Journal of Electroanalytical Chemistry最新文献_第2页

Poly(vinylidene fluoride-co-hexafluoropropylene)/ionic liquid/polydopamine-modified metal-organic framework composite polymer electrolytes for lithium-ion batteries 锂离子电池用聚（偏氟乙烯-共六氟丙烯）/离子液体/聚多巴胺改性金属-有机框架复合聚合物电解质

IF 4.1 3区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Electroanalytical Chemistry

Pub Date : 2026-01-07 DOI: 10.1016/j.jelechem.2026.119806

Juan Wu, Xiaoran Ren, Kai Huang, Bencai Lin

This study develops composite polymer electrolytes (CPEs) by incorporating polydopamine-modified ZIF-8 (PDA@ZIF-8) and an ionic liquid (IL), 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide ([BMIM][TFSI]), into poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) matrices to reduce interfacial resistance and enhance battery stability. Leveraging ZIF-8's nanoporous structure, PDA's adhesion properties, and synergistic PDA-PVDF-HFP interactions, the PDA@ZIF-8 filler achieves uniform dispersion while preserving its integrity and improving polymer-filler compatibility. Compared to CPEs without PDA@ZIF-8 (ionic conductivity: 1.66 × 10⁻⁴ S cm⁻¹ at 25 °C), those containing an optimal amount of PDA@ZIF-8 exhibit significantly higher conductivity. Specifically, the PH/[email protected] membrane achieves a conductivity of 2.09 × 10⁻⁴ S cm⁻¹ at 25 °C. Furthermore, PDA@ZIF-8 incorporation substantially enhances the CPEs' mechanical properties. Owing to the excellent Li-salt dissociation capabilities of both the IL and PDA@ZIF-8, the PH/[email protected] membrane demonstrates a high Li⁺ transference number of 0.54. Li|PH/[email protected]|Li symmetric cells maintain a low steady-state overpotential for over 600 h. Moreover, LiFePO₄|PH/[email protected]|Li batteries deliver a discharge capacity of 132 mAh g⁻¹ and retain over 98 % capacity after 100 cycles under 0.1C at 25 °C, highlighting their strong potential for lithium-ion battery applications. This work provides an effective strategy for preparing high-performance CPEs that enhance lithium-ion battery performance.

本研究通过将聚多巴胺修饰的ZIF-8 （PDA@ZIF-8）和离子液体（IL） 1-丁基-3-甲基咪唑双（三氟甲烷磺酰）亚胺（[BMIM][TFSI]）加入聚偏氟乙烯-共六氟丙烯（PVDF-HFP）基质中，开发复合聚合物电解质（cpe），以降低界面阻力，提高电池稳定性。利用ZIF-8的纳米孔结构、PDA的粘附性能和PDA- pvdf - hfp的协同相互作用，PDA@ZIF-8填料在保持其完整性和提高聚合物填料相容性的同时实现了均匀分散。与不含PDA@ZIF-8（25°C时离子电导率为1.66 × 10−4 S cm−1）的cpe相比，含有最佳量PDA@ZIF-8的cpe电导率显著提高。具体来说，PH/[email protected]膜在25°C时的电导率为2.09 × 10−4 S cm−1。此外，PDA@ZIF-8的掺入大大提高了cpe的力学性能。由于IL和PDA@ZIF-8具有优异的锂盐解离能力，PH/[email protected]膜具有0.54的高锂离子转移数。此外，LiFePO4|PH/[email protected]|锂电池在25°C下0.1C循环100次后，放电容量可达132 mAh g - 1，并保持98%以上的容量，突出了其在锂离子电池应用中的强大潜力。这项工作为制备高性能cpe提供了一种有效的策略，可以提高锂离子电池的性能。

{"title":"Poly(vinylidene fluoride-co-hexafluoropropylene)/ionic liquid/polydopamine-modified metal-organic framework composite polymer electrolytes for lithium-ion batteries","authors":"Juan Wu, Xiaoran Ren, Kai Huang, Bencai Lin","doi":"10.1016/j.jelechem.2026.119806","DOIUrl":"10.1016/j.jelechem.2026.119806","url":null,"abstract":"<div><div>This study develops composite polymer electrolytes (CPEs) by incorporating polydopamine-modified ZIF-8 (PDA@ZIF-8) and an ionic liquid (IL), 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide ([BMIM][TFSI]), into poly(vinylidene fluoride-<em>co</em>-hexafluoropropylene) (PVDF-HFP) matrices to reduce interfacial resistance and enhance battery stability. Leveraging ZIF-8's nanoporous structure, PDA's adhesion properties, and synergistic PDA-PVDF-HFP interactions, the PDA@ZIF-8 filler achieves uniform dispersion while preserving its integrity and improving polymer-filler compatibility. Compared to CPEs without PDA@ZIF-8 (ionic conductivity: 1.66 × 10<sup>−4</sup> S cm<sup>−1</sup> at 25 °C), those containing an optimal amount of PDA@ZIF-8 exhibit significantly higher conductivity. Specifically, the PH/[email protected] membrane achieves a conductivity of 2.09 × 10<sup>−4</sup> S cm<sup>−1</sup> at 25 °C. Furthermore, PDA@ZIF-8 incorporation substantially enhances the CPEs' mechanical properties. Owing to the excellent Li-salt dissociation capabilities of both the IL and PDA@ZIF-8, the PH/[email protected] membrane demonstrates a high Li<sup>+</sup> transference number of 0.54. Li|PH/[email protected]|Li symmetric cells maintain a low steady-state overpotential for over 600 h. Moreover, LiFePO<sub>4</sub>|PH/[email protected]|Li batteries deliver a discharge capacity of 132 mAh g<sup>−1</sup> and retain over 98 % capacity after 100 cycles under 0.1C at 25 °C, highlighting their strong potential for lithium-ion battery applications. This work provides an effective strategy for preparing high-performance CPEs that enhance lithium-ion battery performance.</div></div>","PeriodicalId":355,"journal":{"name":"Journal of Electroanalytical Chemistry","volume":"1004 ","pages":"Article 119806"},"PeriodicalIF":4.1,"publicationDate":"2026-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145975384","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}

引用次数: 0

Label-free molecularly imprinted polymer–based impedimetric biosensor for rapid detection of Morganella morganii in real samples 基于分子印迹聚合物的无标记阻抗生物传感器，用于快速检测真实样品中的莫氏摩根菌

IF 4.1 3区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Electroanalytical Chemistry

Pub Date : 2026-01-06 DOI: 10.1016/j.jelechem.2026.119793

Hüseyin Oğuzhan Kaya , Yamaç Tekintaş , Fatma Kurul , Turku Acıkgoz , Seda Nur Topkaya

Morganella morganii is an emerging opportunistic pathogen associated with urinary tract infections, yet no selective biosensing platform has been reported for its rapid detection. In this study, we present the first molecularly imprinted polymer (MIP)-based electrochemical biosensor specifically tailored for M. morganii, enabling label-free, highly selective, and low-cost detection. The sensor was fabricated by electropolymerizing phenol in the presence of whole-cell bacteria on pencil graphite electrodes, followed by template removal to generate specific recognition cavities. Successful imprinting and selective rebinding were verified by electrochemical impedance spectroscopy and cyclic voltammetry.

The biosensor demonstrated a low LOD of 3.0 CFU/mL in real urine, excellent linearity (R² > 0.99), and high reproducibility (RSD < 10 %), confirming robust analytical performance. Notably, the sensor maintained high sensitivity in complex urine matrices, indicating strong matrix tolerance. Selectivity studies showed imprinting factors of 4.5–10.1 against E. coli, K. pneumoniae, S. aureus, and E. faecalis, confirming excellent discrimination capability. The biosensor retained >95 % of its initial response for 3 days and ∼ 56 % after 14 days, demonstrating satisfactory stability.

Compared to conventional microbiological and molecular assays, this MIP-based platform offers a rapid and label-free strategy for early detection of M. morganii in urinary tract infection diagnostics.

摩根氏摩根氏菌是一种新兴的与尿路感染相关的机会性病原体，但目前还没有选择性的生物传感平台来快速检测它。在这项研究中，我们提出了第一个专门为摩根氏分枝杆菌定制的基于分子印迹聚合物（MIP）的电化学生物传感器，实现无标签、高选择性和低成本的检测。该传感器是通过在铅笔石墨电极上的全细胞细菌存在下电聚合苯酚，然后去除模板以产生特定的识别腔来制造的。通过电化学阻抗谱和循环伏安法验证了印迹和选择性再结合的成功。该生物传感器在真实尿液中的LOD低至3.0 CFU/mL，线性良好（R2 > 0.99），重现性高（RSD < 10%），证实了可靠的分析性能。值得注意的是，该传感器在复杂的尿液基质中保持了高灵敏度，表明具有很强的基质耐受性。选择性研究表明，对大肠杆菌、肺炎克雷伯菌、金黄色葡萄球菌和粪肠杆菌的印迹因子为4.5 ~ 10.1，具有较好的鉴别能力。生物传感器在3天内保持了95%的初始反应，在14天后保持了56%，表现出令人满意的稳定性。与传统的微生物和分子检测相比，这种基于mip的平台为尿路感染诊断中的莫氏分枝杆菌的早期检测提供了快速和无标记的策略。

{"title":"Label-free molecularly imprinted polymer–based impedimetric biosensor for rapid detection of Morganella morganii in real samples","authors":"Hüseyin Oğuzhan Kaya , Yamaç Tekintaş , Fatma Kurul , Turku Acıkgoz , Seda Nur Topkaya","doi":"10.1016/j.jelechem.2026.119793","DOIUrl":"10.1016/j.jelechem.2026.119793","url":null,"abstract":"<div><div><strong><em>Morganella morganii</em></strong> is an emerging opportunistic pathogen associated with urinary tract infections, yet no selective biosensing platform has been reported for its rapid detection. In this study, we present the first molecularly imprinted polymer (MIP)-based electrochemical biosensor specifically tailored for <strong><em>M. morganii,</em></strong> enabling label-free, highly selective, and low-cost detection. The sensor was fabricated by electropolymerizing phenol in the presence of whole-cell bacteria on pencil graphite electrodes, followed by template removal to generate specific recognition cavities. Successful imprinting and selective rebinding were verified by electrochemical impedance spectroscopy and cyclic voltammetry<strong>.</strong></div><div>The biosensor demonstrated a low LOD of 3.0 CFU/mL in real urine<strong>,</strong> excellent linearity (R<sup>2</sup> > 0.99), and high reproducibility (RSD < 10 %), confirming robust analytical performance. Notably, the sensor maintained high sensitivity in complex urine matrices, indicating strong matrix tolerance<strong>.</strong> Selectivity studies showed imprinting factors of 4.5–10.1 against <em>E. coli, K. pneumoniae, S. aureus,</em> and <em>E. faecalis</em>, confirming excellent discrimination capability. The biosensor retained >95 % of its initial response for 3 days and ∼ 56 % after 14 days<strong>,</strong> demonstrating satisfactory stability.</div><div>Compared to conventional microbiological and molecular assays, this MIP-based platform offers a rapid and label-free strategy for early detection of <em>M. morganii</em> in urinary tract infection diagnostics.</div></div>","PeriodicalId":355,"journal":{"name":"Journal of Electroanalytical Chemistry","volume":"1003 ","pages":"Article 119793"},"PeriodicalIF":4.1,"publicationDate":"2026-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922199","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}

引用次数: 0

Chemometrically optimized electrochemical decoupling of the uric acid–xanthine purine pair via single-step co-synthesized composite 单步共合成复合材料对尿酸-黄嘌呤-嘌呤的电化学解耦进行了化学计量学优化

IF 4.1 3区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Electroanalytical Chemistry

Pub Date : 2026-01-06 DOI: 10.1016/j.jelechem.2026.119801

Nguyen Minh Quang , Do Mai Nguyen , Vo Chau Ngoc Anh , Tran Thanh Tam Toan , Anh-Quang Dao

An electrochemical sensor was developed with a modified glassy carbon electrode (GCE) by a poly(bromocresol purple) (PBSP) and electrochemically reduced graphene oxide (RGO) composite. The modified electrode was prepared via a single-step electrochemical co-deposition technique, which represents a methodological refinement aimed at enhancing the simplicity and structural integration of the components. The resulting PBSP-RGO/GCE-modified electrode was evaluated for the dual electrochemical detection of uric acid (URC) and xanthine (XAT). An analytical improvement was achieved as the oxidation electrochemical signals of these two urinary metabolites were clearly resolved, reducing the problem of signal overlap commonly encountered in conventional sensing platforms. The observed enhancement in electrochemical activity is due to the combination of the high electrical conductivity of the RGO support and the functional selectivity imparted by the PBSP polymer layer. The sensor demonstrated good sensitivity and low limits of detection (LODs) for both analytes, with URC being reliably determined in a wide linear concentration range. Furthermore, the actual sample investigation of the technique was indicated through the analysis of real biological matrices (urine), where recovery rates ranging from 96 % to 105 % were consistently documented. The findings were statistically confirmed to be in comparison with the standard high-performance liquid chromatography (HPLC) technique, establishing the accuracy and reliability of the proposed sensor.

采用聚溴甲酚紫（PBSP）和电化学还原氧化石墨烯（RGO）复合材料修饰玻碳电极（GCE），研制了一种电化学传感器。修饰电极是通过一步电化学共沉积技术制备的，这代表了一种方法的改进，旨在提高组件的简单性和结构集成度。采用PBSP-RGO/ gce修饰电极对尿酸（URC）和黄嘌呤（XAT）进行双电化学检测。这两种尿液代谢物的氧化电化学信号得到了清晰的解析，从而实现了分析上的改进，减少了传统传感平台中常见的信号重叠问题。观察到的电化学活性的增强是由于RGO载体的高导电性和PBSP聚合物层赋予的功能选择性的结合。该传感器对两种分析物具有良好的灵敏度和较低的检测限（lod）， URC在较宽的线性浓度范围内可靠地测定。此外，该技术的实际样本调查是通过分析真正的生物基质（尿液）来表明的，其中回收率从96%到105%不等。统计结果与标准高效液相色谱（HPLC）技术进行了比较，建立了所提出传感器的准确性和可靠性。

{"title":"Chemometrically optimized electrochemical decoupling of the uric acid–xanthine purine pair via single-step co-synthesized composite","authors":"Nguyen Minh Quang , Do Mai Nguyen , Vo Chau Ngoc Anh , Tran Thanh Tam Toan , Anh-Quang Dao","doi":"10.1016/j.jelechem.2026.119801","DOIUrl":"10.1016/j.jelechem.2026.119801","url":null,"abstract":"<div><div>An electrochemical sensor was developed with a modified glassy carbon electrode (GCE) by a poly(bromocresol purple) (PBSP) and electrochemically reduced graphene oxide (RGO) composite. The modified electrode was prepared via a single-step electrochemical co-deposition technique, which represents a methodological refinement aimed at enhancing the simplicity and structural integration of the components. The resulting PBSP-RGO/GCE-modified electrode was evaluated for the dual electrochemical detection of uric acid (URC) and xanthine (XAT). An analytical improvement was achieved as the oxidation electrochemical signals of these two urinary metabolites were clearly resolved, reducing the problem of signal overlap commonly encountered in conventional sensing platforms. The observed enhancement in electrochemical activity is due to the combination of the high electrical conductivity of the RGO support and the functional selectivity imparted by the PBSP polymer layer. The sensor demonstrated good sensitivity and low limits of detection (LODs) for both analytes, with URC being reliably determined in a wide linear concentration range. Furthermore, the actual sample investigation of the technique was indicated through the analysis of real biological matrices (urine), where recovery rates ranging from 96 % to 105 % were consistently documented. The findings were statistically confirmed to be in comparison with the standard high-performance liquid chromatography (HPLC) technique, establishing the accuracy and reliability of the proposed sensor.</div></div>","PeriodicalId":355,"journal":{"name":"Journal of Electroanalytical Chemistry","volume":"1003 ","pages":"Article 119801"},"PeriodicalIF":4.1,"publicationDate":"2026-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922363","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}

引用次数: 0

Synthesis of defect-rich metal-free carbon from coconut shell for catalyzing oxygen evolution reaction 椰壳制备富缺陷无金属碳催化析氧反应

IF 4.1 3区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Electroanalytical Chemistry

Pub Date : 2026-01-06 DOI: 10.1016/j.jelechem.2026.119804

Yanmin Jian, Yucheng Chen, Yongjun Chen, Min Wang, Lijie Luo

Biomass-derived carbon materials represent stable, cost-effective and environmentally friendly electrocatalyst for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). In this work, a self-supporting coconut shell carbon (SCC) catalyst featuring a three-dimensional (3D) hierarchical porous structure was reported by in situ ammonia etching. The SCC-1100-NH₃ exhibited outstanding OER performance, achieving a current density of 10 mA cm⁻² at an overpotential of 294 mV and a potential of 1.52 V vs RHE. The unique structural configuration also offered the catalyst excellent durability with stable operation for at least 98 h. It was believed that the hierarchical porous structure enhances electrical conductivity and the formation of vacancy-coupled pentagon defects which act as active sites. This work provides a new strategy for designing defect-rich metal-free biomass-derived carbon electrodes.

生物质源碳材料是一种稳定、经济、环保的析氧反应（OER）和析氢反应（HER）电催化剂。在这项工作中，报道了一种具有三维（3D）分层多孔结构的自支撑椰子壳碳（SCC）催化剂。SCC-1100-NH3表现出优异的OER性能，在过电位294 mV和过电位1.52 V vs RHE下，电流密度达到10 mA cm−2。独特的结构结构也为催化剂提供了优异的耐久性，稳定运行至少98小时。认为分层多孔结构提高了电导率，并形成了作为活性位点的空位耦合五边形缺陷。这项工作为设计富含缺陷的无金属生物质衍生碳电极提供了一种新的策略。

引用次数: 0

Research progress on doping modification of lithium-rich manganese-based layered oxide cathode materials 富锂锰基层状氧化物正极材料掺杂改性研究进展

IF 4.1 3区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Electroanalytical Chemistry

Pub Date : 2026-01-06 DOI: 10.1016/j.jelechem.2026.119795

Yiqi Zheng , Yingjie Ji , Zhen Zhang , Yi Yao , Yi Zhang , Zhoulu Wang , Xiang Liu

With the development of society, lithium-ion batteries are facing higher demands for energy density from electric vehicles, consumer (3C) electronic products, energy storage devices, and other applications. Lithium-rich manganese-based cathode materials have advantages such as high specific capacity (≈ 250 mAh g⁻¹), high operating voltage (≈ 3.6 V), and low cost, making them promising candidates for the next generation of commercial high-specific-energy batteries. However, this material has many problems, such as lattice oxygen evolution, transition metal ion migration, low initial Coulombic efficiency, voltage and capacity fade, and interfacial side reactions, which limit its commercial application. This paper reviews the latest research progress on the doping of lithium-rich manganese-based cathode materials, focusing on aspects such as synthesis methods, reaction mechanisms, and electrochemical properties. Research shows that ion doping can significantly improve the electrochemical performance of lithium-rich manganese-based cathode materials. Finally, the doping directions of lithium-rich manganese-based cathode materials are prospected.

随着社会的发展，电动汽车、消费类（3C）电子产品、储能设备等应用对锂离子电池的能量密度提出了更高的要求。富锂锰基正极材料具有高比容量（≈250 mAh g−1）、高工作电压（≈3.6 V）和低成本等优点，是下一代商用高比能电池的理想候选者。然而，该材料存在晶格析氧、过渡金属离子迁移、初始库仑效率低、电压和容量衰减、界面副反应等问题，限制了其商业应用。本文综述了富锂锰基正极材料掺杂的最新研究进展，重点从合成方法、反应机理、电化学性能等方面进行了综述。研究表明，离子掺杂可以显著提高富锂锰基正极材料的电化学性能。最后对富锂锰基正极材料的掺杂方向进行了展望。

{"title":"Research progress on doping modification of lithium-rich manganese-based layered oxide cathode materials","authors":"Yiqi Zheng , Yingjie Ji , Zhen Zhang , Yi Yao , Yi Zhang , Zhoulu Wang , Xiang Liu","doi":"10.1016/j.jelechem.2026.119795","DOIUrl":"10.1016/j.jelechem.2026.119795","url":null,"abstract":"<div><div>With the development of society, lithium-ion batteries are facing higher demands for energy density from electric vehicles, consumer (3C) electronic products, energy storage devices, and other applications. Lithium-rich manganese-based cathode materials have advantages such as high specific capacity (≈ 250 mAh g<sup>−1</sup>), high operating voltage (≈ 3.6 V), and low cost, making them promising candidates for the next generation of commercial high-specific-energy batteries. However, this material has many problems, such as lattice oxygen evolution, transition metal ion migration, low initial Coulombic efficiency, voltage and capacity fade, and interfacial side reactions, which limit its commercial application. This paper reviews the latest research progress on the doping of lithium-rich manganese-based cathode materials, focusing on aspects such as synthesis methods, reaction mechanisms, and electrochemical properties. Research shows that ion doping can significantly improve the electrochemical performance of lithium-rich manganese-based cathode materials. Finally, the doping directions of lithium-rich manganese-based cathode materials are prospected.</div></div>","PeriodicalId":355,"journal":{"name":"Journal of Electroanalytical Chemistry","volume":"1004 ","pages":"Article 119795"},"PeriodicalIF":4.1,"publicationDate":"2026-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145975385","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}

引用次数: 0

Ce3+ doping modulates low-spin Fe active sites and sodium-ion diffusion kinetics to enhance Prussian blue cathode performance Ce3+掺杂调节低自旋铁活性位点和钠离子扩散动力学，提高普鲁士蓝阴极性能

IF 4.1 3区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Electroanalytical Chemistry

Pub Date : 2026-01-05 DOI: 10.1016/j.jelechem.2026.119792

Binghong Li , Fuliang Zhu , Yanshuang Meng

Iron-based Prussian blue (FeHCF) have garnered significant attention as cathode materials for sodium-ion batteries due to their high theoretical capacity and open 3D framework. However, their practical performance is severely limited by the shielding of low-spin Fe (Fe^LS) active sites due to Fe(CN)₆ vacancies and crystalline water, as well as sluggish kinetics resulting from their semiconducting nature. This study proposes a cerium (Ce³⁺) doping strategy that significantly enhances the sodium storage performance of FeHCF through a dual mechanism of defect repair and electronic modulation. Experimental results demonstrate that Ce³⁺ doping not only fills [Fe(CN) ₆] vacancies and repels crystalline water, thereby reactivating the shielded Fe^LS active sites (increasing capacity contribution from 22.98 mAh g⁻¹ to 47.8 mAh g⁻¹), but also elevates the Fermi-level density of states via 4f-3d orbital hybridization, endowing the material with quasi-metallic characteristics. The optimized FeHCF-5 material delivers a reversible capacity of 120.6 mAh g⁻¹, maintains 88.5 mAh g⁻¹ at a high current density of 500 mA g⁻¹, and achieves a capacity retention of 80.4 % after 200 cycles. Combined with theoretical calculations, this work reveals that Ce³⁺ doping synergistically optimizes electron conduction and ion diffusion kinetics by reducing the sodium-ion diffusion energy barrier (from 0.356 eV to 0.19 eV) and widening ion transport channels (the Na⁺ diffusion coefficient increases by 14.14-fold to 5.373 × 10⁻⁹ cm² s⁻¹). This study provides new insights for designing high-performance sodium storage materials.

铁基普鲁士蓝（FeHCF）作为钠离子电池的正极材料，由于其高理论容量和开放的三维结构而备受关注。然而，由于Fe(CN)6空位和结晶水对低自旋Fe（FeLS）活性位点的屏蔽，以及半导体性质导致的缓慢动力学，它们的实际性能受到严重限制。本研究提出了一种铈（Ce3+）掺杂策略，通过缺陷修复和电子调制双重机制显著提高FeHCF的储钠性能。实验结果表明，Ce3+的掺杂不仅填补了[Fe(CN) 6]空位并排斥晶水，从而使屏蔽的FeLS活性位点重新激活（容量贡献从22.98 mAh g−1增加到47.8 mAh g−1），而且通过4f-3d轨道杂化提高了费米能级密度，赋予材料准金属特性。优化后的FeHCF-5材料的可逆容量为120.6 mAh g−1，在500 mA g−1的高电流密度下保持88.5 mAh g−1，在200次循环后容量保持率为80.4%。结合理论计算，Ce3+掺杂通过降低钠离子扩散能垒（从0.356 eV降低到0.19 eV）和扩大离子传输通道（Na+扩散系数增加14.14倍，达到5.373 × 10−9 cm2 s−1），协同优化了电子传导和离子扩散动力学。该研究为设计高性能钠存储材料提供了新的思路。

{"title":"Ce3+ doping modulates low-spin Fe active sites and sodium-ion diffusion kinetics to enhance Prussian blue cathode performance","authors":"Binghong Li , Fuliang Zhu , Yanshuang Meng","doi":"10.1016/j.jelechem.2026.119792","DOIUrl":"10.1016/j.jelechem.2026.119792","url":null,"abstract":"<div><div>Iron-based Prussian blue (FeHCF) have garnered significant attention as cathode materials for sodium-ion batteries due to their high theoretical capacity and open 3D framework. However, their practical performance is severely limited by the shielding of low-spin Fe (Fe<sup>LS</sup>) active sites due to Fe(CN)<sub>6</sub> vacancies and crystalline water, as well as sluggish kinetics resulting from their semiconducting nature. This study proposes a cerium (Ce<sup>3+</sup>) doping strategy that significantly enhances the sodium storage performance of FeHCF through a dual mechanism of defect repair and electronic modulation. Experimental results demonstrate that Ce<sup>3+</sup> doping not only fills [Fe(CN) <sub>6</sub>] vacancies and repels crystalline water, thereby reactivating the shielded Fe<sup>LS</sup> active sites (increasing capacity contribution from 22.98 mAh g<sup>−1</sup> to 47.8 mAh g<sup>−1</sup>), but also elevates the Fermi-level density of states via 4f-3d orbital hybridization, endowing the material with quasi-metallic characteristics. The optimized FeHCF-5 material delivers a reversible capacity of 120.6 mAh g<sup>−1</sup>, maintains 88.5 mAh g<sup>−1</sup> at a high current density of 500 mA g<sup>−1</sup>, and achieves a capacity retention of 80.4 % after 200 cycles. Combined with theoretical calculations, this work reveals that Ce<sup>3+</sup> doping synergistically optimizes electron conduction and ion diffusion kinetics by reducing the sodium-ion diffusion energy barrier (from 0.356 eV to 0.19 eV) and widening ion transport channels (the Na<sup>+</sup> diffusion coefficient increases by 14.14-fold to 5.373 × 10<sup>−9</sup> cm<sup>2</sup> s<sup>−1</sup>). This study provides new insights for designing high-performance sodium storage materials.</div></div>","PeriodicalId":355,"journal":{"name":"Journal of Electroanalytical Chemistry","volume":"1003 ","pages":"Article 119792"},"PeriodicalIF":4.1,"publicationDate":"2026-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922278","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}

引用次数: 0

In-situ construction of Fe-Co-Ni alloy based ternary sulfide electrode towards alkaline overall water splitting 基于Fe-Co-Ni合金的碱性整体水分解三元硫化电极的原位构建

IF 4.1 3区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Electroanalytical Chemistry

Pub Date : 2026-01-05 DOI: 10.1016/j.jelechem.2026.119802

YuWei Chen , QingWei Wang , LiXia Yang , Jun-e Qu

Compounds of iron, cobalt and nickel elements have demonstrated great potentials as substitutes to the noble metal catalysts for both hydrogen evolution(HER) and oxygen evolution(OER). The simultaneous joint application of the three elements can further improve catalytic activity. However there have been rarely reports on self-supporting Fe-Co-Ni ternary sulfide electrode towards water electrolysis. Herein, in this work, a novel in-situ-growing type bifunctional Fe-Co-Ni alloy based sulfide catalytic electrode for alkaline water splitting is synthesized by one-step hydrothermal sulfuration treatment in an sodium sulfide aqueous medium. The electrochemical characterization results show that among electrodes prepared from alloy substrate with altered Fe:Co:Ni atomic ratios, the as prepared Fe20Co40Ni40-S electrode (with atomic ration of Fe:Co:Ni = 2:4:4) shows the best catalytic performance, achieving low overpotentials of 196 and 261 mV corresponding to the current density of 10 mA·cm⁻² towards OER and HER process in 1 M KOH electrolyte, respectively. It only needs cell voltage of 1.64 V for Fe20Co40Ni40-S to realize fully hydrolyzing water at 10 mA·cm⁻². These features including high nickel content and high S²⁻/SO₄²⁻ ratio in surface elements, great specific surface area, catalyst species in multiple valence states, Ni₃S₄/(Fe,Co,Ni)₉S₈ heterojunction structures, superhydrophilic property, and strong bonding force between matrix and interface are the reasons for the excellent bifunctional catalytic activity of the Fe20Co40Ni40-S electrode.

铁、钴和镍元素的化合物作为贵金属析氢（HER）和析氧（OER）催化剂的替代品显示出巨大的潜力。三种元素同时联合应用可进一步提高催化活性。然而，自支撑的Fe-Co-Ni三元硫化电极用于水电解的报道很少。本文在硫化钠水介质中，采用一步水热硫化法合成了一种新型的原位生长型双功能Fe-Co-Ni合金基硫化物催化裂化电极。电化学表征结果表明，在改变Fe:Co:Ni原子比的合金衬底上制备的电极中，Fe20Co40Ni40-S电极（Fe:Co:Ni = 2:4:4）表现出最好的催化性能，在1 M KOH电解液中，当电流密度为10 mA·cm−2时，对OER和HER过程的过电位分别为196和261 mV。Fe20Co40Ni40-S仅需1.64 V的电池电压即可在10 mA·cm−2下实现水的完全水解。表面元素中镍含量高、S2−/SO42−比高、比表面积大、催化剂种类多价态、Ni3S4/(Fe,Co,Ni)9S8异质结结构、超亲水性以及基体与界面之间的强结合力是Fe20Co40Ni40-S电极具有优异双功能催化活性的原因。

{"title":"In-situ construction of Fe-Co-Ni alloy based ternary sulfide electrode towards alkaline overall water splitting","authors":"YuWei Chen , QingWei Wang , LiXia Yang , Jun-e Qu","doi":"10.1016/j.jelechem.2026.119802","DOIUrl":"10.1016/j.jelechem.2026.119802","url":null,"abstract":"<div><div>Compounds of iron, cobalt and nickel elements have demonstrated great potentials as substitutes to the noble metal catalysts for both hydrogen evolution(HER) and oxygen evolution(OER). The simultaneous joint application of the three elements can further improve catalytic activity. However there have been rarely reports on self-supporting Fe-Co-Ni ternary sulfide electrode towards water electrolysis. Herein, in this work, a novel in-situ-growing type bifunctional Fe-Co-Ni alloy based sulfide catalytic electrode for alkaline water splitting is synthesized by one-step hydrothermal sulfuration treatment in an sodium sulfide aqueous medium. The electrochemical characterization results show that among electrodes prepared from alloy substrate with altered Fe:Co:Ni atomic ratios, the as prepared Fe20Co40Ni40-S electrode (with atomic ration of Fe:Co:Ni = 2:4:4) shows the best catalytic performance, achieving low overpotentials of 196 and 261 mV corresponding to the current density of 10 mA·cm<sup>−2</sup> towards OER and HER process in 1 M KOH electrolyte, respectively. It only needs cell voltage of 1.64 V for Fe20Co40Ni40-S to realize fully hydrolyzing water at 10 mA·cm<sup>−2</sup>. These features including high nickel content and high S<sup>2−</sup>/SO<sub>4</sub><sup>2−</sup> ratio in surface elements, great specific surface area, catalyst species in multiple valence states, Ni<sub>3</sub>S<sub>4</sub>/(Fe,Co,Ni)<sub>9</sub>S<sub>8</sub> heterojunction structures, superhydrophilic property, and strong bonding force between matrix and interface are the reasons for the excellent bifunctional catalytic activity of the Fe20Co40Ni40-S electrode.</div></div>","PeriodicalId":355,"journal":{"name":"Journal of Electroanalytical Chemistry","volume":"1003 ","pages":"Article 119802"},"PeriodicalIF":4.1,"publicationDate":"2026-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922362","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}

引用次数: 0

MXene-integrated rare-earth high-entropy oxide nanocomposites for advanced supercapacitor applications 应用于先进超级电容器的mxene集成稀土高熵氧化物纳米复合材料

IF 4.1 3区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Electroanalytical Chemistry

Pub Date : 2026-01-05 DOI: 10.1016/j.jelechem.2026.119803

Piyush V. Patil , P.E. Lokhande , Vilas Kumkale , Dadaso D. Mohite , M.A. Kadam , Syed Khasim , Taymour A. Hamdalla , Deepak Kumar , Udayabhaskar Rednam

In this study, rare-earth high-entropy oxides (RE-HEO, (Ce₀.₂La₀.₂Pr₀.₂Y₀.₂Sm₀.₂)O_₂-δ and Ti₃C₂Tₓ MXene nanocomposite was synthesized through a hydrothermal process followed by annealing to fabricate advanced electrode materials for supercapacitor applications. While RE-HEOs possess significant promise for energy storage, their performance is often limited by low electrical conductivity. This limitation was effectively overcome by integrating highly conductive MXene sheets. Structural and morphological analyses verified the successful formation of the RE-HEO framework and its stable composite with MXene. Electrochemical evaluation revealed that the RE-HEO–MXene electrode delivered a specific capacity of 405C g⁻¹ at 1 A g⁻¹, along with excellent rate capability and long-term cycling stability. Moreover, a solid-state RE-HEO–MXene//AC asymmetric supercapacitor achieved an energy density of 13.97 Wh kg⁻¹ at a power density of 13,750 W kg⁻¹, while maintaining 93 % of its capacitance after 10,000 cycles. These findings emphasize the synergistic contribution of MXene in improving conductivity, surface area, and electrochemical performance of RE-HEO, underscoring its strong potential for next-generation energy storage devices.

在本研究中，稀土高熵氧化物（RE-HEO）、(Ce 0 . 2 La 0 . 2 Pr 0 . 2 Y 0 . 2 Sm 0。采用水热法和退火法制备了2)O₂-δ和Ti₃C₂TₓMXene纳米复合材料，制备了用于超级电容器的高级电极材料。虽然RE-HEOs在能量存储方面具有重要的前景，但它们的性能通常受到低导电性的限制。通过集成高导电性的MXene片有效地克服了这一限制。结构和形态分析证实了RE-HEO框架的成功形成及其与MXene的稳定复合材料。电化学评价表明，RE-HEO-MXene电极在1 a g−1下的比容量为405C g−1，具有良好的倍率能力和长期循环稳定性。此外，固态RE-HEO-MXene //AC非对称超级电容器在功率密度为13,750 W kg - 1时，能量密度达到13.97 Wh kg - 1，并且在10,000次循环后保持93%的电容。这些发现强调了MXene在提高RE-HEO的电导率、表面积和电化学性能方面的协同作用，强调了其在下一代储能设备中的巨大潜力。

{"title":"MXene-integrated rare-earth high-entropy oxide nanocomposites for advanced supercapacitor applications","authors":"Piyush V. Patil , P.E. Lokhande , Vilas Kumkale , Dadaso D. Mohite , M.A. Kadam , Syed Khasim , Taymour A. Hamdalla , Deepak Kumar , Udayabhaskar Rednam","doi":"10.1016/j.jelechem.2026.119803","DOIUrl":"10.1016/j.jelechem.2026.119803","url":null,"abstract":"<div><div>In this study, rare-earth high-entropy oxides (RE-HEO, (Ce₀.₂La₀.₂Pr₀.₂Y₀.₂Sm₀.₂)O<sub>₂-<em>δ</em></sub> and Ti₃C₂Tₓ MXene nanocomposite was synthesized through a hydrothermal process followed by annealing to fabricate advanced electrode materials for supercapacitor applications. While RE-HEOs possess significant promise for energy storage, their performance is often limited by low electrical conductivity. This limitation was effectively overcome by integrating highly conductive MXene sheets. Structural and morphological analyses verified the successful formation of the RE-HEO framework and its stable composite with MXene. Electrochemical evaluation revealed that the RE-HEO–MXene electrode delivered a specific capacity of 405C g<sup>−1</sup> at 1 A g<sup>−1</sup>, along with excellent rate capability and long-term cycling stability. Moreover, a solid-state RE-HEO–MXene//AC asymmetric supercapacitor achieved an energy density of 13.97 Wh kg<sup>−1</sup> at a power density of 13,750 W kg<sup>−1</sup>, while maintaining 93 % of its capacitance after 10,000 cycles. These findings emphasize the synergistic contribution of MXene in improving conductivity, surface area, and electrochemical performance of RE-HEO, underscoring its strong potential for next-generation energy storage devices.</div></div>","PeriodicalId":355,"journal":{"name":"Journal of Electroanalytical Chemistry","volume":"1004 ","pages":"Article 119803"},"PeriodicalIF":4.1,"publicationDate":"2026-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145950402","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}

引用次数: 0

Droplet corrosion kinetics analysis of welded joints with multi-metallographic structure zones 多金相组织带焊接接头液滴腐蚀动力学分析

IF 4.1 3区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Electroanalytical Chemistry

Pub Date : 2026-01-05 DOI: 10.1016/j.jelechem.2026.119800

Zhendong Li, Zhongqiu Fu, Bohai Ji

Atmospheric corrosion of welded joints in steel structures is a prominent issue. Existing research often simplifies welded joints into weld and base metal, ignoring the characteristics of multi-metallographic structures. Furthermore, most studies focus on liquid film environments, with little research exploring the corrosion kinetics under droplet conditions. To reveal the electrochemical corrosion behavior of welded joints with multi-metallographic structure zones under droplet conditions, a numerical model of a three-electrode system was established, coupling mass transfer and corrosion products. By simulating the evolution of mass transfer and corrosion product accumulation, the electrochemical characteristics during the droplet corrosion process were analyzed, and the key factors driving droplet corrosion were clarified. The results indicate that droplet corrosion of welded joints is jointly driven by differences in electrochemical activity among multi-metallographic structure zones and by droplet geometric effects. The corrosion rate and current density are governed by activity, whereas the surface concentration and potential distribution are mainly regulated by geometric effects. Corrosion products accumulate rapidly in high-activity zones, inhibiting the increasing trend of the corrosion rate. In contrast, the corrosion rate in low-activity zones first increases and then decreases under the same droplet.

钢结构焊接接头的大气腐蚀是一个突出的问题。现有的研究往往将焊接接头简化为焊缝和母材，忽略了多金相组织的特点。此外，大多数研究都集中在液膜环境下，很少有研究探讨液滴条件下的腐蚀动力学。为了揭示多金相组织区焊接接头在液滴条件下的电化学腐蚀行为，建立了耦合传质和腐蚀产物的三电极体系的数值模型。通过模拟传质过程和腐蚀产物积累过程，分析了液滴腐蚀过程的电化学特性，明确了驱动液滴腐蚀的关键因素。结果表明，多金相组织区电化学活性差异和液滴几何效应共同驱动焊接接头的液滴腐蚀。腐蚀速率和电流密度主要受活度的影响，而表面浓度和电位分布主要受几何效应的影响。腐蚀产物在高活性区迅速积累，抑制了腐蚀速率的增加趋势。相比之下，在相同液滴作用下，低活度区域的腐蚀速率先增大后减小。

{"title":"Droplet corrosion kinetics analysis of welded joints with multi-metallographic structure zones","authors":"Zhendong Li, Zhongqiu Fu, Bohai Ji","doi":"10.1016/j.jelechem.2026.119800","DOIUrl":"10.1016/j.jelechem.2026.119800","url":null,"abstract":"<div><div>Atmospheric corrosion of welded joints in steel structures is a prominent issue. Existing research often simplifies welded joints into weld and base metal, ignoring the characteristics of multi-metallographic structures. Furthermore, most studies focus on liquid film environments, with little research exploring the corrosion kinetics under droplet conditions. To reveal the electrochemical corrosion behavior of welded joints with multi-metallographic structure zones under droplet conditions, a numerical model of a three-electrode system was established, coupling mass transfer and corrosion products. By simulating the evolution of mass transfer and corrosion product accumulation, the electrochemical characteristics during the droplet corrosion process were analyzed, and the key factors driving droplet corrosion were clarified. The results indicate that droplet corrosion of welded joints is jointly driven by differences in electrochemical activity among multi-metallographic structure zones and by droplet geometric effects. The corrosion rate and current density are governed by activity, whereas the surface concentration and potential distribution are mainly regulated by geometric effects. Corrosion products accumulate rapidly in high-activity zones, inhibiting the increasing trend of the corrosion rate. In contrast, the corrosion rate in low-activity zones first increases and then decreases under the same droplet.</div></div>","PeriodicalId":355,"journal":{"name":"Journal of Electroanalytical Chemistry","volume":"1003 ","pages":"Article 119800"},"PeriodicalIF":4.1,"publicationDate":"2026-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922198","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}

引用次数: 0

Precious metal oxygen-evolving anodes for electrolytic reduction of metal oxides in molten LiCl-Li2O electrolyte 用于熔融LiCl-Li2O电解液中金属氧化物电解还原的贵金属析氧阳极

IF 4.1 3区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Electroanalytical Chemistry

Pub Date : 2026-01-05 DOI: 10.1016/j.jelechem.2026.119798

Md Ikram Khan , Peyman Asghari-Rad , Stephanie Castro Baldivieso , Aditya Moudgal , Prabhat Tripathy , Steven Herrmann , Dev Chidambaram , Hojong Kim

Understanding the electrochemical stability of oxygen-evolving anode materials in molten salt electrolytes is essential to enable decarbonized electrolytic reduction of metal oxides (e.g., used nuclear oxide fuels). This work investigated three precious metals (Ir, Ru, and Pt) as oxygen-evolving anodes in molten LiCl-Li₂O (99.0–1.0 wt%) at 650 °C. For consistent measurements, this work employed a three-electrode cell comprised of a two-phase Li–Bi (65–35 at%) reference electrode and a NiO counter electrode. Anodic polarization behavior of each anode was investigated via cyclic voltammetry (CV) and chronoamperometry. The onset potential for oxygen evolution was observed at E > 2.9 V (vs. Li/Li⁺) for the Ir and Ru anodes and anodic current density was as high as 1.0 A cm⁻² at 3.23 V. The dimensional stability of each anode was evaluated from long-term electrolysis experiments (10.0–32.1 h) at 3.23 V. Rapid consumption of the Pt anode was observed after the application of 26,453 C cm⁻² with a reduction in diameter of about 15.8 % due to the formation of a non-protective Li₂PtO₃ compound. The formation of this compound was also observed during CV measurements as additional anodic waves at potentials more negative than that of oxygen evolution. In contrast, both the Ir and Ru anodes exhibited excellent dimensional stability with a reduction in diameter or thickness of less than 1.5 % even after applying greater charge density of ∼41,100 C cm⁻², demonstrating superior stability during oxygen evolution in the LiCl-Li₂O electrolyte.

了解熔盐电解质中出氧阳极材料的电化学稳定性对于实现金属氧化物（例如，使用过的核氧化物燃料）的脱碳电解还原至关重要。本文研究了三种贵金属（Ir、Ru和Pt）在650℃熔融LiCl-Li2O （99.0-1.0 wt%）中作为析氧阳极。为了保持测量的一致性，本研究采用了由两相Li-Bi （65-35 at%）参比电极和NiO反电极组成的三电极电池。通过循环伏安法和计时安培法研究了各阳极的阳极极化行为。在E >； 2.9 V （vs. Li/Li+）下，Ir和Ru阳极的析氧起始电位达到了1.0 A cm−2，且在3.23 V下阳极电流密度高达1.0 A cm−2。通过在3.23 V电压下（10.0-32.1 h）的长期电解实验，评价了各阳极的尺寸稳定性。应用26,453 C cm−2后，观察到Pt阳极的快速消耗，由于形成非保护性的Li2PtO3化合物，其直径减小了约15.8%。这种化合物的形成在CV测量中也被观察到作为附加的阳极波，其电位比析氧电位更负。相比之下，Ir和Ru阳极都表现出优异的尺寸稳定性，即使在施加更大的电荷密度（~ 41,100 C cm - 2）后，直径或厚度的减少也小于1.5%，在LiCl-Li2O电解质中表现出优异的出氧稳定性。

{"title":"Precious metal oxygen-evolving anodes for electrolytic reduction of metal oxides in molten LiCl-Li2O electrolyte","authors":"Md Ikram Khan , Peyman Asghari-Rad , Stephanie Castro Baldivieso , Aditya Moudgal , Prabhat Tripathy , Steven Herrmann , Dev Chidambaram , Hojong Kim","doi":"10.1016/j.jelechem.2026.119798","DOIUrl":"10.1016/j.jelechem.2026.119798","url":null,"abstract":"<div><div>Understanding the electrochemical stability of oxygen-evolving anode materials in molten salt electrolytes is essential to enable decarbonized electrolytic reduction of metal oxides (e.g., used nuclear oxide fuels). This work investigated three precious metals (Ir, Ru, and Pt) as oxygen-evolving anodes in molten LiCl-Li<sub>2</sub>O (99.0–1.0 wt%) at 650 °C. For consistent measurements, this work employed a three-electrode cell comprised of a two-phase Li–Bi (65–35 at%) reference electrode and a NiO counter electrode. Anodic polarization behavior of each anode was investigated via cyclic voltammetry (CV) and chronoamperometry. The onset potential for oxygen evolution was observed at <em>E</em> > 2.9 V (vs. Li/Li<sup>+</sup>) for the Ir and Ru anodes and anodic current density was as high as 1.0 A cm<sup>−2</sup> at 3.23 V. The dimensional stability of each anode was evaluated from long-term electrolysis experiments (10.0–32.1 h) at 3.23 V. Rapid consumption of the Pt anode was observed after the application of 26,453 C cm<sup>−2</sup> with a reduction in diameter of about 15.8 % due to the formation of a non-protective Li<sub>2</sub>PtO<sub>3</sub> compound. The formation of this compound was also observed during CV measurements as additional anodic waves at potentials more negative than that of oxygen evolution. In contrast, both the Ir and Ru anodes exhibited excellent dimensional stability with a reduction in diameter or thickness of less than 1.5 % even after applying greater charge density of ∼41,100 C cm<sup>−2</sup>, demonstrating superior stability during oxygen evolution in the LiCl-Li<sub>2</sub>O electrolyte.</div></div>","PeriodicalId":355,"journal":{"name":"Journal of Electroanalytical Chemistry","volume":"1003 ","pages":"Article 119798"},"PeriodicalIF":4.1,"publicationDate":"2026-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922270","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}

引用次数: 0