Electrochimica Acta最新文献

{"title":"Effects of Ag nanoparticles electrodeposited on oxy-nitrocarburized AISI 304 SS into the corrosive and antibacterial activity","authors":"Francisco Martínez-Baltodano, Wilian Pech-Rodríguez, Gregorio Vargas-Gutiérrez","doi":"10.1016/j.electacta.2025.146548","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.146548","url":null,"abstract":"The service life of materials in aggressive environments, such as seawater, is of paramount importance due to the significant risks of mechanical failure and the associated economic costs. Consequently, ongoing research focuses on enhancing materials to withstand corrosion, wear, and microbiological degradation. This study investigates the effects of silver nanoparticles (AgNPs) electrodeposited on an oxy-nitrocarburized AISI 304 stainless steel (SS) substrate. Microstructural and chemical characterizations were performed using X-ray diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM), and X-ray Photoelectron Spectroscopy (XPS). Additionally, wettability, electrochemical corrosion resistance, and bacterial inhibition tests were conducted using the Gram-negative bacterium <em>Escherichia coli</em> to assess the antibacterial activity of the AgNPs. These findings indicate that the initial AgNP layer fails to enhance corrosion resistance, likely due to insufficient surface coverage or weak interfacial bonding. This phenomenon is consistent with the formation of a galvanic couple, wherein the electrochemical potential difference between silver (+0.80 V) and stainless steel (Fe: -0.14 V) promotes electron transfer from the less noble substrate to the AgNPs, thereby accelerating the anodic dissolution of the steel surface. Furthermore, the contact angle was identified as a critical factor influencing both antimicrobial performance and corrosion resistance. All AgNP-modified surfaces exhibited exceptional antibacterial activity, exceeding 99% inhibition efficiency. This study highlights the potential of oxy-nitrocarburization as a robust surface modification technique for facilitating the nucleation and growth of nanoparticles, paving the way for advanced coatings capable of addressing the multifaceted challenges of material degradation in corrosive seawater environments.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"14 1","pages":"146548"},"PeriodicalIF":6.6,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144145949","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Integration of Experimental Techniques and Computational Modeling to Elucidate Charge Stabilization Mechanisms of Ferrocene Encapsulated in β-Cyclodextrin","authors":"Caio Lenon Chaves Carvalho, José Gabriel Aulisio de Oliveira, Luana Cristina Italiano Faria, Rafael Neri Prystaj Colombo, Welter Cantanhêde da Silva, Roberto da Silva Gomes, Filipe Camargo Dalmatti Alves Lima, Frank Nelson Crespilho","doi":"10.1016/j.electacta.2025.146563","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.146563","url":null,"abstract":"The origin of the redox stabilization of ferrocene (Fc) within β-cyclodextrin (β-CD) remain unclear. In this study, a combination of experimental techniques and computational modeling using Density Functional Theory (DFT) was employed to investigate the β-CD/Fc complex. Both structural and entropic factors play key roles in stabilizing the complex, with the structural confinement within β-CD limiting Fc's chemical reactivity, as evidenced by a lowered formal potential and enhanced redox reversibility accompanied by reduced Fukui index values of cyclopentadienyl rings. When Fc enters the hydrophobic cavity of β-CD, a dynamic stabilization mechanism is initiated. The hydrophobic forces drive Fc into the cavity, displacing water molecules, which increases the system’s entropy and results in a favorable energy change. Once encapsulated, the structural confinement within β-CD restricts Fc's mobility, particularly shielding its reactive iron center. The interaction between Fc's cyclopentadienyl rings and the β-CD cavity, along with the exclusion of solvent, enhances redox stability and reversibility, resulting in a well-stabilized host-guest complex driven by both confinement and entropic gains.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"26 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144153819","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Comparative Analysis of Performance Decline and Anode Degradation in Polymer Electrolyte Membrane Fuel Cells under Fuel Starvation: A Strategy for Electrode Condition Assessment Using Full Electrode Equivalent Circuit Model and Anode-Separated Distribution of Relaxation Times","authors":"Pilsoo Choi, JunHwa Kwon, Jungho Oh, Jinsu Hyun, KwangSup Eom","doi":"10.1016/j.electacta.2025.146560","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.146560","url":null,"abstract":"This work investigates the impact of anode catalyst layer (CL) degradation in Polymer Electrolyte Membrane Fuel Cells (PEMFCs) under fuel starvation using accelerated stress tests (ASTs). Anode cycling ASTs simulate intermittent fuel starvation and reveal that reduced hydrogen oxidation reaction (HOR) kinetics drive predominant anode degradation. Cyclic voltammetry results show a significantly greater decline in electrochemical surface area in the anode CL compared to the cathode, emphasizing the impact of anode degradation on PEMFC performance decay. A rapid decrease in ionic resistance in low-humidity non-faradaic EIS and SEM images of aged MEAs reveals that structural changes in the anode carbon support structure are the primary degradation mechanism after ASTs. The increase in anode CL charge transfer resistance as the AST progresses aligns with anode impedance data fitting results using the Transmission Line Model and cathode impedance data fitting results using the Full Electrode Circuit Model. The distribution of relaxation times analysis on the separated anode circuit from cathode ORR impedance data indicates shifts in relaxation time, representing anode resistance changes. This work advances the understanding of anode degradation mechanisms under fuel starvation and provides insights into developing improved AST protocols and impedance analysis techniques to enhance PEMFC durability and performance.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"48 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144145902","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Modifying the aluminum current collector/active material layer interface through physical vapor deposition technology to achieve a high-performance sulfur cathode","authors":"Xuliang Fan, Fang Chen, Gaowei Zhang, Liang Zhan, Xunfu Zhou, Xiaosong Zhou, Ji Cheng Ding, Jing Li, Jun Zheng","doi":"10.1016/j.electacta.2025.146562","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.146562","url":null,"abstract":"Effectively restraining lithium polysulfides diffusion remains a critical challenge for designing advanced sulfur cathodes. In this study, we report a simple and scalable approach to modify the interface between the current collector and the active material layer by depositing CrN onto the Al collector via physical vapor deposition (PVD). The CrN coating offers high electrical conductivity and excellent LiPSs adsorption/catalysis properties, enabling both efficient electron conduction and accelerated reaction kinetics between elemental sulfur and Li₂S. Consequently, even after 500 cycles, the sulfur cathode with the CrN-modified Al collector can deliver a high-capacity retention of 72.9%, which is significantly higher than that of the unmodified Al collector-based cathode (44.3%). The superior electrochemical performance demonstrates that PVD-enabled interface modification of the current collector is an effective strategy for advancing Li-S batteries.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"25 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144153820","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrochemistry of Poly(3,4-ethylenedioxythiophene) coated polyvinyl alcohol (PEDOT/PVA) films as a model for the muscle functions quantification and triggering of sensing neuron pulses","authors":"Lijin Rajan, Toribio F. Otero, Athira Ajayan, Yahya A. Ismail","doi":"10.1016/j.electacta.2025.146561","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.146561","url":null,"abstract":"We present the PEDOT/PVA hybrid film as a model reactive material capable of emulating the sensing functionalities originated by the reactive elements in biological organs through the same reactants: macromolecular electro-chemical motors, ions, and solvent. Here we prove that the reaction energy responds to and senses at any reaction time, any variation in the electrical (current), chemical (electrolyte concentration), or thermal (temperature) working conditions. Under galvanostatic control, the sensing magnitude is the potential evolution during the material reaction. The sensing equations describing the experimental results were attained. Both magnitudes, the current driving the reaction, and the sensing signals (the potential evolution) are embedded simultaneously in the only two connecting wires, mimicking brain-motor neuron-muscle-sensory neuron connections. If translated to parallel biological functions the results should point to a quantitative description of muscular tiredness: the same reaction amplitude requires higher energies under lower concentrations of one of the reactants, i.e. ATP. For a constant reaction amplitude the consumed reaction energy decreases when the reaction temperature increases, indicating the parallel energy-saving mechanisms of cold-blooded animal organs. If the reaction energy of the macromolecular motors adjusts instantaneously to any working energetic conditions each of those components should act on the concomitant sensing ionic channels (chemical, thermal, piezo) of the dendrites from the sensory neurons translating this quantitative information to the brain.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"171 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144145951","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrochemical nanosensors in therapeutic pharmaceutical monitoring: from drug followIng to clinical protocols","authors":"Maritza Fernández, Jahir Orozco","doi":"10.1016/j.electacta.2025.146550","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.146550","url":null,"abstract":"Therapeutic monitoring (TDM) combines the quantification of drug concentrations in the blood, pharmacological interpretation, and treatment guidance, introducing a valuable tool in precision medicine. However, quantifying drug concentrations requires expensive techniques, specialized laboratories, and trained personnel. A plausible alternative to solve this limitation is quantifying pharmaceutical compounds using nanosensors. This review starts by describing the standard methodology used in TDM to emphasize further how to explore electrochemical nanosensors for this purpose. It points out the advantages of electrochemical nanosensors compared to conventional methodologies based on their analytical features, potential for point-of-care applications, fast response, miniaturization, convenient operation, and portability. The review concludes by summarizing the patented work and discussing important points to consider in developing electrochemical nanosensors in clinical settings, as well as challenges and gaps that must be filled to introduce such new technological innovations in TDM and personalized therapy.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"56 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144137036","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"CO2 / H2O co-electrolysis using Single and Stack Solid Oxide Electrolysis Cell (SOEC)","authors":"Riko Inuzuka, Norikazu Osada, Naomi Tsuchiya, Hiroaki Kawamori, Nagayoshi Ichikawa, Tatsumi Ishihara","doi":"10.1016/j.electacta.2025.146535","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.146535","url":null,"abstract":"The production of syngas by co-electrolysis using solid oxide electrolysis cells (SOECs) has been attracting attention as a highly efficient technology for converting CO₂ into useful compounds. However, co-electrolysis is complicated because the main electrolysis reactions and side reactions occur simultaneously. In this study, co-electrolysis of CO₂ and H₂O were conducted using a large size single cell with cell holder used for stack applications and also 3 cells stack. It was found that I-V curves was hardly dependent on the CO₂ and H₂O ratio in feed gas and thermal neutral voltage is also hardly changed, suggesting that the reverse water-gas shift (RWGS) reaction is the primary CO-producing reaction even in the larger size cells. So, the main electrolysis reaction was steam electrolysis occurred at three phase boundary and RWGS mainly occurred in gas phase with unconverted CO₂. Similar dependency was observed on the 3 cells stack indicating that the outlet gas composition and electrochemical properties exhibited similar dependency on CO₂ and H₂O ratio of the large single cell. This finding suggests that stacking multiple cells has minimal impact on the reaction mechanism or outlet gas composition, and that CO production occurred by RWGS reaction similar with the large single cell.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"12 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144137037","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tailoring Polymorphic CoSe2 via Interstitial Doping of Sb for Advanced Counter Electrodes in DSSC applications","authors":"Sruthi Sureshkumar, George Jacob","doi":"10.1016/j.electacta.2025.146558","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.146558","url":null,"abstract":"The counter electrode (CE) layer in dye-sensitized solar cells (DSSCs) acts as a cornerstone in the catalytic reduction of the redox electrolyte, typically the iodide/triiodide (I⁻/I₃⁻) redox electrolyte couple, and facilitates the replenishment of the oxidized dye molecules. The substantial cost, sparse availability, and proneness to corrosion of conventionally used Platinum (Pt) CE with the I⁻/I₃⁻ electrolyte, have spurred extensive research into alternative CE materials. Transition metal dichalcogenides (TMDs), especially cobalt diselenide (CoSe₂), have emerged as potential substitutes for CE material in DSSC due to their good electrochemical properties and high conductivity. This study focuses on the potential of antimony (Sb)-doped CoSe₂ as a novel material for CE application in DSSC, aiming to improve the stability, electrocatalytic activity, and overall device performance. We prepared Sb-doped CoSe₂ with various doping concentrations using a simple hydrothermal technique and analysed the compositional, morphological and structural properties of the prepared materials. The CoSe₂ doped with 4 wt% Sb (4Sb-CoSe₂) exhibited enhanced charge transfer kinetics, low charge transfer resistance, and superior catalytic activity compared to other concentrations, making it comparable to standard Pt CE in electrochemical analysis. DSSC fabricated with 4Sb-CoSe₂ CE achieved a photovoltaic (PV) efficiency of 6.99% under AM 1.5G, which is attributed to the interstitial doping of Sb³⁺ ions, that increases the active sites for redox processes, conductivity and charge transport kinetics of CE. The 16-day stability assessment reveals that the 4Sb-CoSe₂-based DSSC retains stable PV performance with only minor efficiency loss, indicating strong durability against the iodide/triiodide redox electrolyte. Therefore, Sb-doped CoSe₂ can be a viable substitute for Pt CE in DSSC and can be utilised for their large-scale production.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"24 1","pages":"146558"},"PeriodicalIF":6.6,"publicationDate":"2025-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144145955","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Symmetrical-Branched Pyrrolidinium Ionic Plastic Crystal Electrolytes: Synthesis and Sodium-Ion Battery Potential","authors":"Fatihah Najirah Jumaah, Yoshifumi Hirotsu, Morgan L. Thomas, Masahiro Yoshizawa-Fujita","doi":"10.1016/j.electacta.2025.146549","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.146549","url":null,"abstract":"Ionic plastic crystals (IPCs), akin to ionic liquids (ILs) but possessing unique properties, are of interest to remarkably enhance battery safety. However, most IPCs or ILs are commonly synthesized via a conventional method – a substitution reaction with an <em>N</em>-alkyl pyrrolidone and alkyl halide which commonly requires a long reaction time and large volume of organic solvents. In this study, we attempted a greener and facile method to synthesize the symmetrical cation - <em>N,N</em>- diisopropylpyrrolidinium bromide ([C_i3i3pyr][Br]) via a microwave-assisted synthesis procedure followed by a metathesis reaction to obtain [C_i3i3pyr][FSA]. The microwave method provides a viable alternative with potential benefits in reaction speed and environmental impact compared to conventional techniques. Among the three salts tested for anion exchange, KFSA emerged as the most effective in the conversion from Br⁻ to FSA⁻. Comprehensive spectroscopic and thermal analyses were conducted to validate the physicochemical and electrochemical properties of [C_i3i3pyr][FSA]. The material displayed three solid-solid transitions (<em>T</em>_s-s) at −27, 13, and 68°C. The ionic conductivity of [C_i3i3pyr][FSA] at ambient temperature is approximately 10⁻⁷ S cm⁻¹. Investigation into the temperature dependence of ionic conductivity revealed a significant increase from ∼10⁻¹⁰ to ∼10⁻⁸ S cm⁻¹ over the temperature range of −30 to 10°C, followed by a notable jump in conductivity from 60 to 70°C, corresponding to the <em>T</em>_s-s observed at 13 and 68°C. Additionally, the potential for the performance of this material in sodium-ion batteries was evaluated by evaluating electrochemical properties with varying sodium salt concentrations, demonstrating significant improvement in conductivity and redox behavior. These findings highlight the potential of [C_i3i3pyr][FSA] as a promising electrolyte for safer, more efficient sodium-ion batteries, particularly due to its facile and eco-friendly microwave synthesis method.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"47 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144137038","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Low-Loaded Catalyst Layers For Proton Exchange Membrane Fuel Cell Dynamic Operation Part 2: Modeling Study","authors":"Florent Vandenberghe, Fabrice Micoud, Pascal Schott, Marian Chatenet","doi":"10.1016/j.electacta.2025.146542","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.146542","url":null,"abstract":"Numerous models have been developed to simulate the performance and degradation mechanisms of proton exchange membrane fuel cell (PEMFC) components. The Nernst and Butler-Volmer approaches, in a single-step reaction, often describe the hydrogen oxidation reaction (HOR) and the oxygen reduction reaction (ORR), the latter being of higher complexity as it involves numerous intermediate species. The experimental work and dataset from the first part of this study [<span><span>1</span></span>], obtained in differential single-cell (DC) on low-loaded cathode catalyst layers (20 and 100 µg_Pt cm_geo⁻²), have been used to further study the behavior of the cathode Pt/C electrocatalyst. The objective is to introduce a detailed electrocatalytic description in one-dimensional through-thickness models, particularly the Pt surface oxide formation/reduction: the reaction is decomposed into several elementary steps associated with the surface state of Pt, as well as the formation of ‘bulk’ Pt-oxides, formed via the chemical place-exchange reaction under nitrogen (H₂/N₂) and oxygen (H₂/O₂) atmospheres. This electrochemical path was successfully implemented into a complete ORR performance model at the cathode; it provides a more comprehensive description of the physical and electrochemical phenomena involved in low-loaded cathode catalyst layers during non-stationary PEMFC operation, which helps to capture the hysteresis phenomena observed experimentally during polarization curve measurements.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"15 1","pages":"146542"},"PeriodicalIF":6.6,"publicationDate":"2025-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144145953","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}