{"title":"An EDTA-Protonated Polyaniline Cathode for High-Performance Aqueous Zinc-Ion Batteries","authors":"Zhen Sun, Xiaonan Qi, Haixu Wang","doi":"10.1002/elan.70236","DOIUrl":"https://doi.org/10.1002/elan.70236","url":null,"abstract":"<p>Aqueous zinc-ion batteries (AZIBs) have emerged as a highly promising energy storage technology, attributed to their intrinsic safety and low-cost manufacturing. However, polyaniline (PANI)-based cathodes typically encounter critical challenges including significant proton depletion and poor cycling stability when operated in neutral aqueous electrolytes. To address these limitations, this work fabricated an EDTA-protonated PANI (PANI-EDTA) composite cathode via pulse voltammetry-driven in situ electrodeposition on electrochemically exfoliated graphite. EDTA, which contains four carboxyl groups, acts as an embedded proton source to construct local acidic microenvironments. This modification increases the protonation level of nitrogen in PANI from 34% to 62.4%, thereby mitigating irreversible deprotonation. Electrochemical characterizations demonstrate that the PANI-EDTA cathode delivers a specific capacity of up to 257 mAh g<sup>−1</sup> at a current density of 0.5 A g<sup>−1</sup>. Even at an ultrahigh current density of 30 A g<sup>−1</sup>, the cathode retains a specific capacity of 175 mAh g<sup>−1</sup>. Furthermore, after 5000 charge–discharge cycles at 2 A g<sup>−1</sup>, the electrode maintains 86.4% of its initial capacity. This work presents a simple yet effective dopant design strategy for constructing robust organic polymer cathodes for high-performance aqueous AZIBs.</p>","PeriodicalId":162,"journal":{"name":"Electroanalysis","volume":"38 10","pages":""},"PeriodicalIF":2.6,"publicationDate":"2026-10-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149145872","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}
{"title":"An EDTA-Protonated Polyaniline Cathode for High-Performance Aqueous Zinc-Ion Batteries","authors":"Zhen Sun, Xiaonan Qi, Haixu Wang","doi":"10.1002/elan.70236","DOIUrl":"https://doi.org/10.1002/elan.70236","url":null,"abstract":"<p>Aqueous zinc-ion batteries (AZIBs) have emerged as a highly promising energy storage technology, attributed to their intrinsic safety and low-cost manufacturing. However, polyaniline (PANI)-based cathodes typically encounter critical challenges including significant proton depletion and poor cycling stability when operated in neutral aqueous electrolytes. To address these limitations, this work fabricated an EDTA-protonated PANI (PANI-EDTA) composite cathode via pulse voltammetry-driven in situ electrodeposition on electrochemically exfoliated graphite. EDTA, which contains four carboxyl groups, acts as an embedded proton source to construct local acidic microenvironments. This modification increases the protonation level of nitrogen in PANI from 34% to 62.4%, thereby mitigating irreversible deprotonation. Electrochemical characterizations demonstrate that the PANI-EDTA cathode delivers a specific capacity of up to 257 mAh g<sup>−1</sup> at a current density of 0.5 A g<sup>−1</sup>. Even at an ultrahigh current density of 30 A g<sup>−1</sup>, the cathode retains a specific capacity of 175 mAh g<sup>−1</sup>. Furthermore, after 5000 charge–discharge cycles at 2 A g<sup>−1</sup>, the electrode maintains 86.4% of its initial capacity. This work presents a simple yet effective dopant design strategy for constructing robust organic polymer cathodes for high-performance aqueous AZIBs.</p>","PeriodicalId":162,"journal":{"name":"Electroanalysis","volume":"38 10","pages":""},"PeriodicalIF":2.6,"publicationDate":"2026-10-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149145560","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}
Eduardo H. Bindewald, Ediane A. Kavilhuka Metzger, Déborah O. Lopes, Geiser G. Oliveira, Márcio F. Bergamini, Luiz H. Marcolino-Júnior
{"title":"Titanate Nanotubes as a Platform for the Electrosynthesis of Cobalt Hexacyanoferrate: An Electrocatalytic Interface for Hydrazine Sensing","authors":"Eduardo H. Bindewald, Ediane A. Kavilhuka Metzger, Déborah O. Lopes, Geiser G. Oliveira, Márcio F. Bergamini, Luiz H. Marcolino-Júnior","doi":"10.1002/elan.70230","DOIUrl":"https://doi.org/10.1002/elan.70230","url":null,"abstract":"<p>Titanate nanotubes (TiNTs) combine high surface area with remarkable ion-exchange capability, making them attractive scaffolds for the construction of electrocatalytic interfaces. Herein, this property was exploited to promote the incorporation of Co(II) ions into TiNTs, followed by the electrochemical growth of cobalt hexacyanoferrate (CoHCF) on screen-printed electrodes, yielding a robust hybrid electrocatalytic architecture. The resulting TiNT–CoHCF interface exhibited well-defined and stable Fe(II)/Fe(III) and Co(II)/Co(III) redox processes, confirming the successful immobilization of the mediator and efficient electron-transfer characteristics. The hybrid material showed excellent electrocatalytic activity toward hydrazine oxidation through a mediated EC′ mechanism, in which electrochemically generated Co(III) species oxidize hydrazine while being continuously regenerated at the electrode surface. Under optimized chronoamperometric conditions (+0.8 V, phosphate buffer solution pH 9.0), the platform displayed a linear response from 0.76 to 69 μmol L<sup>−1</sup>, a sensitivity of 0.048 μA μmol<sup>−1</sup> L, and a limit of detection of 0.56 μmol L<sup>−1</sup>, together with good repeatability (RSD = 3.1%) and operational stability over ten days. The sensor was successfully applied to the determination of hydrazine in commercial X-ray developer samples using the standard addition method. These findings demonstrate that TiNTs can serve as efficient ion-exchange scaffolds for the electrosynthesis of prussian blue analog films, providing a simple and versatile strategy for engineering robust electrocatalytic interfaces for electrochemical sensing.</p>","PeriodicalId":162,"journal":{"name":"Electroanalysis","volume":"38 10","pages":""},"PeriodicalIF":2.6,"publicationDate":"2026-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/elan.70230","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149145570","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Reactivity of Diethylstilbestrol Toward Electrogenerated Superoxide in N,N-Dimethylformamide Through Proton-Coupled Electron Transfer","authors":"Tatsushi Nakayama, Kaisei Hara","doi":"10.1002/elan.70231","DOIUrl":"https://doi.org/10.1002/elan.70231","url":null,"abstract":"<p>The superoxide radical anion (O<sub>2</sub><sup>•</sup><sup>−</sup>) scavenging mechanism of diethylstilbestrol (DesH<sub>2</sub>) was investigated using in situ UV–vis spectroelectrochemistry, cyclic voltammetry, and DFT/TD-DFT calculations. While thermodynamic evaluation indicates that all tested stilbene derivatives possess favorable free energy changes for scavenging O<sub>2</sub><sup>•−</sup>, comparative cyclic voltammetry revealed that only DesH<sub>2</sub> and 4,4′-dihydroxystilbene exhibit distinct scavenging waves. On the electrochemical timescale, effective scavenging requires a 1:1 stoichiometric proton-coupled electron transfer (PCET) mechanism involving the transfer of two protons and one electron from a single molecule. Thermodynamic and mechanistic analyses supported this PCET pathway. Crucially, the diethyl substituents in DesH<sub>2</sub> stabilize the generated radical anion and maintain the structural integrity of the stilbene core, enabling further two- to four-electron oxidation. Furthermore, subsequent chemical steps (e.g., adduct decomposition or OH addition) pull the reaction equilibrium forward to dynamically drive the initial PCET process.</p>","PeriodicalId":162,"journal":{"name":"Electroanalysis","volume":"38 10","pages":""},"PeriodicalIF":2.6,"publicationDate":"2026-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/elan.70231","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149145571","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Eduardo H. Bindewald, Ediane A. Kavilhuka Metzger, Déborah O. Lopes, Geiser G. Oliveira, Márcio F. Bergamini, Luiz H. Marcolino-Júnior
{"title":"Titanate Nanotubes as a Platform for the Electrosynthesis of Cobalt Hexacyanoferrate: An Electrocatalytic Interface for Hydrazine Sensing","authors":"Eduardo H. Bindewald, Ediane A. Kavilhuka Metzger, Déborah O. Lopes, Geiser G. Oliveira, Márcio F. Bergamini, Luiz H. Marcolino-Júnior","doi":"10.1002/elan.70230","DOIUrl":"https://doi.org/10.1002/elan.70230","url":null,"abstract":"<p>Titanate nanotubes (TiNTs) combine high surface area with remarkable ion-exchange capability, making them attractive scaffolds for the construction of electrocatalytic interfaces. Herein, this property was exploited to promote the incorporation of Co(II) ions into TiNTs, followed by the electrochemical growth of cobalt hexacyanoferrate (CoHCF) on screen-printed electrodes, yielding a robust hybrid electrocatalytic architecture. The resulting TiNT–CoHCF interface exhibited well-defined and stable Fe(II)/Fe(III) and Co(II)/Co(III) redox processes, confirming the successful immobilization of the mediator and efficient electron-transfer characteristics. The hybrid material showed excellent electrocatalytic activity toward hydrazine oxidation through a mediated EC′ mechanism, in which electrochemically generated Co(III) species oxidize hydrazine while being continuously regenerated at the electrode surface. Under optimized chronoamperometric conditions (+0.8 V, phosphate buffer solution pH 9.0), the platform displayed a linear response from 0.76 to 69 μmol L<sup>−1</sup>, a sensitivity of 0.048 μA μmol<sup>−1</sup> L, and a limit of detection of 0.56 μmol L<sup>−1</sup>, together with good repeatability (RSD = 3.1%) and operational stability over ten days. The sensor was successfully applied to the determination of hydrazine in commercial X-ray developer samples using the standard addition method. These findings demonstrate that TiNTs can serve as efficient ion-exchange scaffolds for the electrosynthesis of prussian blue analog films, providing a simple and versatile strategy for engineering robust electrocatalytic interfaces for electrochemical sensing.</p>","PeriodicalId":162,"journal":{"name":"Electroanalysis","volume":"38 10","pages":""},"PeriodicalIF":2.6,"publicationDate":"2026-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/elan.70230","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149145634","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Reactivity of Diethylstilbestrol Toward Electrogenerated Superoxide in N,N-Dimethylformamide Through Proton-Coupled Electron Transfer","authors":"Tatsushi Nakayama, Kaisei Hara","doi":"10.1002/elan.70231","DOIUrl":"https://doi.org/10.1002/elan.70231","url":null,"abstract":"<p>The superoxide radical anion (O<sub>2</sub><sup>•</sup><sup>−</sup>) scavenging mechanism of diethylstilbestrol (DesH<sub>2</sub>) was investigated using in situ UV–vis spectroelectrochemistry, cyclic voltammetry, and DFT/TD-DFT calculations. While thermodynamic evaluation indicates that all tested stilbene derivatives possess favorable free energy changes for scavenging O<sub>2</sub><sup>•−</sup>, comparative cyclic voltammetry revealed that only DesH<sub>2</sub> and 4,4′-dihydroxystilbene exhibit distinct scavenging waves. On the electrochemical timescale, effective scavenging requires a 1:1 stoichiometric proton-coupled electron transfer (PCET) mechanism involving the transfer of two protons and one electron from a single molecule. Thermodynamic and mechanistic analyses supported this PCET pathway. Crucially, the diethyl substituents in DesH<sub>2</sub> stabilize the generated radical anion and maintain the structural integrity of the stilbene core, enabling further two- to four-electron oxidation. Furthermore, subsequent chemical steps (e.g., adduct decomposition or OH addition) pull the reaction equilibrium forward to dynamically drive the initial PCET process.</p>","PeriodicalId":162,"journal":{"name":"Electroanalysis","volume":"38 10","pages":""},"PeriodicalIF":2.6,"publicationDate":"2026-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/elan.70231","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149145636","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Engineering a Protein-Fouling-Resistant Nanocomposite Interface: Poly(Acryloyl Morpholine)-Grafted Chitosan/Graphene for Dopamine Sensing","authors":"Mohamed Rashad, Abdullah Alhendal","doi":"10.1002/elan.70234","DOIUrl":"https://doi.org/10.1002/elan.70234","url":null,"abstract":"<p>Protein fouling at electrified interfaces remains a central bioelectrochemical challenge: coatings resistant to nonspecific biomacromolecule adsorption typically impede the electron-transfer kinetics needed for sensitive detection. Here, we report a graphene nanoplatelet (GNP) electrode covalently grafted with a chitosan-poly(acryloylmorpholine) (CS-g-PACMO) coating, in which rigid morpholine pendant groups sustain a protective hydration layer at the electrode surface. Using a component-resolved benchmarking design (bare electrode, GNP-only, GNP/chitosan, and full composite; <i>n</i> = 5 per group), we show that GNP incorporation alone increases fouling susceptibility relative to bare electrodes, while covalent PACMO grafting restores signal retention in protein-laden synthetic urine to 88.8 ± 5.9%. The composite retained 91.2 ± 3.4% of its initial response after 30 anodic cycles, versus 52.4 ± 5.1% for a PEG-coated analog, indicating improved oxidative stability. A neutral redox probe further isolates the steric hydration contribution from electrostatic exclusion. Applied to the overlapping dopamine, ascorbic acid, and uric acid system, impedance spectroscopy and DFT-level calculations indicate an additional polymer-mediated transport contribution beyond graphene affinity. Under simultaneous conditions, the sensor achieved a dopamine detection limit of 0.23 µM (0.15 µM single-analyte) with good linearity (<i>R</i><sup>2</sup> > 0.99). These results identify PACMO grafting as an oxidatively stable, protein-fouling-resistant strategy for graphene-based biosensors.</p>","PeriodicalId":162,"journal":{"name":"Electroanalysis","volume":"38 10","pages":""},"PeriodicalIF":2.6,"publicationDate":"2026-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149145635","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}
{"title":"Engineering a Protein-Fouling-Resistant Nanocomposite Interface: Poly(Acryloyl Morpholine)-Grafted Chitosan/Graphene for Dopamine Sensing","authors":"Mohamed Rashad, Abdullah Alhendal","doi":"10.1002/elan.70234","DOIUrl":"https://doi.org/10.1002/elan.70234","url":null,"abstract":"<p>Protein fouling at electrified interfaces remains a central bioelectrochemical challenge: coatings resistant to nonspecific biomacromolecule adsorption typically impede the electron-transfer kinetics needed for sensitive detection. Here, we report a graphene nanoplatelet (GNP) electrode covalently grafted with a chitosan-poly(acryloylmorpholine) (CS-g-PACMO) coating, in which rigid morpholine pendant groups sustain a protective hydration layer at the electrode surface. Using a component-resolved benchmarking design (bare electrode, GNP-only, GNP/chitosan, and full composite; <i>n</i> = 5 per group), we show that GNP incorporation alone increases fouling susceptibility relative to bare electrodes, while covalent PACMO grafting restores signal retention in protein-laden synthetic urine to 88.8 ± 5.9%. The composite retained 91.2 ± 3.4% of its initial response after 30 anodic cycles, versus 52.4 ± 5.1% for a PEG-coated analog, indicating improved oxidative stability. A neutral redox probe further isolates the steric hydration contribution from electrostatic exclusion. Applied to the overlapping dopamine, ascorbic acid, and uric acid system, impedance spectroscopy and DFT-level calculations indicate an additional polymer-mediated transport contribution beyond graphene affinity. Under simultaneous conditions, the sensor achieved a dopamine detection limit of 0.23 µM (0.15 µM single-analyte) with good linearity (<i>R</i><sup>2</sup> > 0.99). These results identify PACMO grafting as an oxidatively stable, protein-fouling-resistant strategy for graphene-based biosensors.</p>","PeriodicalId":162,"journal":{"name":"Electroanalysis","volume":"38 10","pages":""},"PeriodicalIF":2.6,"publicationDate":"2026-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149145572","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}
{"title":"Large-Scale and High-Density Microelectrode Array on a Complementary Metal Oxide Semiconductor Chip for Biochemical Applications","authors":"Jingyi Xu, Chao Zhao, Hong Liu","doi":"10.1002/elan.70233","DOIUrl":"https://doi.org/10.1002/elan.70233","url":null,"abstract":"<p>Multichannel electrochemical sensing technology has been widely applied in the fields of chemical and biological applications. By combining complementary metal oxide semiconductor (CMOS) technology to construct microelectrode array (MEA) chips, the throughput and spatiotemporal resolution could be vastly boosted by the tens of thousands of electrodes on the chip. This article describes a large-scale and high-density electrochemical sensing and reactions-driven CMOS MEA chip demonstrated with various chemical and biological applications. The chip integrates 24 576 gold microelectrodes with a 18 µm pitch, achieving a per-electrode sampling rate of 140 kS/s and a full-array frame rate of 5 Hz. It also incorporates an associated switch matrix, 24 integrated potentiostats and digital control circuits. We studied and suppressed the cross talk among multiple electrodes working in the solution with finite element analysis and experiments. The large-scale and high-spatiotemporal resolution electrochemical sensing capability of this chip was proven by 3D voltammetry. For driving electrochemical reactions, bubble generation for primary neuron detachment at selected electrodes, electrode electroplating, and DNA synthesis were demonstrated.</p>","PeriodicalId":162,"journal":{"name":"Electroanalysis","volume":"38 10","pages":""},"PeriodicalIF":2.6,"publicationDate":"2026-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149146915","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}
{"title":"Large-Scale and High-Density Microelectrode Array on a Complementary Metal Oxide Semiconductor Chip for Biochemical Applications","authors":"Jingyi Xu, Chao Zhao, Hong Liu","doi":"10.1002/elan.70233","DOIUrl":"https://doi.org/10.1002/elan.70233","url":null,"abstract":"<p>Multichannel electrochemical sensing technology has been widely applied in the fields of chemical and biological applications. By combining complementary metal oxide semiconductor (CMOS) technology to construct microelectrode array (MEA) chips, the throughput and spatiotemporal resolution could be vastly boosted by the tens of thousands of electrodes on the chip. This article describes a large-scale and high-density electrochemical sensing and reactions-driven CMOS MEA chip demonstrated with various chemical and biological applications. The chip integrates 24 576 gold microelectrodes with a 18 µm pitch, achieving a per-electrode sampling rate of 140 kS/s and a full-array frame rate of 5 Hz. It also incorporates an associated switch matrix, 24 integrated potentiostats and digital control circuits. We studied and suppressed the cross talk among multiple electrodes working in the solution with finite element analysis and experiments. The large-scale and high-spatiotemporal resolution electrochemical sensing capability of this chip was proven by 3D voltammetry. For driving electrochemical reactions, bubble generation for primary neuron detachment at selected electrodes, electrode electroplating, and DNA synthesis were demonstrated.</p>","PeriodicalId":162,"journal":{"name":"Electroanalysis","volume":"38 10","pages":""},"PeriodicalIF":2.6,"publicationDate":"2026-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149146791","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}