Bismuth phosphate thin films (BP) composed of hexagonal BiPO4 and tetragonal Bi7.68P0.32O12.32 were prepared on bismuth substrates by anodization and utilized as working electrode for the simultaneous detection of Cd2+ and Pb2+ through square wave anodic stripping voltammetry (SWASV). The effects of H3PO4 concentration and anodization potential on the sample morphology and detection performance were investigated. And the test conditions (solution pH, deposition potential, deposition time and stripping amplitude) were optimized followed by a systematic discussion of the relevant causes. The results show that the sample morphology varies with the H3PO4 concentration and anodization potential. Different morphologies and test conditions lead to significant differences in the detection performance of the BP electrode. Under the optimal condition, the detection limits of the BP electrode for Cd2+ and Pb2+ are 0.52 μg L−1 and 0.31 μg L−1 (S/N = 3) and the linear range is 1 μg L−1–100 μg L−1. Meanwhile, the electrode exhibits high sensitivity, strong anti-interference, prominent stability and excellent reproducibility. Moreover, successful detection of heavy metal ions in three seawater samples manifests that the electrode can be employed in practical application.
{"title":"High-performance bismuth phosphate thin-film electrode for simultaneous and sensitive detection of Cd2+ and Pb2+","authors":"Mengyao Yang, Xixin Wang, Kai Lin, Yaya Liu, Zihan Li, Jianling Zhao","doi":"10.1016/j.jelechem.2025.119761","DOIUrl":"10.1016/j.jelechem.2025.119761","url":null,"abstract":"<div><div>Bismuth phosphate thin films (BP) composed of hexagonal BiPO<sub>4</sub> and tetragonal Bi<sub>7.68</sub>P<sub>0.32</sub>O<sub>12.32</sub> were prepared on bismuth substrates by anodization and utilized as working electrode for the simultaneous detection of Cd<sup>2+</sup> and Pb<sup>2+</sup> through square wave anodic stripping voltammetry (SWASV). The effects of H<sub>3</sub>PO<sub>4</sub> concentration and anodization potential on the sample morphology and detection performance were investigated. And the test conditions (solution pH, deposition potential, deposition time and stripping amplitude) were optimized followed by a systematic discussion of the relevant causes. The results show that the sample morphology varies with the H<sub>3</sub>PO<sub>4</sub> concentration and anodization potential. Different morphologies and test conditions lead to significant differences in the detection performance of the BP electrode. Under the optimal condition, the detection limits of the BP electrode for Cd<sup>2+</sup> and Pb<sup>2+</sup> are 0.52 μg L<sup><span>−</span>1</sup> and 0.31 μg L<sup><span>−</span>1</sup> (S/N = 3) and the linear range is 1 μg L<sup><span>−</span>1</sup>–100 μg L<sup><span>−</span>1</sup>. Meanwhile, the electrode exhibits high sensitivity, strong anti-interference, prominent stability and excellent reproducibility. Moreover, successful detection of heavy metal ions in three seawater samples manifests that the electrode can be employed in practical application.</div></div>","PeriodicalId":355,"journal":{"name":"Journal of Electroanalytical Chemistry","volume":"1003 ","pages":"Article 119761"},"PeriodicalIF":4.1,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145839423","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The oxygen evolution reaction (OER) involves multiple proton-coupled electron transfer steps and complex reaction intermediates. The influence of interfacial gas evolution on its kinetic responses remains difficult to understand. In this study, nickel electrodes were employed as a model system to elucidate the relationship between O2 bubble dynamics and electrochemical behavior under electrochemical potential control. Video observation coupled with a deep learning analysis pipeline enabled precise recognition and temporal tracking of O₂ bubbles during OER. Quantitative analysis of bubble growth enabled the extraction of current densities based on bubble growth. These findings highlight the critical role of interfacial gas dynamics in governing the kinetics of multi-electron transfer reactions and provide a new framework for mechanistic analysis of OER with respect to the conventional electrochemical measurements.
{"title":"Deep learning-assisted tracking of bubble dynamics for elucidating oxygen evolution reaction on nickel electrodes","authors":"Daiki Ashizawa , Daiki Kurosu , Masaki Itatani , Nobuaki Oyamada , Daiki Sato , Rui Kamada , Kazuyasu Sakaguchi , Tomohiro Fukushima , Kei Murakoshi","doi":"10.1016/j.jelechem.2025.119760","DOIUrl":"10.1016/j.jelechem.2025.119760","url":null,"abstract":"<div><div>The oxygen evolution reaction (OER) involves multiple proton-coupled electron transfer steps and complex reaction intermediates. The influence of interfacial gas evolution on its kinetic responses remains difficult to understand. In this study, nickel electrodes were employed as a model system to elucidate the relationship between O<sub>2</sub> bubble dynamics and electrochemical behavior under electrochemical potential control. Video observation coupled with a deep learning analysis pipeline enabled precise recognition and temporal tracking of O₂ bubbles during OER. Quantitative analysis of bubble growth enabled the extraction of current densities based on bubble growth. These findings highlight the critical role of interfacial gas dynamics in governing the kinetics of multi-electron transfer reactions and provide a new framework for mechanistic analysis of OER with respect to the conventional electrochemical measurements.</div></div>","PeriodicalId":355,"journal":{"name":"Journal of Electroanalytical Chemistry","volume":"1003 ","pages":"Article 119760"},"PeriodicalIF":4.1,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145881869","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-22DOI: 10.1016/j.jelechem.2025.119757
Guixia Wang , Zhuo Yang , Min Wang , Huaxin Xu , Xianming Liu
Polymer-functionalized Ti3C2 MXene nanocomposites enable biocompatible immobilization of horseradish peroxidase (HRP). Using Ti3C2 MXene- Polyacrylamide (PAM) as a model, the resulting Ti3C2-PAM/HRP hybrid electrode exhibits exceptional electrocatalytic activity toward H2O2 reduction in neutral phosphate buffer (containing 1 mM hydroquinone). This electrode demonstrates superior performance with a wider linear range (0.3–0.9 mM) and lower detection limit (1.4 μM, S/N = 3) compared to pristine Ti3C2-PAM and Ti3C2/HRP controls. The enhancement originates from synergistic coupling between MXene conductivity and HRP biocatalysis, facilitated by the polymer-mediated formation of 3D conductive networks that minimize charge-transfer resistance. Structural and electrochemical analysis confirms optimized enzyme-electrode interactions and biocompatibility. This work establishes a versatile interfacial engineering strategy for creating high-performance enzyme-MXene hybrids, demonstrating significant potential for detecting redox biomarkers and adaptable to diverse enzymatic systems.
{"title":"Interfacial engineering of polymer-functionalized Ti3C2 MXene nanocomposites for enhanced enzyme immobilization and high-performance H2O2 biosensing","authors":"Guixia Wang , Zhuo Yang , Min Wang , Huaxin Xu , Xianming Liu","doi":"10.1016/j.jelechem.2025.119757","DOIUrl":"10.1016/j.jelechem.2025.119757","url":null,"abstract":"<div><div>Polymer-functionalized Ti<sub>3</sub>C<sub>2</sub> MXene nanocomposites enable biocompatible immobilization of horseradish peroxidase (HRP). Using Ti<sub>3</sub>C<sub>2</sub> MXene- Polyacrylamide (PAM) as a model, the resulting Ti<sub>3</sub>C<sub>2</sub>-PAM/HRP hybrid electrode exhibits exceptional electrocatalytic activity toward H<sub>2</sub>O<sub>2</sub> reduction in neutral phosphate buffer (containing 1 mM hydroquinone). This electrode demonstrates superior performance with a wider linear range (0.3–0.9 mM) and lower detection limit (1.4 μM, S/N = 3) compared to pristine Ti<sub>3</sub>C<sub>2</sub>-PAM and Ti<sub>3</sub>C<sub>2</sub>/HRP controls. The enhancement originates from synergistic coupling between MXene conductivity and HRP biocatalysis, facilitated by the polymer-mediated formation of 3D conductive networks that minimize charge-transfer resistance. Structural and electrochemical analysis confirms optimized enzyme-electrode interactions and biocompatibility. This work establishes a versatile interfacial engineering strategy for creating high-performance enzyme-MXene hybrids, demonstrating significant potential for detecting redox biomarkers and adaptable to diverse enzymatic systems.</div></div>","PeriodicalId":355,"journal":{"name":"Journal of Electroanalytical Chemistry","volume":"1003 ","pages":"Article 119757"},"PeriodicalIF":4.1,"publicationDate":"2025-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145814243","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-20DOI: 10.1016/j.jelechem.2025.119753
Chenlu Li , Zhenyi Chen , Tao Li , Fengquan Li , Lingxuan Zhang , Wenhui Zhong , Cheng Han , Yunbin Jiang , Huan Deng
To better fit the practical application of the sediment microbial fuel cells (SMFC) based sensors in monitoring heavy metal contaminations, the sensitivity of the SMFC sensors needs to be optimized. In this study, key factors that might influence the sensitivity of SMFC sensors were proposed theoretically, and the external resistance, anode area and the depth of embedded anode were investigated with an orthogonal experiment using coastal sediment as the novel application scenario. The results showed that the external resistance had the greatest influence on the sensing performance to Cu2+ contamination. Enlarging the anode area also contributed to improving sensitivity in groups with 1 kΩ and 20 kΩ external resistors. In addition, the anode depth of 5 cm, anode area of 225 cm2, and external resistance of 20 kΩ were found to be optimal combination that achieved the highest sensitivity of 0.56 mV/mg L−1 and the lowest detection limit of 1 mg L−1 Cu2+, meeting the National Integrated Wastewater Discharge Standard of China (GB 8978-1996). However, increasing external resistance improved sensitivity at the cost of shortening the linear detection range. Notably, the addition of Cu2+ had no impact on the exoelectrogenic bacteria near the anode.
{"title":"Tuning monitoring performance of coastal sediment microbial fuel cell sensor to copper contamination through multiparameter optimization","authors":"Chenlu Li , Zhenyi Chen , Tao Li , Fengquan Li , Lingxuan Zhang , Wenhui Zhong , Cheng Han , Yunbin Jiang , Huan Deng","doi":"10.1016/j.jelechem.2025.119753","DOIUrl":"10.1016/j.jelechem.2025.119753","url":null,"abstract":"<div><div>To better fit the practical application of the sediment microbial fuel cells (SMFC) based sensors in monitoring heavy metal contaminations, the sensitivity of the SMFC sensors needs to be optimized. In this study, key factors that might influence the sensitivity of SMFC sensors were proposed theoretically, and the external resistance, anode area and the depth of embedded anode were investigated with an orthogonal experiment using coastal sediment as the novel application scenario. The results showed that the external resistance had the greatest influence on the sensing performance to Cu<sup>2+</sup> contamination. Enlarging the anode area also contributed to improving sensitivity in groups with 1 kΩ and 20 kΩ external resistors. In addition, the anode depth of 5 cm, anode area of 225 cm<sup>2</sup>, and external resistance of 20 kΩ were found to be optimal combination that achieved the highest sensitivity of 0.56 mV/mg L<sup>−1</sup> and the lowest detection limit of 1 mg L<sup>−1</sup> Cu<sup>2+</sup>, meeting the National Integrated Wastewater Discharge Standard of China (GB 8978-1996). However, increasing external resistance improved sensitivity at the cost of shortening the linear detection range. Notably, the addition of Cu<sup>2+</sup> had no impact on the exoelectrogenic bacteria near the anode.</div></div>","PeriodicalId":355,"journal":{"name":"Journal of Electroanalytical Chemistry","volume":"1002 ","pages":"Article 119753"},"PeriodicalIF":4.1,"publicationDate":"2025-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145837474","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-20DOI: 10.1016/j.jelechem.2025.119755
Dan Gu, Mingyan Liang, Yulin Wang, Zhou Fang, Sha Wu, Mengjiao Liu, Yan Zhao, Xin Lai, Daojiang Gao
Among all kinds of cathode for zinc-ion batteries (ZIBs), δ-MnO2 is one of the most prospective candidates due to its resource abundance, eco-friendly, relatively high operating voltage and higher theoretical capacity. However, it still suffers from structural instability, poor conductivity and sluggish diffusion rate, hindering its further application. Herein, a series of NH4+ intercalated δ-MnO2 (labeled as NMO) have been readily prepared via a straightforward one-step hydrothermal method. The effects of NH4+ intercalation concentration on the microstructure and electrochemical performance have been systematically investigated. Acted as interlayer pillar, NH4+ can not only expand the interlayer spacing but also enhance structural stability, finally attaining the rapid migration of zinc ions and preferable cyclic stability. In addition, the hydrogen bonding networks, owing to NH4+ intercalation, play a vital role in shielding the electrostatic attraction of interlayer oxygen atom. Compared with δ-MnO2, a series of NMO exhibit improved structural stability, higher capacity and cracking rate capability. Especially for the sample NMO-0.5, which can retain 153.1 mAh g−1 at 1 A g−1 after 1000 cycles. This work can afford a guidance for boosting the electrochemical performance of δ-MnO2 cathode material in ZIBs.
在各种锌离子电池正极材料中，δ-MnO2因其资源丰富、环境友好、工作电压较高、理论容量大等优点而成为最有前途的候选材料之一。但其结构不稳定、导电性差、扩散速度慢等问题阻碍了其进一步应用。本文通过简单的一步水热法制备了一系列NH4+插层δ-MnO2（标记为NMO）。系统地研究了NH4+插层浓度对其微观结构和电化学性能的影响。NH4+作为层间支柱，既能扩大层间间距，又能增强结构稳定性，最终实现锌离子的快速迁移和较好的循环稳定性。此外，由于NH4+的嵌入，氢键网络在屏蔽层间氧原子的静电吸引方面起着至关重要的作用。与δ-MnO2相比，一系列NMO具有更好的结构稳定性、更高的容量和裂解速率能力。特别是对于NMO-0.5样品，在1 A g−1下，经过1000次循环后，它可以保持153.1 mAh g−1。本研究对提高zno中δ-MnO2正极材料的电化学性能具有一定的指导意义。
{"title":"NH4+ intercalated δ-MnO2 cathode material for efficient zinc ions storage","authors":"Dan Gu, Mingyan Liang, Yulin Wang, Zhou Fang, Sha Wu, Mengjiao Liu, Yan Zhao, Xin Lai, Daojiang Gao","doi":"10.1016/j.jelechem.2025.119755","DOIUrl":"10.1016/j.jelechem.2025.119755","url":null,"abstract":"<div><div>Among all kinds of cathode for zinc-ion batteries (ZIBs), δ-MnO<sub>2</sub> is one of the most prospective candidates due to its resource abundance, eco-friendly, relatively high operating voltage and higher theoretical capacity. However, it still suffers from structural instability, poor conductivity and sluggish diffusion rate, hindering its further application. Herein, a series of NH<sub>4</sub><sup>+</sup> intercalated δ-MnO<sub>2</sub> (labeled as NMO) have been readily prepared via a straightforward one-step hydrothermal method. The effects of NH<sub>4</sub><sup>+</sup> intercalation concentration on the microstructure and electrochemical performance have been systematically investigated. Acted as interlayer pillar, NH<sub>4</sub><sup>+</sup> can not only expand the interlayer spacing but also enhance structural stability, finally attaining the rapid migration of zinc ions and preferable cyclic stability. In addition, the hydrogen bonding networks, owing to NH<sub>4</sub><sup>+</sup> intercalation, play a vital role in shielding the electrostatic attraction of interlayer oxygen atom. Compared with δ-MnO<sub>2</sub>, a series of NMO exhibit improved structural stability, higher capacity and cracking rate capability. Especially for the sample NMO-0.5, which can retain 153.1 mAh g<sup>−1</sup> at 1 A g<sup>−1</sup> after 1000 cycles. This work can afford a guidance for boosting the electrochemical performance of δ-MnO<sub>2</sub> cathode material in ZIBs.</div></div>","PeriodicalId":355,"journal":{"name":"Journal of Electroanalytical Chemistry","volume":"1002 ","pages":"Article 119755"},"PeriodicalIF":4.1,"publicationDate":"2025-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145837763","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-19DOI: 10.1016/j.jelechem.2025.119749
Jakub Vobořil , Lenka Janíková , Oleksandr Matvieiev , Jiří Váňa , Renáta Šelešovská
A novel voltammetric method for the determination of the broad-spectrum herbicide dicamba (DCB) was developed using a boron-doped diamond electrode (BDDE) as a working electrode. This study presents the first comprehensive characterisation of DCB's voltammetric behaviour. The oxidation mechanism of DCB was proposed through electrolysis followed by gas chromatography – mass spectrometry (GC–MS) analysis. Differential pulse (DPV) and square wave voltammetry (SWV) were optimized and applied for quantitative analysis. The optimized DPV method provided a wide linear dynamic range (0.5–70 μmol L−1) with low detection and quantification limits (LOD = 0.265 μmol L−1, LOQ = 0.885 μmol L−1), and excellent repeatability. The applicability of the method was verified through analysis of commercial pesticide formulations and spiked river water samples following ion-exchange pre-concentration. A detailed interference study confirmed the method's selectivity, especially in the presence of co-applied pesticides such as glyphosate. Results were validated using high-performance liquid chromatography with diode array detection (HPLC-DAD), with no statistically significant differences observed between methods. The optimized DPV method was successfully applied to real samples using both BDDE and screen-printed boron-doped diamond electrodes (SP/BDDE), which demonstrates the potential of the proposed voltammetry method for miniaturized, on-site, and environmental analytical applications.
{"title":"Sensitive voltammetric determination of herbicide dicamba in environmental samples using boron-doped diamond electrodes combined with ion-exchange preconcentration","authors":"Jakub Vobořil , Lenka Janíková , Oleksandr Matvieiev , Jiří Váňa , Renáta Šelešovská","doi":"10.1016/j.jelechem.2025.119749","DOIUrl":"10.1016/j.jelechem.2025.119749","url":null,"abstract":"<div><div>A novel voltammetric method for the determination of the broad-spectrum herbicide dicamba (DCB) was developed using a boron-doped diamond electrode (BDDE) as a working electrode. This study presents the first comprehensive characterisation of DCB's voltammetric behaviour. The oxidation mechanism of DCB was proposed through electrolysis followed by gas chromatography – mass spectrometry (GC–MS) analysis. Differential pulse (DPV) and square wave voltammetry (SWV) were optimized and applied for quantitative analysis. The optimized DPV method provided a wide linear dynamic range (0.5–70 μmol L<sup>−1</sup>) with low detection and quantification limits (LOD = 0.265 μmol L<sup>−1</sup>, LOQ = 0.885 μmol L<sup>−1</sup>), and excellent repeatability. The applicability of the method was verified through analysis of commercial pesticide formulations and spiked river water samples following ion-exchange pre-concentration. A detailed interference study confirmed the method's selectivity, especially in the presence of co-applied pesticides such as glyphosate. Results were validated using high-performance liquid chromatography with diode array detection (HPLC-DAD), with no statistically significant differences observed between methods. The optimized DPV method was successfully applied to real samples using both BDDE and screen-printed boron-doped diamond electrodes (SP/BDDE), which demonstrates the potential of the proposed voltammetry method for miniaturized, on-site, and environmental analytical applications.</div></div>","PeriodicalId":355,"journal":{"name":"Journal of Electroanalytical Chemistry","volume":"1002 ","pages":"Article 119749"},"PeriodicalIF":4.1,"publicationDate":"2025-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145837766","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-19DOI: 10.1016/j.jelechem.2025.119752
João R. Silva , Domingos Cortez , Carolina Vicente , Ana S. Fajardo , Rosa M. Quinta-Ferreira , Luís M. Castro
The increased demand for improved finish quality of cork stoppers has raised significant environmental concerns, particularly regarding the treatment of cork washing wastewater (CWW), which contains high levels of organic and inorganic pollutants. This study investigates the application of a batch electrocoagulation (EC) process, with an iron anode and a stainless-steel cathode, as an effective post-treatment following conventional physicochemical methods. The influence of current density on pollutant removal and treatment cost was systematically evaluated.
Results demonstrated that EC can significantly enhance CWW quality, with pollutant removal efficiencies and costs highly dependent on operational conditions. For scenarios where total nitrogen (TN) removal is not a priority, a current density of 67.6 A/m2 provides optimal cost-efficiency, achieving 93.0 % chemical oxygen demand (COD) in just 1 min, and up to 98.2 % COD, 68.6 % total organic carbon (TOC), 30.9 % TN, and 98.7 % total suspended solids (TSS) after 30 min reaction time, with treatment costs ranging from 0.018 €/m3 to 0.51 €/m3. When higher TN removal is required, a current density of 135 A/m2 achieves maximum removal (99.2 % COD, 70.1 % TOC, 54.4 % TN, and 98.8 % TSS) at a cost of 2.25 €/m3.
These findings confirm that EC is a promising, flexible and scalable technology for CWW treatment, particularly in contexts where biological treatment is limited by low biodegradability or toxicity. The process offers an effective balance between treatment performance and operational cost, supporting more sustainable wastewater management in the cork industry.
对软木塞成品质量的需求不断增加，引起了人们对环境的关注，特别是对含有高浓度有机和无机污染物的软木塞洗涤废水（CWW）的处理。本研究探讨了铁阳极和不锈钢阴极间歇电絮凝（EC）工艺的应用，作为传统物理化学方法的有效后处理。系统评价了电流密度对污染物去除率和处理成本的影响。结果表明，EC可显著提高CWW质量，其污染物去除效率和成本高度依赖于操作条件。在总氮（TN）去除不优先的情况下，67.6 a /m2的电流密度提供了最佳的成本效益，在1分钟内达到93.0%的化学需氧量（COD），在30分钟的反应时间后达到98.2%的COD， 68.6%的总有机碳（TOC）， 30.9%的TN和98.7%的总悬浮固体（TSS），处理成本为0.018欧元/m3至0.51欧元/m3。当需要更高的TN去除率时，135 a /m2的电流密度达到最大去除率（COD为99.2%，TOC为70.1%，TN为54.4%，TSS为98.8%），成本为2.25欧元/m3。这些研究结果证实，EC是一种有前途的、灵活的、可扩展的CWW处理技术，特别是在生物处理受到低生物降解性或毒性限制的情况下。该工艺在处理性能和运营成本之间提供了有效的平衡，支持软木塞行业更可持续的废水管理。
{"title":"Advanced cork washing wastewater treatment using combined physicochemical and electrocoagulation techniques","authors":"João R. Silva , Domingos Cortez , Carolina Vicente , Ana S. Fajardo , Rosa M. Quinta-Ferreira , Luís M. Castro","doi":"10.1016/j.jelechem.2025.119752","DOIUrl":"10.1016/j.jelechem.2025.119752","url":null,"abstract":"<div><div>The increased demand for improved finish quality of cork stoppers has raised significant environmental concerns, particularly regarding the treatment of cork washing wastewater (CWW), which contains high levels of organic and inorganic pollutants. This study investigates the application of a batch electrocoagulation (EC) process, with an iron anode and a stainless-steel cathode, as an effective post-treatment following conventional physicochemical methods. The influence of current density on pollutant removal and treatment cost was systematically evaluated.</div><div>Results demonstrated that EC can significantly enhance CWW quality, with pollutant removal efficiencies and costs highly dependent on operational conditions. For scenarios where total nitrogen (TN) removal is not a priority, a current density of 67.6 A/m<sup>2</sup> provides optimal cost-efficiency, achieving 93.0 % chemical oxygen demand (COD) in just 1 min, and up to 98.2 % COD, 68.6 % total organic carbon (TOC), 30.9 % TN, and 98.7 % total suspended solids (TSS) after 30 min reaction time, with treatment costs ranging from 0.018 €/m<sup>3</sup> to 0.51 €/m<sup>3</sup>. When higher TN removal is required, a current density of 135 A/m<sup>2</sup> achieves maximum removal (99.2 % COD, 70.1 % TOC, 54.4 % TN, and 98.8 % TSS) at a cost of 2.25 €/m<sup>3</sup>.</div><div>These findings confirm that EC is a promising, flexible and scalable technology for CWW treatment, particularly in contexts where biological treatment is limited by low biodegradability or toxicity. The process offers an effective balance between treatment performance and operational cost, supporting more sustainable wastewater management in the cork industry.</div></div>","PeriodicalId":355,"journal":{"name":"Journal of Electroanalytical Chemistry","volume":"1002 ","pages":"Article 119752"},"PeriodicalIF":4.1,"publicationDate":"2025-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145837473","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-19DOI: 10.1016/j.jelechem.2025.119754
Xuan Yang , Yuxin Tian , Borong Lu , Jing Zhao , Jinling Yin , Kai Zhu , Ke Ye
The auxiliary electrolysis of water to produce hydrogen by urea is crucial for regenerating green energy and controlling environmental pollution. Leveraging the advantages of transition metal metaphosphates and phosphides, we designed a bifunctional Co(PO3)2@Ni2P/NF electrocatalyst with a heterointerface. The synergistic effect between Co(PO3)2 and Ni2P enhances the catalytic capability, enabling the simultaneous efficient promotion of hydrogen evolution reaction (HER) and urea oxidation reaction (UOR) over a wide range of current density. Electrochemical measurements reveal that the HER on this catalyst requires an overpotential of only 40.4 mV to achieve 10 mA cm−2, while the UOR is driven at merely 1.27 V (vs RHE). Moreover, a full urea electrolyzer (HER||UOR) constructed with Co(PO3)2@Ni2P/NF delivers 10 mA cm−2 at cell voltage as low as 1.36 V and demonstrates remarkable stability in a prolonged chronopotentiometry test. This study thereby provides a novel approach to the UOR assisted electrolytic water hydrogen production system.
尿素辅助电解水制氢对再生绿色能源和控制环境污染具有重要意义。利用过渡金属偏磷酸盐和磷化物的优势，我们设计了一种具有异质界面的双功能Co(PO3)2@Ni2P/NF电催化剂。Co(PO3)2和Ni2P之间的协同作用增强了催化能力，可以在大电流密度范围内同时有效促进析氢反应（HER）和尿素氧化反应（UOR）。电化学测量表明，该催化剂上的HER只需要40.4 mV的过电位就能达到10 mA cm - 2，而UOR仅在1.27 V （vs RHE）下驱动。此外，用Co(PO3)2@Ni2P/NF构建的全尿素电解槽（HER||UOR）在低至1.36 V的电池电压下提供10 mA cm - 2，并在长时间的时间电位测定测试中表现出显著的稳定性。因此，本研究为UOR辅助电解水制氢系统提供了一种新的途径。
{"title":"Bifunctional Co(PO3)2@Ni2P/NF interface catalyst for efficient hydrogen production assisted by urea electrooxidation","authors":"Xuan Yang , Yuxin Tian , Borong Lu , Jing Zhao , Jinling Yin , Kai Zhu , Ke Ye","doi":"10.1016/j.jelechem.2025.119754","DOIUrl":"10.1016/j.jelechem.2025.119754","url":null,"abstract":"<div><div>The auxiliary electrolysis of water to produce hydrogen by urea is crucial for regenerating green energy and controlling environmental pollution. Leveraging the advantages of transition metal metaphosphates and phosphides, we designed a bifunctional Co(PO<sub>3</sub>)<sub>2</sub>@Ni<sub>2</sub>P/NF electrocatalyst with a heterointerface. The synergistic effect between Co(PO<sub>3</sub>)<sub>2</sub> and Ni<sub>2</sub>P enhances the catalytic capability, enabling the simultaneous efficient promotion of hydrogen evolution reaction (HER) and urea oxidation reaction (UOR) over a wide range of current density. Electrochemical measurements reveal that the HER on this catalyst requires an overpotential of only 40.4 mV to achieve 10 mA cm<sup>−2</sup>, while the UOR is driven at merely 1.27 V (vs RHE). Moreover, a full urea electrolyzer (HER||UOR) constructed with Co(PO<sub>3</sub>)<sub>2</sub>@Ni<sub>2</sub>P/NF delivers 10 mA cm<sup>−2</sup> at cell voltage as low as 1.36 V and demonstrates remarkable stability in a prolonged chronopotentiometry test. This study thereby provides a novel approach to the UOR assisted electrolytic water hydrogen production system.</div></div>","PeriodicalId":355,"journal":{"name":"Journal of Electroanalytical Chemistry","volume":"1002 ","pages":"Article 119754"},"PeriodicalIF":4.1,"publicationDate":"2025-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145837762","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-18DOI: 10.1016/j.jelechem.2025.119751
Pascalin Tiam Kapen
Hydride-ion batteries (HIBs) have recently emerged as a promising class of solid-state energy storage systems, offering high energy density, intrinsic safety, and access to abundant hydride-based materials. Yet their electrochemical behavior remains insufficiently understood, and predictive modeling tools are still lacking. This work presents the first comprehensive electrochemical model for a solid-state HIB based on the newly developed CeH₂ | 3CeH₃@BaH₂ | NaAlH₄ architecture (Cui et al., 2025). A one-dimensional finite-volume framework couples hydride transport, ionic/electronic potential distributions, and Butler-Volmer interfacial kinetics to simulate galvanostatic discharge and quantify the origin of voltage losses. The model successfully reproduces key operational features of HIBs, including plateau-like voltage-capacity curves, physically consistent activation and ohmic polarization, and electrolyte potential profiles. High-current and thick-electrolyte simulations generate hydride-concentration gradients exceeding 10 % across the solid electrolyte, confirming the onset of diffusion-limited regimes consistent with solid hydride conductors. The framework also captures how improved hydride transport, via higher diffusivity or reduced electrolyte thickness, sustains voltage at higher utilization, while limited transport accelerates polarization growth. A systematic sensitivity analysis demonstrates the expected kinetic ordering: increasing the interfacial exchange current density raises the discharge voltage and reduces activation losses. Aging multiphysics simulations further reveal monotonic interfacial-resistance growth and a corresponding decline in delivered capacity over 50 cycles, reproducing experimentally observed degradation phenomenology. Mesh-independence tests, analytical diffusion benchmarks, and normalized root-mean-square comparisons with synthetic experimental voltage–capacity data confirm the numerical robustness and the overall consistency of the model validation. Overall, the modeling framework provides a physically grounded and quantitatively coherent tool for diagnosing transport and kinetic limitations in HIBs. The results highlight actionable design levers, enhancing hydride-ion diffusivity, thinning the electrolyte, and strengthening interfacial kinetics, offering a predictive basis for the optimization of next-generation solid-state hydride-ion batteries.
氢化物离子电池（HIBs）最近成为一种有前途的固态储能系统，具有高能量密度、固有安全性和丰富的氢化物基材料。然而，它们的电化学行为仍然没有得到充分的了解，而且预测建模工具仍然缺乏。这项工作提出了基于新开发的CeH₂| 3CeH₃@BaH₂| NaAlH₄结构的固态HIB的第一个综合电化学模型（Cui et al., 2025）。一维有限体积框架耦合氢化物输运、离子/电子势分布和Butler-Volmer界面动力学来模拟恒流放电并量化电压损失的来源。该模型成功再现了HIBs的关键操作特征，包括类似平台的电压-容量曲线、物理一致的激活和欧姆极化以及电解质电位分布。大电流和厚电解质模拟产生的氢化物浓度梯度在整个固体电解质中超过10%，证实了与固体氢化物导体一致的扩散限制机制的开始。该框架还捕获了如何通过更高的扩散率或减少电解质厚度来改善氢化物传输，从而在更高的利用率下维持电压，而有限的传输加速极化生长。系统的灵敏度分析证明了预期的动力学顺序：增加界面交换电流密度可以提高放电电压并降低活化损失。老化多物理场模拟进一步揭示了单调的界面阻力增长和相应的传递能力下降，超过50个循环，再现了实验观察到的退化现象。网格无关性测试、分析扩散基准测试以及与综合实验电压容量数据的归一化均方根比较证实了模型验证的数值鲁棒性和总体一致性。总体而言，建模框架为诊断HIBs的传输和动力学限制提供了物理基础和定量一致的工具。研究结果突出了可操作的设计杠杆，提高了氢化物离子扩散率，稀释了电解质，加强了界面动力学，为下一代固态氢化物离子电池的优化提供了预测基础。
{"title":"Electrochemical modeling of solid-state hydride-ion batteries based on a CeH₂ | 3CeH₃@BaH₂ | NaAlH₄ architecture","authors":"Pascalin Tiam Kapen","doi":"10.1016/j.jelechem.2025.119751","DOIUrl":"10.1016/j.jelechem.2025.119751","url":null,"abstract":"<div><div>Hydride-ion batteries (HIBs) have recently emerged as a promising class of solid-state energy storage systems, offering high energy density, intrinsic safety, and access to abundant hydride-based materials. Yet their electrochemical behavior remains insufficiently understood, and predictive modeling tools are still lacking. This work presents the first comprehensive electrochemical model for a solid-state HIB based on the newly developed CeH₂ | 3CeH₃@BaH₂ | NaAlH₄ architecture (Cui et al., 2025). A one-dimensional finite-volume framework couples hydride transport, ionic/electronic potential distributions, and Butler-Volmer interfacial kinetics to simulate galvanostatic discharge and quantify the origin of voltage losses. The model successfully reproduces key operational features of HIBs, including plateau-like voltage-capacity curves, physically consistent activation and ohmic polarization, and electrolyte potential profiles. High-current and thick-electrolyte simulations generate hydride-concentration gradients exceeding 10 % across the solid electrolyte, confirming the onset of diffusion-limited regimes consistent with solid hydride conductors. The framework also captures how improved hydride transport, via higher diffusivity or reduced electrolyte thickness, sustains voltage at higher utilization, while limited transport accelerates polarization growth. A systematic sensitivity analysis demonstrates the expected kinetic ordering: increasing the interfacial exchange current density raises the discharge voltage and reduces activation losses. Aging multiphysics simulations further reveal monotonic interfacial-resistance growth and a corresponding decline in delivered capacity over 50 cycles, reproducing experimentally observed degradation phenomenology. Mesh-independence tests, analytical diffusion benchmarks, and normalized root-mean-square comparisons with synthetic experimental voltage–capacity data confirm the numerical robustness and the overall consistency of the model validation. Overall, the modeling framework provides a physically grounded and quantitatively coherent tool for diagnosing transport and kinetic limitations in HIBs. The results highlight actionable design levers, enhancing hydride-ion diffusivity, thinning the electrolyte, and strengthening interfacial kinetics, offering a predictive basis for the optimization of next-generation solid-state hydride-ion batteries.</div></div>","PeriodicalId":355,"journal":{"name":"Journal of Electroanalytical Chemistry","volume":"1002 ","pages":"Article 119751"},"PeriodicalIF":4.1,"publicationDate":"2025-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145798456","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-18DOI: 10.1016/j.jelechem.2025.119750
Rahul Agarwal
Eliezer Gileadi introduced a straightforward graphical method for estimating the standard rate constant () of quasireversible redox couples using cyclic voltammetry. Despite its simplicity, the method is seldom referenced due to the inherent limitation of requiring large variations in scan rate. Moreover, its improper application—particularly in determining the critical scan rate (), a key parameter for evaluating —has led to frequent misinterpretation of kinetic data in the literature. To overcome these challenges and improve its applicability, a revised approach, here referred to as the corrected Gileadi method, is proposed. This method involves plotting or against , enabling a more precise determination of . Importantly, this adjustment extends the applicability of the technique to irreversible redox couples, which was not feasible with the original Gileadi method. The validity of this approach is supported by a robust theoretical framework, including digital simulations, and further confirmed through experimental determination of values for the , and redox couples. This correction enhances the original Gileadi approach and mitigates recurrent misinterpretations in kinetic analysis based on cyclic voltammetry.
{"title":"A corrected Gileadi method for accurate determination of standard rate constants from cyclic voltammetry","authors":"Rahul Agarwal","doi":"10.1016/j.jelechem.2025.119750","DOIUrl":"10.1016/j.jelechem.2025.119750","url":null,"abstract":"<div><div>Eliezer Gileadi introduced a straightforward graphical method for estimating the standard rate constant (<span><math><mrow><msup><mi>k</mi><mn>0</mn></msup></mrow></math></span>) of quasireversible redox couples using cyclic voltammetry. Despite its simplicity, the method is seldom referenced due to the inherent limitation of requiring large variations in scan rate. Moreover, its improper application—particularly in determining the critical scan rate (<span><math><mrow><msub><mi>ν</mi><mi>c</mi></msub></mrow></math></span>), a key parameter for evaluating <span><math><mrow><msup><mi>k</mi><mn>0</mn></msup></mrow></math></span>—has led to frequent misinterpretation of kinetic data in the literature. To overcome these challenges and improve its applicability, a revised approach, here referred to as the corrected Gileadi method, is proposed. This method involves plotting <span><math><mrow><msub><mi>E</mi><mi>pc</mi></msub><mo>−</mo><msubsup><mi>E</mi><mi>f</mi><mn>0</mn></msubsup></mrow></math></span> or <span><math><mrow><msub><mi>ΔE</mi><mi>p</mi></msub></mrow></math></span> against <span><math><mrow><mspace></mspace><mi>log</mi><mi>ν</mi></mrow></math></span>, enabling a more precise determination of <span><math><mrow><mspace></mspace><msub><mi>ν</mi><mi>c</mi></msub></mrow></math></span>. Importantly, this adjustment extends the applicability of the technique to irreversible redox couples, which was not feasible with the original Gileadi method. The validity of this approach is supported by a robust theoretical framework, including digital simulations, and further confirmed through experimental determination of <span><math><mrow><mspace></mspace><msup><mi>k</mi><mn>0</mn></msup></mrow></math></span> values for the <span><math><mrow><mspace></mspace><msup><mrow><mfenced><mrow><mi>Fe</mi><msub><mrow><mfenced><mi>CN</mi></mfenced></mrow><mn>6</mn></msub></mrow></mfenced></mrow><mrow><mn>3</mn><mo>−</mo></mrow></msup><mo>/</mo><msup><mrow><mfenced><mrow><mi>Fe</mi><msub><mrow><mfenced><mi>CN</mi></mfenced></mrow><mn>6</mn></msub></mrow></mfenced></mrow><mrow><mn>4</mn><mo>−</mo></mrow></msup></mrow></math></span>, <span><math><mrow><msup><mi>Fe</mi><mrow><mn>3</mn><mo>+</mo></mrow></msup><mo>/</mo><msup><mi>Fe</mi><mrow><mn>2</mn><mo>+</mo></mrow></msup></mrow></math></span> and <span><math><mrow><msup><mi>Eu</mi><mrow><mn>3</mn><mo>+</mo></mrow></msup><mo>/</mo><msup><mi>Eu</mi><mrow><mn>2</mn><mo>+</mo></mrow></msup></mrow></math></span> redox couples. This correction enhances the original Gileadi approach and mitigates recurrent misinterpretations in kinetic analysis based on cyclic voltammetry.</div></div>","PeriodicalId":355,"journal":{"name":"Journal of Electroanalytical Chemistry","volume":"1002 ","pages":"Article 119750"},"PeriodicalIF":4.1,"publicationDate":"2025-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145837764","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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