Understanding how the bulk structure of a material affects catalysis on its surface is critical to the development of action-able catalyst design principles. Bulk defects have been shown to affect electrocatalytic materials that are important for energy conversion systems, but the structural origins of these effects have not been fully elucidated. Here we use a combi-nation of high-resolution scanning electrochemical cell microscopy and electron backscatter diffraction to visualize the potential-dependent electrocatalytic carbon dioxide ðCO2ÞI electroreduction and hydrogen ðH2ÞI evolution activity on Au elec-trodes and probe the effects of bulk defects. Comparing colocated activity maps and videos to the underlying microstructure and lattice deformation supports a model in which CO2 electroreduction is selectively enhanced by surface-terminating disloca-tions, which can accumulate at grain boundaries and slip bands. Our results suggest that the deliberate introduction of disloca-tions into materials is a promising strategy for improving catalytic properties.
Lifting the Lid on the Potentiostat: A Beginners Guide to Understanding Electrochemical Circuitry and Practical Operation
Students who undertake practical electrochemistry experiments for the first time, will come face to face with the potentiostat. To many this is simply a box containing electronics which enables a potential to be applied between a working and reference electrode, and a current to flow between the working and counter electrode, both of which are outputted to the experimentalist. Given the broad generality of electrochemistry across many disciplines it is these days very common for students entering the field to have a minimal background in electronics. This article serves as an introductory tutorial to those with no formalized training in this area. The reader is introduced to the operational amplifier, which is at the heart of the different potentiostatic electronic circuits and its role in enabling a potential to be applied and a current to be measured is explained. Voltage follower op-amp circuits are also highlighted, given their importance in measuring voltages accurately. We also discuss digital to analogue and analogue to digital conversion, the processes by which the electrochemical cell receives input signals and outputs data and data filtering. By reading the article, it is intended the reader will also gain a greater confidence in problem solving issues that arise with electrochemical cells, for example electrical noise, uncompensated resistance, reaching compliance voltage, signal digitisation and data interpretation. We also include trouble shooting tables that build on the information presented and can be used when undertaking practical electrochemistry.
Unveiling the contribution of the reproductive system of individual Caenorhabditis elegans on oxygen consumption by single-point scanning electrochemical microscopy measurements
Metabolic analysis in animals is usually either evaluated as whole-body measurements or in isolated tissue samples. To reveal tissue specificities in vivo, this study uses scanning electrochemical microscopy (SECM) to provide localized oxygen consumption rates (OCRs) in different regions of single adult Caenorhabditis elegans individuals. This is achieved by measuring the oxygen reduction current at the SECM tip electrode and using a finite element method model of the experiment that defines oxygen concentration and flux at the surface of the organism. SECM mapping measurements uncover a marked heterogeneity of OCR along the worm, with high respiration rates at the reproductive system region. To enable sensitive and quantitative measurements, a self-referencing approach is adopted, whereby the oxygen reduction current at the SECM tip is measured at a selected point on the worm and in bulk solution (calibration). Using genetic and pharmacological approaches, our SECM measurements indicate that viable eggs in the reproductive system are the main contributors in the total oxygen consumption of adult Caenorhabditis elegans. The finding that large regional differences in OCR exist within the animal provides a new understanding of oxygen consumption and metabolic measurements, paving the way for tissue-specific metabolic analyses and toxicity evaluation within single organisms.
Nanoscale Electrochemistry in a Copper/Aqueous/Oil Three-phase System: Surface Structure-Activity-Corrosion Potential Relationships
Practically important metal electrodes are usually polycrystalline, comprising surface grains of many different crystallographic orientations, as well as grain boundaries. In this study, scanning electrochemical cell microscopy (SECCM) is applied in tandem with co-located electron backscattered diffraction (EBSD) to give a holistic view of the relationship between the surface structure and the electrochemical activity and corrosion susceptibility of polycrystalline Cu. An unusual aqueous nanodroplet/oil (dodecane)/metal three-phase is employed, which opens up new prospects for fundamental studies of multiphase electrochemical systems, and mimics the environment of corrosion in certain industrial and automotive applications. In this configuration, the nanodroplet formed at the end of the SECCM probe (nanopipette) is surrounded by dodecane, which acts as a reservoir for oil-soluble species (e.g., O2) and can give rise to enhanced flux(es) across the immiscible liquid-liquid interface, as shown by finite element method (FEM) simulations. This unique three-phase configuration is used to fingerprint nanoscale corrosion in a nanodroplet cell, and to analyse the interrelationship between the Cu oxidation, Cu2+ deposition and oxygen reduction reaction (ORR) processes, together with nanoscale open circuit (corrosion) potential, in a grain-by-grain manner. Complex patterns of surface reactivity highlight the important role of grains of high-index orientation and microscopic surface defects (e.g., microscratches) in modulating the corrosion-properties of polycrystalline Cu. This work provides a roadmap for in-depth surface structure−function studies in (electro)materials science and highlights how small variations in surface structure (e.g., crystallographic orientation) can give rise to large differences in nanoscale reactivity.
Scanning Ion Conductance Microscopy Reveals Differences in the Ionic Environments of Gram-Positive and Negative Bacteria
This paper reports on the use of scanning ion conductance microscopy (SICM) to locally map the ionic properties and charge environment of two live bacterial strains: the Gram-negative Escherichia coli and the Gram-positive Bacillus subtilis. SICM results find heterogeneities across the bacterial surface and significant differences among the Gram-positive and Gram-negative bacteria. The bioelectrical environment of the B. subtilis was found to be considerably more negatively charged compared to E. coli. SICM measurements, fitted to a simplified finite element method (FEM) model, revealed surface charge values of −80 to −140 mC m–2 for the Gram-negative E. coli. The Gram-positive B. subtilis show a much higher conductivity around the cell wall, and surface charge values between −350 and −450 mC m–2 were found using the same simplified model. SICM was also able to detect regions of high negative charge near B. subtilis, not detected in the topographical SICM response and attributed to the extracellular polymeric substance. To further explore how the B. subtilis cell wall structure can influence the SICM current response, a more comprehensive FEM model, accounting for the physical properties of the Gram-positive cell wall, was developed. The new model provides a more realistic description of the cell wall and allows investigation of the relation between its key properties and SICM currents, building foundations to further investigate and improve understanding of the Gram-positive cellular microenvironment.
Combined Voltammetric Measurement of pH and Free Chlorine Speciation Using a Micro-Spot sp2 Bonded Carbon–Boron Doped Diamond Electrode
This work demonstrates the use of an sp2-bonded carbon microspot boron doped diamond (BDD) electrode for voltammetric measurement of both pH and analyte concentration in a pH-dependent speciation process. In particular, the electrode was employed for the voltammetric detection of pH and hypochlorite (OCl–) in unbuffered, aerated solutions over the pH range 4–10. Knowledge of both pH and [OCl–] is essential for determination of free chlorine concentration. The whole surface of the microspot BDD electrode was found active toward the voltammetric oxidation of OCl–, with OCl– showing a characteristic response at +1.5 V vs SCE. In contrast, it was only the surface integrated quinones (Q) in sp2-bonded carbon regions of the BDD electrode that were responsible for the voltammetric pH signal. A Nernstian response for pH (gradient = 63 ± 1 mV pH–1) was determined from proton coupled electron transfer at the BDD-Q electrode, over the potential range −0.4–0.5 V vs SCE. By measuring both OCl– and pH voltammetrically, over the pH range 4–10, the OCl– oxidative current was found to correlate extremely well with the predicted pH-dependent [OCl–] speciation profile.