Electrochimica Acta最新文献

{"title":"Layered Mn-MOF modified with carbon quantum dots for efficient detection of trace hydrogen peroxide in beverages","authors":"Yin-Xia Sun ,&nbsp;Li-Ping Liu ,&nbsp;Xue Bai ,&nbsp;Lu-Lu Gao ,&nbsp;Wen-Qing Hu ,&nbsp;Wen-Yu Han ,&nbsp;Yu Sun ,&nbsp;Zhe-Peng Deng ,&nbsp;Wan-Hong Sun ,&nbsp;Jian-Jun Wang ,&nbsp;Li Xu","doi":"10.1016/j.electacta.2025.146469","DOIUrl":"10.1016/j.electacta.2025.146469","url":null,"abstract":"<div><div>Developing high-sensitivity hydrogen peroxide (H₂O₂) sensors is crucial. Metal organic frameworks (MOFs) are considered one of the ideal materials for developing H₂O₂ sensors for their adjustable pore size and diverse topological structures. In this work, solvothermal synthesis is utilized CQD@Mn-MOF using carbon quantum dots (CQDs) and two-dimensional Mn-MOF ([Mn(Tib)(H₂O)₃]·(TPA)·3H₂O, Tib = 1,3,5-triamidazolylbenzene, TPA = terephthalic acid) as precursors. Interestingly, CQD@Mn-MOF as an electrochemical sensor can effectively detect H₂O₂ with a lower detection limit of 14.7 μM, and higher sensitivity (approximately 5 times that of pure Mn-MOF). CQD@Mn-MOF sensor is capable of detecting H₂O₂ with high selectivity in the presence of other interfering agents such as proline, ascorbic acid, glucose, and various metal salts. In addition, CQD@Mn-MOF electrochemical sensor has been used to effectively determine the H₂O₂ content in actual beverages such as fruit juice and beer. The sensing mechanism has been reasonably analyzed that the MnO₂ produced by Mn²⁺ + H₂O₂ = MnO₂ + 2H⁺ reaction acts as a specific catalyst for H₂O₂ decomposition reaction (MnO₂ + H₂O₂ + 2H⁺ = Mn²⁺ + O₂ + 2H₂O). This sensing mechanism further ensures the high selectivity of the sensor for H₂O₂. Significantly, the introduction of CQD not only improves the conductivity of Mn-MOF, but also can provide more active sites in the catalytic reaction, improve the contact area and reaction rate of the reaction, and improve the catalytic performance of Mn-MOF, further improve the sensitivity.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"532 ","pages":"Article 146469"},"PeriodicalIF":5.5,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143946296","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":"Silver-cuprous oxide nanocomposites and nanohybrids-based electrochemical nanoplatform for ultrasensitive chloramphenicol detection: Influence of external and internal nano-heterojunctions","authors":"Tuan-Anh Nguyen ,&nbsp;Ho Anh Tu ,&nbsp;Phung Thi Lan Huong ,&nbsp;Ong Van Hoang ,&nbsp;Pham Duc Thang ,&nbsp;Nguyen Quang Hoa ,&nbsp;Ngo Xuan Dinh ,&nbsp;Anh-Tuan Le","doi":"10.1016/j.electacta.2025.146472","DOIUrl":"10.1016/j.electacta.2025.146472","url":null,"abstract":"<div><div>A new facile, green, and time-saving one-/two-step electrosynthesis approach is utilized for the preparation of Ag, Cu₂O nanomaterials (NMs), Ag-Cu₂O nanocomposites (c-Ag-Cu₂O), and Ag-Cu₂O nanohybrids (h-Ag-Cu₂O), which are applied as electrode modifiers for developing high-performance electrochemical nanosensors towards chloramphenicol (CAP) detection. We have attempted to evaluate the electrochemical activity of c-Ag-Cu₂O and h-Ag-Cu₂O with the intention of investigating the influence of external and internal metal-semiconductor nano-heterojunction on the kinetic pathway for interfacial electron transfer, electrocatalytic activity, and adsorption/diffusion capacity. Compared to c-Ag-Cu₂O, a more intimate contact and strong interfacial interactions between two single components at the nanoscale in h-Ag-Cu₂O can expand the heterojunction contact area at the inner interface and provide a more tightly combined interface. The excellent intrinsic electrical conductivity and high electron mobility of Ag NMs and Cu₂O NMs's superior electrocatalytic activity, coupled with novel properties that are only existent in Ag-Cu₂O nanohybrids such as tight contact interfaces and internal electron transfer pathways across abundant heterojunction interfaces, contributed to the significantly improved analytical sensing performance towards CAP. Under the optimized experimental conditions, the h-Ag-Cu₂O-modified electrode possessed a wide linear response in the CAP concentration range of 0.5 – 150 µM with high electrochemical sensitivity (1.64 µA µM^–1 cm^–2), and the detection limit was found to be 0.16 µM. Moreover, the developed electrochemical nanosensor demonstrated good repeatability, acceptable anti-interference ability, and excellent long-term storage stability. This work may provide a crucial intersection of interfacial engineering of internal metal-semiconductor nano-heterojunctions and high-performance electrochemical sensing platforms, opening up a new class of novel, hypersensitive, and ultraselective electrochemical sensors.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"532 ","pages":"Article 146472"},"PeriodicalIF":5.5,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143946294","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":"Imidazole- and mercaptobenzimidazole-derivatives as corrosion inhibitors for Cu, Cu–Zn alloys, and Zn in chloride solution","authors":"Chenyang Xie ,&nbsp;Ingrid Milošev ,&nbsp;Anton Kokalj ,&nbsp;Pere Bruna ,&nbsp;Daniel Crespo","doi":"10.1016/j.electacta.2025.146460","DOIUrl":"10.1016/j.electacta.2025.146460","url":null,"abstract":"<div><div>The electrochemical behaviour and surface conditions of Cu, Cu₇₀Zn₃₀ (at%), Cu₃₀Zn₇₀, and Zn in 3 wt% NaCl solution were investigated with and without the addition of 1 mM imidazole- and mercaptobenzimidazole-derivatives. In total, seven different inhibitor compounds were considered. Polarisation resistance and electrochemical impedance values at 0.01 Hz indicated that the corrosion inhibitor 2-mercapto-5-methoxybenzimidazole performed best on Cu and Cu₇₀Zn₃₀, whereas 5-amino-2-mercaptobenzimidazole was most effective for Zn and Cu₃₀Zn₇₀. The inhibitors significantly increased the polarisation resistance and impedance values for the studied metals and alloys, with Cu₇₀Zn₃₀ exhibiting an improvement of nearly two orders of magnitude. Potentiodynamic polarisation tests revealed that the inhibitors act as mixed-type inhibitors, primarily affecting anodic reactions. The XPS analysis demonstrated that the efficacy of these inhibitors is closely related to their functional groups: Cu, Cu₇₀Zn₃₀, Cu₃₀Zn₇₀, and Zn benefit from the mercapto group, while the amino group is particularly effective for Zn-rich alloys. DFT adsorption calculations, performed with an implicit aqueous solvent, revealed a strong adsorption affinity of both mercapto and amino groups toward Cu and Zn surfaces, with the amino group exhibiting a more notable interaction than the mercapto group on Zn—consistent with its experimentally observed inhibition effect.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"532 ","pages":"Article 146460"},"PeriodicalIF":5.5,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143940106","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":"Enhanced catalytic performance of CoN4 single atom catalysts by engineering the first coordination spheres","authors":"Feifei Li,&nbsp;Lujing Zhao,&nbsp;Weizhong Tan,&nbsp;Changmin Shi,&nbsp;Dongchao Wang,&nbsp;Guangliang Cui,&nbsp;Youchun Wang,&nbsp;Hongmei Liu","doi":"10.1016/j.electacta.2025.146463","DOIUrl":"10.1016/j.electacta.2025.146463","url":null,"abstract":"<div><div>Single-atom catalysts (SACs) exhibit significant potential as high-efficiency catalysts with enhanced energy density in aprotic Li-O₂ battery. In this study, we investigated the influence of the coordination environment of CoN₄ SACs on the electrochemical performance of Li-O₂ battery using density functional theory (DFT) calculations. Our findings indicate that CoN₄ SACs preferentially adsorb O₂, while C-coordinated CoN_4-xC_x (x = 1–4) SACs demonstrate a tendency to adsorb Li in the initial step of the reaction. The computed Gibbs free energies for each reaction step suggest that CoN_4-xC_x (x = 0–4) SACs are promising candidates for cathode electrocatalysts in Li-O₂ batteries. Notably, the calculated overpotentials for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) reveal that CoN₃C (η_ORR/η_OER = 0.14/0.23 V) and CoNC₃ (η_ORR/η_OER = 0.22/0.14 V) SACs exhibit significantly low values, highlighting their potential as high-performance cathode electrocatalysts. Additionally, the adsorption free energy of *Li₃O₂ serves as a simple activity descriptor for CoN_4-xC_x (x = 0–4) SACs. These insights suggest that CoN_4-xC_x (x = 0–4) SACs may have promising applications in facilitating efficient ORR and/or OER, providing guidance for the design of advanced aprotic Li-O₂ batteries.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"531 ","pages":"Article 146463"},"PeriodicalIF":5.5,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143946293","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":"Transpassive corrosion mechanisms in Ni revisited with electrochemistry coupled in situ respirometry","authors":"Karthikeyan Hariharan,&nbsp;Ann-Kathrin Bach,&nbsp;Mark P. Bruns,&nbsp;Sannakaisa Virtanen","doi":"10.1016/j.electacta.2025.146461","DOIUrl":"10.1016/j.electacta.2025.146461","url":null,"abstract":"<div><div>In this study, we investigate the transpassive corrosion mechanisms in Ni using <em>in situ</em> respirometry coupled with electrochemical experiments to decouple contributions from multiple anodic reactions occurring simultaneously. In the transpassive regime, the dissolution clearly starts prior to the onset of oxygen evolution reaction (OER) as confirmed with potentiodynamic and potentiostatic measurements. The onset of OER also coincides with formation of a secondary passive film, likely comprising of Ni (III) species, suppressing the dissolution. We show that acidification of the electrolyte occurs after the onset of OER, but it does not trigger the transpassive dissolution in Ni. Furthermore, the post-mortem characterization revealed a selective grain boundary attack. The findings are discussed considering existing literature concerning the interplay between OER, secondary passivation and dissolution in the transpassive regime.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"531 ","pages":"Article 146461"},"PeriodicalIF":5.5,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143940101","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":"Fabrication of zinc tetramethoxyphenyl porphyrin-CNTs nanosensor for efficient sensing of the anticancer drug, 5-fluorouracil in human serum","authors":"Zaineb Noor Siddiqui,&nbsp;Syeda Aqsa Batool Bukhari,&nbsp;Habib Nasir","doi":"10.1016/j.electacta.2025.146453","DOIUrl":"10.1016/j.electacta.2025.146453","url":null,"abstract":"<div><div>5-Fluorouracil (5-FU) is a widely used anticancer drug for treating various types of cancer. Rapid and precise monitoring of 5-FU is critical to minimize its adverse effects on patients. This study presents the synthesis and application of a zinc tetramethoxyphenyl porphyrin-carbon nanotubes (ZnTMPP-CNTs) composite-based electrochemical sensor for detecting 5-FU. The sensor was developed by modifying a glassy carbon electrode (GCE) with the ZnTMPP-CNTs composite, which was synthesized via a one-step process. Comprehensive characterization of the composite was conducted using UV–visible spectrophotometry, Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) spectroscopy, and scanning electron microscopy (SEM). The modified GCE was fabricated using a drop-casting method. Electrochemical performance was assessed through cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The modified GCE performed superior to the bare electrode in a 0.1 M phosphate buffer solution (PBS) at pH 7. The electro-oxidation mechanism of 5-FU was identified as a one-electron process, primarily adsorption-controlled on the modified electrode's surface. The sensor demonstrated a linear response in the concentration ranges of 0.1 - 1.0 μM and 2.0 - 14.0 μM, with a sensitivity characterized by a limit of detection (LoD) of 0.098 μM and a limit of quantification (LoQ) of 0.327 μM. The sensor showed excellent stability, repeatability, and reproducibility. Its practical applicability was validated with real human blood serum samples, achieving remarkable recovery results. This research highlights the sensor's potential industrial, environmental, and medical applications, particularly in monitoring 5-FU in clinical settings.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"531 ","pages":"Article 146453"},"PeriodicalIF":5.5,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143940104","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":"Enhancing the electrochemical performance of Na₄MnV(PO₄)₃ cathode material by Zr substitution","authors":"Qi Qi ,&nbsp;Wei Zhang ,&nbsp;Yanjiang Zhang ,&nbsp;Mingxuan Zong ,&nbsp;Jiayu Song ,&nbsp;Yueyang Liu ,&nbsp;Ao Liu ,&nbsp;Li Zhao ,&nbsp;Changsong Dai","doi":"10.1016/j.electacta.2025.146456","DOIUrl":"10.1016/j.electacta.2025.146456","url":null,"abstract":"<div><div>The NASICON - structured Na₄MnV(PO₄)₃ is considered as a promising cathode material for sodium-ion batteries on account of its open three - dimensional framework, high redox potential, and excellent cycling stability. Nonetheless, the material's electrochemical performance is constrained by its inherently low electronic conductivity and the Jahn - Teller effect of Mn³⁺. In this work, a series of Na_4–2xMn_1-xZr_xV(PO₄)₃ (<em>x</em> = 0, 0.1, 0.125, 0.15, 0.175, 0.2, 0.3, 0.4, 0.5) materials were synthesized by substituting Zr at the Mn site to investigate the effects of Zr substitution on the cycling and rate performance of the NMVP material. XRD refinement was employed to ascertain the alterations in the crystal structure. In-situ XRD testing has also demonstrated that the substitution of Zr improves the stability of the material during high-voltage charge and discharge processes. The galvanostatic intermittent titration technique (GITT) test results demonstrate the variations in the diffusion coefficient of sodium-ions. 30 %Zr-NMVP sample exhibits excellent electrochemical performance. At a current density of 0.2 C, the initial discharge specific capacity reaches 89.26 mAh g^-1. After undergoing 100 cycles, the material maintains a capacity retention rate of 94.98 %. At 1 C, the initial discharge specific capacity is 85.32 mAh g^-1, and after 500 cycles, a reversible capacity of 74.30 mAh g^-1 is released, with a capacity retention rate of 86.03 %. In conclusion, Zr substitution can contribute to the improvement of the electrochemical performance of the NMVP material, providing the possibility of developing high - performance sodium-ion cathode materials in the future.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"531 ","pages":"Article 146456"},"PeriodicalIF":5.5,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143940107","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":"Strategic modulation of hydrogen bonding networks in aqueous electrolytes using green deep eutectic solvents: Experimental and computational insights for enhanced capacitive performance in symmetric supercapacitors","authors":"Fatema T. Zohura ,&nbsp;Akter Hossain Reaz ,&nbsp;Md. Minhajul Alam Khan ,&nbsp;Md. Rahadul Islam ,&nbsp;Raisul A. Mahmood ,&nbsp;Chanchal Kumar Roy ,&nbsp;Shakhawat H. Firoz","doi":"10.1016/j.electacta.2025.146455","DOIUrl":"10.1016/j.electacta.2025.146455","url":null,"abstract":"<div><div>This study explores the integration of deep eutectic solvents (DESs) with aqueous electrolytes, paving a pathway to modulate the hydrogen-bonding network, suppress water decomposition, and enhance electrochemical performance of a well-established electroactive reduced graphene oxide (rGO) based symmetrical supercapacitor (SSC). A strategic approach is proposed to control water dissociation in aqueous Na₂SO₄ electrolytes by incorporating a choline chloride (ChCl) based green DES, specifically ChCl and ethylene glycol (EG) (commonly referred to as ethaline, ETH). Systematic investigations reveal that varying water content (0 %, 40 %, 60 %, and 90 %) in the DES-water mixture affects its physicochemical properties, including conductivity, viscosity, and capacitive performance. The conductivity of neat ETH (ETH-1000) increased with up to 60 % water addition (ETH-4060) but dropped sharply to 90 % water content (ETH-1090) due to excessive dilution. The viscosity of ETH-1090 was six times lower than ETH-1000, reflecting hydrogen bond weakening among ETH components due to dilution. Among these, ETH-1090 demonstrated the highest capacitive performance compared to ETH-1000. Furthermore, the addition of ETH-1090 DES to the aqueous Na₂SO₄ electrolyte simultaneously disturbed the pre-existing hydrogen bonding network while fostering new and unique types of hydrogen bonds in ETH-1090-NS based electrolyte. Thus, this strategic modulation suppressed water decomposition and enhanced the electrochemical stability of aqueous Na₂SO₄ electrolyte for application in rGO-based SSC. This leads to a significant increase in the capacitive performance of aqueous Na₂SO₄ electrolyte from 445 to 645 mF cm^-2 with greater conductivity and extended electrochemical potential window up to 1.6 V. To support these findings, classical molecular dynamics (MD) simulations and quantum chemical calculations were conducted. Computational study provides insights into molecular interactions between ETH DES and aqueous electrolyte, revealing the unique role of hydrogen bonds in manipulating the conventional aqueous electrolyte. The excellent long-term cyclic stability (70 % retention of capacitance up to 10,000 cycles at high current density) is profoundly validating the robustness of the developed ETH-1090-NS based electrolyte system. This comprehensive study highlights the potential of unique DES based modifications of conventional aqueous electrolytes at the atomic level to enhance performance and advance energy storage systems.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"532 ","pages":"Article 146455"},"PeriodicalIF":5.5,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143940100","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":"Mesopore matters: Hierarchically porous metal–organic framework with facilitated redox-hopping and electrochemical behaviors toward the use in supercapacitors","authors":"Tzu-Hsien Yang ,&nbsp;Chi-Lun Chuang ,&nbsp;Yu-Chi Wang ,&nbsp;Ya-Mei Weng ,&nbsp;Cheng-Yan Hsieh ,&nbsp;Hsin-Ya Tsai ,&nbsp;Kuan-Chu Wu ,&nbsp;Cheng-Hui Shen ,&nbsp;Chung-Wei Kung","doi":"10.1016/j.electacta.2025.146458","DOIUrl":"10.1016/j.electacta.2025.146458","url":null,"abstract":"<div><div>A chemically robust zirconium-based metal–organic framework (MOF, UiO-66-NH₂) possessing both micropores from its crystalline structure and large mesopores is synthesized by employing the soft-template-assisted synthesis, and redox-active manganese ions are post-synthetically coordinated on the nodes of MOF where missing-linker defects are located. Regular UiO-66-NH₂ without mesopores and its manganese-installed material with a similar manganese loading per node are also synthesized. Crystallinity, porosity and morphologies of these materials are characterized. Thereafter, thin films of these MOFs are fabricated on conducting electrodes to measure their electrochemical behaviors in aqueous Na₂SO₄-based electrolytes, where the MOF is found structurally robust. The redox activity of immobilized manganese sites, the electrochemically addressable fraction of manganese sites in the MOF thin film, as well as the apparent diffusivity for the redox-based charge-hopping process occurring in the MOF are examined for both manganese-installed MOFs with and without mesopores. The redox-active MOFs are also blended with carbon nanotubes to form composites, aiming for the use in aqueous supercapacitors, and galvanostatic tests are performed to quantify the capacitance. Compared to the manganese-installed MOF without the hierarchical porosity, its counterpart possessing large mesopores can render more manganese sites electrochemically addressable and achieve an around 20-fold faster ion-coupled charge-hopping phenomenon occurring in the MOF thin film, resulting in a better performance when it is employed in supercapacitors. Findings here highlight the importance of creating large mesopores in redox-active MOFs in order to accelerate the mass transfer of ionic species within MOFs during electrochemical reactions and shed light on utilizing such hierarchically porous and stable MOFs in numerous electrochemical applications.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"531 ","pages":"Article 146458"},"PeriodicalIF":5.5,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143940102","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 and mechanism of mercaptobenzoheterocyclic derivatives as brighteners in acid sulfate tin electroplating","authors":"Yuxuan Huang ,&nbsp;Zhihua Tao ,&nbsp;Zewei Lin ,&nbsp;Songlin Zhang ,&nbsp;Hongwei Chen ,&nbsp;Tianpeng Liang ,&nbsp;Libin Gao ,&nbsp;Jihua Zhang","doi":"10.1016/j.electacta.2025.146459","DOIUrl":"10.1016/j.electacta.2025.146459","url":null,"abstract":"<div><div>Three mercaptobenzoheterocyclic derivatives including 2-mercaptobenzimidazole (MBI), 2-mercaptobenzoxazole (MBO), and 2-mercaptobenzothiazole (MBT) were investigated for their potential application as brighteners in tin electrodeposition. Electrochemical measurements demonstrated that all three brighteners effectively inhibited tin electrodeposition and hydrogen evolution, with MBT exhibiting the strongest inhibitory effect, which was evidenced by a negative shift of 14 mV in the potential of tin deposition and a reduction of 8 mA·cm⁻² in peak current density. Optical microscopy (OM) and scanning electron microscopy (SEM) images revealed significant improvements in the uniformity and brightness of the tin coatings. Quantum chemical calculations indicated that the adsorption sites of the brighteners on metallic surfaces were primarily the nitrogen atoms in imine groups and sulfur atoms in thiol groups. It is noteworthy that MBT displayed the highest reactivity due to its lowest energy gap (Δ<em>E</em> = 4.5685 eV). Molecular dynamics simulations suggested that the brighteners were adsorbed in both parallel and tilted configurations on specific tin planes maximizing the inhibition of tin electrodeposition.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"531 ","pages":"Article 146459"},"PeriodicalIF":5.5,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143946297","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}