Electrochimica Acta最新文献

{"title":"A simple and efficient approach for simulation of adsorbed species in the diffusionless case: A new look on chronoamperometry data","authors":"Fernando M. de Oliveira, Wallans T.P. dos Santos","doi":"10.1016/j.electacta.2024.145445","DOIUrl":"https://doi.org/10.1016/j.electacta.2024.145445","url":null,"abstract":"In this work the electrochemical response of adsorbed species without mass-transport effects was revisited. Finite difference formulas were tested for simulation of current versus potential even considering lateral interactions between adsorbates. This approach was significantly simpler than others present in the literature. Excellent results were observed for cyclic voltammetry and chronoamperometry in any kinetics range. Exact solutions for chronoamperometry were tested using multiple-pulsed simulated data. More than one path was pointed out to determine the kinetic parameters involved such as <em>E°’_ads, n, α</em> and <em>k_s</em>.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"69 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142756365","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":"Designing ternary 2D/2D nitrogen-enriched porous g-C3N4/rGO embedded in zinc cobaltite as efficient triiodide reduction for a platinum-free counter electrode in dye-sensitized solar cell applications","authors":"S. Kamesh ,&nbsp;S. Harish ,&nbsp;Hiroya Ikeda ,&nbsp;M. Navaneethan ,&nbsp;J. Archana","doi":"10.1016/j.electacta.2024.145370","DOIUrl":"10.1016/j.electacta.2024.145370","url":null,"abstract":"<div><div>The counter electrode (CE) plays a pivotal role in enhancing the performance of dye-sensitized solar cells (DSSCs). Recently, platinum (Pt) has served as the preferred catalyst for CEs; however, due to its elevated cost, constrained accessibility, and vulnerability to deterioration, a compelling need exists to investigate alternative materials with superior performance for CEs. This research endeavours to tackle the inherent low conductivity challenge associated with ZnCo₂O₄ and systematically explores avenues for augmenting its electrical characteristics. To accomplish this, we employed a facile hydrothermal technique to synthesise four different CE materials: pure ZnCo₂O₄ (Z), ZnCo₂O₄ combined with reduced graphene oxide (rGO) (ZG), ZnCo₂O₄/rGO combined with g-C₃N₄ (ZGC), and ZnCo₂O₄/rGO combined with N-doped porous g-C₃N₄ (ZGNC). Subsequently, we evaluated their suitability as CE materials for DSSC application. To ascertain the purity of the materials, we conducted X-ray diffraction (XRD) and FT-IR analyses, which revealed the absence of impurities. Morphological and elemental assessments were carried out using Field Emission Scanning Electron Microscopy (FE-SEM), Electron Probe Micro-Analyzer (EPMA), and Transmission Electron Microscopy (TEM). These analyses confirmed the desired morphology and elemental distribution in all synthesised samples and CEs. Chemical composition and purity were determined through X-ray Photoelectron Spectroscopy (XPS) analysis. Additionally, we conducted BET analysis, which demonstrated that the ZGNC sample possessed a greater specific surface area (94.3 m² g⁻¹) and pore volume (0.6 cm³ g⁻¹) than the other samples. To evaluate the electrochemical performance of the coated CEs, cyclic voltammetry (CV) analysis was conducted using an iodine-based electrolyte in a three-electrode configuration. The analysis revealed that the ZGNC CE exhibited significantly enhanced catalytic properties compared to the Z, ZG, and ZGC CEs. Subsequently, the fabricated CEs were integrated into DSSC devices, and the ZGNC CE attained a photovoltaic PCE of 6.9 ± 0.6 %, outperforming the Z (3.6 ± 0.4 %), ZG (5.3 ± 0.6 %) and ZGC (6.3 ± 0.2 %) CEs.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"512 ","pages":"Article 145370"},"PeriodicalIF":5.5,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142756265","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":"Real-time Neurochemical Sensing of Hydrogen Peroxide Production in Brain Tissue using Advanced Nanostructured Au Microelectrodes Functionalized with Ruthenium Purple Film","authors":"A. Ledo, E. Fernandes, RM. Barbosa","doi":"10.1016/j.electacta.2024.145447","DOIUrl":"https://doi.org/10.1016/j.electacta.2024.145447","url":null,"abstract":"Real-time monitoring of H₂O₂ is essential for understanding its role in neurological physio(path)ology. In this study, we developed an advanced electrochemical sensor utilizing nanostructured gold wire microelectrodes functionalized with a Ruthenium Purple (RP) film, a polynuclear transition metal hexacyanoferrate analog of the prototypical Prussian blue (PB). The RP film exhibits enhanced stability in neutral buffer solutions and reduced interference from biologically relevant cations such as Na⁺, Mg²⁺, and Ca²⁺. By integrating gold nanoparticles onto a nanoporous gold surface, we significantly increased the electroactive surface area of the microwire (ρ=26.1 ± 10.2). The electrodeposition of a thin RP film (4.23 ± 1.2 nm) resulted in a highly selective H₂O₂ sensor, operating at an optimal potential of -0.05 V vs. Ag/AgCl, with a linear detection range of 0.5-500 µM, sensitivity of 1.18 ± 0.37 µA µM^-1 cm^-2, and a low limit of detection (LOD) of 66.6 ± 34.9 nM. Adding a Nafion® layer enhanced the sensor's operational stability, maintaining optimal performance over three hours under physiological conditions of pH and ion concentration. We validated the sensor's capability to monitor transient changes in H₂O₂ concentration in brain tissue by assessing its response to exogenously applied H₂O₂. Furthermore, we demonstrated that glutamate receptor activation in hippocampal slices induces a rapid and transient increase in extracellular H₂O₂ levels, underscoring the sensor's potential for studying oxidative stress in neurobiological contexts.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"18 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142756363","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":"INSIGHTS INTO THE ELECTROCHEMICAL PROPERTIES OF GERMANIUM-COBALT-INDIUM NANOSTRUCTURES IN A WIDE TEMPERATURE RANGE","authors":"I.M. Gavrilin, V.V. Emets, I.S. Marinkin, E.V. Kovtushenko, A.M. Skundin, T.L. Kulova, R.L. Volkov, N.I. Borgardt, S.A. Gavrilov","doi":"10.1016/j.electacta.2024.145441","DOIUrl":"https://doi.org/10.1016/j.electacta.2024.145441","url":null,"abstract":"Germanium-cobalt-indium (Ge-Co-In) nanostructures are a promising material for negative electrodes of lithium-ion batteries aimed for arctic exploitation. Electrochemical impedance spectroscopy was used for a detailed study of the interaction of Ge-Co-In nanostructures with lithium in a temperature range from ‒35 to +20°C. The discharge capacity at temperatures of 20, 0, ‒10, ‒20, and ‒35°C amounted to 1400, 1228, 1040, 907, and 793 mAh g^‒1, respectively. The impedance spectra measured at various lithiation degrees were found to differ but insignificantly whereas temperature variation resulted in notable changes in the spectra. A normalized charge transfer resistance for Ge-Co-In nanostructures was significantly (more than an order of magnitude) less than for Ge-In nanowires (obtained by the same method, but without the addition of cobalt salt into the electrolysis solution). It is this difference in charge transfer resistance that can explain the difference in the shapes of the impedance spectra for both objects. Also, in contrast to data for Ge-In nanowires, the dependences of the lithium diffusion coefficient in Ge-Co-In nanostructures on potential had a clearly defined minimum. The lithium diffusion coefficient in Ge-Co-In nanostructures slightly exceeded that in Ge-In nanowires, and the activation energy of lithium diffusion in Ge-Co-In nanostructures was marginally less than in Ge-In nanowires.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"10 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2024-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142752820","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":"Electroactive ferrocene-based ionic liquids: transport and electrochemical properties of their acetonitrile solutions","authors":"Ekaterina A. Arkhipova, Mikhail M. Levin, Anton S. Ivanov, Maxim A. Zakharov, Ivan D. Kozhatkin, Konstantin I. Maslakov, Pramod K. Singh, Serguei V. Savilov","doi":"10.1016/j.electacta.2024.145443","DOIUrl":"https://doi.org/10.1016/j.electacta.2024.145443","url":null,"abstract":"The increasing global demand for energy stimulates the development of advanced energy storage and conversion technologies. Modification of electrolyte with redox-active additives is a promising way to enhance the electrochemical performance of energy storage devices. In this work new electroactive ferrocene-based ionic liquids (Fc-ILs) (N-methyl-N-(ferrocenylmethyl)piperidinium bis(trifluoromethanesulfonyl)imide [PipFcMe][NTf₂], N-methyl-N-(ferrocenylmethyl)pyrrolidinium bis(trifluoromethanesulfonyl)imide [PyrFcMe][NTf₂], N-ethyl-N-(ferrocenylmethyl)pyrrolidinium bis(trifluoromethanesulfonyl)imide [PyrFcEt][NTf₂]) were synthesized. The structure of the Fc-ILs was confirmed by NMR and XRD. [PipFcMe][NTf₂] and [PyrFcMe][NTf₂] demonstrated nearly similar crystal structures consisting of cation and anion columns, while alternating cation and anion layers are stacked in the [PyrFcEt][NTf₂] crystal. The effects of the Fc-IL mole fraction and temperature on the transport properties of the acetonitrile solutions of the Fc-ILs have been established. The highest electrical conductivities of the [PipFcMe][NTf₂], [PyrFcEt][NTf₂] and [PyrFcMe][NTf₂] solutions calculated using the Casteel-Amis equation were, respectively, 38.06 ± 0.63, 40.34 ± 0.93 and 41.09 ± 0.58 mS/cm at 348.15 K. The activation energies of conductivity were calculated using the Arrhenius and Vogel-Fulcher-Tamman approaches. The Fc-ILs demonstrated a high electrochemical stability range up to 4.67 V. The introduction of electron-withdrawing substituents into the cyclopentadienyl ring of Fc-ILs shifted the half-wave potential to the positive direction. The diffusion coefficients were calculated using the Randles–Ševčík equation for a quasi-reversible process.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"27 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2024-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142756382","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":"The Effect of Atmospherically Formed Films on Cu Corrosion Properties using Single Droplet Electrochemistry","authors":"Ghazal Shafiee, Mia Tripp, Jeffrey Daniel Henderson, Emmanuel Mena-Morcillo, Mehran Behazin, Peter George Keech, Samantha Michelle Gateman","doi":"10.1016/j.electacta.2024.145444","DOIUrl":"https://doi.org/10.1016/j.electacta.2024.145444","url":null,"abstract":"This study explored the effects of atmospherically formed surface films and surface roughness on Cu corrosion behavior. A comprehensive suite of surface analysis techniques, including X-ray photoelectron spectroscopy, scanning electron microscopy, contact angle measurements, and confocal microscopy, were utilized to characterize the physicochemical properties of the surface films formed over 30 days. Then, both macroscale and droplet electrochemical measurements, such as open circuit potential and linear sweep voltammetry, were performed to explore the films’ effects on the aqueous and atmospheric corrosion behavior of Cu respectively. The results showed that the polarization resistance measured within the droplets was lower than that observed in macroscale experiments, attributable to the varying oxygen diffusion profiles. During atmospheric corrosion, the polarization resistance was dependent on the surface finish due to its impact on the film's composition. Surface characterization revealed the formation of hydroxide and defect oxides that varied between the different surface finishes, resulting in differences in polarization resistances over a 30-day period. However, the films did not affect the polarization resistance measured for samples that underwent aqueous electrochemical corrosion testing, possibly due to their solubility during the open circuit potential period prior to reaching a steady state. This study underscores the importance of surface films on atmospheric corrosion properties and brings skepticism to the need for cathodic cleaning of Cu during aqueous corrosion studies under aerated conditions.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"26 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2024-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142756379","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":"Pitch-derived C coated three-dimensional CNTs/reduced graphene oxide microsphere encapsulating Si nanoparticles as anodes for lithium-ion batteries","authors":"Jae Seob Lee, Beom Su Jo, Jin-Sung Park, Jung Sang Cho","doi":"10.1016/j.electacta.2024.145440","DOIUrl":"https://doi.org/10.1016/j.electacta.2024.145440","url":null,"abstract":"This study presents an innovative strategy for synthesizing a sophisticated three-dimensional conductive framework that contains well-dispersed silicon nanoparticles. This framework features silicon nanoparticles encapsulated by a composite of one-dimensional carbon nanotubes (CNTs), two-dimensional reduced graphene oxide (rGO), and amorphous carbon, all of which are further coated with a pitch-derived carbon (PDC) layer. This unique nanostructured anode was prepared from a one-pot spray drying process, heat-treatment and subsequent pitch-derived carbon coating. Combining 1D CNTs and 2D rGO nanosheets creates a 3D conductive network that can facilitate the electrochemical reaction kinetics. Furthermore, pitch-derived carbon coating at the interior and on the surface densified the electrode, ensuring both lithium-ion and electron transport and enhancing the Coulombic efficiency. Therefore, the composite plays the role of an effective mixed ionic and electronic conductor (MIEC), which can highly enhance the electrochemical performance of Si-based anode. Also, the volume expansion issues of silicon materials could be resolved by compositing with 3D conductive carbon matrix and reinforcing the structural robustness by coating with PDC layer, which could effectively alleviate the stress occurring from repetitive cycling. When used as the anode in lithium-ion batteries, the microspheres exhibited exceptional initial discharge/charge capacities of 3814/2791 mA h g^–1 at 0.1 A g^–1 with high Coulombic efficiency of 73.2%, and demonstrated highly stable cycle performance, delivering a discharge capacity of 947 mA h g^–1 after 350 cycles at a current density of 1.0 A g^–1.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"7 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2024-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142756395","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":"Effect of gas compositions on co-electrolysis performance of solid oxide cells: electromotive force and polarization resistance","authors":"Masashi Kishimoto, Riki Nakamura, Hiroshi Iwai","doi":"10.1016/j.electacta.2024.145439","DOIUrl":"https://doi.org/10.1016/j.electacta.2024.145439","url":null,"abstract":"Co-electrolysis performance of solid oxide cells is experimentally investigated with a focus on the electromotive force (EMF) and reaction resistance. Outlet gas composition is also analyzed to investigate the effect of the reverse-water-gas-shift (rWGS) reaction. The open-circuit voltage (OCV) of the cell is analyzed under various gas compositions with different reactant ratios. The mixed potential theory is employed to predict the EMF values based on the surface coverage ratio in the hydrogen electrode. The reaction resistance under co-electrolysis operation obtained from the equivalent circuit fitting analysis of the impedance spectra is compared with that under H₂O and CO₂ electrolysis operations. The results obtained in this study indicate that, near the OCV condition, H₂O electrolysis is the main reaction under co-electrolysis operation to determine the OCVs and reaction resistance, and the main conversion pathway of CO₂ into CO is the rWGS reaction.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"14 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2024-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142742712","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":"Gold-etching redox reactions at the gold interface of an ionic liquid monitored using electrochemical surface plasmon resonance","authors":"Naoya Nishi, Hiroyuki Miyatake, Tetsuo Sakka","doi":"10.1016/j.electacta.2024.145428","DOIUrl":"https://doi.org/10.1016/j.electacta.2024.145428","url":null,"abstract":"I²/I⁻ redox reaction on the gold interface of an ionic liquid, 1-octyl-3-methylimidazolium bis(nonafluorobutanesulfonyl)amide, has been studied using electrochemical surface plasmon resonance (SPR) to investigate how SPR can sense the dissolution/deposition of gold film accompanied with the two-step processes of the I²/I⁻ redox reaction. The SPR response measured simultaneously with cyclic voltammetry (CV) has clearly shown that SPR can sense the change in the gold film thickness due to the gold dissolution/deposition. The classical least squares method has successfully separated the two contributions to the SPR response: one from the gold thickness and the other from the surface concentration of dissolved redox species. Model simulations for CV and light reflectivity have reproduced the two SPR contributions well. Furthermore, a systematic deviation of the experimental data from the simulation results observed at positive potentials has suggested that the gold dissolution/deposition processes induce the surface roughness change of the gold film on the Angstrom level.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"3 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2024-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142735682","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":"Optimizing anode performance of (La,Sr)1-αTi1-βNiβO3-δ in solid oxide fuel cells via synergistic a-site deficiency and b-site doping regulation strategy","authors":"Rui Ling,&nbsp;Chenxiao Meng,&nbsp;Wenyun Wang,&nbsp;Chao Yang,&nbsp;Wentao Qi","doi":"10.1016/j.electacta.2024.145424","DOIUrl":"10.1016/j.electacta.2024.145424","url":null,"abstract":"<div><div>This study introduces an innovative approach to enhance the electrochemical performance of La-substituted SrTiO₃ anode materials in solid oxide fuel cells (SOFCs) through the strategic combination of A-site deficiency and B-site doping. The effective method leverages the synergistic effects of A-site deficiency and B-site doping on Ni in situ exsolution and the electrochemical behavior of the SOFCs. The tailored (La,Sr)_1-αTi_1-βNi_βO_3-δ (α=0.2, β=0.15, (LS)_0.8TN_0.15) anode, modified with Ni nanoparticles, significantly boosts the power output of YSZ-supported single cells, achieving peak power densities of 720.5, 535.8, and 376.3 mW cm^-2 at 800, 700, and 600 °C, respectively, under a humidified hydrogen atmosphere (3 % H₂O-97 % H₂). The findings underscore the pivotal role of optimized A-site deficiency and B-site doping in fine-tuning the morphology and dispersion of Ni nanoparticles, thereby markedly enhancing the catalytic activity and the overall electrochemical efficiency of the electrodes. These results indicate the promising candidacy of (La,Sr)_1-αTi_1-βNi_βO_3-δ as an anode material for SOFCs, opening new avenues for the design of high-performance fuel cell components.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"512 ","pages":"Article 145424"},"PeriodicalIF":5.5,"publicationDate":"2024-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142735684","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}