Electrochemically generated radical anions (R•−) of several polycyclic aromatic hydrocarbons (R) were used for the surface treatment of polytetrafluoroethylene (PTFE). R•− works as an electron donor, which causes reductive elimination of F− on the PTFE surface. It was shown that the reduction potential of R significantly affects the rate of the reductive elimination of F−. By the reductive treatment of the PTFE surface, the contact angle of a water droplet decreased from 110° to about 60°. The contact angle change was analyzed to determine a standard rate constant of the reductive elimination (k0) with the radical anion of pyrene (Py•−) and anthracene (An•−), based on the Butler-Volmer model, and k0 = 5.7 × 10−4 and 4.6 × 10−4 M−1 s−1 for An•− and Py•−, respectively, were obtained. Furthermore, electroless deposition of Au and Cu on the treated PTFE sheets was carried out. Due to the reductive surface treatment, the Au and Cu layer was formed more uniformly than in the case of the untreated PTFE by the electroless deposition.
{"title":"Reductive surface treatment of polytetrafluoroethylene with electrochemically generated radical anions of several polycyclic aromatic hydrocarbons","authors":"Shogo Kawashima, Arata Nagashima, Yojiro Yamamoto, Hiroshi Shiigi, Ryoichi Ishimatsu","doi":"10.1016/j.electacta.2026.148407","DOIUrl":"https://doi.org/10.1016/j.electacta.2026.148407","url":null,"abstract":"Electrochemically generated radical anions (R<sup>•−</sup>) of several polycyclic aromatic hydrocarbons (R) were used for the surface treatment of polytetrafluoroethylene (PTFE). R<sup>•−</sup> works as an electron donor, which causes reductive elimination of F<sup>−</sup> on the PTFE surface. It was shown that the reduction potential of R significantly affects the rate of the reductive elimination of F<sup>−</sup>. By the reductive treatment of the PTFE surface, the contact angle of a water droplet decreased from 110° to about 60°. The contact angle change was analyzed to determine a standard rate constant of the reductive elimination (<em>k</em><sup>0</sup>) with the radical anion of pyrene (Py<sup>•−</sup>) and anthracene (An<sup>•−</sup>), based on the Butler-Volmer model, and <em>k</em><sup>0</sup> = 5.7 × 10<sup>−4</sup> and 4.6 × 10<sup>−4</sup> M<sup>−1</sup> s<sup>−1</sup> for An<sup>•−</sup> and Py<sup>•−</sup>, respectively, were obtained. Furthermore, electroless deposition of Au and Cu on the treated PTFE sheets was carried out. Due to the reductive surface treatment, the Au and Cu layer was formed more uniformly than in the case of the untreated PTFE by the electroless deposition.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"211 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135584","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}
This study aims to develop a high-performance, low-cost non-enzymatic electrochemical sensing materials for glucose detection, addressing the limitations of existing technologies. A three-dimensional porous hierarchical layered-nanoflower heterostructured CuCoP/MXene composite was synthesized through in situ growth of CuCo-MOF nanoflowers on Ti3C2-MXene via a one-step hydrothermal method, followed by oxidation and phosphidation treatments. This unique architecture significantly increases the specific reactive surface area, exposes abundant active sites, and provides sufficient interfacial regions for glucose oxidation. The synergistic effect between copper (Cu) and cobalt (Co) further enhances the electrocatalytic performance. Meanwhile, MXene serves as a conductive scaffold that not only facilitates electron transfer but also promotes the diffusion and adsorption of glucose molecules, owing to its excellent conductivity and continuous interlayer channels. The fabricated sensor exhibits an extensive linear detection range (0.5-6000 μM), high sensitivity (1408.49 μA mM-1·cm-2), a low detection limit (0.14 μM, S/N=3), along with excellent selectivity, reproducibility, and stability, together with a swift response time (3 s). Moreover, the sensor has been successfully applied to the accurate detection of glucosein samples of serum, showing high reliability and promising practical value.
{"title":"3D porous layered CuCoP/MXene nanoflowers via MXene-assisted in situ growth for non-enzymatic glucose biosensing","authors":"Qiao Wan, Yajun Li, Yahong Su, Wenqing Jia, Jiang Zhu, Qiang Yu, Zhen Chen, Lingli Lei, Yuanyuan Zhang","doi":"10.1016/j.electacta.2026.148403","DOIUrl":"https://doi.org/10.1016/j.electacta.2026.148403","url":null,"abstract":"This study aims to develop a high-performance, low-cost non-enzymatic electrochemical sensing materials for glucose detection, addressing the limitations of existing technologies. A three-dimensional porous hierarchical layered-nanoflower heterostructured CuCoP/MXene composite was synthesized through <em>in situ</em> growth of CuCo-MOF nanoflowers on Ti<sub>3</sub>C<sub>2</sub>-MXene <em>via</em> a one-step hydrothermal method, followed by oxidation and phosphidation treatments. This unique architecture significantly increases the specific reactive surface area, exposes abundant active sites, and provides sufficient interfacial regions for glucose oxidation. The synergistic effect between copper (Cu) and cobalt (Co) further enhances the electrocatalytic performance. Meanwhile, MXene serves as a conductive scaffold that not only facilitates electron transfer but also promotes the diffusion and adsorption of glucose molecules, owing to its excellent conductivity and continuous interlayer channels. The fabricated sensor exhibits an extensive linear detection range (0.5-6000 μM), high sensitivity (1408.49 μA mM<sup>-1</sup>·cm<sup>-2</sup>), a low detection limit (0.14 μM, S/N=3), along with excellent selectivity, reproducibility, and stability, together with a swift response time (3 s). Moreover, the sensor has been successfully applied to the accurate detection of glucosein samples of serum, showing high reliability and promising practical value.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"31 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135095","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}
Pub Date : 2026-02-07DOI: 10.1016/j.electacta.2026.148397
Nathanael Brandt, Julia Pross-Brakhage, Jinglin Huang, Hassan Akhtar, Sonia Dsoke, Kai Peter Birke, Lea Eisele, Oliver Fitz
Accurate information about the local pH on electrode surfaces is critical to understand the underlying reaction mechanism and side reactions in Aqueous Zinc-Manganese Dioxide Batteries (AZMBs). Previously reported pH measurements lack sufficient quality and accuracy due to the placement of the pH sensor in the bulk electrolyte and significant excess of electrolyte, which dilutes the pH effects during operation. We present a locally resolved, application‑oriented measurement technique using flat‑tip surface pH sensors placed in direct contact with both electrodes in a setup with minimized electrolyte volumes. The novel pH measurement technique is combined with visual observations from a windowed coin cell operando microscopy setup. In this work, we demonstrate the severity of the cathode-driven pH shifting between 2 and ∼5.5 during cycling in an unbuffered sulfate electrolyte, which induces hydrogen evolution reaction (HER) on the anode, zinc hydroxy-sulfate (ZHS) precipitation at the anode and incomplete ZHS dissolution upon charge. Also, the pH buffering by an acetate-sulfate electrolyte and its limitations with high capacities are investigated. We demonstrate that local pH phenomena influenced by the apparent current density and buffer concentration determine the cell voltage and the onset of HER and ZHS precipitation. The results show the crucial role of the electrolyte composition - controlling both the local and global pH by developing new buffers, cell concepts or adjusted cycling protocols will be essential to make AZMBs an application-ready battery cell technology.
{"title":"Locally Resolved Operando pH Measurement Technique in Aqueous Zinc-Manganese Dioxide Batteries","authors":"Nathanael Brandt, Julia Pross-Brakhage, Jinglin Huang, Hassan Akhtar, Sonia Dsoke, Kai Peter Birke, Lea Eisele, Oliver Fitz","doi":"10.1016/j.electacta.2026.148397","DOIUrl":"https://doi.org/10.1016/j.electacta.2026.148397","url":null,"abstract":"Accurate information about the local pH on electrode surfaces is critical to understand the underlying reaction mechanism and side reactions in Aqueous Zinc-Manganese Dioxide Batteries (AZMBs). Previously reported pH measurements lack sufficient quality and accuracy due to the placement of the pH sensor in the bulk electrolyte and significant excess of electrolyte, which dilutes the pH effects during operation. We present a locally resolved, application‑oriented measurement technique using flat‑tip surface pH sensors placed in direct contact with both electrodes in a setup with minimized electrolyte volumes. The novel pH measurement technique is combined with visual observations from a windowed coin cell operando microscopy setup. In this work, we demonstrate the severity of the cathode-driven pH shifting between 2 and ∼5.5 during cycling in an unbuffered sulfate electrolyte, which induces hydrogen evolution reaction (HER) on the anode, zinc hydroxy-sulfate (ZHS) precipitation at the anode and incomplete ZHS dissolution upon charge. Also, the pH buffering by an acetate-sulfate electrolyte and its limitations with high capacities are investigated. We demonstrate that local pH phenomena influenced by the apparent current density and buffer concentration determine the cell voltage and the onset of HER and ZHS precipitation. The results show the crucial role of the electrolyte composition - controlling both the local and global pH by developing new buffers, cell concepts or adjusted cycling protocols will be essential to make AZMBs an application-ready battery cell technology.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"16 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135580","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}
Pub Date : 2026-02-06DOI: 10.1016/j.electacta.2026.148395
Divyansh Anil Khurana, Cyrille Sébert, Philippe M. Vereecken
Nano-semiconductor electrodes are employed for light harvesting applications in (photo-)electrochemical conversion reactions and dye-sensitized solar cells. Accurate determination of their band edge energetic positions is central to their efficacy for isoenergetic charge transfer to the electrolyte. Yet, conventional methods fail for nano-dimensional semiconductor electrodes due to full depletion and extremely small potential-independent space charge widths. In this regard, a new approach was demonstrated on thin film nano-TiO2 electrodes where the current-potential (i-U) characteristics in high and low work function redox probes were interpreted to infer band edge positions in darkness. The methodology is now extended for nano-TiO2 band edge interpretation to illuminated interfaces. Using compact 30 nm TiO2 thin films of both anatase and amorphous phases, we analyze open-circuit potentials and onset potentials in darkness and illumination across varying pH conditions to infer band edge shifts. We also examine temperature rise due to solution heating under illumination from the diffusion-limited currents in the i-U characteristics. Additionally, signatures from surface states in the i-U characteristics are identified, their densities estimated, and their implications discussed. The findings are consolidated through energy band diagrams, offering a comprehensive view of the fully depleted nano-semiconductor/electrolyte interface under operational conditions.
{"title":"Electrochemical redox probes to map light-modulated band edge shifts of nano-TiO2 thin film electrodes in aqueous solutions","authors":"Divyansh Anil Khurana, Cyrille Sébert, Philippe M. Vereecken","doi":"10.1016/j.electacta.2026.148395","DOIUrl":"https://doi.org/10.1016/j.electacta.2026.148395","url":null,"abstract":"Nano-semiconductor electrodes are employed for light harvesting applications in (photo-)electrochemical conversion reactions and dye-sensitized solar cells. Accurate determination of their band edge energetic positions is central to their efficacy for isoenergetic charge transfer to the electrolyte. Yet, conventional methods fail for nano-dimensional semiconductor electrodes due to full depletion and extremely small potential-independent space charge widths. In this regard, a new approach was demonstrated on thin film nano-TiO<sub>2</sub> electrodes where the current-potential (i-U) characteristics in high and low work function redox probes were interpreted to infer band edge positions in darkness. The methodology is now extended for nano-TiO<sub>2</sub> band edge interpretation to illuminated interfaces. Using compact 30 nm TiO<sub>2</sub> thin films of both anatase and amorphous phases, we analyze open-circuit potentials and onset potentials in darkness and illumination across varying pH conditions to infer band edge shifts. We also examine temperature rise due to solution heating under illumination from the diffusion-limited currents in the i-U characteristics. Additionally, signatures from surface states in the i-U characteristics are identified, their densities estimated, and their implications discussed. The findings are consolidated through energy band diagrams, offering a comprehensive view of the fully depleted nano-semiconductor/electrolyte interface under operational conditions.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"43 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135092","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}
Pub Date : 2026-02-06DOI: 10.1016/j.electacta.2026.148390
Hao Hu, Bo Sun, Kexing Song, Zhipeng Zhao, Shuaiyu Ma, Lin Ji, Xujun Wang, Haoyan Cheng
Electrodeposited copper foils serve as indispensable materials for both electronic circuits and lithium-ion batteries, where their mechanical properties play a decisive role in determining device reliability. Despite the widespread use of chemical additives to tailor copper foil properties, the intricate interactions among multiple additives and their underlying mechanisms remain poorly understood. In this study, we systematically investigate the synergistic effects of sodium alcohol thiyl propane sulfonate (HP) and hydroxyethyl cellulose (HEC) on Cu2+ ions electrodeposition, copper microstructure, and mechanical performance. Through optimization, the simultaneous addition of 4.0 mg/L HP and 80 mg/L HEC produced copper foils with the excellent mechanical performance, tensile strength of 674 MPa and elongation of 8.2%. Comprehensive electrochemical and structural analyses reveal that the HP+HEC binary system strongly influences cathodic polarization, promoting refined grain growth and increasing the density of Σ3 twin boundaries, thereby synergistically enhance both strength and ductility. This work deepens our understanding of additive-modulated electrodeposition mechanisms and offers a valuable design framework for engineering high-performance copper foils tailored for demanding applications.
{"title":"Unveiling the synergistic mechanism of binary additives for tailoring microstructure and enhancing the properties of high-performance electrodeposited copper foils","authors":"Hao Hu, Bo Sun, Kexing Song, Zhipeng Zhao, Shuaiyu Ma, Lin Ji, Xujun Wang, Haoyan Cheng","doi":"10.1016/j.electacta.2026.148390","DOIUrl":"https://doi.org/10.1016/j.electacta.2026.148390","url":null,"abstract":"Electrodeposited copper foils serve as indispensable materials for both electronic circuits and lithium-ion batteries, where their mechanical properties play a decisive role in determining device reliability. Despite the widespread use of chemical additives to tailor copper foil properties, the intricate interactions among multiple additives and their underlying mechanisms remain poorly understood. In this study, we systematically investigate the synergistic effects of sodium alcohol thiyl propane sulfonate (HP) and hydroxyethyl cellulose (HEC) on Cu<sup>2+</sup> ions electrodeposition, copper microstructure, and mechanical performance. Through optimization, the simultaneous addition of 4.0 mg/L HP and 80 mg/L HEC produced copper foils with the excellent mechanical performance, tensile strength of 674 MPa and elongation of 8.2%. Comprehensive electrochemical and structural analyses reveal that the HP+HEC binary system strongly influences cathodic polarization, promoting refined grain growth and increasing the density of Σ3 twin boundaries, thereby synergistically enhance both strength and ductility. This work deepens our understanding of additive-modulated electrodeposition mechanisms and offers a valuable design framework for engineering high-performance copper foils tailored for demanding applications.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"48 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135302","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}
Pub Date : 2026-02-06DOI: 10.1016/j.electacta.2026.148389
Shaojie Lei, Dezhang Ren, Jian Yang, Fan Lin, Zichen Li, Tengfei Li, Yan Jin, Zhibao Huo
{"title":"Ti-induced construction of RuO2 solid solution for achieving high selectivity in ·OH generation and long lifespan electrocatalytic degradation of Methylene Blue","authors":"Shaojie Lei, Dezhang Ren, Jian Yang, Fan Lin, Zichen Li, Tengfei Li, Yan Jin, Zhibao Huo","doi":"10.1016/j.electacta.2026.148389","DOIUrl":"https://doi.org/10.1016/j.electacta.2026.148389","url":null,"abstract":"","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"2 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135110","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}
Pub Date : 2026-02-06DOI: 10.1016/j.electacta.2026.148399
Rippei Suzuki, Mikiko Saito, Takayuki Homma
{"title":"Electrodeposition of CoPd and CoNiPd ultrathin films with low Co composition and perpendicular magnetic anisotropy for magnetic memory applications","authors":"Rippei Suzuki, Mikiko Saito, Takayuki Homma","doi":"10.1016/j.electacta.2026.148399","DOIUrl":"https://doi.org/10.1016/j.electacta.2026.148399","url":null,"abstract":"","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"23 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135301","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}
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