An Artificial Electrode/Electrolyte Interface for CO2 Electroreduction by Cation Surfactant Self-Assembly

In this work, an artificial electrode/electrolyte (E/E) interface, made by coating the electrode surface with a quaternary ammonium cation (R₄N⁺) surfactant, was successfully developed, leading to a change in the CO₂ reduction reaction (CO₂RR) pathway. This artificial E/E interface, with high CO₂ permeability, promotes CO₂ transportation and hydrogenation, as well as suppresses the hydrogen evolution reaction (HER). Linear and branched surfactants facilitated formic acid and CO production, respectively. Molecular dynamics simulations show that the artificial interface provided a facile CO₂ diffusion pathway. Moreover, density-functional theory (DFT) calculations revealed the stabilization of the key intermediate, OCHO*, through interactions with R₄N⁺. This strategy might also be applicable to other electrocatalytic reactions where gas consumption is involved.     

Recent advances in high surface area electrodes for bioelectrochemical applications

The search for high surface area electrodes for bioelectrochemical applications is becoming more intense. In the last few years, new strategies have emerged to develop three-dimensional electrode materials with very well controlled architecture providing at the same time high specific surface, bendability and flexibility. This review will highlight some of the recent work published in the last 2 years and will discuss the issue of mathematical modeling of porous electrodes and what could be the future of high surface area electrodes materials.     

Production of a NiO/Al primary battery employing powder-based electrodes

This paper describes the use of aluminum and zinc as anodic materials for a battery employing nickel (II) oxide (NiO) as cathode. Comparison of both materials resulted in the development of a compact, cost effective, and easy to use primary NiO/Al battery employing an alkaline electrolyte. The system features electrodes composed of powder forms of the active materials on modified paper substrates that are contained in a simple multilayer design utilizing thin laminated plastic materials to provide structure and flexibility to the battery as well as a paper separator. Various concentrations of potassium hydroxide (KOH) electrolyte were examined and maximum performance was observed at 6 M KOH. A maximum current density and power density of 1.94 mA/cm² and 1 mW/cm², respectively was achieved. This user-friendly device was able to produce a maximum capacity of 2.33 mAh/g when 2 mA/g was applied. This work demonstrates the viability of a paper-based battery featuring powder electrodes as a possible power source for microelectronic devices.     

Numerical investigation of cavitation generated by an ultrasonic dental scaler tip vibrating in a compressible liquid

Bacterial biofilm accumulation around dental implants is a significant problem leading to peri-implant diseases and implant failure. Cavitation occurring in the cooling water around ultrasonic scaler tips can be used as a novel solution to remove debris without any surface damage. However, current clinically available instruments provide insufficient cavitation around the activated tip surface. To solve this problem a critical understanding of the vibro-acoustic behaviour of the scaler tip and the associated cavitation dynamics is necessary. In this research, we carried out a numerical study for an ultrasound dental scaler with a curved shape tip vibrating in water, using ABAQUS based on the finite element method. We simulated the three-dimensional, nonlinear and transient interaction between the vibration and deformation of the scaler tip, the water flow around the scaler and the cavitation formation and dynamics. The numerical model was well validated with the experiments and there was excellent agreement for displacement at the free end of the scaler. A systematic parametric study has been carried out for the cavitation volume around the scaler tip in terms of the frequency, amplitude and power of the tip vibration. The numerical results indicate that the amount of cavitation around the scaler tip increases with the frequency and amplitude of the vibration. However, if the frequency is far from the natural frequency, the cavitation volume around the free end decreases due to reduced free end vibration amplitude.     

Electrochemical Behaviour of Microwave‐assisted Oxidized MWCNTs Based Disposable Electrodes: Proposal of a NADH Electrochemical Sensor

The effect of the oxidation degree of multiwalled carbon nanotubes (MWCNTs) for the detection of NADH was evaluated in this paper. MWCNTs were oxidized by microwave‐assisted sulfonitic treatment at different times (5, 10, 15, and 30 min) and deposited onto a graphite screen printed electrodes. Oxidized MWCNTs were characterized and the electrochemical performance evaluated. The best sensor in terms of sensitivity and stability was obtained after 15 minutes of oxidation (SPE/CNT15). A significant reduction of the NADH oxidation potential was recorded for oxidized MWCNTs compared with unmodified MWCNTs (0.270 V and 0.500 V, respectively vs. Ag/AgCl pseudo reference electrode), increasing the selectivity of the system. Chronoamperometric calibration curves carried out applying a potential of 0.3 V for 1 min were linear in the 4–35 μM range of NADH. A limit of detection of 1 μM was achieved with negligible surface fouling (three consecutive calibration curves, 30 total measurements: slope decrease 5.9 %). Inter electrode reproducibility (n=13) was good resulting in RSD of 15.2 % and 5.0 % for the peak intensity and the oxidation potential, respectively. Quantification of glucose in white wine samples was carried out to demonstrate the ability of the NADH sensor to work in real samples. A good correlation with a spectrophotometric kit for the glucose quantification was achieved.     

Carbon Nanodots as Electrocatalysts towards the Oxygen Reduction Reaction

Electrocatalysts perform a key role in increasing efficiency of the oxygen reduction reaction (ORR) and as a result, efforts have been made by the scientific community to develop novel and cheap materials that have the capability to exhibit low ORR overpotentials and allow the reaction to occur via a 4 electron pathway, thereby mimicking as close as possible to traditionally utilised platinum. In that context, two different types of carbon nanodots (CNDs) with amide (CND‐CONH₂) and carboxylic (CND‐COOH) surface groups, have herein been fabricated and shown to exhibit excellent electrocatalytic activity towards the ORR in acid and basic media (0.1 M H₂SO₄ and 0.1 M KOH). CND surface modified carbon screen‐printed electrodes allow for a facile electrode modification and enabling the study of the CNDs electrocatalytic activity towards the ORR. CND‐COOH modified SPEs are found to exhibit improved ORR peak current and reduced overpotential by 21.9 % and 26.3 %, respectively compared to bare/unmodified SPEs. Additionally, 424 μg cm⁻² CND‐COOH modified SPEs in oxygenated 0.1 M KOH are found to facilitate the ORR via a near optimal 4 (3.8) electron ORR pathway. The CNDs also exhibited excellent long‐term stability and tolerance with no degradation being observed in the achievable current with the ORR current returning to the baseline level within 100 seconds of exposure to a 1.5 M solution of methanol. In summary, the CND‐COOH could be utilised as a cathodic electrode for PEMFCs offering greater stability than a commercial Pt electrode.     

Spatially Confined Assembly of Monodisperse Ruthenium Nanoclusters in a Hierarchically Ordered Carbon Electrode for Efficient Hydrogen Evolution

The redox units of polyaniline (PAni) are used cooperatively, and in situ, to assemble ruthenium (Ru) nanoclusters in a hierarchically ordered carbon electrode. The oxidized quinonoid imine (QI) units in PAni bond Ru complex ions selectively, whereas reduced benzenoid amine (BA) units cannot. By electrochemically tuning the ratio of QI to BA, Ru complexes are spatially confined in the outer layer of hierarchical PAni frameworks. Carbonization of Ru‐PAni hybrids induces nucleation on the outer surface of the carbon support, generating nearly monodisperse Ru nanoclusters. The optimized catalyst has a low loading of approximately 2 wt % Ru, but exhibits a mass activity for the hydrogen evolution reaction that is about 6.8 times better than commercial 20 wt % Pt/C catalyst.     

Determination of amitriptyline,imipramine and orphenadrine in antidepressant drugs by potentiometry,spectrophotometry and atomic absorption spectrometry

Methods are described for the determination of amitriptyline, imipramine and orphenadrine in some antidepressant drugs. They are based on a prior reaction with ammonium reineckate to form 11 water-insoluble drugreineckate ion-pair complexes. These complexes are (i) used as ion-exchangers in liquid-membrane electrodes responsive to the drug cations, (ii) extracted with nitrobenzene or dissolved in acetonitrile and spectrophotometrically measured at 525 nm and (iii) dissolved in 90% acetone followed by nebulization in an air-acetylene flame for atomic absorption spectrometric measurements of Cr at 358.6 nm. The reaction and monitoring conditions are optimized to permit determination of as little as 10 g/ml of the drugs. Determination of the drugs in some pharmaceutical preparations shows an average recovery of 98.8% of the nominal and a mean standard deviation of 0.8%. The results compare favorably with data obtained by the United States and British Pharmacopoeia methods.     

Electrochemical immunosensor for determination of aflatoxin B1 in barley

This paper reports the assembly of a disposable electrochemical immunosensor based on the indirect competitive enzyme linked immunosorbent assay (ELISA), for simple and fast measurement of aflatoxin B₁ (AFB₁) in barley using differential pulse voltammetry (DPV). The immunosensor strip was assembled immobilising the biological component (i.e. the AFB₁ conjugated to bovine serum albumin, incubation the sample (or standard) with the monoclonal antibody anti-AFB₁ (MAb). A spectrophotometric ELISA was used in a preliminary phase of development, prior to transferring the assay to the SPEs.

Results showed a detection limit of 20 and 30 pg/mL for the spectrophotometric ELISA and the electrochemical immunosensor, respectively.

The extraction efficiency and the matrix effect have been evaluated by spiking blank barley with AFB₁ before and after the sample treatment. After treatment, samples were analysed using a 1:10 (v/v) dilution in PBS (phosphate-buffered saline, pH 7.4) in order to minimise the matrix effect. Good recoveries were obtained, which demonstrated the suitability of the proposed method for routine screening of AFB₁ in barley.