Electronic Circuit Simulations as a Tool to Understand Distorted Signals in Single-Entity Electrochemistry

Electrochemical analysis relies on precise measurement of electrical signals, yet the distortions caused by potentiostat circuitry and filtering are rarely addressed. Elucidation of these effects is essential for gaining insights behind sensitive low-current and short-duration electrochemical signals, e.g., in single-entity electrochemistry. We present a simulation approach utilizing the Electrical Simulation Program with Integrated Circuit Emphasis (SPICE), which is extensively used in electronic circuit simulations. As a proof-of-concept, we develop a universal electrical circuit model for single nanoparticle impact experiments, incorporating potentiostat and electronic filter circuitry. Considering these alterations, the experimentally observed transients of silver nanoparticle oxidation were consistently shorter and differently shaped than those predicted by established models. This reveals the existence of additional processes, e.g., migration, partial or asymmetric oxidation. These results highlight the SPICE approach’s ability to provide valuable insights into processes occurring during single-entity electrochemistry, which can be applied to various electrochemical experiments, where signal distortions are inevitable

Piece by Piece-Electrochemical Synthesis of Individual Nanoparticles and their Performance in ORR Electrocatalysis

The impact of individual HAuCl4 nanoreactors is measured electrochemically, which provides operando insights and precise control over the modification of electrodes with functional nanoparticles of well‐defined size. Uniformly sized micelles are loaded with a dissolved metal salt. These solution‐phase precursor entities are then reduced electrochemically—one by one—to form nanoparticles (NPs). The charge transferred during the reduction of each micelle is measured individually and allows operando sizing of each of the formed nanoparticles. Thus, particles of known number and sizes can be deposited homogenously even on nonplanar electrodes. This is demonstrated for the decoration of cylindrical carbon fibre electrodes with 25±7 nm sized Au particles from HAuCl4‐filled micelles. These Au NP‐decorated electrodes show great catalyst performance for ORR (oxygen reduction reaction) already at low catalyst loadings. Hence, collisions of individual precursor‐filled nanocontainers are presented as a new route to nanoparticle‐modified electrodes with high catalyst utilization

Electrochemical quantification of iodide ions in synthetic urine using silver nanoparticles: a proof-of-concept.

Typical urinary iodide concentrations range from 0.3 μM to 6.0 μM. The conventional analytical method is based on the Sandell-Kolthoff reaction. It involves the toxic reagent, arsenic acid, and a waiting time of 30 minutes for the iodide ions to reduce the cerium(iv) ions. In the presented work, an alternative fast electrochemical method based on a silver nanoparticle modified electrode is proposed. Cyclic voltammetry was performed with a freshly modified electrode in presence of iodide ions and the voltammetric peaks corresponding to the oxidation of silver to silver iodide and the reverse reaction were recorded. The peak height of the reduction signal of silver iodide was used to plot a calibration line for the iodide ions. Two calibration plots for the iodide ions were obtained, one in 0.1 M sodium nitrate (a chloride-ion free environment to circumvent any interference from the other halides) and another in synthetic urine (which contains 0.2 M KCl). In both of the calibration plots, linear relationships were found between the reduction peak height and the iodide ion concentration of 0.3 μM to 6.0 μM. A slope of 1.46 × 10(-2) A M(-1) and a R(2) value of 0.999 were obtained for the iodide detection in sodium nitrate. For the synthetic urine experiments, a slope of 3.58 × 10(-3) A M(-1) and a R(2) value of 0.942 were measured. A robust iodide sensor with the potential to be developed into a point-of-care system has been validated

Facet-Dependent Intrinsic Activity of Single Co₃O₄ Nanoparticles for Oxygen Evolution Reaction

Deciphering the influence of nanocatalyst morphology on their catalytic activity in the oxygen evolution reaction (OER), the limiting reaction in water splitting process, is essential to develop highly active precious metal-free catalysts, yet poorly understood. The intrinsic OER activity of Co3O4 nanocubes and spheroids is probed at the single particle level to unravel the correlation between exposed facets, (001) vs. (111), and activity. Single cubes with predominant (001) facets show higher activity than multi-faceted spheroids. Density functional theory calculations of different terminations and reaction sites at (001) and (111) surfaces confirm the higher activity of the former, expressed in lower overpotentials. This is rationalized by a change in the active site from octahedral to tetrahedral Co and the potential-determining step from *OH to *O for the cases with lowest overpotentials at the (001) and (111) surfaces, respectively. This approach enables the identification of highly active facets to guide shape-selective syntheses of improved metal oxide nanocatalysts for water oxidation

Multimodal characterization of carbon electrodes\u27 thermal activation for vanadium redox flow batteries

Thermal activation has proven to be a valuable procedure to improve the performance of carbon electrodes in vanadium redox flow batteries (VRFBs). This work investigates how different activation temperatures impact the rayon-based carbon felt\u27s structure, surface composition, wettability, and electrochemical activity. A unique combination of non-standard techniques, including atomic force microscopy (AFM), dynamic vapor sorption (DVS), and electrochemical impedance spectroscopy (EIS) combined with the distribution of relaxation times (DRT) analysis, was used for the first time in the context of VRFB electrodes. The wettability of the carbon felts improved, and the process impedances decreased with higher activation temperatures. However, severe carbon decomposition occurs at high activation temperatures. The optimum electrochemical performance of the carbon felts in the vanadium(IV)/vanadium(V) redox reaction was observed after activation at 400 °C. Thus, we conclude that the optimum activation temperature for this type of carbon felt concerning the investigated properties is around 400 °C. Furthermore, we want to highlight the successful approach of using AFM, DVS, and EIS combined with DRT analysis for an integral investigation of key properties such as structure, wettability, and performance of VRFB electrodes

A versatile and easy method to calibrate a two-compartment flow cell for differential electrochemical mass spectrometry measurements

Catalysis and Surface Chemistr

Electrochemical dealloying as a tool to tune the porosity, composition and catalytic activity of nanomaterials

Electrochemical dealloying as a post-Treatment can greatly improve the catalytic activity of nanoparticles. To date, selecting suitable conditions to reach desired porosity, composition and catalytic activity is based on trial-And-error-Attempts, due to insufficient understanding of the electrochemically induced morphological and compositional changes of the nanoparticles. These changes are elucidated here by combining electrochemistry with identical location electron microscopy analyses and linking them to the electrocatalytic properties of the obtained nanocatalysts. Using AgAu alloy nanoparticles and the hydrogen evolution reaction as a model system, the influence of cyclic voltammetry parameters on the catalytic activity upon electrochemical dealloying is investigated. Increasing the number of cycles initially results in a decreased Ag content and a sharp improvement in activity. Additional dealloying increases the nanoparticle porosity, while marginally altering their composition, due to surface motion of atoms. Since this is accompanied by particle aggregation, a decrease in catalytic activity results upon extensive cycling. This transition between porosity formation and particle aggregation marks the optimum for nanocatalyst post-production. The gained insights may aid speeding up the development of new materials by electrochemical dealloying as an easy-To-control post-processing route to tune the properties of existing nanoparticles, instead of having to alter usually delicate synthesis routes as a whole. © The Royal Society of Chemistry

Partikel für Partikel – elektrochemische Einschlagsexperimente zur Synthese oberflächenimmobilisierter Goldnanopartikel für die Elektrokatalyse

Wir demonstrieren die sukzessive elektrochemische Umsetzung einzelner HAuCl4-gefüllter Nanoreaktoren auf einer Kohlefaserelektrode zur Funktionalisierung mit Nanopartikeln (NP). Dabei können Größe und Anzahl der einzeln abgeschiedenen NP während des Prozesses kontrolliert werden. Zunächst werden Mizellen von enger Größenverteilung mit Metallsalz beladen. Der sporadische Einschlag dieser Mizellen auf einer polarisierten Elektrode führt zur Reduktion der Metallionen und es entsteht ein einzelner NP. Die während eines Einschlags übertragene Ladung wird gemessen und ermöglicht die operando‐Größenbestimmung des gebildeten NP. Wir zeigen dies für die Beladung von zylindrischen Kohlefaserelektroden mit 25±7 nm großen AuNP, die bereits bei niedrigen Katalysatorbeladungen eine hervorragende Leistung für die Sauerstoffreduktion (ORR) zeigen. Diese Form der Nanoeinschlagsmethode wird daher als neuer Weg zu nanopartikelmodifizierten Elektroden mit effektiver Katalys‐atorausnutzung vorgestellt