Electrochemical studies and self diffusion coefficients in cyclic ammonium based ionic liquids with allyl substituents

Several cyclic ammonium-based ionic liquids (ILs) with allyl substituent are synthesized, these allyl substituent ILs have high ionic conductivity (up to 4.72 mS cm⁻¹ at 30 °C) and wide electrochemical window of 5 V. The electrochemical behaviors of two organometallic redox couples Fc/Fc⁺ (ferrocene/ferrocenium) and Cc/Cc⁺ (cobaltocene/cobaltocenium) have been studied in these ILs, the calculated Stokes–Einstein product (Dη T⁻¹) of ferrocene in ILs is larger than that of cobaltocenium in ILs. The self-diffusion coefficients of cation and anion in these ILs are studied using pulsed gradient spin-echo NMR technique. There are very few reports where electrochemically derived diffusion coefficients and self diffusion coefficients are available for comparison, so a new key concept in electrochemistry could be developed in this paper.     

Preparation and electrochemical performance of flower-like hematite for lithium-ion batteries

Flower-like hematite (α-Fe₂O₃) has been successfully prepared by heat-treatment from the iron(III)-oxyhydroxide precursor, which is obtained by the hydrolysis of FeCl₃ solution in the presence of NaClO. In this process, no templates or catalysts are required. SEM and TEM characterizations confirm that micro-flowers are composed of several dozen self-assembled nanopetals with the thickness of about 20 nm. On the basis of the morphology investigations in time-dependent experiments, the possible growth mechanism of the flower-like α-Fe₂O₃ is proposed, which is similar to a two-stage growth process. Furthermore, as an anode electrode material for rechargeable lithium-ion batteries, the flower-like α-Fe₂O₃ exhibits excellent electrochemical performance, which can be attributed to the high surface area induced by the flower-like structure, the short lithium diffusion length and the restriction of volume change of the Li⁺ insertion/extraction.     

Impedance study on calcium nitrite as a penetrating corrosion inhibitor for steel in concrete

Penetrating corrosion inhibitors are thought to be able to penetrate through the capillary structure of concrete to reinforcing steel and to reduce the already initiated corrosion of steel. In this work the ability of calcium nitrite to inhibit the chloride induced corrosion of steel was studied. The test protocol was adjusted to simulate the performance of penetrating corrosion inhibitors in concrete structures. Steel samples were first prepassivated in saturated solution of Ca(OH)₂ and then exposed to the same solution with 1% NaCl addition, simulating pore liquid in chloride contaminated concrete. After the initiation of steel corrosion, the first dose of calcium nitrite was added, and then its concentration was gradually increased and the inhibition effect was related to the molar ratio of chloride to nitrite ions [Cl⁻]/[NO₂⁻]. Different rates of the increase in the inhibitor concentration were applied.Electrochemical impedance spectroscopy was used to follow the behaviour of steel at different stages of the corrosion process. The evolution of acquired spectra reflected the initiation of localized corrosion of steel and then the gradual inhibition with increasing concentration of the inhibitor. It was found, that calcium nitrite is able to inhibit the initiated corrosion (pitting) of steel and the optimum inhibitor efficiency was observed for the [Cl⁻]/[NO₂⁻] ratio below 1. The inhibition efficiency was larger, when this value of the [Cl⁻]/[NO₂⁻] ratio was reached in early stages of the corrosion development. Calcium nitrite can be effective as a penetrating corrosion inhibitor for steel in concrete, if it will be present in the sufficient concentration at the steel surface in early stages of the corrosion development.     

Nanosilver-penetrated polyion graphene complex membrane for mediator-free amperometric immunoassay of alpha-fetoprotein using nanosilver-coated silica nanoparticles

A facile and sensitive mediator-free electrochemical immunosensor for detection of alpha-fetoprotein (AFP) was designed by using nanosilver-coated silica nanoparticles (Ag-SiO₂) as bionanolabels. To construct such an electrochemical immunosensor, silver ions/single-stranded DNA/graphene nanosheets were initially immobilized on a gold electrode in turn, then silver ions were in situ reduced to silver nanoparticles with the aid of NaBH₄, and anti-AFP antibodies conjugated to silver nanoparticles were used. In the presence of AFP analyte, the sandwiched immunocomplex was formed on the electrode surface by using horseradish peroxidase-anti-AFP conjugate-labeled Ag-SiO₂ (HRP-anti-AFP-Ag-SiO₂) as secondary antibodies. Compared with pure silver nanoparticles, Ag-SiO₂ nanocomposites could provide a large room for the immobilization of HRP-anti-AFP, and improve the electrochemical responses of the immunosensor. Meanwhile, the presence of highly conductive graphene nanosheets and silver nanoparticles provided a good pathway for electron transfer. Under optimal conditions, the immunosensor exhibited good electrochemical responses toward AFP ranging from 0.3 to 200 ng/mL with a detection limit (LOD) of 0.05 ng/mL (at 3σ) in pH 6.0 PBS-H₂O₂ system. Intra- and inter-assay displayed good precisions with coefficient of variation below 9.5%. In addition, the method was evaluated with 23 clinical serum samples, receiving good correlation with results from commercially available electrochemiluminescent analyzer.     

Electrosynthesis of Pd/Au hollow cone-like microstructures for electrocatalytic formic acid oxidation

Pd/Au hollow cone-like microstructures (HCMs) have been electrodeposited on indium tin oxide (ITO) using a two-step protocol, which involves the nucleation pulse and succedent constant potential reduction in the presence of metal precursors and polyvinylpyrrolidone (PVP). Scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscope (XPS) were used to characterize the Pd/Au HCMs. The electrochemical results (cyclic voltammetry and chronoamperometry) testify that the Pd/Au HCMs exhibit significantly higher electrocatalytic activity and stability for the oxidation of formic acid than that of Pd/Au solid microhemispheres (SMHs). These attractive features are attributable to the unique hollow structures of Pd/Au with much higher electrochemical active surface areas and the exposure of favorable planes. Our work points to a new path for the preparation of Pd/Au HCMs, which are promising as electrocatalysts in direct formic acid fuel cell (DFAFC).     

TiO2-graphene nanocomposite for electrochemical sensing of adenine and guanine

TiO₂-graphene nanocomposite was prepared by hydrolysis of titanium isopropoxide in colloidal suspension of graphene oxide and in situ hydrothermal treatment. It provides an efficient and facile approach to yield nanocomposite with TiO₂ nanoparticles uniformly embedded on graphene substrate. The electrochemical behavior of adenine and guanine at the TiO₂-graphene nanocomposite modified glassy carbon electrode was investigated. The results show that the incorporation of TiO₂ nanoparticles with graphene significantly improved the electrocatalytic activity and voltammetric response towards these species comparing with that at the graphene film. The TiO₂-graphene based electrochemical sensor exhibits wide linear range of 0.5–200 μM with detection limit of 0.10 and 0.15 μM for adenine and guanine detection, respectively. The excellent performance of this electrochemical sensor can be attributed to the high adsorptivity and conductivity of TiO₂-graphene nanocomposite, which provides an efficient microenvironment for electrochemical reaction of these purine bases.     

Kinetic investigation of sulfurized polyacrylonitrile cathode material by electrochemical impedance spectroscopy

To understand more about the sulfur composite prepared by sulfurized polyacrylonitrile at 300 °C, electrochemical impedance spectroscopy (EIS) is employed to investigate the electrochemical properties of the sulfur composite cathode during discharge process. The impact of discharge depth on the performance of sulfur composite materials is investigated. The electrolyte solution resistance, the charge transfer resistance and the interface impedance are evaluated from the EIS analysis. The charge transfer resistance and the interface impedance increase during delithiation and decrease during lithiation, while the concentration of Li⁺ in the composite decreases and increases, respectively. Meanwhile the electrolyte solution resistance is likely to keep stable. The interface resistance and charge transfer resistance of the sulfur composite cathode decrease rapidly after initial lithiation, while Li⁺ diffusion coefficient and exchange current density increase rapidly. After the initial lithiation, they are likely to keep stable. This study reveals more characteristics of the sulfur composite, which is considered to be a promising candidate for large capacity cathode material.     

Kinetics and Efficiency Analysis of Electrochemical Oxidation of Phenol: Influence of Anode Materials and Operational Conditions

The influence of operational parameters and anode materials on degradation kinetics, mineralization current efficiency, and energy consumption for electrochemical oxidation of phenol was studied. Phenol elimination follows pseudo‐first‐order kinetics in most cases except for the Ti/RuO₂ anode with a phenol concentration of 500 mg L^–1, where pseudo‐zero‐order kinetics is observed. The total organic carbon removal by a Ti/Sb‐SnO₂ anode follows pseudo‐first‐order kinetics in contrast to pseudo‐zero‐order kinetics by Pt and Ti/RuO₂ anodes. For a certain anode, a higher current or voltage input results in a higher reaction rate. With a Ti/Sb‐SnO₂ anode, the highest current efficiency and the lowest energy consumption are obtained, but the current efficiency decreases (increases for energy consumption) quickly as the reaction is prolonged due to the reduction of organics.     

Determination of Membrane Protein Fouling by UV Spectroscopy and Electrochemical Impedance Spectroscopy

UV spectroscopy and electrochemical impedance spectroscopy were used to investigate the properties and performances of ultrafiltration membranes fabricated with different polymers. Membrane performances were studied by means of permeability and bovine serum albumin filtration. UV spectroscopy results showed that bovine serum albumin rejection was lowest in polyvinylidene fluoride membranes, whereas it was highest in polysulfone membranes. Electrochemical impedance spectroscopy data revealed that after bovine serum albumin filtration, resistance of the membranes was increased though double layer capacitances were decreased. Performance data of UV spectroscopy and electrochemical impedance spectroscopy were in correlation with each other. This study demonstrated that electrochemical impedance spectroscopy can be successfully used in filtration membrane studies.     

Electrochemical synthesis and characterization of polyaniline thin film and polyaniline powder

The polyaniline thin film electrode and powder have been synthesized on graphite electrodes from 0.5 M hydrochloric acid solution under galvanostatic conditions. The water insoluble and acetone soluble polyaniline mass fractions of the powder, as well as the polymerization efficiency, based on the emeraldine salt have been determined. The morphology of the obtained emeraldine salt powder has been investigated by the optical microscopy.