Electrochemical Systems Research Articles

Motional Resistance as Highly Selective Descriptor to Probe Dynamic Formation of Surface Films on Zinc Anode

AbstractZinc anodes are expected as a promising alternative to lithium‐based anodes in energy storage systems due to their low cost, high theoretical capacity, and environmental friendliness. However, the development of efficient and stable zinc anode requires a fundamental understanding of the interfacial processes occurring during zinc deposition and dissolution cycling. In this study, we employed electrochemical quartz crystal microbalance (EQCM) analysis to investigate the potential‐dependent formation and decomposition of surface films on zinc metal anodes in sulfate‐based aqueous electrolytes. Changes in frequency and motional resistance served as complementary descriptors, with motional resistance being a highly selective indicator for probing dynamic surface film formation driven by side reactions at the zinc anode. While the frequency change provided the overall changes in the mass of both zinc metal and surface films, changes in the motional resistance selectively reflected the amount and nature of the visco‐elastic interface that comprise the surface films. The two descriptors provide quantitative and complementary means to discover the complex interfacial processes such as the formation of surface visco‐elastic films, guiding to the development of more stable and efficient zinc‐based electrochemical systems.

Lateral Electronic Junction of a Single Ultrathin Silicon Induced by Interfacial Dipole of Self-Assembled Monolayer.

Interface engineering is pivotal for enhancing the performance and stability of devices with layered structures, including solar cells, electronic devices, and electrochemical systems. Incorporating the interfacial dipole between the bulk layers effectively modulates the energy level difference at the interface and does not significantly influence adjacent layers overall. However, interfaces can drastically affect adjoining layers in ultrathin devices, which are essential for next-generation electronics with high integrity, excellent performance, and low power consumption. In particular, the interfacial effect is pronounced in ultrathin semiconductors, which have a weak electric field screening effect. Herein, the substantial interfacial impact on the ultrathin silicon is shown, the p- to n-type inversion of the semiconductor solely through the deposition of a self-assembled monolayer (SAM) without external bias. The effects of SAMs with different interfacial dipoles are investigated by using Hall measurement and surface analytic techniques, such as UPS, XPS, and KPFM. Furthermore, the lateral electronic junction of the ultrathin silicon is engineered by the regioselective deposition of SAMs with opposite dipoles, and the device exhibits rectification behavior. When the interfacial dipole of SAM is manipulated, the rectification ratio changes sensitively, and thus the fabricated diode shows potential to be developed as a sensing platform.

Sulfamethoxazole degradation in tri-electrode microbial electrochemical systems: Metabolomic and Metagenomic insights into organic pollution effects

Organic pollutants can alter the physicochemical properties and microbial communities of water bodies. In water contaminated with organic pollutants, the unique extracellular electron transfer mechanisms that promote sulfamethoxazole (SMX) degradation in tri-electrode microbial electrochemical systems (TE-MES) may be impacted. To simulate biodegradable organic matter contamination, glucose (GLU) was added. Metagenomics and metabolomics were used to analyze changes in microbial community structure, metabolism, and function on the electrodes. GLU addition accelerated water quality deterioration, and enhanced SMX degradation. Microbial taxa on the electrodes experienced selective enrichment. Notably, methanogens and SMX-degrading bacteria were enriched, while denitrifying bacteria and antibiotic-resistant bacteria were suppressed. Enriched metabolites were linked to 15 metabolic pathways and other functions like microbial signaling and genetics. Non-redundant genes also clustered in metabolic pathways, aligning with metabolite enrichment results. Additional pathways involved life cycle processes and protein interactions. Enzymes related to carbon metabolism, particularly glycoside hydrolases, increased significantly, indicating a shift in carbon metabolism on microbial electrodes after GLU addition. The abundance of intracellular electron transfer enzymes rose, while outer membrane proteins decreased. This contrasts with the typical TE-MES mechanism where outer membrane proteins facilitate SMX degradation. The presence of organic pollution may shift SMX degradation from an extracellular electrochemical process to an intracellular metabolic process, possibly involving co-metabolism with simple organic compounds. This study provides mechanistic insights and theoretical guidance for using TE-MES with embedded microbial electrodes to treat antibiotic-contaminated water affected by organic pollution.

Transport numbers of ion-exchange membranes in ternary mixtures of KCl, H2O and ethanol relevant for electrodialysis and desalination processes

Understanding the transport phenomena in electrolyte mixtures involved in electrochemical processes is of utmost importance for the modelling and improvement of battery technology, fuel cells, ion-exchange membrane processes, and much more. In this work, we derive relations and present methods for the analysis of electric potential measurements of concentration cells and ion-exchange membrane permselectivity with ternary mixtures of KCl, H2O and ethanol (EtOH). Measurements of electric potentials across the Selemion CMVN (cation-exchange) and AMVN (anion-exchange) membranes in this ternary mixture suggest that the presence of EtOH affects the membrane permselectivity, but that the transference of EtOH is zero; i.e., ta=0. Instead, the decrease in membrane permselectivity can be explained by a varying water transference coefficient, tw. In the absence of EtOH we find tw≈4 in both membranes, and that the decrease in tw is proportional to the average thermodynamic activity of EtOH in mixtures adjacent to the membranes. The membranes were also found to be charge selective, as quantified by the ionic transport numbers; i.e., tK+=1 for the Selemion CMVN and tK+=0 for the Selemion AMVN. The presented method can readily be extended and leveraged to determine transference coefficients in other electrochemical systems.

Exploring the impact of fulvic acid on electrochemical hydrogen-driven autotrophic denitrification system: Performance, microbial characteristics and mechanism

In this study, the effect of modulating fulvic acid (FA) concentrations (0, 25 and 50 mg/L) on nitrogen removal in a bioelectrochemical hydrogen autotrophic denitrification system (BHDS) was investigated. Results showed that FA increased the nitrate (NO3–-N) removal rate of the BHDSs from 37.8 to 46.2 and 45.2 mg N/(L·d) with a current intensity of 40 mA. The metagenomic analysis revealed that R2 (25 mg/L) was predominantly populated by autotrophic denitrifying microorganisms, which enhanced denitrification performance by facilitating electron transfer. Conversely, R3 (50 mg/L) exhibited an increase in genes related to the heterotrophic process, which improved the denitrification performance through the collaborative action of both autotrophic and heterotrophic denitrification pathways. Besides, the study also identified a potential for nitrogen removal in Serpentinimonas, which have been rarely studied. The interesting set of findings provide valuable reference for optimizing BHDS for nitrogen removal and promoting specific denitrifying genera within the system.

Development of tetravalent antibody–enzyme complexes employing a lactate oxidase and the application to electrochemical immunosensors

Antibody–enzyme complexes (AECs) are ideal for immunosensing. Although AECs using antibody fragments can be produced by bacterial hosts, their low affinity limits their sensing applications. We have improved the affinity of AECs by combining two antibodies using Catcher/Tag systems; however, it requires multiple antibodies and an enzyme production process. In this study, to realize the production of AECs harboring multiple antibody fragments in a single production process, we report a versatile development method of unique AECs based on a multimeric enzyme structure. Using the homotetrameric enzyme, lactate oxidase (LOx), as a labeling enzyme, tetravalent AECs were developed as an electrochemical immunosensor. Homogeneous tetravalent AECs were successfully fabricated by fusing the anti-epidermal growth factor receptor (EGFR) variable domain of a heavy chain of heavy chain antibody to the N-terminus of LOx. The prepared AECs bound to EGFR, maintain their enzyme activity, and worked well as sensing elements in electrochemical sandwich enzyme-linked immunosorbent assay. Moreover, tetravalent AECs exhibited higher sensitivity than monovalent AECs because of their avidity. The fabricated AECs were successfully used in a wash-free homogeneous electrochemical detection system combined with magnetic separation. Our findings offer new insights into the applications of the LOx tetrameric enzyme for the fabrication of AECs with tetravalent antibodies, which may serve as scaffolds for immunosensors.

Efficient removal and separation of cationic dyes by microbubbles for electroflotation coupling membrane electrosorption

In order to enhance the treatment efficiency of cationic dyes wastewater, a dual chamber reactor was ingeniously designed to combine electroflotation and electrosorption technologies. The electrochemical system effectively removed representative single and mixed cationic dyes within 64 min at 150 mA. The observable reaction process phenomena, microbubble photos, clear Tyndall effect phenomena, and electrochemical experimental results all indicated the crucial role of electroflotation in removing cations dyes. Furthermore, changes in surface color, morphology, and functional groups of the anion exchange membrane before and after electrolysis suggested that the electrosorption process also contributed significantly to the removal process. Analysis using UV–vis absorption spectrum and high-resolution mass spectroscopy indicated that no significant chemical reaction occurred with the cationic dye during this process; thus, confirming that the separation of the cationic dye was a physical removal process. This study provides valuable theoretical guidance for efficient removal and separation of cationic dyes in wastewaters.

Uncovering accurate values of the polarization resistance in molten fluorides using electrochemical impedance spectroscopy

High-temperature operation and the presence of oxidizing impurities in molten chloride and fluoride salts pose significant corrosion risks to structural alloys in molten salt nuclear reactors. Electrochemical impedance spectroscopy (EIS) offers an operando, real-time method to study the instantaneous corrosion behavior of these materials non-destructively. However, signal noises may originate from sources extraneous to the electrochemical systems that limit the ability to perform quality impedance measurements in low-frequency regime where polarization resistance (Rp) dominates. Using the exposure of pure Cr in molten LiF-NaF-KF containing 1 wt% EuF3 at 600 °C as a model corrosion system, the extent of Non-Uniform Current and Potential (NUCP) distribution during an AC perturbation associate with the disk electrodes is evaluated in terms of two dimensionless correction factors kfRct(=Rct/Reff) and kfCdl(=Cdl/Ceff). Results show that a small area Cr disk electrode increases the transition frequency that marks the dominance of Rp to a conventional terminational frequency above 10−2 Hz, enabling a reliable charge-transfer resistance (Rct) value to be determined via circle fitting of an electrical equivalent circuit model (ECM) model. Experimental results were supported by EIS simulations considering commonly used ECM models that factor in the NUCP effect of disk geometries.

CeCl3 concentration effects on cyclic voltammogram overlap in LiCl-KCl eutectic molten salt

In the present study, cyclic voltammetry was performed to investigate CeCl3 in a LiCl-KCl eutectic molten salt at various concentrations. The results indicate that the overlap degree of cyclic voltammograms at different cycles deteriorates with the increasing CeCl3 concentration in the molten salt. This phenomenon was attributed to higher concentrations of CeCl3, which led to a non-uniform film on the electrode surface. This was evidenced by material characterization of the working electrode after cyclic voltammetry (CV) testing and the simulated cyclic voltammograms of a reversible electrochemical reaction. This study will provide new insights that enhance our understanding of the electrochemistry of the CeCl3-LiCl-KCl system and offer valuable reference for other soluble-insoluble electrochemical systems.

Radiation Chemistry as a Tool to Accelerate and Predict Calendar Ageing in Lithium-Ion Batteries

Electrochemical energy storage systems such as batteries are in a resting mode most of the time. Even when no current is passing through them, they undergo ageing phenomena, more or less detrimental to their lifespan, known as calendar ageing. Limiting these ageing processes requires a better understanding of them, but studies on calendar ageing are generally time-consuming. Here, we show that radiolysis, i.e. chemistry induced by ionizing radiation, generates similar degradation compounds and can significantly accelerate calendar ageing phenomena (by a factor of 30 under our experimental conditions). Using electrochemical impedance spectroscopy (EIS), we studied symmetrical coin cells containing an electrolyte between two identical electrodes, with or without various additives commonly used in batteries. EIS makes it possible to monitor the change in resistance in the device over time and therefore the formation of the electrode/electrolyte interphase and the charge transfer kinetics. Among the various additives tested (vinylene carbonate, fluoroethylene carbonate and ethyl acetate), the first two proved to be those with the best properties for the cell as a whole. In all cases, just a few hours of irradiation were sufficient to simulate the equivalence of several weeks of calendar ageing.

20 Seconds to fabricate high-performance NiFe-based anode for seawater electrolysis via bidirectional pulse current method

Direct electrolysis of seawater to produce green hydrogen has attracted great attention. While the development of efficient and rapid manufacturing processes for high-performance electrodes, particularly for the oxygen evolution reaction (OER), remains trail. Here, we introduce an innovative approach to fabricate high-performance NiFe-based OER electrodes using an ultrafast and eco-friendly bidirectional pulse current (BPC) method, which remarkably shortens the production time to only 20 s. Our BPC method alternates oxidation and reduction currents within a single period, promoting the in-situ formation of porous NiFe(oxy)hydroxide nanosheets through dissolution/deposition processes. Moreover, this methodology creatively utilizes the “Cl− induced effect”, typically a hindrance in other electrochemical systems involving seawater or brine, to enhance the synthesis of electrodes from NaCl-based electrolyte devoid of additional Ni/Fe cations. The prepared NiFe-based electrode (NFF O-R 20 s) demonstrates remarkable OER catalytic activity, with optimal overpotentials (ηj) of 272, 308 and 367 mV at current densities (j) of 10, 100 and 1000 mA cm−2, respectively. Impressively, it maintains a low cell voltage of 1.59 V after enduring 1000 h of operation under the industrially current density of 300 mA cm−2, with a direct current energy consumption of 3.8 kWh Nm−3 H2 for overall alkaline seawater electrolysis. Our BPC preparation approach provides a promising path to construction high-catalytic activity, good-stability electrode, and low-energy consumption direct seawater electrolyzer.

Energy storage chemistry: Atomic and electronic fundamental understanding insights for high-performance supercapacitors

The scarcity of fuels, high pollution levels, climate change, and other major environmental issues are critical challenges that modern societies are facing, mostly originating from fossil fuels-based economies. These challenges can be addressed by developing green, eco-friendly, inexpensive energy sources and energy storage devices. Electrochemical energy storage materials possess high capacitance and superior power density. To engineer highly efficient next-generation electrochemical energy storage devices, the mechanisms of electrochemical reactions and redox behavior must be probed in operational environments. They can be studied by investigating atomic and electronic structures using in situ x-ray absorption spectroscopy (XAS) analysis. Such a technique has attracted substantial research and development interest in the field of energy science for over a decade. The mechanisms of charge/discharge, carrier transport, and ion intercalation/deintercalation can be elucidated. Supercapacitors generally store energy by two specific mechanisms—pseudocapacitance and electrochemical double-layer capacitance. In situ XAS is a powerful tool for probing and understanding these mechanisms. In this Review, both soft and hard x rays are used for the in situ XAS analysis of various representative electrochemical energy storage systems. This Review also showcases some of the highly efficient energy and power density candidates. Furthermore, the importance of synchrotron-based x-ray spectroscopy characterization techniques is enlightened. The impact of the electronic structure, local atomic structure, and electronically active elements/sites of the typical electrochemical energy storage candidates in operational conditions is elucidated. Regarding electrochemical energy storage mechanisms in their respective working environments, the unknown valence states and reversible/irreversible nature of elements, local hybridization, delocalized d-electrons spin states, participation of coordination shells, disorder, and faradaic/non-faradaic behavior are thoroughly discussed. Finally, the future direction of in situ XAS analysis combined with spatial chemical mapping from operando scanning transmission x-ray microscopy and other emerging characterization techniques is presented and discussed.

Research of electrode materials for the creation of multifunctional current sources with increased capacity as a components of the energy sector of an efficient urban environment

As part of creating a comfortable and safe environment, constructing energy-efficient residential and industrial buildings and structures that meet modern requirements and standards, the development of the production of environmentally friendly renewable and new individual energy sources is becoming especially relevant. In this regard, there is a need to increase the energy capacity of electrochemical cells. Research has been carried out on the metallized conductive materials creation based on rolled carbon non-woven material “Busofit” with the sequential application of metal coatings of titanium and silver using ion-plasma sputtering and electric pulse dispersion methods. It has been shown that surface layer metallization of the electrode material with titanium can improve the electrochemical cell characteristics. Additional silver film deposition leads to further cell performance improvement. It has been confirmed that the multilayer structure interfacial resistance between the carbon and the current collector has a significant effect on the conductivity of the electrochemical cell and the stability of its operation. The contact area increase of the electrode with the electrolyte leads to an increase in the rate processes occurring on the electrode surface and in the near-electrode space, which opens up prospects for increasing the energy intensity of the electrochemical system. A significant capacity increase of a water-based capacitor structure is achieved by the formation of a nanostructured dielectric layer of potassium titanate in the interelectrode space. It has been confirmed that the cell voltage cycling helps to stabilize the processes occurring in the surface layer of the electrode material at the interface and determining the range of mechanisms for transmitting electrical energy, which makes it possible to achieve higher energy intensity of the samples. Improvement of technological solutions in the field of ion-plasma technologies and the use of new perspective nanostructured materials creates the prerequisites for the creation of advanced automation and energy supply systems with a higher resource, which expands the possibilities of their use in various construction projects.

Rural Septic Tank Wastewater Treatment Based on Enhanced Microalgae Growth in a Photosynthetic Electrochemical System

Rural Septic Tank Wastewater Treatment Based on Enhanced Microalgae Growth in a Photosynthetic Electrochemical System

A single-use electrochemical biosensor system for ultrasensitive detection of Aflatoxin B1 in rice, corn, milk, peanut, chili pepper samples

Aflatoxin B1, a common food contaminant in peanuts and corn and a genotoxic carcinogen in humans poses a significant risk for hepatocellular carcinoma, making its detection crucial; this study aims to develop a label-free electrochemical biosensor using a disposable indium tin oxide polyethylene terephthalate (ITO-PET) electrode modified with 3-Aminopropyltriethoxysilane for detecting Aflatoxin B1 in real food samples. Initially, optimization steps for the proposed biosensor were conducted using electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) techniques. Characterization steps such as storage capacity, regeneration, and single frequency impedance (SFI) were completed for the proposed disposable biosensor after the optimization steps. The electrochemical biosensor, based on AFB1, exhibited excellent repeatability and reproducibility. It had a broad dynamic detection range from 0.1 fg/mL to 500 fg/mL, with low limits of detection (LOD) and quantitation (LOQ) at 0.19 fg/mL and 0.65 fg/mL, respectively. Finally, the proposed AFB1-based biosensor system was applied to real food samples (rice, chili pepper, milk, corn, and peanuts) for testing and validation.

TENG-driven single-droplet green electrochemical etching and deposition for chemical sensing applications

Selected area electrochemical etching (EE) and electrochemical deposition (ED) are widely used for fabricating microstructures and devices, but they require complex processes and expensive equipment and generate significant electrolyte waste. This study demonstrates a novel single-droplet electrochemical system using a triboelectric nanogenerator (TENG) for self-powered selected area EE and ED reactions. Utilizing TENG's pulsed power, Al nanostructures were created by EE, while nano-Ag and Cu2O nanocubes were synthesized by ED. The generated nanomaterials were applied to detect trace chemicals through the Surface-Enhanced Raman Scattering effect. The electrochemical reaction area can be controlled by droplet size, and patterns can be created using a needle movement platform. The size and density of nanostructures can be adjusted by the TENG's current, collision frequency, and electrolyte concentration. The deposition gradient from the center to the edge of the droplet is controlled by the distance between the needle and the substrate. COMSOL Multiphysics calculations show that a smaller D creates a larger electric field gradient. However, the varied deposition gradients were attributed to competition of electric field, diffusion effects, and capillary flow. This proposed green technology offers low cost, simplicity, no waste electrolyte, and self-powering capabilities, pioneering new research directions in EE and ED.

Transition metal embedded MoS2 as efficient trifunctional electrocatalyst: A computational study

In the advancement of electrochemical energy systems, multifunctional catalysts for the oxygen reduction reaction (ORR), hydrogen evolution reaction (HER), and oxygen evolution reaction (OER) are indispensable. Moreover, catalysts produced by incorporating transition metals into two-dimensional materials via substitutional modification have demonstrated remarkable efficacy. The present study examines the prospective uses of transition metal (TM= Nb, Co, In, and Re) dopants comprising 10% Niobium, Rhenium, Cobalt, and Indium in 2D MoS2. The density functional theory has been utilized to study the atomic level interaction. Based on the result, it can be observed that Nb-doped MoS2 has a ΔGH value of 0.06 eV, which signifies its remarkable HER capability when compared to pristine MoS2 and other doped versions. Our analysis for OER and ORR activities reveals that Co doped MoS2 exhibit superior performance compared to both the pristine and other doped versions of TM-MoS2, with an overpotential value ɳOER = 1.00 V and ɳORR = 0.77 V. A modification in electronic properties is examined by analysing the partial density of states during the HER and OER processes. The number of potential candidates suggested by the present findings will aid in the development of TM-doped MoS2-based electrocatalysts.

Electrochemical membrane systems for remediating ammonium-containing wastewater via coupling capacitance adsorption and oxygen reduction

As the main nitrogen-containing pollutant of industrial and agricultural wastewater, ammonium (NH4+) is obtainable from the natural nitrogen cycle and industrial emission. Electrochemical recovering nitrogen (N) from nitrate-polluted wastewater to produce ammonia (NH3) is a promising route to mitigate pollution risks and create economic values. Since side reactions at the electrodes are inevitable, and the competition mechanism between electric double layer capacitance (EDLC) behavior and side reactions is still unclear. Herein, electrochemical selective NH4+ recovery from wastewater was achieved by coupling NH4+ adsorption and side oxygen reduction reaction (ORR) in a novel electrochemical membrane extraction system using Ti3C2TX-based gas-diffusion cathodes. Batch experiments showcase simultaneous NH4+ removal and recovery, with TiOX/TiC-C exhibiting the highest removal capability of 408 mgN g−1. In situ Raman spectroscopy revealed the critical role of the four-electron transfer ORR reaction in the conversion of NH4+ to NH3. Density functional theory (DFT) showed that excellent electron-donating ability for NH4+ of TiOX/TiC-C electrode (1.97 eV) facilitated NH4+ diffusion onto electrode interface. The study sheds light on the intricate interplay between NH4+ adsorption and ORR, highlighting the significance of tailored support and vacancy engineering in advancing wastewater treatment and resource recovery.

Performance and mechanism of antibiotic resistance removal by biochar-enhanced sediment microbial fuel cell

This study is the first to explore the performance and mechanism of biochar-impacted sediment microbial fuel cell for removing antibiotic resistance genes (ARGs), and examines the effects of different biochar contents. The addition of 5% biochar produced the highest output voltage and power density, which increased by 100% and 219%, respectively, while simultaneously reducing the abundance and risk of ARGs. Comparatively, the addition of moderate amount of biochar (1–5%) promoted the removal of ARGs, while the opposite was true for excessive (10%) biochar. Biochar affected ARGs through prophages, insertion sequence, and transposons. Biological factors and voltage jointly influenced ARGs variation, with the former accounting for 56%. Further analysis of functional genes indicated that biochar controlled ARGs by regulating the synthesis of genetic material and amino acids to influence metabolism. Overall, findings of this study shed light on the potential removal of ARGs in microbial electrochemical systems.

Control Circuits for Potentiostatic/Galvanostatic Polarization and Simultaneous Chemical Sensing by a Light-Addressable Potentiometric Sensor.

A light-addressable potentiometric sensor (LAPS) is a semiconductor-based sensor platform for sensing and imaging of various chemical species. Being a potentiometric sensor, no faradaic current flows through its sensing surface, and no electrochemical reaction takes place in the course of LAPS measurement. In this study, a four-electrode system is proposed, in which a LAPS is combined with the conventional three-electrode electrochemical system. A LAPS is included as the fourth electrode for potentiometric sensing and imaging of the target analyte in the course of an electrochemical reaction taking place on the surface of the working electrode. The integrated system will be useful for analyzing dynamic processes, where both the electrochemical process on the electrode surface and the ion distribution in the solution need to be simultaneously investigated. Different grounding modes of control circuits that can simultaneously conduct potentiostatic/galvanostatic polarization and LAPS measurement are designed, and their functionalities are tested. The interference between polarization and LAPS measurement will also be discussed.