Electrochemical Methods Research Articles

TRIBOLOGICAL PROPERTIES OF AAO COATINGSCATALYTICALLY MODIFIED WITH NICKEL

The purpose of this work is to determine the possibility of modifying oxide coating with nickel in the catalyticprocess and to verify the tribological properties of the coatings as a result of such modification. The coatingswere made on the EN AW-5251 aluminum alloy by electrochemical method. Nickel dispersions were obtainedthrough thermochemical treatment of the coatings. Tribological tests were carried out in a combination ofcoatings with polymer, cast iron, and steel, in a reciprocating motion on the T-17 tester. The paper presentsthe results of tribological tests and roughness of AAO coatings modified with nickel, before and after thetribological test. The results of tribological tests were supplemented with SEM tests and statistical analysis.The tests showed the possibility of modifying the AAO coatings with nickel compounds, which, in the case ofa sliding combination of the modified coating with steel, causes a significant reduction of friction forces bothin the case of technically dry friction and friction with lubrication.

A brief review of bisphenol derivatives and their electrochemical detection methods

A brief review of bisphenol derivatives and their electrochemical detection methods

Preparation of the LiGa Intermetallic Alloy by Electrochemical or Thermal Method for Ammonia Synthesis

Preparation of the LiGa Intermetallic Alloy by Electrochemical or Thermal Method for Ammonia Synthesis

Impact of Antioxidants on Mechanical Properties and ROS levels of Neuronal Cells Exposed to β-amyloid peptide.

This study aims to investigate the potential role of antioxidants in oxidative stress and its consequent impact on the mechanical properties of neuronal cells, particularly the stress induced by amyloid-beta (1-42) (Aβ42) aggregates. A key aspect of our research involved using scanning ion-conductance microscopy (SICM) to assess the mechanical properties (Young's modulus) of neuronal cells under oxidative stress. Reactive oxygen species (ROS) level was measured in single-cell using the electrochemical method by low-invasive Pt nanoelectrode. We investigated the effects of the low molecular weight antioxidant N-acetylcysteine (NAC) and the antioxidant enzyme superoxide dismutase 1 (SOD1) on the physiological and mechanical properties of neuronal cells using SICM. Using electrochemical method and SICM, NAC effectively reduces oxidative stress and restores Young's Modulus in SH-SY5Y cells exposed to hydrogen peroxide and Aβ42 oligomers. Our study first examined the influence of SOD1 on intracellular ROS levels in the presence of Aβ oligomers. The investigation into the effects of SOD1 and its nanoparticle form SOD1 on SH-SY5Y cells reveals impacts on mechanical properties and oxidative stress. The combined use of SICM and electrochemical measurements provided a comprehensive understanding of how oxidative stress, including that triggered by the Aβ oligomers affects the mechanical properties of cells.

Thermal Quenching of Intrinsic Photoluminescence in Amorphous and Monoclinic HfO2 Nanotubes

Nanotubular hafnia arrays hold significant promise for advanced opto- and nanoelectronic applications. However, the known studies concern mostly the luminescent properties of doped HfO2-based nanostructures, while the optical properties of nominally pure hafnia with optically active centers of intrinsic origin are far from being sufficiently investigated. In this work, for the first time we have conducted research on the wide-range temperature effects in the photoluminescence processes of anion-defective hafnia nanotubes with an amorphous and monoclinic structure, synthesized by the electrochemical oxidation method. It is shown that the spectral parameters, such as the position of the maximum and half-width of the band, remain almost unchanged in the range of 7–296 K. The experimental data obtained for the photoluminescence temperature quenching are quantitatively analyzed under the assumption made for two independent channels of non-radiative relaxation of excitations with calculating the appropriate energies of activation barriers—9 and 39 meV for amorphous hafnia nanotubes, 15 and 141 meV for monoclinic ones. The similar temperature behavior of photoluminescence spectra indicates close values of short-range order parameters in the local atomic surrounding of the active emission centers in hafnium dioxide with amorphous and monoclinic structure. Anion vacancies VO− and VO2− appeared in the positions of three-coordinated oxygen and could be the main contributors to the spectral features of emission response and observed thermally stimulated processes. The recognized and clarified mechanisms occurring during thermal quenching of photoluminescence could be useful for the development of light-emitting devices and thermo-optical sensors with functional media based on oxygen-deficient hafnia nanotubes.

Advancements in ascorbic acid quantification: from macroscopic analysis to miniaturized nano-sensing for quality control in food and beverage

Abstract Ascorbic acid (AA) or vitamin C, is vital in food safety, pharmaceutical and biomedical industries. This review discusses recent advancements in biosensors for AA detection. Traditional macro-analysis techniques such as high-performance liquids chromatography (HPLC), and flow injection analysis (FIA) provide accurate measurements but are costly and require specialized handling. Miniaturized nano-sensors are emerging as promising alternatives, offering advantages such as portability, cost effectiveness, and rapid response. This review explores the working principles of these nano-sensors, highlighting colorimetric, fluorometric and electrochemical detection methods. It also outlines the current AA biosensing landscape, detailing strategies to improve selectivity and specificity, including the choice of biorecognition elements and material selection for detection probe synthesis. Emerging nanomaterials and their applicability to support sensing activity are explored. This review serves as a valuable resource, suggesting future research directions to address existing challenges and further advance biosensor technology.

Recent Advances in the Electrochemical Functionalization of Imidazoheterocycles

AbstractImidazoheterocycles have extensive applications in the pharmaceutical industry and agrochemicals. A comprehensive overview has been provided on the current advancements in the electrochemical functionalization of imidazo‐fused heterocycles, which have been classified into ten different types of reactions. Electrochemical synthesis has emerged as a highly effective method for producing organic molecules, especially in the context of sustainable development. Employing electrons as the traceless oxidant, several C−H functionalization reactions of imidazo‐fused heterocycles have been achieved at either the C3 or C5 positions. Electrons may serve as the reducing agent to synthesize pyridine rings that are either partially or fully saturated in imidazo[1,2‐a]pyridines. The purpose of the review is to attract the interest of the scientific community and promote additional research on the functionalization of imidazoheterocycles using electrochemical methods.

On the Quest for Oxygen Evolution Reaction Catalysts Based on Layered Double Hydroxides: An Electrochemical and Chemometric Combined Approach

The oxygen evolution reaction (OER) is a crucial process in various energy conversion and storage technologies, such as water electrolysis. Developing efficient and cost‐effective electrocatalysts is essential to achieve the commercialization of devices for the transition toward sustainable energy solutions. Herein, ternary layer double hydroxides (LDHs) are synthesized and characterized as electrocatalysts for OER using a potentiodynamic electrochemical deposition method on Grafoil. A chemometric approach based on experimental design is employed to rationalize the effort in the investigation of the LDHs which are based on Ni, Co, and Fe. The deposited films are characterized using cyclic voltammetry and X‐ray diffraction to determine peak currents and potentials, and crystal size. Furthermore, the electrocatalyst performances are assessed by linear sweep voltammetry in 1M KOH from which the Tafel slope and onset potential are calculated. The obtained data are used to derive models describing the material properties and electrocatalyst performance as a function of the electrolyte composition used during the LDHs electrodeposition. This study provides valuable insights into the relationship between the electrocatalyst composition and its OER activity, enabling the design of more efficient and sustainable electrochemical systems for energy applications.

Wear and Corrosion Resistance of ZrN Coatings Deposited on Ti6Al4V Alloy for Biomedical Applications

Zirconium nitrides films were synthesized on Ti6Al4V substrates at a bias voltage of −50 V, −80 V, −110 V and −150 V by the direct current (DC) reactive magnetron sputtering technique. The as-deposited coatings were characterized by X-ray diffraction (XRD), Fourier-transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and atomic force microscopy (AFM). The wear and corrosion resistance of the obtained ZrN coatings were evaluated to determine the possibility for their implementation in modern biomedical applications. It was found that the intensity of the diffraction peak of the Zr-N phase corresponding to the (1 1 1) crystallographic plane rose as the bias voltage increased, while the ZrN coatings’ thickness reduced from 1.21 µm to 250 nm. The ZrN films’ surface roughness rose up to 75 nm at −150 V. Wear tests showed an increase in the wear rate and wear intensity as the bias voltage increased. Corrosion studies of the ZrN coatings were carried out by three electrochemical methods: open circuit potential (OCP), cyclic voltammetry (polarization measurements) and electrochemical impedance spectroscopy (EIS). All electrochemical measurements confirmed that the highest protection to corrosion is the ZrN coating, which was deposited on the Ti6Al4V substrate at a bias voltage of −150 V.

Three-chamber electrochemical reactor for selective lithium extraction from brine

Efficient lithium recovery from geothermal brines is crucial for the battery industry. Current electrochemical separation methods struggle with the simultaneous presence of Na+, K+, Mg2+, and Ca2+ because these cations are similar to Li+, making it challenging to separate effectively. We address these challenges with a three-chamber reactor featuring a polymer porous solid electrolyte in the middle layer. This design improves the transference number of Li+ (tLi+) by 2.1 times compared to the two-chamber reactor and also reduces the chlorine evolution reaction, a common side reaction in electrochemical lithium extraction, to only 6.4% in Faradaic Efficiency. Employing a lithium-ion conductive glass ceramic (LICGC) membrane, the reactor achieved high tLi+ of 97.5% in LiOH production from simulated brine, while the concentrations of Na+ K+, Mg2+, and Ca2+ are below the detection limit. Electrochemical experiments and surface analysis elucidated the cation transport mechanism, highlighting the impact of Na+ on Li+ migration at the LICGC interface.

Ultra-fast synthesis of transition metal-MXene nanocomposite electrocatalyst for energy-saving seawater hydrogen production: Experiment and theory

Switching from the urea oxidation reaction (UOR) to the oxygen evolution reaction (OER) is a beneficial way to lower the amount of energy needed to make hydrogen gas during the hydrogen evolution reaction (HER). Due to the sluggish reaction kinetics of the six electrons reaction of UOR, designing a privileged bifunctional electrocatalyst for both HER and UOR necessitates. The 2D nano-sized non-noble metal electrocatalysts make it possible to speed up reactions and improve their electrocatalytic performance. We synthesized nickel-cobalt-MXene composite nanosheets (NiCoMXene) on the surface of copper foam using a one-pot, simple, and ultra-fast electrochemical method. This 2D electrocatalyst demonstrates high electrocatalytic performance towards HER (overpotential of 76 mV at −10 mA cm−2) with excellent durability in alkaline media. Furthermore, NiCoMXene nanocomposite served as a bifunctional electrocatalyst to investigate hydrogen gas production by a hybrid system HER coupled with UOR in seawater. The NiCoMXene requires a low overpotential for HER (81 mV) and UOR (1.38 V) to achieve a current density of 10 mA cm−2 in seawater, and the needed cell voltage to reach the same current density is 1.42 V in seawater. Our DFT analysis found a significant synergy between MXene and NiCo in the electrocatalyst. PDOS analysis showed remarkably that introducing Ni atoms to MXene shifts the d-band center to the left (lower energy), while Co atoms shifts it to the right (higher energy) and increased states near the Fermi level. This electronic structure makes the nanocomposite an ideal electrocatalyst, with MXene providing electrons and Co atoms serving as active sites for both HER and UOR.This research work can provide a useful directive to explore the electrocatalysts with outstanding catalytic activity.

Simplification of solvation shell with water clusters in the simulation of electrochemical nitrogen reduction reaction.

Electrochemical methods for nitrogen reduction have received extensive attention due to the mild reaction conditions. In order to gain an insight into the mechanism of the electrochemical nitrogen reduction process, theoretical simulations are necessary. However, current simulation studies contain many imprecise approximations that may hinder the real recognition of the reaction process. Although solvation methods have recently been developed to provide efficient descriptions, their further applications are hindered by controversy over modeling of solvents and the enormous computational effort required. In this work, we simplify the solvation conditions by using water clusters and compare them with an accurate water layer model. The results demonstrate that the simplified water clusters can effectively capture protons, simulate the surface electric environment, and enable the calculation of the activation energy of the reaction. This method offers an affordable approach for simulating the surface potentials and solvents and provides a new reference for the theoretical study of the electrochemical nitrogen reduction reaction.

Amino-functionalized vertically ordered mesoporous silica film on electrochemically polarized screen-printed carbon electrodes for the construction of gated electrochemical aptasensors and sensitive detection of carcinoembryonic antigens

Disposable electrochemical biosensors with high sensitivity are very fit for point-of-care testing in clinical diagnosis. Herein, amino-functionalized, vertically ordered mesoporous silica films (NH2-VMSF) attached to an electrochemically polarized screen-printed carbon electrode (p-SPCE) are prepared using a simple electrochemical method and then utilized to construct a gated electrochemical aptasensor for rapid and sensitive determination of carcinoembryonic antigen (CEA). After being treated with the electrochemical polarization procedure, p-SPCE has plentiful oxygen-containing groups and improved catalytic ability, which help promote the stability of NH2-VMSF on SPCE without the use of an adhesive layer and simultaneously generate a highly electroactive sensing interface. Owing to the numerous uniform and ultrasmall nanopores of NH2-VMSF, CEA-specific aptamer anchored on the external surface of NH2-VMSF/p-SPCE serves as the gatekeeper, allowing the specific recognition and binding of CEA and eventually impeding the ingress of electrochemical probes [Fe(CN)63−/4−] through the silica nanochannels. The declined electrochemical responses of Fe(CN)63−/4− can be used to quantitatively detect CEA, yielding a wide detection range (100 fg/mL to 100 ng/mL) and a low limit of detection (24 fg/mL). Moreover, the proposed NH2-VMSF/p-SPCE-based electrochemical aptasensor can be applied to detect the amount of CEA in spiked human serum samples, which extends the biological application of a disposable NH2-VMSF/p-SPCE sensor by modulating the biological recognition species.

Deciphering Electrocatalytic Hydrogen Production in Water Through a Bioinspired Water-Stable Copper(II) Complex Adorned with (N2S2)-Donor Sites.

Electrocatalytic hydrogen production stands as a pivotal cornerstone in ushering the revolutionary era of the hydrogen economy. With a keen focus on emulating the significance of hydrogenase-like active sites in sustainable H2 generation, a meticulously designed and water-stable copper(II) complex, [Cl-Cu-LN2S2]ClO4, featuring the N,S-type ligand, LN2S2 (2,2'-((butane-2,3-diylbis(sulfanediyl))bis(methylene))dipyridine), has been crafted and assessed for its prowess in electrocatalytic H2 production in water, leveraging acetic acid as a proton source. The molecular catalyst, adopting a square pyramidal coordination geometry, undergoes -Cl substitution by H2O during electrochemical conditions yielding [H2O-Cu-LN2S2]2+ as the true catalyst, showcases outstanding activity in electrochemical proton reduction in acidic water, achieving an impressive rate of 241.75 s-1 for hydrogen generation. Controlled potential electrolysis at -1.2 V vs. Ag/AgCl for 1.6 h reveals a high turnover number of 73.06 with a commendable Faradic efficiency of 94.2 %. A comprehensive analysis encompassing electrochemical, spectroscopic, and analytical methods reveals an insignificant degradation of the molecular catalyst. However, the post-CPE electrocatalyst, present in the solution domain, signifies the coveted stability and effective activity under the specified electrochemical conditions. The synergy of electrochemical, spectroscopic, and computational studies endorses the proton-electron coupling mediated catalytic pathways, affirming the viability of sustainable hydrogen production.

Computational supported experimental insights in adsorption of Congo Red using ZnO/doped ZnO in aqueous solution

The rapid growth of industrialisation has led to the discharge of harmful effluents into water bodies, severely disrupting the balance of ecosystems. The detection and removal of dyes from wastewater remains a significant challenge. In this study, we report the synthesis of zinc oxide (ZnO) and its doped derivatives through a facile chemical method, followed by comprehensive characterisation and analysis to assess their potential in various applications. The structural properties of the synthesised materials were confirmed by X-ray diffraction (XRD), which verified their crystalline nature and phase purity. Morphological analysis using field emission scanning electron microscopy (FE-SEM) coupled with energy dispersive X-ray analysis (EDAX) revealed well-defined nanostructures and uniform elemental distribution. The adsorption ability of the synthesized adsorbents was investigated through electrochemical methods, cyclic voltammetry and Tafel plots, which demonstrated enhanced conductivity and charge transfer characteristics. Additionally, theoretical studies through molecular modelling and molecular dynamic simulations were employed to elucidate the interactions between Congo red molecules and the surface of the synthesized compounds. Adsorption experiments were conducted to evaluate the efficacy of ZnO and its doped variants as adsorbents. To investigate any structural or functional changes after dye adsorption FTIR and XRD were compared, provided a deeper insight into the adsorption mechanism. This multi-faceted approach highlights the potential of ZnO-based materials for effective wastewater treatment and other environmental applications.

Electrochemical Methods for Nutrient Removal in Wastewater: A Review of Advanced Electrode Materials, Processes, and Applications

In response to the increasing global water demand and the pressing environmental challenges posed by climate change, the development of advanced wastewater treatment processes has become essential. This study introduces novel electrochemical technologies and examines the scalability of industrial-scale electrooxidation (EO) methods for wastewater treatment, focusing on simplifying processes and reducing operational costs. Focusing on the effective removal of key nutrients, specifically nitrogen and phosphorus, from wastewater, this review highlights recent advancements in electrode materials and innovative designs, such as high-performance metal oxides and carbon-based electrodes, that enhance efficiency and sustainability. Additionally, a comprehensive discussion covers a range of electrochemical methods, including electrocoagulation and electrooxidation, each evaluated for their effectiveness in nutrient removal. Unlike previous studies, this review not only examines nutrient removal efficiency, but also assesses the industrial applicability of these technologies through case studies, demonstrating their potential in municipal and industrial wastewater contexts. By advancing durable and cost-effective electrode materials, this study emphasizes the potential of electrochemical wastewater treatment technologies to address global water quality issues and promote environmental sustainability. Future research directions are identified with a focus on overcoming current limitations, such as high operational costs and electrode degradation, and positioning electrochemical treatment as a promising solution for sustainable water resource management on a larger scale.

Electrochemical C−O and C−N Arylation using Alternating Polarity in flow for Compound Libraries

AbstractEtherification and amination of aryl halide scaffolds are commonly used reactions in parallel medicinal chemistry to rapidly scan structure–activity relationships with abundant building blocks. Electrochemical methods for aryl etherification and amination demonstrate broad functional group tolerance and extended nucleophile scope compared to traditional methods. Nevertheless, there is a need for robust and scale‐transferable workflows for electrochemical compound library synthesis. Herein we describe a platform for automated electrochemical synthesis of C−X arylation (X=NH, OH) in flow to access compound libraries. A comprehensive Design of Experiment (DoE) study identifies an optimal protocol which generates high yields across>30 aryl halide scaffolds, diverse amines (including electron‐deficient sulfonamides, sulfoximines, amides, and anilines) and alcohols (including serine residues within peptides). Reaction sequences are automated on commercially available equipment to generate libraries of anilines and aryl ethers. The unprecedented application of potentiostatic alternating polarity in flow is essential to avoid accumulating electrode passivation. Moreover, it enables reactions to be performed in air, without supporting electrolyte and with high reproducibility over consecutive runs. Our method represents a powerful means to rapidly generate nucleophile independent C−X arylation compound libraries using flow electrochemistry.

Oxygen‐Stable Electrochemical CO2 Capture using Redox‐Active Heterocyclic Benzodithiophene Quinone

AbstractElectrochemical carbon capture offers a promising alternative to thermal amine technology, which serves as the traditional benchmark method for CO2 capture. Despite its technological maturity, the widespread deployment of thermal amine technologies is hindered by high energy consumption and sorbent degradation. In contrast, electrochemical methods, with their inherently isothermal operation, address these challenges, offering enhanced energy efficiency and robustness. Among emerging strategies, electrochemical carbon capture systems using redox‐active materials such as quinones stand out for their potential to capture CO2. However, their practical application is currently limited by their low stability in the presence of oxygen. We demonstrate that benzodithiophene quinone (BDT‐Q), a heterocyclic quinone, exhibits high stability in electrochemical carbon capture processes with oxygen‐containing feed gas. Conducted in a cyclic flow system with a simulated flue gas mixture containing 13 % CO2 and 3.5 % O2 for over 100 hours, the process demonstrates high oxygen stability with an electron utilization of 0.83 without significant degradation, indicating a promising approach for real world applications. Our study explores the potential of new heterocyclic quinone compounds in the context of carbon capture technologies.

Oxygen-Stable Electrochemical CO2 Capture using Redox-Active Heterocyclic Benzodithiophene Quinone.

Electrochemical carbon capture offers a promising alternative to thermal amine technology, which serves as the traditional benchmark method for CO2 capture. Despite its technological maturity, the widespread deployment of thermal amine technologies is hindered by high energy consumption and sorbent degradation. In contrast, electrochemical methods, with their inherently isothermal operation, address these challenges, offering enhanced energy efficiency and robustness. Among emerging strategies, electrochemical carbon capture systems using redox-active materials such as quinones stand out for their potential to capture CO2. However, their practical application is currently limited by their low stability in the presence of oxygen. We demonstrate that benzodithiophene quinone (BDT-Q), a heterocyclic quinone, exhibits high stability in electrochemical carbon capture processes with oxygen-containing feed gas. Conducted in a cyclic flow system with a simulated flue gas mixture containing 13 % CO2 and 3.5 % O2 for over 100 hours, the process demonstrates high oxygen stability with an electron utilization of 0.83 without significant degradation, indicating a promising approach for real world applications. Our study explores the potential of new heterocyclic quinone compounds in the context of carbon capture technologies.

CRISPR-Cas14a and allosteric transcription factors empowered cell-free electrochemical biosensor for highly sensitive and stable detection of progesterone in multiple scenarios

In this study, a cell-free electrochemical assay based on allosteric transcription factors (aTFs) and CRISPR-Cas14a was developed for the detection of progesterone in trace samples. This electrochemical biosensor helps to overcome the drawbacks of the traditional fluorescence assay based on the CRISPR-Cas system and aTFs combined for non-nucleic acid targets that is poorly effective for the detection of colored samples. By comparing and optimizing the concentration and length of the probes in the straight chain and hairpin structure, the sensor performance was improved. In addition, different sgRNA from other studies was designed to overcome the effect of sequence folding in the space region on Cas14a activation. Based on these optimization results, we constructed an electrochemical sensor for progesterone quantification in the range of 66.7pM to 3.33 × 10−1μM. This method requires only 2 μL of sample and does not necessitate complex pretreatment steps, with detection completed within 1.5 h. The method has been successfully applied to food, environmental, and biological samples, with recovery rates between 82.65% and 109%. This suggests that CRISPR and allosteric transcription factor-powered electrochemical detection methods have significant potential for use in the field of small molecule detection under various scenarios.