Electrochimica Acta最新文献

{"title":"Structural control of activated carbons derived from rice husks for sustainable and enhanced lithium-ion battery anodes","authors":"Cu Dang Van ,&nbsp;Thu Thuy Luong Thi ,&nbsp;Khu Le Van ,&nbsp;Min Hyung Lee","doi":"10.1016/j.electacta.2025.146169","DOIUrl":"10.1016/j.electacta.2025.146169","url":null,"abstract":"<div><div>Activated carbon (AC) derived from rice husk is synthesized through a chemical activation method using dual activation agents of KOH and NaOH. The resulting AC materials demonstrate a moderate degree of graphitization, a large specific surface area, and are enriched with abundant oxygenate surface functional groups. These characteristics make them promising candidates as anode materials for Li ion batteries. Upon evaluating the performance of the synthesized ACs as anode materials, remarkable charge/discharge properties are observed, showcasing reversible capacities surpassing the theoretical value of graphite by 1.77 to 2.27 times. Notably, the AC sample obtained with the weight ratio of KOH/NaOH/char of 2 : 2 : 1 (designated as RH-K2N2) exhibits the highest reversible capacities, reaching an impressive 857 mAh⋅g⁻¹ at a current density of 50 mA⋅g⁻¹. Additionally, even after 100 fully discharge-charge cycles at the current density of 100 mA⋅g⁻¹, the reversible capacity remains as high as 525 mAh⋅g⁻¹.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"526 ","pages":"Article 146169"},"PeriodicalIF":5.5,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143800334","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":"Integrated electrochemical sensing platform based on Au/MXene/PU three-dimensional scaffold for real-time monitoring of H2O2 release from cells under drug stimulation","authors":"Sufei Wang ,&nbsp;Guidan Wang ,&nbsp;Jiling Shi ,&nbsp;Xiaorui Zhu ,&nbsp;Aihua Jing ,&nbsp;Gaofeng Liang","doi":"10.1016/j.electacta.2025.146206","DOIUrl":"10.1016/j.electacta.2025.146206","url":null,"abstract":"<div><div>Compared with traditional two-dimensional (2D) culture systems, three-dimensional (3D) culture systems can better simulate the physiological environment of cells in vivo, providing more accurate and real-time data. Although many reported 3D culture scaffolds can simulate the in vivo microenvironment, their use in real-time electrochemical sensing still limited by their insulating and non-compressible nature. In this research, we developed a simple and efficient way for preparing 3D cell culture-integrated electrochemical sensing platform for real-time monitoring of hydrogen peroxide (H₂O₂) release from cells under drug stimulation. The 3D integrated platform was a polyurethane (PU) scaffold modified MXene and gold nanoparticles (Au NPs) (Au/MXene/PU). The prepared Au/MXene/PU scaffold showed excellent electrocatalytic activity for H₂O₂ with a detection linear range of 0.1 to 100 μM. Furthermore, MDA-MB-231 cells were cultured on the 3D Au/MXene/PU scaffold and H₂O₂ released by cells were in situ monitored. These results indicate that the 3D Au/MXene/PU scaffold exhibits excellent potential applications in cell in vivo research cancer-related disease diagnosis and drug screening.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"527 ","pages":"Article 146206"},"PeriodicalIF":5.5,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143798158","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":"Characterization of Ni-GDC based electrolyte-supported cell under processed biogas composition: Electrochemical performance, degradation and recovery","authors":"Hangyu Yu ,&nbsp;Cédric Frantz ,&nbsp;Louis Savioz ,&nbsp;Dante Fronterotta ,&nbsp;Philippe Aubin ,&nbsp;Christian Geipel ,&nbsp;Hamza Moussaoui ,&nbsp;Guillaume Jeanmonod ,&nbsp;Ligang Wang ,&nbsp;Jan Van herle","doi":"10.1016/j.electacta.2025.146163","DOIUrl":"10.1016/j.electacta.2025.146163","url":null,"abstract":"<div><div>Biogas-fed solid oxide fuel cell (SOFC) technology based on Ni-GDC electrolyte-supported cell (ESC) offers a sustainable solution for European farms’ heat and power demands with superior efficiency. However, the understanding of the degradation and recovery behavior of the Ni-GDC based ESC under processed biogas environment is limited. This study investigates the responses of various electrochemical processes to the degradation under two cases: (1) cold recirculation before reformer (CB) and hot recirculation before reformer (HB) with no risk of carbon deposition. Chronopotentiometry and current–voltage (IV) results indicated that CB case had the highest degradation rate of -11.6 mV/kh, followed by the HB case with -6.4 mV/kh and the dry H<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> case with -0.42 mV/kh. With the electrochemical impedance spectroscopy (EIS) measurements and distribution of relaxation time (DRT) method, it was found that CB and HB case demonstrated much lower gas conversion resistance than the dry H<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> case, while two peaks representing the electrode gas diffusion process integrated with O<span><math><msup><mrow></mrow><mrow><mn>2</mn><mo>−</mo></mrow></msup></math></span> surface exchange merged into one peak in HB and dry H<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> case but split in CB case. Complex nonlinear least squares (CNLS) fit was used to quantify the resistance degradation under CB and HB environments, which depended mainly on the ohmic resistance and two electrode charge transfer resistances. The recovery process under dry H<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> environment showed that the total resistance increased after 134 h, validating the degradation inertia under biogas environment, while the time constants of RQ elements and the peak shifting indicated that the electrochemical performance was partially recovering to the initial state. This study provides insights into the long-term performance degradation of Ni-GDC based ESC under processed biogas environment and guidelines to the operating conditions with a lower degradation rate.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"526 ","pages":"Article 146163"},"PeriodicalIF":5.5,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806208","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":"Nanoarchitectonics with yttrium role in controlled structural transformations and enhanced electrochemical performance of Y-BiVO4 nanorods for supercapacitor electrode applications","authors":"Khudija Munir ,&nbsp;Ghulam Nabi","doi":"10.1016/j.electacta.2025.146135","DOIUrl":"10.1016/j.electacta.2025.146135","url":null,"abstract":"<div><div>Structural transformations at the nanoscale, along with crystal imperfections introduced by ion doping, plays a critical role in improving electrochemical performance. In this study, a series of Y-doped BiVO₄ samples, with compositions Y_xBi_1-xVO₄ (<em>x</em> = 0, 0.01, 0.03, 0.05), were synthesized and studied for supercapacitor applications. The structural and morphological investigations verified that Y-ion incorporation significantly influences the transition, transforming spherical nanoparticles into rod-like nanostructure. This increases the electrochemical active surface area for higher redox activity. The electrochemical examinations confirmed notable improvements in specific capacitance, with the electrode containing 3 % Y doping achieving a maximum capacitance of 2127 F/g at a scan rate of 5 mV/s, along with excellent retention of 90.9 % after 6000 charge-discharge cycles. This remarkable performance is attributed to the enhanced charge transport and conductivity due to rod-like nanostructure. Power-law analysis (<em>b</em> = 0.68) and Dunn's method (54.93 % capacitive contribution at 100 mV/s scan rate) further substantiate the pseudocapacitive behavior of the material. The low R_s values from EIS and high specific capacitance of 3 % Y-BiVO₄ nanorods as promising candidates for high-performance supercapacitor applications, underscoring its potential to advance energy storage technology.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"526 ","pages":"Article 146135"},"PeriodicalIF":5.5,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143791035","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":"Eco-friendly solvent alternative to N-methyl-2-pyrrolidone in lithium-ion battery electrode safe manufacturing","authors":"Chaeeun Kang ,&nbsp;Chaekyung Kim ,&nbsp;Sang-Min Lee ,&nbsp;Ying Liu ,&nbsp;Jae-Kwang Kim","doi":"10.1016/j.electacta.2025.146209","DOIUrl":"10.1016/j.electacta.2025.146209","url":null,"abstract":"<div><div>Over the past decade, the rapid growth in lithium-ion battery (LIB) production has been driven by the rising demand for portable electronic devices, electric vehicles, and stationary energy storage systems. However, the widespread use of N-methyl-2-pyrrolidone (NMP) as a solvent in LIB electrode manufacturing poses significant environmental and health concerns. NMP is classified as a reproductive toxicant and is known to cause severe irritation and health risks during the manufacturing process. Accordingly, this study investigates the potential of gamma-valerolactone (GVL), an eco-friendly solvent, and dimethyl sulfoxide (DMSO), a relatively environmentally friendly solvent, as alternatives for NMP in LIB electrode manufacturing. The electrochemical performances of LiFePO₄ cathodes and electrode surfaces were compared and evaluated using NMP-, GVL-, and DMSO-based solvents through field emission scanning electron microscopy (FE-SEM), thermogravimetric analysis (TGA), differential thermogravimetric analysis (DTG), X-ray photoelectron spectroscopy (XPS), and solid-state nuclear magnetic resonance (solid-NMR). The analysis revealed that GVL- and DMSO-based electrodes exhibited performance levels comparable to NMP, confirming their feasibility as alternative solvents in the electrode fabrication process. These findings suggest that GVL and DMSO have the potential for real-world application in the LIB industry, thus contributing to sustainable battery production.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"526 ","pages":"Article 146209"},"PeriodicalIF":5.5,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143798156","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":"Preparation and performance study of high-performance lignin carbon-based sulfur host materials","authors":"Shi Mengqi ,&nbsp;Bu Yonglin ,&nbsp;Xia Guangmei ,&nbsp;Tian Yihui ,&nbsp;Wang Shoujuan ,&nbsp;Xi Yuebin ,&nbsp;Wang Huan ,&nbsp;Kong Fangong","doi":"10.1016/j.electacta.2025.146205","DOIUrl":"10.1016/j.electacta.2025.146205","url":null,"abstract":"<div><div>The development of lithium-sulfur batteries, which are a new type of energy storage device, is hindered by the poor performance of sulfur cathodes and the shuttle effect of polysulfides.In this study, a composite precursor was successfully constructed through the hydrophobic self-assembly of lignin, carbon nanotubes (CNTs), and zinc carbonate, wherein lignin molecules encapsulate CNTs. Subsequently, high-temperature gas-phase exfoliation and in-situ activation of the precursor yielded a three-dimensionally interconnected lignin carbon/CNTs composite material (LPC/CNTs), as sulfur host to enhance the electrochemical performance. The results indicate that LPC/CNTs as a sulfur-hosting material, under calcination at 700 °C with a 10 % CNTs addition, the initial discharge specific capacity reaches 1138 mAh g⁻¹ at 0.1 C and maintains a discharge specific capacity of 504.09 mAh g⁻¹ after 300 cycles at 1 C. These findings suggest that the LPC/CNTs composite material, featuring abundant pore structures and three-dimensionally interconnected conductive networks, is a promising sulfur-hosting material for lithium-sulfur batteries. This study not only offers a novel approach for the high-value utilization of industrial lignin but also provides fundamental data for the development of new energy materials.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"526 ","pages":"Article 146205"},"PeriodicalIF":5.5,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143798154","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":"Fe2VO4 nanoparticles embedded in CNTs with fast reaction kinetics for high-performance lithium storage","authors":"Hong Liu ,&nbsp;Litao Han ,&nbsp;Chen Lu ,&nbsp;Shi Tao ,&nbsp;Bin Qian ,&nbsp;Fanjun Kong","doi":"10.1016/j.electacta.2025.146200","DOIUrl":"10.1016/j.electacta.2025.146200","url":null,"abstract":"<div><div>Iron vanadium oxides have large exploration potentiality as anode materials for lithium ion batteries owing to their abundant resource and high capacity based on multi-electron transfer process. However, low electrical conductivity and large volume change may lead to the sluggish reaction kinetics and rapid capacity decay. Herein, Fe₂VO₄ nanoparticles are uniformly embedded in the carbon nanotubes (FVO/CNT) though the hydrothermal reaction and subsequent heat treatment. Benefiting from high electrical conductivity and structural stability of CNT, FVO/CNT composite delivers excellent lithium storage performance with superior kinetics and high reversible capacity. Furthermore, the lithium-ion full cell with LiFePO₄ as cathode presents superior cycling stability (181.5 mAh g⁻¹ after 100 cycles at 0.2 A g^-1 and 96.4 mAh g^-1 after 500 cycles at 2.0 A g^-1). This work opens up a promising path for electrochemical reaction analysis of energy storage materials and provides valuable guidance for durable lithium ion batteries with high performance.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"526 ","pages":"Article 146200"},"PeriodicalIF":5.5,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143789966","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 oxygen reduction reaction using polyoxometalates as mediators in near neutral electrolytes for zinc-air batteries","authors":"A. Inclán ,&nbsp;A. Crespo-Villanueva ,&nbsp;Y. Navarro ,&nbsp;F. López-Ortiz ,&nbsp;R. Argurio ,&nbsp;R.M. González-Gil ,&nbsp;P. Gómez-Romero ,&nbsp;N. Casañ-Pastor ,&nbsp;L.N. Bengoa","doi":"10.1016/j.electacta.2025.146180","DOIUrl":"10.1016/j.electacta.2025.146180","url":null,"abstract":"<div><div>The quest for effective and sustainable energy storage solutions has led to the exploration of devices like Metal-air batteries, whose performance heavily depends on the efficiency of electrocatalysts in oxygen reduction reactions (ORR) at the cathode. Zinc-Air batteries (ZABs) are a great option, since its components are low cost, safe and eco-friendly. Despite significant efforts, creating cost-effective electrocatalysts with high activity for ORR remains a major challenge. Furthermore, most of the research in the ORR field is carried out in highly alkaline electrolytes, which allow for favorable ORR kinetics but lead to corrosion and low durability of the catalysts and the cells. This work explores the possibility to use polyoxometalate clusters as homogeneous (i.e. in solution) catalysts/mediators in near-neutral pH, evidencing an alternative path to facilitate ORR. Several cobalt containing POMs with Keggin (K₅H[Co²⁺W₁₂O₄₀], K₈[Co²⁺Co²⁺(H₂O)W₁₁Co²⁺O₄₀]·15H₂O, K₇ [Co³⁺Co²⁺(H₂O)W₁₁O₃₉]·14H₂O), Dawson (K₁₂[Co²⁺⁽H₂O)H₂P₂W₁₂O₄₈]) or Superlacunary (K₁₂Li₁₆Co²⁺₂[Co²⁺₄(H₂O)₁₆P₈W₄₈O₁₈₄]) nanocluster, were used in solution showing significant activity on the ORR. The unique existence of redox processes for both Co and W moieties within the cluster suggests the possibility of bifunctional electrocatalysis, and redox mediation with a potential impact in aqueous rechargeable metal-air batteries operating in near – neutral media. The electrochemical action of easily reduced soluble POM clusters on ORR shows an increased activity when the Co-substituted Keggin POMs are dissolved at pH 5. Keggin based structures containing Co offer optimal kinetic parameters, as compared with POMs based on Dawson structures, with the possible involvement of the tetrahedral Co present in the former.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"526 ","pages":"Article 146180"},"PeriodicalIF":5.5,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143789964","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":"CeO2 enhancement on self-grown Ni(OH)2 on nickel foam for 5-hydroxymethylfurfural electrooxidation","authors":"Zhijun Kang ,&nbsp;Yongming Zeng ,&nbsp;Xiaofei Li ,&nbsp;Haifeng Shi ,&nbsp;Jingshuai Zhu ,&nbsp;Lili Geng ,&nbsp;Ley Boon Sim ,&nbsp;Binghui Chen","doi":"10.1016/j.electacta.2025.146201","DOIUrl":"10.1016/j.electacta.2025.146201","url":null,"abstract":"<div><div>This study focuses on developing a novel high-performance electrocatalyst to enhance the electrochemical synthesis efficiency of 2,5-furandicarboxylic acid (FDCA) from 5-hydroxymethylfurfural (HMF). The self-grown, binder-free Ni(OH)₂_<img>CeO₂ on nickel foam nanosheet catalyst was prepared via a one-step hydrothermal method without additional Ni sources. XRD, HRTEM, and SAED confirmed the Ni(OH)₂ and CeO₂ phases and demonstrated their heterojunction, revealing the flake-like morphology of Ni(OH)₂ and the particulate nature of CeO₂. XPS analysis showed that the introduction of CeO₂ modulates the catalyst electronic environment, shifting the Ni 2p3/2 peak to higher binding energies which favors more Ni³⁺ formation. The Ni(OH)₂_<img>CeO₂/NF electrode outperformed Ni(OH)₂/NF in oxidizing HMF. Electrochemical tests demonstrated that at 1.504 V, Ni(OH)₂_<img>CeO₂/NF achieved an HMF conversion rate of 98.9 % and FDCA selectivity of 98.8 % with a Faradaic efficiency of 98.4 %, while showing excellent stability. DFT calculations corroborated that CeO₂ optimizes HMF adsorption on the catalyst and lowers the activation energies for all reaction intermediates. This research developed the robust electrocatalyst Ni(OH)₂_<img>CeO₂/NF for FDCA production, and also elucidated the indirect reaction mechanism of the catalyst and the catalytic mechanism by which CeO₂ enhances the electrocatalytic oxidation performance of HMF.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"526 ","pages":"Article 146201"},"PeriodicalIF":5.5,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143789965","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":"Covalent bonding in perimidine-containing perinone systems: a case study using potentiodynamic oxidation of 14H-benzo[4,5]isoquino[2,1-a]perimidin-14-one","authors":"Patryk Janasik ,&nbsp;Malgorzata Czichy ,&nbsp;Radosław Motyka ,&nbsp;Dawid Janasik ,&nbsp;Jacek Miskow ,&nbsp;Mieczyslaw Lapkowski","doi":"10.1016/j.electacta.2025.146199","DOIUrl":"10.1016/j.electacta.2025.146199","url":null,"abstract":"<div><div>In recent years, we have focused our research on the oxidative addition/coupling of monomers from the perinone group, where the reaction occurs between perimidine segments. So far, we have used rather complex and difunctional isoidolo-[2,1-<em>a</em>]perimidinones and isoquino-[2,1-<em>a</em>]perimidinones, which resulted in solid products that were difficult to analyze. The primary objective of these studies was to propose simple, monofunctional perimidine monomers and evaluate their reactivity through the characterization of their soluble electrooxidation products. The reference compounds were structural analogues lacking perimidine, yet derived from the same anhydrides, i.e. 11<em>H</em>-isoindolo[2,1-<em>a</em>]benzimidazole-11-on (1,2-benzoylenebenzimidazole) (<strong>A1</strong>), and 7<em>H</em>-benzimidazo[2,1-<em>a</em>]benzo[<em>de</em>]isoquinolin-7-one (1,8-naphthoylene-1′,2′-benzimidazole) (<strong>A2</strong>). In this work we investigated the electrooxidation of 12<em>H</em>-isoindolo-[2,1-<em>a</em>]perimidin-12-one (12-phthaloperinone) (<strong>B1</strong>) and 14<em>H</em>-benzo[4,5]isoquinolino[2,1-<em>a</em>]perimidin-14-one (naphthaloperinone) (<strong>B2</strong>) to compare their oxidative reactivity and define the bis-perimidine bonding. While the <strong>A</strong> series did not form electroactive material after oxidation, the <strong>B</strong> series successfully formed the conductive layer, indicating that perimidine unit is capable of oxidative addition. However, the <strong>B2</strong> electrocoupling process was characterized by the best efficiency. Mass spectrometry (MS), quantum chemical calculations, as well as UV–Vis-NIR and ESR spectroelectrochemistry analyses of the dissolved and solid electrooxidation products of <strong>B2</strong> (i.e. <strong>1pFr, 2pB2</strong>, respectively) revealed the presence of multiple products, including one-bonded deprotonated bis-perimidine dimers, especially in <strong>1pFr</strong> fraction. We propose that specific intermolecular interactions more promote the suitable orientation of the singly-linked dimer and by its subsequent oxidation under alternating potential giving transition from the semi-ladder (<strong>1pB2</strong>) to the ladder structure presented by <strong>2pB2</strong>. The conditions of the electrodynamic oxidation process determine the deprotonation and discharge of some dimers. However, in certain cases, the bonds remain protonated due to stabilization by hydrogen bonds, which arises from the proximity of the carbonyl group. The multiredox nature of the solid product <strong>2pB2</strong> is related to the presence of a mixture of different dimers: one- or two-bonded, and also protonated dimers. Our findings offer new insights into the mechanisms of perimidine bonding within group of perinone compunds, highlighting their potential for synthesising a novel class of organic compounds through electrochemical methods.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"526 ","pages":"Article 146199"},"PeriodicalIF":5.5,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143789962","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}