Hupd) results in Ptn/ITO (n = 4, 7, and 8) adsorbing ∼2H atoms/Pt atom at the HER threshold potential, equal to ca. double the Hupd observed for Pt bulk or nanoparticles. The cluster catalysts under electrocatalytic conditions are hence best described as a Pt hydride compound, significantly departing from a metallic Pt cluster. The exception is Pt1/ITO, where H adsorption at the HER threshold potential is energetically unfavorable. The theory combines global optimization with grand canonical approaches for the influence of potential, uncovering the fact that several metastable structures contribute to the HER, changing with the applied potential. It is hence critical to include reactions of the ensemble of energetically accessible PtnHx/ITO structures to correctly predict the activity vs Ptn size and applied potential. For the small clusters, spillover of Hads from the clusters to the ITO support is significant, resulting in a competing channel for loss of Hads, particularly at slow potential scan rates.

Simulation of the cyclic voltammetric response of an outer-sphere redox species with inclusion of electrical double layer structure and ohmic potential drop.

A finite-element model has been developed to simulate the cyclic voltammetric (CV) response of a planar electrode for a 1e outer-sphere redox process, which fully accounts for cell electrostatics, including ohmic potential drop, ion migration, and the structure of the potential-dependent electric double layer. Both reversible and quasi-reversible redox reactions are treated. The simulations compute the time-dependent electric potential and ion distributions across the entire cell during a voltammetric scan. In this way, it is possible to obtain the interdependent faradaic and non-faradaic contributions to a CV and rigorously include all effects of the electric potential distribution on the rate of electron transfer and the local concentrations of the redox species Oz and Rz-1. Importantly, we demonstrate that the driving force for electron transfer can be different to the applied potential when electrostatic interactions are included. We also show that the concentrations of Oz and Rz-1 at the plane of electron transfer (PET) significantly depart from those predicted by the Nernst equation, even when the system is characterised by fast electron transfer/diffusion control. A mechanistic rationalisation is also presented as to why the electric double layer has a negligible effect on the CV response of such reversible systems. In contrast, for quasi-reversible electron transfer the concentrations of redox species at the PET are shown to play an important role in determining CV wave shape, an effect also dependant on the charge of the redox species and the formal electrode potential of the redox couple. Failure to consider electrostatic effects could lead to incorrect interpretation of electron-transfer kinetics from the CV response. Simulated CVs at scan rates between 0.1 and 1000 V s-1 are found to be in good agreement with experimental data for the reduction of 1.0 mM Ru(NH3)63+ at a 2 mm diameter gold disk electrode in 1.0 M potassium nitrate.

Critical Nucleus Size and Activation Energy of Ag Nucleation by Electrochemical Observation of Isolated Nucleation Events.

The induction times for electrodeposition of individual Ag nanoparticles on Pt nanodisk electrodes in acetonitrile were used to determine the critical nucleus size and activation energy barrier associated with the formation of Ag nuclei. Induction times for the nucleation and growth of a single Ag nanoparticle were determined following the application of a potential step to reduce Ag+ at overpotentials, η, ranging from -130 to -70 mV. Sufficiently small Pt electrodes (5.1 × 10-10-2.6 × 10-11 cm2) were used to ensure that the detection of a single Ag nucleation event occurred during the experimental observation time (150 ms-1000 s). Multiple measurements of Ag nucleation induction times were recorded to determine nucleation rates as a function of η using cumulative probability theory. Both classical nucleation theory (CNT) and the atomistic theory of electrochemical nucleation were employed to analyze experimental nucleation rates, without a requisite knowledge of the nucleus geometry or surface free energy. Using the CNT, the number of atoms comprising the critical size nucleus, Nc, was estimated to be 1-9 atoms for η ranging from -130 to -70 mV, in good agreement with 1-5 atoms obtained using atomistic theory. The experimental nucleation rates were also used to determine the activation energy barriers for nucleation from the CNT, which varied from 3.31 ± 0.05 to 13 ± 1 kT over the same range of η.

Oxidation by Reduction: Efficient and Selective Oxidation of Alcohols by the Electrocatalytic Reduction of Peroxydisulfate.

Alcohol oxidation is an important class of reaction that is traditionally performed under harsh conditions and most often requires the use of organometallic compounds or transition metal complexes as catalysts. Here, we introduce a new electrochemical synthetic method, referred to as reductive oxidation, in which alcohol oxidation is initiated by the redox-mediated electrocatalytic reduction of peroxydisulfate to generate the highly oxidizing sulfate radical anion. Thus, and counter-intuitively, alcohol oxidation occurs as a result of an electrochemical reduction reaction. This approach provides a selective synthetic route for the oxidation of alcohols carried out under mild conditions to aldehydes, ketones, and carboxylic acids with up to 99% conversion yields. First-principles density functional theory calculations, ab initio molecular dynamics simulations, cyclic voltammetry, and finite difference simulations are presented that support and provide additional insights into the S2O82--mediated oxidation of benzyl alcohol to benzaldehyde.

Finite Element Modeling of the Combined Faradaic and Electrostatic Contributions to the Voltammetric Response of Monolayer Redox Films.

The voltammetric response of electrodes coated with a redox-active monolayer is computed by finite element simulations based on a generalized model that couples the Butler-Volmer, Nernst-Planck, and Poisson equations. This model represents the most complete treatment of the voltammetric response of a redox film to date and is made accessible to the experimentalist via the use of finite element modeling and a COMSOL-generated report. The model yields a full description of the electric potential and charge distributions across the monolayer and bulk solution, including the potential distribution associated with ohmic resistance. In this way, it is possible to properly account for electrostatic effects at the molecular film/electrolyte interface, which are present due to the changing charge states of the redox head groups as they undergo electron transfer, under both equilibrium and nonequilibrium conditions. Specifically, our numerical simulations significantly extend previous theoretical predictions by including the effects of finite electron-transfer rates (k0) and electrolyte conductivity. Distortion of the voltammetric wave due to ohmic potential drop is shown to be a function of electrolyte concentration and scan rate, in agreement with experimental observations. The commonly used Laviron analysis for the determination of k0 fails to account for ohmic drop effects, which may be non-negligible at high scan rates. This model provides a more accurate alternative for k0 determination at all scan rates. The electric potential and charge distributions across an electrochemically inactive monolayer and electrolyte solution are also simulated as a function of applied potential and are found to agree with the Gouy-Chapman-Stern theory.

Electroprecipitation of Nanometer-Thick Films of Ln(OH)3 [Ln = La, Ce, and Lu] at Pt Microelectrodes and Their Effect on Electron-Transfer Reactions.

We report investigations of the deposition of nanometer-thick Ln(OH)3 films (Ln = La, Ce, and Lu) and their effect on outer-sphere and inner-sphere electron-transfer reactions. Insoluble Ln(OH)3 films are deposited from aqueous solutions of LaCl3 onto the surface of 12.5 µm radius Pt microdisk electrodes during water or oxygen reduction. Both reactions produce interfacial OH-, which complexes with Ln3+, resulting in the precipitation of Ln(OH)3. Surface analyses by scanning electron microscopy (SEM), SEM-energy-dispersive X-ray spectroscopy, and atomic force microscopy indicate the formation of a 1-2 nm thick uniform film. Outer-sphere electron-transfer reactions (Ru(NH3)63+ reduction, FcMeOH oxidation, and Fe(CN)64-/3- oxidation/reduction) were investigated at Ln(OH)3-modified electrodes of different film thicknesses. The results demonstrate that the steady-state transport-limited current for these reactions decreases with an increase in the film thickness. Moreover, the degree of blockage depends upon the redox species, suggesting that the Ln(OH)3 films are free from pinholes greater than the size of the redox molecules. This suggests that the films are either ionically conducting or that electron tunneling occurs across these thin layers. A similar blocking effect was observed for the inner-sphere reductions of H2O and O2. We further demonstrate that the thickness of La(OH)3 films can be controlled by anodic dissolution. Additionally, we show that La3+ lowers the supersaturation of dissolved H2 required to nucleate a stable nanobubble.

Visualization and Quantification of Electrochemical H2 Bubble Nucleation at Pt, Au, and MoS2 Substrates.

Electrolytic gas evolution is a significant phenomenon in many electrochemical technologies from water splitting, chloralkali process to fuel cells. Although it is known that gas evolution may substantially affect the ohmic resistance and mass transfer, studies focusing on the electrochemistry of individual bubbles are critical but also challenging. Here, we report an approach using scanning electrochemical cell microscopy (SECCM) with a single channel pipet to quantitatively study individual gas bubble nucleation on different electrode substrates, including conventional polycrystalline Pt and Au films, as well as the most interesting two-dimensional semiconductor MoS2. Due to the confinement effect of the pipet, well-defined peak-shaped voltammetric features associated with single bubble nucleation and growth are consistently observed. From stochastic bubble nucleation measurement and finite element simulation, the surface H2 concentration corresponding to bubble nucleation is estimated to be ∼218, 137, and 157 mM, with critical nuclei contact angles of ∼156°, ∼161°, and ∼160° at polycrystalline Pt, Au, and MoS2 substrates, respectively. We further demonstrated the surface faceting at polycrystalline Pt is not specifically correlated with the bubble nucleation behavior.

Electrochemical Generation of Individual Nanobubbles Comprising H2, D2, and HD.

The electrochemical reduction of deuterons (2D+ + 2e- → D2) at Pt nanodisk electrodes (radius = 15-100 nm) in D2O solutions containing deuterium chloride (DCl) results in the formation of a single gas nanobubble at the electrode surface. Analogous to that previously observed for the electrochemical generation of H2 nanobubbles, the nucleation and growth of a stable D2 nanobubble is characterized in voltammetric experiments by a highly reproducible and well-resolved sudden drop in the faradaic current, a consequence of restricted mass transport of D+ to the electrode surface following the liquid-to-gas phase transition. D2 nanobubbles are stable under potential control due to a dynamic equilibrium existing between D2 gas dissolution and electrochemical generation of D2 at the circumference of the Pt nanodisk electrode. Remarkably, within the error of the experimental measurement (<6%), the electrochemical current required to nucleate a D2 gas phase in a D2O solution is identical to that for the H2 gas phase in a H2O solutions, indicating that the concentration required for nucleating a D2 nanobubble in D2O (0.29 M) is ∼1.25 times larger than that for a H2 nanobubble (0.23 M), while the supersaturation is ∼300 in each case. We further demonstrate that individual nanobubbles can be electrogenerated in mixed D2O/H2O solutions containing both D+ and H+ at respective individual concentrations well below those required to nucleate a gas phase containing either pure D2 or H2. This latter finding indicates that the resulting nanobubbles comprise a mixture of D2, H2, and HD molecules with the chemical composition of a nanobubble determined by the concentrations and diffusivities of D+ and H+ in the mixed D2O/H2O solutions.

Visualization of Hydrogen Evolution at Individual Platinum Nanoparticles at a Buried Interface.

Electrochemical processes occurring at solid/solid and solid/membrane interfaces govern the behavior of a variety of energy storage devices, including electrocatalytic reactions at electrode/membrane interfaces in fuel cells and ion insertion at electrode/electrolyte interfaces in solid-state batteries. Due to the heterogeneity of these systems, interrogation of interfacial activity at nanometer length scales is desired to understand system performance, yet the buried nature of the interfaces makes localized activity inaccessible to conventional electrochemical techniques. Herein, we demonstrate nanoscale electrochemical imaging of hydrogen evolution at individual Pt nanoparticles (PtNPs) positioned at a buried interface using scanning electrochemical cell microscopy (SECCM). Specifically, we image the hydrogen evolution reaction (HER) at individual carbon-supported PtNP electrocatalysts covered by a 100 to 800 nm thick layer of the proton exchange membrane Nafion. The rate of hydrogen evolution at PtNP at this buried interface is shown to be a function of Nafion thickness, with the highest activity observed for ∼200 nm thick films.

Nitrogen Bubbles at Pt Nanoelectrodes in a Nonaqueous Medium: Oscillating Behavior and Geometry of Critical Nuclei.

Gas bubble evolution is present in many electrochemical and photoelectrochemical processes. We previously reported the formation of individual H2, N2, and O2 nanobubbles generated from electrocatalytic reduction of H+ and oxidation of N2H4 and H2O2, respectively, at Pt nanodisk electrodes in an aqueous solution. All the nanobubbles formed display a dynamic stationary state of a three-phase boundary with an invariant residual current. Here, we test the hypothesis that gas nanobubbles can also be electrogenerated in a nonaqueous medium. Interestingly, we found oscillating bubble behavior corresponding to nucleation, growth, and dissolution in dimethyl sulfoxide and methanol. One possible explanation of the oscillation mechanism is provided by the instable dynamic equilibrium between the gas influx due to supersaturation and outflux due to Laplace pressure. Furthermore, the critical gas concentrations for N2 nanobubble nucleation are estimated to be 148, 386, 200, and 16 times supersaturation and the contact angles of the critical nuclei to be 164°, 151°, 160°, and 174° in water, dimethyl sulfoxide, ethylene glycol, and methanol, respectively. This is the first report on electrochemical nucleation of gas bubbles in nonaqueous solvents. Our electrochemical gas bubble study based on a nanoelectrode platform has proven to be a prototypical example of single-entity electrochemistry.

Electrochemically Controlled Nucleation of Single CO2 Nanobubbles via Formate Oxidation at Pt Nanoelectrodes.

CO2 is an anodic product of many liquid fuel cells. The nucleation of CO2 nanobubbles during cell operation may block the transport of the fuel to the anode, lowering the overall conversion efficiency. Herein, we report the controlled formation of individual CO2 nanobubbles at Pt nanoelectrodes via the electrooxidation of formate. The electrochemical data are used to extract key parameters of CO2 gas nucleation. We determine that CO2 bubbles nucleate when the concentration of CO2 at the Pt electrode is greater than ∼0.6 M, corresponding to supersaturation of ∼18. The critical nucleus required for the formation of a CO2 bubble is measured to have a radius of curvature of ∼100 nm, a contact angle of 173°, and contains ∼70 CO2 molecules.

Coupled Electron- and Phase-Transfer Reactions at a Three-Phase Interface.

Coupled electron- and phase-transfer reactions are fundamentally important in electrochemical energy conversion and storage, e.g., intercalation of Li+ in batteries and electrochemistry at the three-phase boundary in fuel cells. The mechanism, energetics, and kinetics of these complex reactions play an important role in device performance. Herein, we describe experimental methodology to quantitatively investigate coupled electron- and phase-transfer reactions at an individual, geometrically well-defined, three-phase interface. Specifically, a Pt-Ir wire electrode is placed across a H2O/1,2-dichloroethane (DCE) interface, creating a Pt-Ir/H2O/DCE boundary that is defined mathematically by a line around the surface of the wire. We investigated the oxidation of ferrocene (Fc), initially present in DCE (but essentially insoluble in water), at the three-phase boundary, and the transfer of its charged reaction product ferrocenium (Fc+) across the interface into the aqueous phase. In cyclic voltammetry, a reversible wave at E1/2 ∼ 0.58 V is observed for Fc oxidation in DCE on the first scan. The Fc+ produced near the H2O/DCE interface transfers into the aqueous phase. On the second and subsequent cycles, a second reversible wave at more negative potentials, E1/2 ∼ 0.33 V, is observed, corresponding to the reduction of Fc+ (and reoxidation back to Fc) in the aqueous phase. Finite-element simulations quantitatively capture the voltammetric response of coupled electron and phase transfer at the three-phase interface and indicate that the electrochemical response observed in the aqueous phase occurs within ∼200 µm of the Pt-Ir/H2O/DCE boundary. Finally, we demonstrate that the rate of transfer of Fc+ is strongly dependent on the concentration of supporting electrolyte, reaching a maximum at an intermediate electrolyte concentration, suggesting a critical role of the electric field distribution in determining the reaction rates at the three-phase interface.

A synthetic chemist's guide to electroanalytical tools for studying reaction mechanisms.

Monitoring reactive intermediates can provide vital information in the study of synthetic reaction mechanisms, enabling the design of new catalysts and methods. Many synthetic transformations are centred on the alteration of oxidation states, but these redox processes frequently pass through intermediates with short life-times, making their study challenging. A variety of electroanalytical tools can be utilised to investigate these redox-active intermediates: from voltammetry to in situ spectroelectrochemistry and scanning electrochemical microscopy. This perspective provides an overview of these tools, with examples of both electrochemically-initiated processes and monitoring redox-active intermediates formed chemically in solution. The article is designed to introduce synthetic organic and organometallic chemists to electroanalytical techniques and their use in probing key mechanistic questions.