Pub Date : 2026-04-20Epub Date: 2026-02-05DOI: 10.1016/j.electacta.2026.148384
Wenhui Li, Da Qiu, Junwei Huang, Haoyi Li, Hongna Xing, Xiuhong Zhu, Juan Feng, Yan Zong, Xinghua Li, Xinliang Zheng
The intrinsically low conductivity of CuCo2S4 severely limits its electrochemical performance as an electrode. Herein, we propose an atomic-level doping strategy via a ternary Cu-Co-Ni MOF precursor to precisely incorporate Ni into the CuCo2S4 lattice. First-principle calculations reveal that Ni doping introduces localized electronic states near the Fermi level, effectively narrowing the bandgap and inducing a semiconductor-to-metallic transition. This electronic structure modulation significantly enhances bulk electron mobility and strengthens the adsorption of electrolyte OH- ions. Coupled with the preserved porous carbon framework and multi-metal synergistic interface, the optimized Ni-CuCo2S4@C electrode achieves a high specific capacitance of 1046 F g-1 at 1 A g-1. The assembled asymmetric supercapacitor delivers an energy density of 32 Wh kg-1 at 750 W kg-1, alongside excellent cycling stability. This work elucidates the electronic origin of performance enhancement and provides a doping-guided design principle for high-conductivity metal sulfide electrodes.
CuCo2S4固有的低电导率严重限制了其作为电极的电化学性能。在此，我们提出了一种原子级掺杂策略，通过三元Cu-Co-Ni MOF前驱体将Ni精确地掺入CuCo2S4晶格中。第一性原理计算表明，镍掺杂在费米能级附近引入了局域电子态，有效地缩小了带隙，并诱导了半导体到金属的转变。这种电子结构调制显著提高了体电子迁移率，增强了电解质OH-离子的吸附。再加上保留的多孔碳骨架和多金属协同界面，优化后的Ni-CuCo2S4@C电极在1 a g-1时获得了1046 F -1的高比电容。组装的非对称超级电容器在750 W kg-1时提供32 Wh kg-1的能量密度，并具有出色的循环稳定性。这项工作阐明了性能增强的电子来源，并提供了高导电性金属硫化物电极的掺杂指导设计原则。
{"title":"Electronic structure modulation via atomic Ni doping for metallization-driven high-performance CuCo2S4 supercapacitors","authors":"Wenhui Li, Da Qiu, Junwei Huang, Haoyi Li, Hongna Xing, Xiuhong Zhu, Juan Feng, Yan Zong, Xinghua Li, Xinliang Zheng","doi":"10.1016/j.electacta.2026.148384","DOIUrl":"10.1016/j.electacta.2026.148384","url":null,"abstract":"<div><div>The intrinsically low conductivity of CuCo<sub>2</sub>S<sub>4</sub> severely limits its electrochemical performance as an electrode. Herein, we propose an atomic-level doping strategy via a ternary Cu-Co-Ni MOF precursor to precisely incorporate Ni into the CuCo<sub>2</sub>S<sub>4</sub> lattice. First-principle calculations reveal that Ni doping introduces localized electronic states near the Fermi level, effectively narrowing the bandgap and inducing a semiconductor-to-metallic transition. This electronic structure modulation significantly enhances bulk electron mobility and strengthens the adsorption of electrolyte OH<sup>-</sup> ions. Coupled with the preserved porous carbon framework and multi-metal synergistic interface, the optimized Ni-CuCo<sub>2</sub>S<sub>4</sub>@C electrode achieves a high specific capacitance of 1046 F g<sup>-1</sup> at 1 A g<sup>-1</sup>. The assembled asymmetric supercapacitor delivers an energy density of 32 Wh kg<sup>-1</sup> at 750 W kg<sup>-1</sup>, alongside excellent cycling stability. This work elucidates the electronic origin of performance enhancement and provides a doping-guided design principle for high-conductivity metal sulfide electrodes.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"556 ","pages":"Article 148384"},"PeriodicalIF":5.6,"publicationDate":"2026-04-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146187416","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 : 2026-04-20Epub Date: 2026-02-10DOI: 10.1016/j.electacta.2026.148422
Wu Wang , Shu-Hu Yin , Xiao-Yang Cheng , Long Chen , Rui Huang , Yu-Cheng Wang , Tao Wang , Zhi-You Zhou , Yan-Xia Jiang , Shi-Gang Sun
Iron-nitrogen-carbon (Fe/N/C) catalysts have emerged as the most promising platinum-group-metal-free electrocatalysts for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). Although significant progress has been made in improving their intrinsic activity, practical application is still hindered by insufficient stability and a notable performance gap between idealized rotating disk electrode (RDE) measurements and real membrane electrode assembly (MEA) performance. This review systematically summarizes up-to-date progress in the rational design and synthesis of high-performance Fe/N/C catalysts based on mechanistic understanding. It begins with examining the atomic configuration, electronic structure, and spatial distribution of active sites, establishing relationships between electrocatalytic performance and intrinsic catalytic activity, active site structure and density, as well as device performance. Following discussions then detail catalyst synthesis methods, from conventional high-temperature pyrolysis to emerging low-temperature routes, revealing active site formation mechanisms and highlighting strategies for controllable construction of high-density single-atom sites. For performance enhancement, the review comprehensively summarizes activity-boosting strategies including introducing nanoparticles/clusters, heteroatom doping, and carbon support engineering, alongside stability-improving approaches such as mitigating radical attack, strengthening Fe-N coordination, and enhancing graphitization. Finally, future research directions are outlined to guide the rational design and synthesis of Fe/N/C catalysts that integrate high activity, durability, and superior MEA performance. This review provides valuable insights for developing next-generation Fe/N/C catalysts towards practical PEMFC applications.
{"title":"A critical review: Rational design and synthesis of high-performance Fe/N/C catalysts for PEMFCs based on mechanistic understanding","authors":"Wu Wang , Shu-Hu Yin , Xiao-Yang Cheng , Long Chen , Rui Huang , Yu-Cheng Wang , Tao Wang , Zhi-You Zhou , Yan-Xia Jiang , Shi-Gang Sun","doi":"10.1016/j.electacta.2026.148422","DOIUrl":"10.1016/j.electacta.2026.148422","url":null,"abstract":"<div><div>Iron-nitrogen-carbon (Fe/N/C) catalysts have emerged as the most promising platinum-group-metal-free electrocatalysts for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). Although significant progress has been made in improving their intrinsic activity, practical application is still hindered by insufficient stability and a notable performance gap between idealized rotating disk electrode (RDE) measurements and real membrane electrode assembly (MEA) performance. This review systematically summarizes up-to-date progress in the rational design and synthesis of high-performance Fe/N/C catalysts based on mechanistic understanding. It begins with examining the atomic configuration, electronic structure, and spatial distribution of active sites, establishing relationships between electrocatalytic performance and intrinsic catalytic activity, active site structure and density, as well as device performance. Following discussions then detail catalyst synthesis methods, from conventional high-temperature pyrolysis to emerging low-temperature routes, revealing active site formation mechanisms and highlighting strategies for controllable construction of high-density single-atom sites. For performance enhancement, the review comprehensively summarizes activity-boosting strategies including introducing nanoparticles/clusters, heteroatom doping, and carbon support engineering, alongside stability-improving approaches such as mitigating radical attack, strengthening Fe-N coordination, and enhancing graphitization. Finally, future research directions are outlined to guide the rational design and synthesis of Fe/N/C catalysts that integrate high activity, durability, and superior MEA performance. This review provides valuable insights for developing next-generation Fe/N/C catalysts towards practical PEMFC applications.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"556 ","pages":"Article 148422"},"PeriodicalIF":5.6,"publicationDate":"2026-04-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146609","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 : 2026-04-20Epub Date: 2026-02-09DOI: 10.1016/j.electacta.2026.148386
Pengfa Li , Jie Yang , Xiaoguang Li , Cunjing Wang , Zhihua Ma , Quanzhou Du , Jiao Guo , Xiaowei Guo , Liujie Wang
Lithium-O2 batteries (LOBs) are considered potential energy storage systems, given their very high theoretical energy density. Nevertheless, the sluggish kinetics of the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) may lead to elevated overpotentials and diminished cycle stability. In this research, composite heterostructured Co3O4@CeO2 hollow nanospheres (Co3O4@CeO2 HNs) were prepared using a convenient hydrothermal approach, and then subjected to an annealing step, which exhibited good performance as a bi-functional catalyst for LOBs. The heterostructured hollow nanospheres provided an extensive catalytic surface to facilitate reaction kinetics. In addition, benefitting from the interfacial electron rearrangement of Co3O4@CeO2 heterostructure, the synergistic interaction can be contributed to ameliorate the chemisorption of intermediates and decrease the discharge and charge overpotentials, as validated-by density functional theory (DFT) calculations and experimental tests. Consequently, the assembled LOBs exhibited a narrow voltage gap (1.02 V at a middle capacity of 500 mAh g-1), an enhanced discharge capacity of 8988.8 mAh g-1, and cycling stability over 50 cycles at a controlled capacity of 500 mAh g-1. Notably, the Co3O4@CeO2 HNs exhibited superior electrocatalytic activity than the individual Co3O4 nanospheres (Co3O4 Ns) and CeO2 nanospheres (CeO2 Ns). Overall, this work presents an innovative methodology for designing heterojunctions to improve the electrocatalytic performance of LOBs.
锂- o2电池（lob）被认为是潜在的能量存储系统，因为它们具有非常高的理论能量密度。然而，析氧反应（OER）和氧还原反应（ORR）的缓慢动力学可能导致过电位升高和循环稳定性降低。本研究采用水热法制备了复合异质结构Co3O4@CeO2空心纳米球（Co3O4@CeO2 HNs），并对其进行了退火处理，获得了良好的双功能lob催化剂性能。异质结构的空心纳米球提供了广泛的催化表面，以促进反应动力学。此外，利用Co3O4@CeO2异质结构的界面电子重排，协同作用可以改善中间体的化学吸附，降低放电和充电过电位，密度泛函理论（DFT）计算和实验测试验证了这一点。结果表明，组装的lob具有较窄的电压间隙（中等容量为500 mAh g-1时为1.02 V），增强的放电容量为8988.8 mAh g-1，并且在500 mAh g-1的控制容量下循环超过50次的稳定性。值得注意的是，Co3O4@CeO2纳米微球的电催化活性优于单个Co3O4纳米微球（Co3O4 Ns）和CeO2纳米微球（CeO2 Ns）。总的来说，这项工作提出了一种创新的方法来设计异质结，以提高lob的电催化性能。
{"title":"Composite heterostructured Co3O4@CeO2 hollow nanospheres as an effective cathode catalyst for lithium-O2 battery","authors":"Pengfa Li , Jie Yang , Xiaoguang Li , Cunjing Wang , Zhihua Ma , Quanzhou Du , Jiao Guo , Xiaowei Guo , Liujie Wang","doi":"10.1016/j.electacta.2026.148386","DOIUrl":"10.1016/j.electacta.2026.148386","url":null,"abstract":"<div><div>Lithium-O<sub>2</sub> batteries (LOBs) are considered potential energy storage systems, given their very high theoretical energy density. Nevertheless, the sluggish kinetics of the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) may lead to elevated overpotentials and diminished cycle stability. In this research, composite heterostructured Co<sub>3</sub>O<sub>4</sub>@CeO<sub>2</sub> hollow nanospheres (Co<sub>3</sub>O<sub>4</sub>@CeO<sub>2</sub> HNs) were prepared using a convenient hydrothermal approach, and then subjected to an annealing step, which exhibited good performance as a bi-functional catalyst for LOBs. The heterostructured hollow nanospheres provided an extensive catalytic surface to facilitate reaction kinetics. In addition, benefitting from the interfacial electron rearrangement of Co<sub>3</sub>O<sub>4</sub>@CeO<sub>2</sub> heterostructure, the synergistic interaction can be contributed to ameliorate the chemisorption of intermediates and decrease the discharge and charge overpotentials, as validated-by density functional theory (DFT) calculations and experimental tests. Consequently, the assembled LOBs exhibited a narrow voltage gap (1.02 V at a middle capacity of 500 mAh g<sup>-1</sup>), an enhanced discharge capacity of 8988.8 mAh g<sup>-1</sup>, and cycling stability over 50 cycles at a controlled capacity of 500 mAh g<sup>-1</sup>. Notably, the Co<sub>3</sub>O<sub>4</sub>@CeO<sub>2</sub> HNs exhibited superior electrocatalytic activity than the individual Co<sub>3</sub>O<sub>4</sub> nanospheres (Co<sub>3</sub>O<sub>4</sub> Ns) and CeO<sub>2</sub> nanospheres (CeO<sub>2</sub> Ns). Overall, this work presents an innovative methodology for designing heterojunctions to improve the electrocatalytic performance of LOBs.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"556 ","pages":"Article 148386"},"PeriodicalIF":5.6,"publicationDate":"2026-04-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138784","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 : 2026-04-20Epub Date: 2026-02-01DOI: 10.1016/j.electacta.2026.148350
Alenzo Murray , Giovanni Valenti , Priscilla Baker
The design of a sensitive and accurate electrochemiluminescence (ECL) immunosensor for the early detection of cardiac biomarkers at low concentrations is essential to improve patient outcomes. In this study, a conductive metal-organic framework (c-MOF), Cu3(HHTP)2, was drop-coated onto a screen-printed carbon electrode (SPCE) to produce an ultra-efficient electrochemical sensing platform which was subsequently functionalized with cTnI antibodies (Ab) and bovine serum albumin (BSA) for selective detection of the cardiac Troponin I. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) confirmed the successful stepwise fabrication of the immunosensor. We investigated the ECL behaviour of the Cu3(HHTP)2-modified SPCE using [Ru(bpy)3]2+ as the luminophore and found that a significant increase in ECL intensity was achieved compared to that of the unmodified SPCE. This enhancement was attributed to the high conductivity, porous structure, the increased surface area of the c-MOF and crucially the HHTP ligand plays a critical role in enabling ECL generation in this system. The analytical performance of the immunosensor was evaluated by monitoring the ECL responses at varying cTnI concentrations. The immunosensor achieved a detection limit of 10.23 ± 1.06 pg/mL in vitro, well below the clinically relevant cTnI thresholds, highlighting its potential for rapid and early-stage cardiac biomarker detection. These findings suggest the Cu3(HHTP)2-based ECL immunosensor represents a viable sensing platform that significantly increases conductivity and ECL efficiency without the need of additional co-reactant species.
{"title":"A conductive metal-organic framework-modified electrode for sensitive electrochemiluminescent detection of cardiac Troponin I","authors":"Alenzo Murray , Giovanni Valenti , Priscilla Baker","doi":"10.1016/j.electacta.2026.148350","DOIUrl":"10.1016/j.electacta.2026.148350","url":null,"abstract":"<div><div>The design of a sensitive and accurate electrochemiluminescence (ECL) immunosensor for the early detection of cardiac biomarkers at low concentrations is essential to improve patient outcomes. In this study, a conductive metal-organic framework (c-MOF), Cu<sub>3</sub>(HHTP)<sub>2</sub>, was drop-coated onto a screen-printed carbon electrode (SPCE) to produce an ultra-efficient electrochemical sensing platform which was subsequently functionalized with cTnI antibodies (Ab) and bovine serum albumin (BSA) for selective detection of the cardiac Troponin I. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) confirmed the successful stepwise fabrication of the immunosensor. We investigated the ECL behaviour of the Cu<sub>3</sub>(HHTP)<sub>2</sub>-modified SPCE using [Ru(bpy)<sub>3</sub>]<sup>2+</sup> as the luminophore and found that a significant increase in ECL intensity was achieved compared to that of the unmodified SPCE. This enhancement was attributed to the high conductivity, porous structure, the increased surface area of the c-MOF and crucially the HHTP ligand plays a critical role in enabling ECL generation in this system. The analytical performance of the immunosensor was evaluated by monitoring the ECL responses at varying cTnI concentrations. The immunosensor achieved a detection limit of 10.23 ± 1.06 pg/mL in vitro, well below the clinically relevant cTnI thresholds, highlighting its potential for rapid and early-stage cardiac biomarker detection. These findings suggest the Cu<sub>3</sub>(HHTP)<sub>2</sub>-based ECL immunosensor represents a viable sensing platform that significantly increases conductivity and ECL efficiency without the need of additional co-reactant species.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"556 ","pages":"Article 148350"},"PeriodicalIF":5.6,"publicationDate":"2026-04-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098423","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 : 2026-04-20Epub Date: 2026-02-09DOI: 10.1016/j.electacta.2026.148426
Juliana M.S. de Jesus, Caroline de O. Carrilho, João P.C. Moura, Aline B. Trench, Caroline C. Augusto, Bruno L. Batista, Mauro C. dos Santos
The widespread presence of synthetic progestins, such as levonorgestrel (LNG) and gestodene (GES), in aquatic environments poses significant ecotoxicological risks due to their endocrine-disrupting properties. In this study, nano-octahedral magnetite (Fe3O4NO) was synthesized via a hydrothermal route and incorporated into gas diffusion electrodes (GDEs) supported on Vulcan XC72 to enhance the in-situ electrogeneration of hydrogen peroxide (H2O2). High-resolution Transmission Electron Microscopy, X-ray diffraction, SEM, X-ray photoelectron spectroscopy, and contact angle measurements thoroughly characterized the physicochemical and morphological properties of the materials. 3 % Fe3O4NO/C provided a 2-fold increase on H2O2 selectivity in comparison with Vulcan XC72. Electrochemical performance was optimized using a 23 factorial design and principal component analysis (PCA), with current density, pH, and Na2SO4 concentration as variables. The optimized GDE (3 % Fe3O4NO/C) achieved a maximum H2O2 production of 0.44 ± 0.02 g L⁻¹ with a current efficiency of 43.1 ± 0.23 % and a specific energy consumption of 0.012 ± 0.009 kWh g⁻¹. The electrode was further applied to the degradation of LNG and GES using solar and anodic-assisted electro-Fenton processes. Under optimal conditions, over 70 % removal of both progestins was achieved, with stable performance across three operational cycles. These findings demonstrate the potential of 3 % Fe3O4NO/C-GDEs as efficient, reusable cathodes for sustainable electrochemical advanced oxidation processes (EAOPs) in water treatment.
合成孕激素，如左炔诺孕酮（LNG）和孕酮（GES），由于其内分泌干扰特性，在水生环境中广泛存在，造成了重大的生态毒理学风险。本研究采用水热法合成纳米八面体磁铁矿（Fe3O4-NO），并将其掺入支撑在Vulcan XC72上的气体扩散电极（GDEs）中，以增强过氧化氢（H2O2）的原位发电能力。高分辨率透射电子显微镜、x射线衍射、扫描电镜、x射线光电子能谱和接触角测量彻底表征了材料的物理化学和形态特性。与Vulcan XC72相比，3% Fe3O4-NO/C的H2O2选择性提高了2倍。以电流密度、pH和Na2SO4浓度为变量，采用23因子设计和主成分分析（PCA）对电化学性能进行优化。优化后的GDE （3% Fe3O4-NO/C）的最大H2O2产量为0.44±0.02 g L -⁻，电流效率为43.1±0.23%，比能量消耗为0.012±0.009 kWh g -⁻。该电极进一步应用于太阳能和阳极辅助电fenton法降解LNG和GES。在最佳条件下，两种黄体酮的去除率均超过70%，并且在三个操作周期内性能稳定。这些发现证明了3% Fe3O4-NO/C-GDEs作为可持续电化学高级氧化过程（EAOPs）中高效、可重复使用的阴极在水处理中的潜力。
{"title":"Fe3O4 nano-octahedra/Vulcan XC72: Optimization and combination with solar-based electro-fenton for progestins degradation","authors":"Juliana M.S. de Jesus, Caroline de O. Carrilho, João P.C. Moura, Aline B. Trench, Caroline C. Augusto, Bruno L. Batista, Mauro C. dos Santos","doi":"10.1016/j.electacta.2026.148426","DOIUrl":"10.1016/j.electacta.2026.148426","url":null,"abstract":"<div><div>The widespread presence of synthetic progestins, such as levonorgestrel (LNG) and gestodene (GES), in aquatic environments poses significant ecotoxicological risks due to their endocrine-disrupting properties. In this study, nano-octahedral magnetite (Fe<sub>3</sub>O<sub>4</sub><sub><img></sub>NO) was synthesized via a hydrothermal route and incorporated into gas diffusion electrodes (GDEs) supported on Vulcan XC72 to enhance the <em>in-situ</em> electrogeneration of hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>). High-resolution Transmission Electron Microscopy, X-ray diffraction, SEM, X-ray photoelectron spectroscopy, and contact angle measurements thoroughly characterized the physicochemical and morphological properties of the materials. 3 % Fe<sub>3</sub>O<sub>4</sub><sub><img></sub>NO/C provided a 2-fold increase on H<sub>2</sub>O<sub>2</sub> selectivity in comparison with Vulcan XC72. Electrochemical performance was optimized using a 2<sup>3</sup> factorial design and principal component analysis (PCA), with current density, pH, and Na<sub>2</sub>SO<sub>4</sub> concentration as variables. The optimized GDE (3 % Fe<sub>3</sub>O<sub>4</sub><sub><img></sub>NO/C) achieved a maximum H<sub>2</sub>O<sub>2</sub> production of 0.44 ± 0.02 g L⁻¹ with a current efficiency of 43.1 ± 0.23 % and a specific energy consumption of 0.012 ± 0.009 kWh g⁻¹. The electrode was further applied to the degradation of LNG and GES using solar and anodic-assisted electro-Fenton processes. Under optimal conditions, over 70 % removal of both progestins was achieved, with stable performance across three operational cycles. These findings demonstrate the potential of 3 % Fe<sub>3</sub>O<sub>4</sub><sub><img></sub>NO/C-GDEs as efficient, reusable cathodes for sustainable electrochemical advanced oxidation processes (EAOPs) in water treatment.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"556 ","pages":"Article 148426"},"PeriodicalIF":5.6,"publicationDate":"2026-04-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146611","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 : 2026-04-20Epub Date: 2026-02-09DOI: 10.1016/j.electacta.2026.148410
Jiahao Sun , Xu Wang , Yang Li , Jinping Yuan , Yun Zou
The effects of homogenization treatment on the mechanical properties and corrosion behavior of an LA126 (Mg-12.31Li-5.62Al-0.14Y, wt.%) alloy were systematically investigated. The as-cast alloy was homogenized at 250 and 400°C for 1, 4, and 7 h, and its mechanical properties and corrosion behavior in 3.5 wt.% NaCl solution were evaluated. Homogenization at 400°C increased strength but reduced ductility, a trade-off primarily attributed to the precipitation of MgLiAl₂ within the β-Li matrix. While this intermetallic phase contributes to strengthening, its coarser morphology tends to induce local stress concentration, thereby compromising plasticity. In contrast, treatment at 250°C enhanced ductility with only a slight reduction in strength, mainly by alleviating casting-induced elemental segregation. Notably, the specimen homogenized at 400°C for 7 h exhibited superior corrosion resistance, characterized by a more noble corrosion potential (-1.571 V), a lower corrosion current density (5.11 × 10⁻⁵ A·cm⁻²), and the lowest mass-loss rate (0.67 mg·cm⁻²·d⁻¹). This enhancement is ascribed to the dissolution of anodic AlLi phases and improved microstructural uniformity, which effectively suppresses micro-galvanic coupling and localized corrosion.
{"title":"Homogenization-induced improvements in mechanical and corrosion properties of Mg-12.31Li-5.62Al-0.14Y alloy","authors":"Jiahao Sun , Xu Wang , Yang Li , Jinping Yuan , Yun Zou","doi":"10.1016/j.electacta.2026.148410","DOIUrl":"10.1016/j.electacta.2026.148410","url":null,"abstract":"<div><div>The effects of homogenization treatment on the mechanical properties and corrosion behavior of an LA126 (Mg-12.31Li-5.62Al-0.14Y, wt.%) alloy were systematically investigated. The as-cast alloy was homogenized at 250 and 400°C for 1, 4, and 7 h, and its mechanical properties and corrosion behavior in 3.5 wt.% NaCl solution were evaluated. Homogenization at 400°C increased strength but reduced ductility, a trade-off primarily attributed to the precipitation of MgLiAl₂ within the β-Li matrix. While this intermetallic phase contributes to strengthening, its coarser morphology tends to induce local stress concentration, thereby compromising plasticity. In contrast, treatment at 250°C enhanced ductility with only a slight reduction in strength, mainly by alleviating casting-induced elemental segregation. Notably, the specimen homogenized at 400°C for 7 h exhibited superior corrosion resistance, characterized by a more noble corrosion potential (-1.571 V), a lower corrosion current density (5.11 × 10⁻⁵ A·cm⁻²), and the lowest mass-loss rate (0.67 mg·cm⁻²·d⁻¹). This enhancement is ascribed to the dissolution of anodic AlLi phases and improved microstructural uniformity, which effectively suppresses micro-galvanic coupling and localized corrosion.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"556 ","pages":"Article 148410"},"PeriodicalIF":5.6,"publicationDate":"2026-04-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146565","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 : 2026-04-10Epub Date: 2026-01-20DOI: 10.1016/j.electacta.2026.148282
Daxue Fu , Jiuhua Wu , Chengyu Wang , Chunxin Wang , Qunzhao Xu , Jianshe Chen , Qing Han , Shuchen Sun
Scandium is one of the key alloying elements for aluminum. This study presents an innovative upward-flow liquid aluminum cathode molten salt electrolysis method for producing composition stability Al-Sc alloys. A system NaF-AlF3-BaF2 (molar ratio of NaF to AlF3 = 2.2) containing 25 wt% BaF2 was used as the electrolyte to achieve the floating molten aluminum cathode. The electrodeposition behavior of Sc at a tungsten cathode was analyzed in the electrolyte and experiments were carried out to produce Al-Sc alloys by the proposed process. The results show that the reduction of Sc (III) at 1273 K involved a one-step reaction with three-electron transfer. The process was limited by the diffusion of Sc (III) ions from the electrolyte to the electrode interface with a diffusion coefficient of 1.943 × 10–5 cm2/s. SEM-EDS and XRD analyses revealed that the early electrolysis products contained Al3Sc phase and W-Sc enrichment zones, while the final cooled products exhibited Sc in the surrounding Al layer, which primarily precipitates via aluminothermic reduction. Spherical products with the maximum scandium content of 3.68 wt% were obtained under a current density of 1.0 A/cm2 at 1273 K.
{"title":"Electrochemical behavior of Sc (III) and preparation of Al-Sc alloys in NaF-AlF3-BaF2 by a floating molten aluminum cathode","authors":"Daxue Fu , Jiuhua Wu , Chengyu Wang , Chunxin Wang , Qunzhao Xu , Jianshe Chen , Qing Han , Shuchen Sun","doi":"10.1016/j.electacta.2026.148282","DOIUrl":"10.1016/j.electacta.2026.148282","url":null,"abstract":"<div><div>Scandium is one of the key alloying elements for aluminum. This study presents an innovative upward-flow liquid aluminum cathode molten salt electrolysis method for producing composition stability Al-Sc alloys. A system NaF-AlF<sub>3</sub>-BaF<sub>2</sub> (molar ratio of NaF to AlF<sub>3</sub> = 2.2) containing 25 wt% BaF<sub>2</sub> was used as the electrolyte to achieve the floating molten aluminum cathode. The electrodeposition behavior of Sc at a tungsten cathode was analyzed in the electrolyte and experiments were carried out to produce Al-Sc alloys by the proposed process. The results show that the reduction of Sc (III) at 1273 K involved a one-step reaction with three-electron transfer. The process was limited by the diffusion of Sc (III) ions from the electrolyte to the electrode interface with a diffusion coefficient of 1.943 × 10<sup>–5</sup> cm<sup>2</sup>/s. SEM-EDS and XRD analyses revealed that the early electrolysis products contained Al<sub>3</sub>Sc phase and W-Sc enrichment zones, while the final cooled products exhibited Sc in the surrounding Al layer, which primarily precipitates via aluminothermic reduction. Spherical products with the maximum scandium content of 3.68 wt% were obtained under a current density of 1.0 A/cm<sup>2</sup> at 1273 K.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"555 ","pages":"Article 148282"},"PeriodicalIF":5.6,"publicationDate":"2026-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146014665","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 : 2026-04-10Epub Date: 2026-02-09DOI: 10.1016/j.electacta.2026.148405
Jin Li , Jiaqi Zhu , Qianqian Tang , Heng Zhang
To improve platinum (Pt) utilization and electrocatalytic performance, selecting a suitable support material is essential. In this study, Pt was successfully incorporated into a self-supported molybdenum dioxide (MoO2) framework via an electrodeposition technique, with the Pt content measuring around 0.56 wt %. The resulting catalyst exhibits an overpotential of 11.2 mV at a current density of −10 mA cm−2 and remarkable durability that extends beyond 50 h. Moreover, the practical proton exchange membrane water electrolysis (PEMWE) system with this catalyst achieves a current density of 1 A cm−2 at 1.75 V and operates stably for 100 h. Experimental findings verify that the improved performance of the catalyst is attributed to the strong interaction between Pt and MoO2, its distinctive nanosheet morphology, as well as the self-supporting characteristic of the electrode. This strategy provides an effective means for developing freestanding heterojunctions and promotes progress in the field of electrocatalytic hydrogen generation.
为了提高铂（Pt）的利用率和电催化性能，选择合适的支撑材料至关重要。在这项研究中，Pt通过电沉积技术成功地结合到自支撑的二氧化钼（MoO2）框架中，其含量约为0.56 wt%。该催化剂在电流密度为- 10 mA cm - 2时的过电位为11.2 mV，并且具有超过50小时的显着耐久性。此外，使用该催化剂的质子交换膜水电解（PEMWE）系统在1.75 V时的电流密度为1 a cm - 2，并稳定运行100小时。实验结果验证了催化剂性能的提高是由于Pt和MoO2之间的强相互作用，其独特的纳米片形貌以及电极的自支撑特性。该策略为开发独立异质结提供了有效手段，并促进了电催化制氢领域的进展。
{"title":"Designing Pt-decorated MoO2 catalysts for enhanced hydrogen evolution reaction in proton exchange membrane water electrolysis","authors":"Jin Li , Jiaqi Zhu , Qianqian Tang , Heng Zhang","doi":"10.1016/j.electacta.2026.148405","DOIUrl":"10.1016/j.electacta.2026.148405","url":null,"abstract":"<div><div>To improve platinum (Pt) utilization and electrocatalytic performance, selecting a suitable support material is essential. In this study, Pt was successfully incorporated into a self-supported molybdenum dioxide (MoO<sub>2</sub>) framework via an electrodeposition technique, with the Pt content measuring around 0.56 wt %. The resulting catalyst exhibits an overpotential of 11.2 mV at a current density of −10 mA cm<sup>−2</sup> and remarkable durability that extends beyond 50 h. Moreover, the practical proton exchange membrane water electrolysis (PEMWE) system with this catalyst achieves a current density of 1 A cm<sup>−2</sup> at 1.75 V and operates stably for 100 h. Experimental findings verify that the improved performance of the catalyst is attributed to the strong interaction between Pt and MoO<sub>2</sub>, its distinctive nanosheet morphology, as well as the self-supporting characteristic of the electrode. This strategy provides an effective means for developing freestanding heterojunctions and promotes progress in the field of electrocatalytic hydrogen generation.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"555 ","pages":"Article 148405"},"PeriodicalIF":5.6,"publicationDate":"2026-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138786","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 : 2026-04-10Epub Date: 2026-02-10DOI: 10.1016/j.electacta.2026.148402
Marvin Malchau, Jan Philipp Schmidt
We propose a time-domain method for estimating the Distribution of Relaxation Times (DRT) in electrochemical systems based on a recursive RC modeling framework. By discretizing the system response via bilinear transformation, this approach enables direct reconstruction of the DRT from arbitrary current excitation signals, without relying on frequency-domain impedance data or predefined excitation profiles, as required by established methods such as pulse-fitting. The method integrates multiple electrochemical contributions into a unified linear model and solves the resulting inverse problem using nonnegative least squares with Tikhonov regularization. Validation with synthetic and experimental data demonstrates high accuracy, numerical stability, and excellent agreement with conventional impedance spectroscopy. The approach significantly reduces measurement time, especially in the low-frequency regime, and offers robust performance under realistic noise conditions.
{"title":"Recursive RC Modeling for Time-Domain Estimation of the Distribution of Relaxation Times","authors":"Marvin Malchau, Jan Philipp Schmidt","doi":"10.1016/j.electacta.2026.148402","DOIUrl":"10.1016/j.electacta.2026.148402","url":null,"abstract":"<div><div>We propose a time-domain method for estimating the Distribution of Relaxation Times (DRT) in electrochemical systems based on a recursive RC modeling framework. By discretizing the system response via bilinear transformation, this approach enables direct reconstruction of the DRT from arbitrary current excitation signals, without relying on frequency-domain impedance data or predefined excitation profiles, as required by established methods such as pulse-fitting. The method integrates multiple electrochemical contributions into a unified linear model and solves the resulting inverse problem using nonnegative least squares with Tikhonov regularization. Validation with synthetic and experimental data demonstrates high accuracy, numerical stability, and excellent agreement with conventional impedance spectroscopy. The approach significantly reduces measurement time, especially in the low-frequency regime, and offers robust performance under realistic noise conditions.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"555 ","pages":"Article 148402"},"PeriodicalIF":5.6,"publicationDate":"2026-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146153154","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 : 2026-04-10Epub Date: 2026-01-29DOI: 10.1016/j.electacta.2026.148340
Zhiya Han , Shuqi Wang , Miaosen Yang , Hua Shi , Na He , Jiayin Yang , Xiyang Liu , Yue Kang , Yixin Liu , Huiting Ni , Facai Wei , Sheng Han
Ammonia synthesis via electrocatalytic nitrogen reduction reaction offers a sustainable alternative to the energy-intensive Haber-Bosch process. In this study, we fabricated covalent triazine-modified, carbon-loaded Cu single-atom materials (Cu SA/NSPC and Cu SA/NPC) as novel catalysts by pyrolyzing Cu single-atom-containing polymers to address current limitations. It is characterized by the introduction of S prompting electron migration to the metal active site, inhibiting side reactions and reducing energy consumption, while lowering bond energies, promoting nitrogen activation and intermediate formation, and increasing the reaction rate, and the formation of coordination structures between Cu single-atom and covalent triazine carriers, providing new NRR active sites to further enhance the activation and reduction of nitrogen molecules. Our results show that Cu SA/NSPC achieves an ammonia yield of 66.87 ± 2.13 µg h-1 mgcat-1 and a Faraday efficiency of 33.2 ± 1.4 %. In the flow cell, the ammonia yield is further improved to reach 242 ± 2.43 µg h-1 mgcat-1. In-situ Raman and density functional theory (DFT) calculations helped to understand the intrinsic mechanism of the reaction, and stability and flow cell tests showed excellent durability. By coupling with the ethylene glycol oxidation reaction, it provides a new idea for efficient electroconversion of biomass resources and coupling with renewable energy. This study realizes the innovative fusion of single-atom catalysis and organic framework materials, which opens up a new direction for the development of high-performance electrocatalysts for energy and environment.
{"title":"Electrocatalytic nitrogen fixation and coupling reactions of copper single-atom catalysts","authors":"Zhiya Han , Shuqi Wang , Miaosen Yang , Hua Shi , Na He , Jiayin Yang , Xiyang Liu , Yue Kang , Yixin Liu , Huiting Ni , Facai Wei , Sheng Han","doi":"10.1016/j.electacta.2026.148340","DOIUrl":"10.1016/j.electacta.2026.148340","url":null,"abstract":"<div><div>Ammonia synthesis via electrocatalytic nitrogen reduction reaction offers a sustainable alternative to the energy-intensive Haber-Bosch process. In this study, we fabricated covalent triazine-modified, carbon-loaded Cu single-atom materials (Cu SA/NSPC and Cu SA/NPC) as novel catalysts by pyrolyzing Cu single-atom-containing polymers to address current limitations. It is characterized by the introduction of S prompting electron migration to the metal active site, inhibiting side reactions and reducing energy consumption, while lowering bond energies, promoting nitrogen activation and intermediate formation, and increasing the reaction rate, and the formation of coordination structures between Cu single-atom and covalent triazine carriers, providing new NRR active sites to further enhance the activation and reduction of nitrogen molecules. Our results show that Cu SA/NSPC achieves an ammonia yield of 66.87 ± 2.13 µg h<sup>-1</sup> mg<sub>cat</sub><sup>-1</sup> and a Faraday efficiency of 33.2 ± 1.4 %. In the flow cell, the ammonia yield is further improved to reach 242 ± 2.43 µg h<sup>-1</sup> mg<sub>cat</sub><sup>-1</sup>. In-situ Raman and density functional theory (DFT) calculations helped to understand the intrinsic mechanism of the reaction, and stability and flow cell tests showed excellent durability. By coupling with the ethylene glycol oxidation reaction, it provides a new idea for efficient electroconversion of biomass resources and coupling with renewable energy. This study realizes the innovative fusion of single-atom catalysis and organic framework materials, which opens up a new direction for the development of high-performance electrocatalysts for energy and environment.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"555 ","pages":"Article 148340"},"PeriodicalIF":5.6,"publicationDate":"2026-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146072732","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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