Pub Date : 2026-01-26DOI: 10.1016/j.electacta.2026.148317
Harmesa Harmesa, A'an J. Wahyudi, Asep Saefumillah, Andrea Fiorani, Yasuaki Einaga, Tribidasari A. Ivandini
Anodic stripping voltammetry (ASV) was successfully integrated into an electrochemiluminescence arsenic (III) sensor to enhance its sensitivity. The cathodic reduction step plays a crucial role in anodic stripping voltammetry, making it more sensitive than cyclic voltammetry. In the ASV-ECL technique, the preconcentration step involves applying a potential of –500 mV for 60 s, which potentially reduces the As(III) species to As0 and allows it to spontaneously deposit onto the electrode surface. Simultaneously, a co-reactant of H2O2 is electrochemically reduced to generate hydroxyl radicals (•OH) during the cathodic reduction step, thereby significantly amplifying the ECL response and enhancing detection sensitivity. The analytical measurement of ASV-ECL was successfully performed by the quenching effect of As(III) on luminol-emitted light. The proposed ECL sensor demonstrated excellent performance for As(III) detection with a low detection limit of 0.0152 µM (15.2 nM), high sensitivity of 6.5865 a.u. µM⁻¹ cm–2, and great stability (RSD = 2.49%). High selectivity was achieved by using an optimized pH 10 buffer solution, supporting efficient luminol deprotonation and retaining As(III) in its soluble state, while forcing interfering metal ions to form insoluble metal (hydro)oxides. Therefore, it is essential to perform the precipitation method as a pretreatment step for real seawater samples before quantifying the level of As(III), ensuring that the presence of interfering ions does not significantly affect the measurement accuracy. Successfully detecting the level of As(III) in a seawater sample demonstrates the sensor's practical applicability and confirms its reliability for environmental monitoring.
{"title":"Electrochemiluminescent Detection of Arsenic(III) Enhanced by Anodic Stripping Voltammetry","authors":"Harmesa Harmesa, A'an J. Wahyudi, Asep Saefumillah, Andrea Fiorani, Yasuaki Einaga, Tribidasari A. Ivandini","doi":"10.1016/j.electacta.2026.148317","DOIUrl":"https://doi.org/10.1016/j.electacta.2026.148317","url":null,"abstract":"Anodic stripping voltammetry (ASV) was successfully integrated into an electrochemiluminescence arsenic (III) sensor to enhance its sensitivity. The cathodic reduction step plays a crucial role in anodic stripping voltammetry, making it more sensitive than cyclic voltammetry. In the ASV-ECL technique, the preconcentration step involves applying a potential of –500 mV for 60 s, which potentially reduces the As(III) species to As<ce:sup loc=\"post\">0</ce:sup> and allows it to spontaneously deposit onto the electrode surface. Simultaneously, a co-reactant of H<ce:inf loc=\"post\">2</ce:inf>O<ce:inf loc=\"post\">2</ce:inf> is electrochemically reduced to generate hydroxyl radicals (•OH) during the cathodic reduction step, thereby significantly amplifying the ECL response and enhancing detection sensitivity. The analytical measurement of ASV-ECL was successfully performed by the quenching effect of As(III) on luminol-emitted light. The proposed ECL sensor demonstrated excellent performance for As(III) detection with a low detection limit of 0.0152 µM (15.2 nM), high sensitivity of 6.5865 a.u. µM⁻¹ cm<ce:sup loc=\"post\">–2</ce:sup>, and great stability (RSD = 2.49%). High selectivity was achieved by using an optimized pH 10 buffer solution, supporting efficient luminol deprotonation and retaining As(III) in its soluble state, while forcing interfering metal ions to form insoluble metal (hydro)oxides. Therefore, it is essential to perform the precipitation method as a pretreatment step for real seawater samples before quantifying the level of As(III), ensuring that the presence of interfering ions does not significantly affect the measurement accuracy. Successfully detecting the level of As(III) in a seawater sample demonstrates the sensor's practical applicability and confirms its reliability for environmental monitoring.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"30 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146048093","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 : 2026-01-25DOI: 10.1016/j.electacta.2026.148314
Natália M. Caldas , Amanda G. Batista , Gustavo S.G. de Carvalho , Dayenny L. D’ Amato , Celia M. Ronconi , Fernando de C. da Silva , Lucas V. de Faria , Diego P. Rocha , Rafael M. Dornellas
3D printing has emerged as an innovative technology, enabling the large-scale development of improved, low-cost electrochemical devices with high applicability potential. In this sense, this study highlights the use of electrodes printed via additive manufacturing from conductive filament composed of polylactic acid (PLA), graphite (G) modified with kaolinite (Al₂Si₂O₅(OH)₂), for the electrochemical biosensing of tyrosine (TYR). The electrodes were fabricated using both a 3D printer and a 3D pen to obtain cylindrical and flat geometries, respectively, without requiring any prior electrochemical treatment. The kaolinite-modified sensor was coupled to a 3D-printed batch injection analysis cell (BIA) for amperometric detection, showing superior performance compared to the kaolinite-free sensor (G/PLA). The system demonstrated a wide linear response range (0.1 to 200 μmol L-1), low detection limit (0.02 μmol L-1), and high precision (RSD < 7.5%). Additionally, high analytical frequency (180 analyses per hour) and selectivity were observed against possible interferents present in biological matrices. The applicability of the method was demonstrated through the analysis of artificial human serum and synthetic saliva samples, which yielded recoveries ranging from 92% to 98%, confirming its reliability and accuracy. Thus, the 3D-printed G/Al₂Si₂O₅(OH)₄/PLA electrode stands out as a robust, user-friendly, and highly sensitive analytical platform with great potential for biological and clinical research applications.
{"title":"A new carbon–kaolinite composite conductive filament for 3D-printed electrochemical tyrosine sensors","authors":"Natália M. Caldas , Amanda G. Batista , Gustavo S.G. de Carvalho , Dayenny L. D’ Amato , Celia M. Ronconi , Fernando de C. da Silva , Lucas V. de Faria , Diego P. Rocha , Rafael M. Dornellas","doi":"10.1016/j.electacta.2026.148314","DOIUrl":"10.1016/j.electacta.2026.148314","url":null,"abstract":"<div><div>3D printing has emerged as an innovative technology, enabling the large-scale development of improved, low-cost electrochemical devices with high applicability potential. In this sense, this study highlights the use of electrodes printed via additive manufacturing from conductive filament composed of polylactic acid (PLA), graphite (G) modified with kaolinite (Al₂Si₂O₅(OH)₂), for the electrochemical biosensing of tyrosine (TYR). The electrodes were fabricated using both a 3D printer and a 3D pen to obtain cylindrical and flat geometries, respectively, without requiring any prior electrochemical treatment. The kaolinite-modified sensor was coupled to a 3D-printed batch injection analysis cell (BIA) for amperometric detection, showing superior performance compared to the kaolinite-free sensor (G/PLA). The system demonstrated a wide linear response range (0.1 to 200 μmol L<sup>-1</sup>), low detection limit (0.02 μmol L<sup>-1</sup>), and high precision (RSD < 7.5%). Additionally, high analytical frequency (180 analyses per hour) and selectivity were observed against possible interferents present in biological matrices. The applicability of the method was demonstrated through the analysis of artificial human serum and synthetic saliva samples, which yielded recoveries ranging from 92% to 98%, confirming its reliability and accuracy. Thus, the 3D-printed G/Al₂Si₂O₅(OH)₄/PLA electrode stands out as a robust, user-friendly, and highly sensitive analytical platform with great potential for biological and clinical research applications.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"554 ","pages":"Article 148314"},"PeriodicalIF":5.6,"publicationDate":"2026-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146048096","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 : 2026-01-25DOI: 10.1016/j.electacta.2026.148313
Masahiro Shimizu, Hikari Inoshita, Rui Yoshida
Magnesium metal offers high theoretical capacities, natural abundance, and a low tendency toward dendrite formation, making it a promising negative electrode for next-generation rechargeable batteries. However, the development of electrolyte formulations that are simultaneously compatible with both positive and negative electrodes remains highly challenging. Notably, Mg(TFSA)2-based electrolytes exhibit superior compatibility toward specific positive-electrode materials, but they suffer from severe passivation of the Mg surface, leading to extremely large deposition/stripping overpotentials. Recent studies have shown that artificial interphases can expand the range of electrolyte compositions that support Mg deposition and stripping even in electrolytes that intrinsically induce passivation. In this study, we reveal that temperature-controlled electropolishing in 0.5 M NaCl/ethylene glycol provides an operator-independent method to prepare smooth and oxide-free Mg surfaces suitable for constructing artificial interphases. Electropolished Mg enables homogeneous displacement plating of Bi, forming a dense and continuous Bi layer, whereas mechanically polished Mg yields a rough and nonuniform layer. These results establish electropolishing as a robust platform for reproducible surface preparation for rechargeable Mg batteries.
金属镁具有较高的理论容量、天然丰度和低枝晶形成倾向，使其成为下一代可充电电池的极负极。然而，开发同时与正极和负极兼容的电解质配方仍然具有很高的挑战性。值得注意的是，Mg(TFSA)2基电解质对特定正极材料表现出优异的相容性，但它们受到Mg表面严重钝化的影响，导致极大的沉积/剥离过电位。最近的研究表明，即使在本质上诱导钝化的电解质中，人工界面也可以扩大支持Mg沉积和剥离的电解质成分的范围。在这项研究中，我们揭示了在0.5 M NaCl/乙二醇中控制温度的电抛光提供了一种不依赖操作者的方法来制备光滑和无氧化的Mg表面，适合构建人工界面。电抛光Mg可以实现均匀位移镀Bi，形成致密和连续的Bi层，而机械抛光Mg则产生粗糙和不均匀的层。这些结果确立了电抛光作为可再生镁电池表面制备的强大平台。
{"title":"Electrochemical activation process for Mg metal as a negative electrode without mechanical polishing","authors":"Masahiro Shimizu, Hikari Inoshita, Rui Yoshida","doi":"10.1016/j.electacta.2026.148313","DOIUrl":"10.1016/j.electacta.2026.148313","url":null,"abstract":"<div><div>Magnesium metal offers high theoretical capacities, natural abundance, and a low tendency toward dendrite formation, making it a promising negative electrode for next-generation rechargeable batteries. However, the development of electrolyte formulations that are simultaneously compatible with both positive and negative electrodes remains highly challenging. Notably, Mg(TFSA)<sub>2</sub>-based electrolytes exhibit superior compatibility toward specific positive-electrode materials, but they suffer from severe passivation of the Mg surface, leading to extremely large deposition/stripping overpotentials. Recent studies have shown that artificial interphases can expand the range of electrolyte compositions that support Mg deposition and stripping even in electrolytes that intrinsically induce passivation. In this study, we reveal that temperature-controlled electropolishing in 0.5 M NaCl/ethylene glycol provides an operator-independent method to prepare smooth and oxide-free Mg surfaces suitable for constructing artificial interphases. Electropolished Mg enables homogeneous displacement plating of Bi, forming a dense and continuous Bi layer, whereas mechanically polished Mg yields a rough and nonuniform layer. These results establish electropolishing as a robust platform for reproducible surface preparation for rechargeable Mg batteries.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"553 ","pages":"Article 148313"},"PeriodicalIF":5.6,"publicationDate":"2026-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146048097","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 : 2026-01-25DOI: 10.1016/j.electacta.2026.148316
Gonzalo Cima, José R. Sosa-Acosta, Erik Castañeda, Nicolás Veloso, María J. Aguirre, Mauricio Isaacs, Francisco Armijo
Ammonia oxidation reaction (AOR) is an intriguing field of research with significant potential to address global energy challenges and advance a greener, more sustainable future by harnessing its role as a renewable energy source. In this study, we present a hybrid platform composed of carbon microfibres that have been modified with poly(3,4-ethylenedioxythiophene) and nickel hydroxide/oxyhydroxide (CP/PEDOT@Ni(OH)2. Morphological and spectroscopic analyses (SEM-EDS, XPS, and FTIR-ATR) confirmed that the PEDOT film uniformly surrounds the carbon microfibre, creating a surface platform suitable for electrodepositing Ni species. The electrochemical parameters that were ascertained included the surface coverage of Ni active species (Γ0* = 1.77 nmol·cm−2), the electrochemically active surface area (EASA = 113.3 cm2), the electron transfer coefficient (α = 0.32), and the heterogeneous electron transfer rate constant (ks = 16.68 s−1). Electrochemical evaluation for AOR revealed that CP/PEDOT@Ni(OH)2 exhibits a Tafel slope of ∼30 mV·dec−1, confirming enhanced charge transfer properties. Electrochemical impedance spectroscopy (EIS) revealed a decline in capacitance and charge-transfer resistance in the presence of ammonia, suggesting the presence of active sites for charge storage and transfer, which are controlled by the diffusion process at the PEDOT@Ni(OH)2/solution interface. These findings underscore the synergistic contribution of PEDOT and Ni oxyhydroxide in facilitating electron and ion transport, thereby establishing CP/PEDOT@Ni(OH)2 as a promising anode electrocatalyst for low-temperature direct ammonia fuel cells.
{"title":"Electrodeposition of Poly(3,4-ethylenedioxythiophene) @Ni(OH)2 hybrid material on carbon microfibres for ammonia oxidation in alkaline media","authors":"Gonzalo Cima, José R. Sosa-Acosta, Erik Castañeda, Nicolás Veloso, María J. Aguirre, Mauricio Isaacs, Francisco Armijo","doi":"10.1016/j.electacta.2026.148316","DOIUrl":"https://doi.org/10.1016/j.electacta.2026.148316","url":null,"abstract":"Ammonia oxidation reaction (AOR) is an intriguing field of research with significant potential to address global energy challenges and advance a greener, more sustainable future by harnessing its role as a renewable energy source. In this study, we present a hybrid platform composed of carbon microfibres that have been modified with poly(3,4-ethylenedioxythiophene) and nickel hydroxide/oxyhydroxide (CP/PEDOT@Ni(OH)<ce:inf loc=\"post\">2</ce:inf>. Morphological and spectroscopic analyses (SEM-EDS, XPS, and FTIR-ATR) confirmed that the PEDOT film uniformly surrounds the carbon microfibre, creating a surface platform suitable for electrodepositing Ni species. The electrochemical parameters that were ascertained included the surface coverage of Ni active species (<ce:italic>Γ<ce:inf loc=\"post\">0</ce:inf>*</ce:italic> = 1.77 nmol·cm<ce:sup loc=\"post\">−2</ce:sup>), the electrochemically active surface area (EASA = 113.3 cm<ce:sup loc=\"post\">2</ce:sup>), the electron transfer coefficient (<ce:italic>α</ce:italic> = 0.32), and the heterogeneous electron transfer rate constant (<ce:italic>k<ce:inf loc=\"post\">s</ce:inf></ce:italic> = 16.68 s<ce:sup loc=\"post\">−1</ce:sup>). Electrochemical evaluation for AOR revealed that CP/PEDOT@Ni(OH)<ce:inf loc=\"post\">2</ce:inf> exhibits a Tafel slope of ∼30 mV·dec<ce:sup loc=\"post\">−1</ce:sup>, confirming enhanced charge transfer properties. Electrochemical impedance spectroscopy (EIS) revealed a decline in capacitance and charge-transfer resistance in the presence of ammonia, suggesting the presence of active sites for charge storage and transfer, which are controlled by the diffusion process at the PEDOT@Ni(OH)<ce:inf loc=\"post\">2</ce:inf>/solution interface. These findings underscore the synergistic contribution of PEDOT and Ni oxyhydroxide in facilitating electron and ion transport, thereby establishing CP/PEDOT@Ni(OH)<ce:inf loc=\"post\">2</ce:inf> as a promising anode electrocatalyst for low-temperature direct ammonia fuel cells.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"290 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2026-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146048095","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 : 2026-01-24DOI: 10.1016/j.electacta.2026.148312
Zhongning Gan , Yeming Li , Chun Li , Chao Ma , Jiajia Li , Yinfang Zhu , Shanshan Yao
Commercial lithium ion batteries (LIBs) typically employ polyolefin separators, yet these materials exhibit poor thermal tolerance, insufficient electrolyte wettability, and limited porosity, ultimately restricting both safety and electrochemical efficiency. Electrospun polyimide (PI) nanofibers separators have emerged as attractive alternatives due to their outstanding heat resistance, and strong affinity for electrolytes. In this work, PI nanofibers separators with adjustable fiber diameters were obtained by controlling electrospinning conditions, and their structural, physicochemical, and electrochemical characteristics were systematically evaluated. The optimized electrospun PI nanofibers, featuring an average fiber diameter of approximately 370 nm, displayed superior tensile strength, excellent electrolyte absorption, high ionic conductivity, reduced interfacial resistance, and stable electrochemical behaviors when compared with the conventional polyolefin-based separators. Overall, the results emphasize the decisive influence of fiber diameter modulation on separator behavior and provide valuable guidance for the rational development of advanced PI nanofibers separators for future high-performance LIBs applications. In addition, the optimized PI nanofiber separator was attempted to apply in sodium-ion batteries, where it exhibited cycling stability when paired with a biomass-derived hard carbon anode.
{"title":"Electrospinning-derived polymide membranes with optimized fiber diameter as lithium ion batteries separators","authors":"Zhongning Gan , Yeming Li , Chun Li , Chao Ma , Jiajia Li , Yinfang Zhu , Shanshan Yao","doi":"10.1016/j.electacta.2026.148312","DOIUrl":"10.1016/j.electacta.2026.148312","url":null,"abstract":"<div><div>Commercial lithium ion batteries (LIBs) typically employ polyolefin separators, yet these materials exhibit poor thermal tolerance, insufficient electrolyte wettability, and limited porosity, ultimately restricting both safety and electrochemical efficiency. Electrospun polyimide (PI) nanofibers separators have emerged as attractive alternatives due to their outstanding heat resistance, and strong affinity for electrolytes. In this work, PI nanofibers separators with adjustable fiber diameters were obtained by controlling electrospinning conditions, and their structural, physicochemical, and electrochemical characteristics were systematically evaluated. The optimized electrospun PI nanofibers, featuring an average fiber diameter of approximately 370 nm, displayed superior tensile strength, excellent electrolyte absorption, high ionic conductivity, reduced interfacial resistance, and stable electrochemical behaviors when compared with the conventional polyolefin-based separators. Overall, the results emphasize the decisive influence of fiber diameter modulation on separator behavior and provide valuable guidance for the rational development of advanced PI nanofibers separators for future high-performance LIBs applications. In addition, the optimized PI nanofiber separator was attempted to apply in sodium-ion batteries, where it exhibited cycling stability when paired with a biomass-derived hard carbon anode.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"553 ","pages":"Article 148312"},"PeriodicalIF":5.6,"publicationDate":"2026-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146048098","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 : 2026-01-24DOI: 10.1016/j.electacta.2026.148307
Yucheng Liu, Hantao Du, Tao Tian, Shuo Wang, Zian Li, Lizhang Wang
Electrocatalytic oxidation technology demonstrates promising potential for treating high-salinity organic wastewater. However, the mechanism by which sulfate influences electrocatalytic efficiency remains unclear. This study reveals the sulfate ion-mediated tridentate electron channel on the surface facilitates electron transfer between organic pollutants and the electrode. Conventional electron-transfer models often neglect competitive reactions such as water oxidation to simplify calculations, leading to inadequate accuracy in describing the actual oxidation efficiency of organic pollutants. To address this, we developed a computational model for electron transfer numbers by incorporating surface coverage correction into the Butler-Volmer equation. This model fully accounts for the complex multi-reaction processes at the electrode surface, enabling a more accurate description of the electrochemical oxidation behavior of organic pollutants. The results show a significant linear correlation (R2 = 0.98) between the calculated electron transfer numbers and the removal rate of organic pollutants, indicating that electron transfer numbers can serve as an effective quantitative indicator for evaluating pollutant removal efficiency. Furthermore, using the electron transfer numbers derived from this model, the quantitative evaluation of anode current efficiency was successfully achieved. The proposed electron transfer number model overcomes the limitations of traditional methods in describing complex interfaces and reactions, providing a methodological foundation for predicting and quantitatively assessing electron transfer efficiency.
{"title":"A surface coverage-based computational model for electron transfer number calculation accurately measures electron transfer efficiency in organic pollutant oxidation","authors":"Yucheng Liu, Hantao Du, Tao Tian, Shuo Wang, Zian Li, Lizhang Wang","doi":"10.1016/j.electacta.2026.148307","DOIUrl":"10.1016/j.electacta.2026.148307","url":null,"abstract":"<div><div>Electrocatalytic oxidation technology demonstrates promising potential for treating high-salinity organic wastewater. However, the mechanism by which sulfate influences electrocatalytic efficiency remains unclear. This study reveals the sulfate ion-mediated tridentate electron channel on the surface facilitates electron transfer between organic pollutants and the electrode. Conventional electron-transfer models often neglect competitive reactions such as water oxidation to simplify calculations, leading to inadequate accuracy in describing the actual oxidation efficiency of organic pollutants. To address this, we developed a computational model for electron transfer numbers by incorporating surface coverage correction into the Butler-Volmer equation. This model fully accounts for the complex multi-reaction processes at the electrode surface, enabling a more accurate description of the electrochemical oxidation behavior of organic pollutants. The results show a significant linear correlation (R<sup>2</sup> = 0.98) between the calculated electron transfer numbers and the removal rate of organic pollutants, indicating that electron transfer numbers can serve as an effective quantitative indicator for evaluating pollutant removal efficiency. Furthermore, using the electron transfer numbers derived from this model, the quantitative evaluation of anode current efficiency was successfully achieved. The proposed electron transfer number model overcomes the limitations of traditional methods in describing complex interfaces and reactions, providing a methodological foundation for predicting and quantitatively assessing electron transfer efficiency.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"553 ","pages":"Article 148307"},"PeriodicalIF":5.6,"publicationDate":"2026-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146048155","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 : 2026-01-24DOI: 10.1016/j.electacta.2026.148310
Saurabh Kumar Nishad, Dheerendra Kumar Dwivedi
This study investigates the role of chromium (Cr) precipitates and diffusible hydrogen content (HD) in high-temperature stress corrosion cracking (HT SCC) of SS304-P91 dissimilar steel welds exposed to boiling MgCl2 solution. Welds were produced by activated TIG (A-TIG) welding using constant and pulsed current modes, with and without a Ni-based filler, to tailor thermal cycles and weld microstructure. Pulsed-current welding significantly reduced Cr precipitation and HD while promoting molybdenum carbide formation, resulting in a 65 % reduction in crack growth rate (CGR) and a marked increase in fracture time. The addition of Ni-based filler further enhanced SCC resistance, and the combined pulsed-current, filler-assisted weld exhibited the best performance, achieving a 93 % reduction in CGR compared to the constant-current weld without filler. Potentiodynamic polarization results revealed a 62 % reduction in corrosion rate for the optimized weld, indicating improved electrochemical stability under high-temperature chloride exposure. Fractographic analysis identified Cr2O3- and Fe-rich oxides with chloride species at crack-tip regions, confirming corrosion-assisted crack propagation. Overall, the results demonstrate that controlling chromium precipitation and diffusible hydrogen through welding process optimization provides an effective strategy for mitigating HT SCC in SS304-P91 dissimilar welds.
{"title":"Role of Cr-precipitates and diffusible hydrogen on SCC of SS304-P91 dissimilar steel welds under boiling MgCl2 solution","authors":"Saurabh Kumar Nishad, Dheerendra Kumar Dwivedi","doi":"10.1016/j.electacta.2026.148310","DOIUrl":"10.1016/j.electacta.2026.148310","url":null,"abstract":"<div><div>This study investigates the role of chromium (Cr) precipitates and diffusible hydrogen content (H<sub>D</sub>) in high-temperature stress corrosion cracking (HT SCC) of SS304-P91 dissimilar steel welds exposed to boiling MgCl<sub>2</sub> solution. Welds were produced by activated TIG (A-TIG) welding using constant and pulsed current modes, with and without a Ni-based filler, to tailor thermal cycles and weld microstructure. Pulsed-current welding significantly reduced Cr precipitation and H<sub>D</sub> while promoting molybdenum carbide formation, resulting in a 65 % reduction in crack growth rate (CGR) and a marked increase in fracture time. The addition of Ni-based filler further enhanced SCC resistance, and the combined pulsed-current, filler-assisted weld exhibited the best performance, achieving a 93 % reduction in CGR compared to the constant-current weld without filler. Potentiodynamic polarization results revealed a 62 % reduction in corrosion rate for the optimized weld, indicating improved electrochemical stability under high-temperature chloride exposure. Fractographic analysis identified Cr<sub>2</sub>O<sub>3</sub>- and Fe-rich oxides with chloride species at crack-tip regions, confirming corrosion-assisted crack propagation. Overall, the results demonstrate that controlling chromium precipitation and diffusible hydrogen through welding process optimization provides an effective strategy for mitigating HT SCC in SS304-P91 dissimilar welds.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"553 ","pages":"Article 148310"},"PeriodicalIF":5.6,"publicationDate":"2026-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146048152","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 : 2026-01-24DOI: 10.1016/j.electacta.2026.148306
Wen Xing , Christelle Denonville , Rune Bredesen , Peter Veenstra , Arian Nijmeijer , Paul-Emmanuel Just , Marie-Laure Fontaine
Electrochemical pumping of CO₂ across molten carbonate electrolytes is demonstrated using tape-cast LiAlO₂/NiO membrane–electrode assemblies operated at 650 °C. To gain insight about the transport properties under different conditions we systematically evaluate five configurations to decouple the roles of oxygen availability and humidity: (1) symmetric CO₂ + O₂ feeds on both sides, (2) a CO₂ gradient with O₂ on both sides, (3) CO₂ and O₂ supplied to opposite sides, (4) no oxygen on either side, and (5) steam as the sole oxygen source on one side. With applied biases of 0.3–1.3 V, bidirectional CO₂ transport is reversibly controlled by voltage polarity in cases 1–3, whereas no pumping occurs without oxygen (case 4), confirming the necessity of O₂-derived oxide for forming mobile carbonate ions. Using steam (case 5), the cell simultaneously pumps CO₂ and performs water splitting, producing H₂ on the humid side while transporting CO₃²⁻; reversing polarity exchanges electrode roles and introduces mixed CO₃²⁻/OH⁻ charge transport under moist conditions. CO₂ sensors and on-line micro-GC corroborate synchronized concentration/current responses. The membrane exhibits stable, mirror-symmetric current–voltage behavior over hours-long cycling and maintains durable operation for ∼1200 h under a sustained CO₂ gradient at 500 mV. These results establish a robust, electrically driven platform for high-temperature CO₂ separation, concentration, and co-generation of O₂ and H₂, and motivate further quantitative studies of rate, faradaic efficiency, and interfacial kinetics.
{"title":"Electrochemical pumping of CO2 and O2 using molten carbonate electrolytes","authors":"Wen Xing , Christelle Denonville , Rune Bredesen , Peter Veenstra , Arian Nijmeijer , Paul-Emmanuel Just , Marie-Laure Fontaine","doi":"10.1016/j.electacta.2026.148306","DOIUrl":"10.1016/j.electacta.2026.148306","url":null,"abstract":"<div><div>Electrochemical pumping of CO₂ across molten carbonate electrolytes is demonstrated using tape-cast LiAlO₂/NiO membrane–electrode assemblies operated at 650 °C. To gain insight about the transport properties under different conditions we systematically evaluate five configurations to decouple the roles of oxygen availability and humidity: (1) symmetric CO₂ + O₂ feeds on both sides, (2) a CO₂ gradient with O₂ on both sides, (3) CO₂ and O₂ supplied to opposite sides, (4) no oxygen on either side, and (5) steam as the sole oxygen source on one side. With applied biases of 0.3–1.3 V, bidirectional CO₂ transport is reversibly controlled by voltage polarity in cases 1–3, whereas no pumping occurs without oxygen (case 4), confirming the necessity of O₂-derived oxide for forming mobile carbonate ions. Using steam (case 5), the cell simultaneously pumps CO₂ and performs water splitting, producing H₂ on the humid side while transporting CO₃²⁻; reversing polarity exchanges electrode roles and introduces mixed CO₃²⁻/OH⁻ charge transport under moist conditions. CO₂ sensors and on-line micro-GC corroborate synchronized concentration/current responses. The membrane exhibits stable, mirror-symmetric current–voltage behavior over hours-long cycling and maintains durable operation for ∼1200 h under a sustained CO₂ gradient at 500 mV. These results establish a robust, electrically driven platform for high-temperature CO₂ separation, concentration, and co-generation of O₂ and H₂, and motivate further quantitative studies of rate, faradaic efficiency, and interfacial kinetics.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"553 ","pages":"Article 148306"},"PeriodicalIF":5.6,"publicationDate":"2026-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146048156","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 : 2026-01-24DOI: 10.1016/j.electacta.2026.148311
Zhenbiao Dong , Meng Chen , Miao Yu , Zhujunyan Liu , Bowen Zhang , Sheng Han
Suitable energy band alignment and hetero-interface design in Bi-based photoanodes is an effective way to address the poor hole transport and slow water oxidation kinetics. This work successfully fabricated a ternary BiVO4/CoFe2O4/CoAl-LDH photoanode with a continuous type-II heterostructure for highly efficient PEC water oxidation. Comprehensive physicochemical characterization and density functional theory (DFT) calculations demonstrated that CoFe2O4 acted as an effective HTL, owing to its abundance of active sites and p-n type built-in electric field, which greatly facilitated migration and separation of photogenerated charge carriers. Meanwhile, introduced CoAl-LDH with favorable hole-extraction ability and strong hydrophilicity, further facilitated oxygen evolution reaction (OER) kinetics. Continuous type-II heterojunction formed in the composite photoanode through quantitative analysis of energy band positions. Optimized hetero-interface enabled a notable enhancement in bulk-phase separation efficiency (85.61%) and solid-liquid injection efficiency (78.61%). In comparison with pristine system, ternary photoanode exhibited a remarkable photocurrent density of 4.53 mA cm-2 at 1.23 VRHE and an ABPE of 1.03% at 0.83 VRHE, representing enhancements of 3.54 and 4.68 times. This work highlighted potential of hetero-interfacial engineering involved in BiVO4/HTLs/OECs configuration, may provide beneficial guidance in rationally design of effective multicomponent photoanodes for solar-driven water splitting.
合适的能带对准和异质界面设计是解决铋基光阳极空穴输运差和水氧化动力学缓慢的有效途径。本文成功制备了具有连续ii型异质结构的BiVO4/CoFe2O4/CoAl-LDH三元光阳极，用于高效的PEC水氧化。综合物理化学表征和密度泛函理论（DFT）计算表明，CoFe2O4作为一种有效的HTL，由于其丰富的活性位点和p-n型内置电场，极大地促进了光生载流子的迁移和分离。同时，引入具有良好的孔提取能力和较强亲水性的煤- ldh，进一步促进析氧反应动力学。通过对复合光阳极能带位置的定量分析，形成了连续的ii型异质结。优化后的杂界面可显著提高料相分离效率（85.61%）和固液注射效率（78.61%）。与原始系统相比，三元光阳极在1.23 VRHE下的光电流密度为4.53 mA cm-2，在0.83 VRHE下的ABPE为1.03%，分别提高了3.54倍和4.68倍。本研究突出了BiVO4/HTLs/OECs结构的异质界面工程的潜力，为合理设计有效的多组分太阳能驱动水分解光阳极提供了有益的指导。
{"title":"Hetero-interface engineering of ternary BiVO4/CoFe2O4/CoAl-LDH photoanode with fast charge separation-transfer for boosted photoelectrochemical water splitting","authors":"Zhenbiao Dong , Meng Chen , Miao Yu , Zhujunyan Liu , Bowen Zhang , Sheng Han","doi":"10.1016/j.electacta.2026.148311","DOIUrl":"10.1016/j.electacta.2026.148311","url":null,"abstract":"<div><div>Suitable energy band alignment and hetero-interface design in Bi-based photoanodes is an effective way to address the poor hole transport and slow water oxidation kinetics. This work successfully fabricated a ternary BiVO<sub>4</sub>/CoFe<sub>2</sub>O<sub>4</sub>/CoAl-LDH photoanode with a continuous type-II heterostructure for highly efficient PEC water oxidation. Comprehensive physicochemical characterization and density functional theory (DFT) calculations demonstrated that CoFe<sub>2</sub>O<sub>4</sub> acted as an effective HTL, owing to its abundance of active sites and p-n type built-in electric field, which greatly facilitated migration and separation of photogenerated charge carriers. Meanwhile, introduced CoAl-LDH with favorable hole-extraction ability and strong hydrophilicity, further facilitated oxygen evolution reaction (OER) kinetics. Continuous type-II heterojunction formed in the composite photoanode through quantitative analysis of energy band positions. Optimized hetero-interface enabled a notable enhancement in bulk-phase separation efficiency (85.61%) and solid-liquid injection efficiency (78.61%). In comparison with pristine system, ternary photoanode exhibited a remarkable photocurrent density of 4.53 mA cm<sup>-2</sup> at 1.23 V<sub>RHE</sub> and an ABPE of 1.03% at 0.83 V<sub>RHE</sub>, representing enhancements of 3.54 and 4.68 times. This work highlighted potential of hetero-interfacial engineering involved in BiVO<sub>4</sub>/HTLs/OECs configuration, may provide beneficial guidance in rationally design of effective multicomponent photoanodes for solar-driven water splitting.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"553 ","pages":"Article 148311"},"PeriodicalIF":5.6,"publicationDate":"2026-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146048099","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 : 2026-01-24DOI: 10.1016/j.electacta.2026.148309
Lvliang Song , Jiaxin He , Yongjiang Wang , Yinlong Huang , Jiacheng Zhang , Tao Xiong , Lei Zhou , Lin Li , Dingyu Yang , Xumei Cui
O3-type layered oxides are promising cathode materials because of their high energy density and cost-effectiveness. Researchers often use doping strategies to improve their electrochemical performance. However, in actual synthesis, its overall performance is still limited by multiple variables other than doping concentration, and various influencing factors need to be comprehensively considered. In this work, an orthogonal experimental design was employed to efficiently minimize the number of experiments required for multivariable optimization. The structural stability of the NaNi0.4Fe0.2Mn0.4O2 cathode material (NFM424) was enhanced by in-situ doping with Ti during the solution combustion process. The synergistic effect of titanium improves the diffusion kinetics of sodium ions, reduces the interfacial polarization, and suppresses the Jahn–Teller distortion, thereby achieving a significant improvement in electrochemical performance. After optimizing the three factors of fuel, pH and Ti doping amount, the reversible capacity of the layered cathode NFMTB at 0.2 C is 165.67 mAhg−1, and the specific capacity at 10 C is still 90.15 mAhg−1. After 200 cycles at 2 C rate, the capacity retention rate is 80.53 %, which is higher than that of the undoped sample. This study is based on an effective modification strategy, which provides a certain supplement and reference for the study of sodium ion cathode material modification.
{"title":"Optimization of the synthesis and modification process of NaNi0.4Fe0.2Mn0.4O2 cathode via orthogonal experiments for enhanced electrochemical performance","authors":"Lvliang Song , Jiaxin He , Yongjiang Wang , Yinlong Huang , Jiacheng Zhang , Tao Xiong , Lei Zhou , Lin Li , Dingyu Yang , Xumei Cui","doi":"10.1016/j.electacta.2026.148309","DOIUrl":"10.1016/j.electacta.2026.148309","url":null,"abstract":"<div><div>O3-type layered oxides are promising cathode materials because of their high energy density and cost-effectiveness. Researchers often use doping strategies to improve their electrochemical performance. However, in actual synthesis, its overall performance is still limited by multiple variables other than doping concentration, and various influencing factors need to be comprehensively considered. In this work, an orthogonal experimental design was employed to efficiently minimize the number of experiments required for multivariable optimization. The structural stability of the NaNi<sub>0.4</sub>Fe<sub>0.2</sub>Mn<sub>0.4</sub>O<sub>2</sub> cathode material (NFM424) was enhanced by in-situ doping with Ti during the solution combustion process. The synergistic effect of titanium improves the diffusion kinetics of sodium ions, reduces the interfacial polarization, and suppresses the Jahn–Teller distortion, thereby achieving a significant improvement in electrochemical performance. After optimizing the three factors of fuel, pH and Ti doping amount, the reversible capacity of the layered cathode NFMTB at 0.2 C is 165.67 mAhg<sup>−1</sup>, and the specific capacity at 10 C is still 90.15 mAhg<sup>−1</sup>. After 200 cycles at 2 C rate, the capacity retention rate is 80.53 %, which is higher than that of the undoped sample. This study is based on an effective modification strategy, which provides a certain supplement and reference for the study of sodium ion cathode material modification.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"553 ","pages":"Article 148309"},"PeriodicalIF":5.6,"publicationDate":"2026-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146048153","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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