Metals often are classified as “noble” or “base”—characterizing their reduction potential as one of the most important chemical properties. We show that metals are only as noble as allowed by their environment, i.e. this is a relative term, and the “frame of reference” simply is the solvent in which the redox system is present. We prove that silver is a prime example for a noble metal that forfeits its noble character in the simple ionic liquid HMIM Br (1-hexyl-3-methylimidazolium bromide) as an example for such a solvent.
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Aluminum sacrificial anodes are currently the first choice for cathodic protection in numerous applications. The galvanic performance of aluminum-based sacrificial anodes is considerably enhanced by addition of certain alloying elements called activators. Recent researches proved that incorporation of specific metal oxides like MnO2, CeO2, RuO2, and IrO2 into the aluminum matrix could enhance the galvanic efficiency of aluminum anodes; however, the mechanism by which metal oxides improve galvanic properties of aluminum is still subject to discussion. The present work investigates the effect of incorporating commercially available low-cost manganese dioxide concentrate into Al-5Zn-0.1Sn sacrificial anodes in different volume fractions. It also studies the influence of heat treatment on anode’s galvanic performance by performing solution treatment at 3 different temperatures (250 °C, 400 °C, 550 °C). The electrochemical testing results proved an increase in efficiency of anodes incorporated with metal oxides and solution treated at 550 °C. The SEM imaging and EDX elemental mapping declared that the presence of SiO2 particles in the anode matrix which might cause effective and uniform corrosion of Al anodes and decreased non-coulombic losses.
Graphical abstractWe present a new observation of electrochemical oscillation during the reduction of Co2+ from sulfate solution in the presence of but-2-yne-1,4-diol (butynediol) as an additive. Cyclic voltammetry, hydrodynamic voltammetry at galvanostatic condition, and electrochemical impedance spectroscopic studies suggest that the electrochemical oscillation observed was a relaxation type and was the manifestation of adsorbed hydrogen formation by electrochemical reduction of protons on cobalt and their chemical removal by semi-hydrogenation of butynediol to butenediol during the initial stages of electrodeposition.
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With the purpose of fast characterization of electrode reactions, a dynamic electrochemical impedance spectrum (dEIS) measurement system has been assembled which permits the continuous collection of audio-frequency impedance spectra while performing cyclic voltammetry measurements with the usual scan rates of up to 200 mV/s. The performance of this system was tested by analyzing the CV curves and impedance spectra taken simultaneously in ferro-/ferricyanide containing aqueous solutions yielding an experimental demonstration of the connection of the semi-integrated reversible voltammograms and the Warburg coefficients.
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Despite the success of lithium-ion batteries, recognized through the award of the 2019 Nobel Prize in Chemistry, the forecast of a wide application of these systems to avoid the use of fossil fuels and their effect on global warming has raised doubts about their safety, sustainability, and performance. To make a post-lithium era possible, other reducing metals are investigated. While sodium shows certain analogies with lithium, some advantages with respect to its abundance and availability or the lack of Al alloy that could substantially reduce production costs make sodium-ion batteries a good alternative, particularly for stationary applications. On the other hand, other abundant multivalent elements such as Mg can provide even higher energy densities. The possibility of using dual ions can be a strategy to get the best of each element in a synergistic battery system. Dual Na+/Mg2+ systems have been considered a potential option by different researchers. In this review, we shall discuss different results on dual-metal-ion systems studied in our laboratory, particularly vanadium oxides and phosphates and layered manganese oxides.
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Hydrogen permeation through a pure palladium film (25 μm thickness, optically dense) is employed to trigger electron transfer (hydrogen-driven) reactions at the external palladium | aqueous electrolyte interface of a two-compartment electrochemical cell. Two systems are investigated to demonstrate feasibility for (i) indirect hydrogen-mediated silver electrodeposition with externally applied potential and (ii) indirect hydrogen-mediated silver electrodeposition driven by external formic acid decomposition. In both cases, porous metal deposits form as observed by optical and electron microscopies. Processes are self-limited as metal deposition blocks the palladium surface and thereby slows down further hydrogen permeation. The proposed methods could be employed for a wider range of metals, and they could provide an alternative (non-electrochemical or indirect) procedure for metal removal or metal recovery processes or for indirect metal sensing.
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An electrochemical cycle for the grid energy storage in the redox potential of Fe involves the electrolysis of a highly concentrated aqueous FeCl2 solution yielding solid iron deposits. For the high overall energy efficiency of the cycle, it is crucial to maximize the energy efficiency of the electrolysis process. Here we present a study of the influence of electrolysis parameters on the energy efficiency of such electrolysis, performed in an industrial-type electrolyzer. We studied the conductivity of the FeCl2 solution as a function of concentration and temperature and correlated it with the electrolysis energy efficiency. The deviation from the correlation indicated an important contribution from the conductivity of the ion-exchange membrane. Another important studied parameter was the applied current density. We quantitatively showed how the contribution of the resistance polarization increases with the current density, causing a decrease in overall energy efficiency. The highest energy efficiency of 89 ± 3% was achieved using 2.5 mol L−1 FeCl2 solution at 70 °C and a current density of 0.1 kA m−2. In terms of the energy input per Fe mass, this means 1.88 Wh g−1. The limiting energy input per mass of the Fe deposit was found to be 1.76 Wh g−1.
Graphical abstractIn this work, the electrochemical performance of Na-doped layered cathode material LiCoO2 for Li-ion batteries is studied using first-principles calculations. The results show that the doped Na ion acts as a pillar, which can greatly increase the diffusion rate of Li ions, but it is not conducive to improving cycle performance and delithiation potential. These research results provide a theoretical reference for the study of Li-ion batteries with high-rate performance. Due to the conflicting role of single element doping, the multi-element co-doping strategy will be the best way to develop high-performance Li-ion batteries.
Graphical abstractNickel oxide (NiO) nanosheets (NSs) deposited on different amounts (0.025, 0.05, 0.1, and 0.2 wt%) of reduced graphene oxide (rGO) are synthesized through hydrothermal method. The NiO NSs on rGO (rGO-NiO) are characterized by using X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, high resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED) analyses, and electrochemical analysis. Electrocatalytic activity of rGO-NiO nanocomposite modified glassy carbon (GC/rGO-NiO) electrode is examined towards electrocatalytic oxidation of urea in 0.1 M NaOH using cyclic voltammetry and amperometry techniques. The GC/rGO0.1-NiO nanocomposite modified electrode shows enhanced electrocatalytic oxidation of urea than that of other modified electrodes due to the incorporation of NiO NSs on an optimum amount of rGO. The GC/rGO0.1-NiO modified electrode is used for designing electrochemical sensor for urea, and the detection limit is estimated as 0.47 μM using the amperometry technique. The sensitivity of GC/rGO0.1-NiO modified electrode is found to be 2450 μA mM−1 cm−2. In addition to good electroanalytical performance, the present urea sensor displayed good stability and acceptable anti-interference ability in the presence of 20-fold excess concentration of relevant interferents. The GC/rGO0.1-NiO nanocomposite modified electrode is successfully used for the determination of urea in water sample.
Schematic representation of electrocatalytic oxidation of urea at GC/rGO-NiO nanocomposite modified electrode.
A straightforward process for synthesis of hybrid porous electrode material composed of reduced graphene oxide (rGO) and copper sulfide (CuS) with layered structure on the stainless steel substrate is developed. As-synthesized hybrid electrode shows hexagonal crystal structure of CuS with 77 m2 gm−1 specific surface area and 22 nm average pore size. The specific capacitance obtained with rGO-CuS5 hybrid electrode is 1201 F g−1 at the sweep rate of 5 mV s−1 in 1 M LiClO4 aqueous electrolyte. The majority of charge stored by diffusion-controlled process indicates benefits of layered structures for solid-state energy storage. The rGO-CuS5-based hybrid symmetric supercapacitor delivers a specific capacitance (Cs) as high as 109 F g−1 at a sweep rate of 5 mV s−1 with polyvinyl alcohol (PVA)-LiClO4 gel electrolyte. Also, the specific energy of 44 Wh kg−1 and specific power of 1.4 kW kg−1 with 87% stability after 6000 cycles at an applied current of 5 mA are obtained. The simple process of synthesis of layered hybrid electrode material for flexible supercapacitor promises its use in smart textile and wearable electronic devices.
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Metal surfaces covered with oxides have attracted considerable scientific attention in various applications. In particular, anodic films fabricated by cost-effective anodizing have been widely used in nano-structured engineering to provide various surface functionalities. However, understanding of alloy film stability, having individual elements with widely varying structures and morphologies, is very limited due to lack of thermodynamic information and effects of electrolyte chemistry. This requires many tedious efforts on a trial and error basis in selecting suitable electrolytes that can produce the protective film at high efficiency on alloys having mixed chemistries. It is, therefore, crucial to develop a combination of high throughput theoretical analysis and automated rapid localized electrochemical probing that provides a fast and simple solution for electrolyte choice and paves the way to the remarkable expansion of industrial applications of oxides. Herein, we demonstrate that combinatorial Al–Gd alloys covering 1.0 to 10.0 at.% Gd can be oxidized into ultra-thin anodic films of controlled thickness through a selection of electrolyte based on thermodynamics (phosphate buffer with a pH of 8.20). We propose that growth of anodic films on alloys at high efficiency is possible if Gibbs free energy minimization criteria would be systematically contemplate.
Graphical abstractIn this research, a new heterogeneous catalyst is fabricated through covalent modification of iron-based metal–organic framework with ionic liquid. In more detail, using 2-aminoterephthalic acid and iron (III) chloride hexahydrate, amino-functionalized metal–organic framework has been synthesized and then reacted with 2,4,6-trichloro-1,3,5-triazine and 1,4-diazabicyclo[2.2.2]octane successively to furnish ionic liquid on metal–organic framework. The as-prepared catalyst was characterized by FTIR, TGA, BET, SEM/EDS, XRD and elemental mapping analysis and then employed for catalyzing synthesis of pyrano [2,3‐d]pyrimidines (with yields of 80–100%) from one-pot three-component reaction of aldehydes, barbituric acid and malononitrile in aqueous media. The catalytic test inferred high catalytic activity of the catalyst, superior to that of IL and metal–organic framework. Furthermore, the catalyst could be recovered and recycled for five reaction runs with preserving its morphology.
Graphic abstractFor the first time, the synergistic effect of graphene oxide nanocolloids (nano-GO) and silicon dioxide (silica) nanoparticles (SiO2-nanoparicles) has been used to modify a glassy carbon electrode (GCE) for the determination of gallic acid (GA). The modified electrode surface was characterised by using scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDXA) and Fourier transform infrared spectroscopy (FTIR). The electrochemical behaviour of the modified electrode was then studied, using cyclic voltammetry (CV) and differential pulse voltammetry (DPV), showing that the electrode was sensitive to GA in a concentration range of 6.25 × 10−6 to 1.0 × 10−3 mol L−1, with a correlation coefficient R2 of 0.9956 and a limit of detection of 2.09 × 10−6 mol L−1 (S/N = 3). The proposed method was successfully used for the determination of GA in red wine, white wine and orange juice, with recoveries of 102.3, 95.4 and 97.6%, respectively.
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The existing energy situation demands not only the huge energy in a short time but also clean energy. In this regard, an integrated photo-supercapacitor device has been fabricated in which photoelectric conversion and energy storage are achieved simultaneously. A novel carbazole-based dye is synthesized and characterized for photosensitizer. The silver-doped titanium dioxide (Ag-TiO2) is synthesized, and it is used as photoanode material. Different concentrations of tetrabutylammonium iodide (TBAI)-doped polyvinyl alcohol–polyvinylpyrrolidone (PVA-PVP) blend polymer electrolytes are prepared, and their conductivity and dielectric properties were studied. Reduced graphene oxide (r-GO) is synthesized by a one-pot synthesis method and confirmed using Raman spectroscopy for counter electrode material in dye-sensitized solar cell (DSSC) and supercapacitor electrodes. The DSSC having 4% Ag-TiO2–based photoanode showed the highest efficiency of 1.06% (among r-GO counter electrodes) and 2.37% (among platinum counter electrodes). The supercapacitor before integration and after integration exhibits specific capacitance of 1.72 Fg−1 and 1.327 Fg−1, respectively.
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Anodic oxides were grown to 50 V on Ta in several organic ions containing anodizing baths. Their properties were compared with anodic Ta oxide film grown to the same formation voltage in 0.1 M NaOH. Anodizing process carried out in sodium citrate led to the growth of the anodic oxide with the best blocking properties whilst, when Ta is anodized in sodium adipate, a significant part of the circulated charge is wasted in side reactions, such as oxygen evolution. Photoelectrochemical measurements showed the presence of optical transitions at energy lower than the band gap for the anodic films grown in citrate and tartrate electrolytes, attributed to localized electronic states located close to the valence band mobility edge of the films generated by anions incorporation into the oxide. Differential capacitance measurements proved an increase by 17% in capacitance value for the oxide grown in citrate-containing solution with respect to that grown in NaOH electrolyte. A sketch of the energetic of the metal/oxide interface is provided.
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In this work, Cu-Zn-Sn (CZT) is co-electrodeposited onto a flexible Mo substrate exploiting an alkaline bath (pH 10). The plating solution is studied by cyclic voltammetry, highlighting the effects of potassium pyrophosphate (K4P2O7) and EDTA-Na2 on the electrochemical behavior and stability of the metallic ionic species. The optimized synthesis results in a homogeneous precursor layer, with composition Cu 44 ± 2 at. %, Zn 28 ± 1 at. %, and Sn 28 ± 2 at. %. Soft and reactive annealing are employed respectively to promote intermetallic phase formation and sulfurization of the precursor to obtain CZTS. Microstructural (XRD, Raman), morphological (SEM), and compositional (EDX, XRF) characterization is carried out on CZT and CZTS films, showing a minor presence of secondary phases. Finally, photo-assisted water splitting tests are performed considering a CZTS/CdS/Pt photoelectrode, showing a photocurrent density of 1.01 mA cm−2 at 0 V vs. RHE under 1 sun illumination.
Graphical abstractA simple, efficient and green approach to the synthesis of 1H-pyrazolo[1,2-b]phthalazine-5,10-diones has been developed via one-pot three-component reaction of aromatic aldehyde, malononitrile and phthalhydrazide catalyzed by zinc–proline complex (Zn[L-proline]2) using H2O: PEG400?=?6: 4 as solvent. Atom economy, good to excellent yield, operational simplicity and easy workup are important features of this method.
Graphical abstractCommercial resin microbeads are widely applied in ion exchange and extraction. Here, a single anion-selective and phosphate binding resin microbead (FerrIX™) is mounted into an epoxy membrane and investigated by 4-electrode membrane voltammetry and membrane impedance spectroscopy. Anion transport properties are observed to dominate associated with three distinct potential domains: (I) a low bias ohmic potential domain (dominant at high electrolyte concentration), (II) a concentration polarisation potential domain, and (III) an over-limiting potential domain. Voltammetric responses show transient diffusion-migration features at higher scan rates and quasi-steady state features at lower scan rates. Inherent microbead conductivity is shown to be linked to two resistive elements, electrolyte concentration dependent and independent, in series. The effects of phosphate binding are revealed as transient pattern in impedance spectroscopy data. Preliminary data suggest phosphate concentration-dependent peak features in the imaginary impedance versus frequency plot due to phosphate binding into the microbead.
Graphical abstractThis paper reports on the use of a novel microcapillary system for solid contact electrochemical measurements. The probe is made of moveable micropipettes, with orifice of 1–30-μm radii, filled with a conducting hydrogel, which forms a thin-gelled meniscus at the pipette end. The hydrogel is made of 2 % (w/v) agarose and water solutions, containing KCl or KNO3 as supporting electrolytes. The micropipette can be brought in contact with a conducting substrate to form a microcell, which allows performing voltammetric measurements confined within limited contact regions. The suitability of the proposed probe for local electrochemical measurements are tested using two electroactive species, dissolved in the hydrogel, namely [Fe (CN6)]4- and Ag+ ions. Mass transport characteristics of the two species, in bulk hydrogel and at micropipette meniscuses of different radii, are examined in detail in the frame of existing theory. For comparison, voltammetric measurements are also performed with micropipettes filled with the corresponding aqueous solutions. It is shown that the gel-filled micropipette, at variance with the aqueous one, prevents the spreading and leakage of solution on the sample surface. The microprobe developed here can be useful to perform electrochemical measurements on surfaces, which suffer from direct contact with liquid electrolytes. A proof-of-concept hydrogel-capillary measurement is performed to distinguish the presence of metallic silver deposited on a graphite-on-paper–based material, realized through simple pencil strokes.
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Permselective modifier films are very important in preparing highly sensitive electrochemical sensors. In this work, for the first time, the behavior of gold and glassy carbon electrodes coated with biocompatible zein film as a permselective membrane for the electrochemical detection of various compounds has been investigated. For this purpose, several electroactive cationic (methylene blue, brilliant green, and thionine) and anionic (potassium ferricyanide, alizarin red S, and riboflavin-5’-phosphate) compounds have been used as model. Atomic force microscopy (AFM) and scanning electron microscopy (SEM) showed that zein membranes prepared from casting solution containing 1% zein in ethanol/water have porous structures with high nanometric roughness. The capacitance values of electrical double layers of electrodes modified with zein film were very high for hydrophilic ions in comparison with hydrophobic ions. Point of zero charge pH (pHpzc) of zein membrane was 4.8. The results of cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) as well as pHpzc study indicated that zein permselective membrane acts as ion exchanger film for selected cationic compounds with fast electrochemical kinetics responses in aqueous solution (pH=7). This behavior was confirmed by circulating solutions containing model compounds from homemade continuous cell equipped with polyamide membranes modified with zein film.
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