Pub Date : 2026-04-10Epub Date: 2026-02-05DOI: 10.1016/j.electacta.2026.148392
Xinping Wang , Hongchao Wang , Qing Xiao , Lipeng Guo , Liangjun Hong , Zhefei Zhao , Huajun Zheng
Photoelectrochemical (PEC) glyoxal oxidation to highly valuable glyoxylic acid is a promising avenue for alleviating the strict reaction conditions and environmental pollution caused by the current chemical method. However, constructing efficient photoanode to achieve production of glyoxylic acid with high selectivity remains a challenge. In this study, the uniformly grown WO3 nanoplates array with oxygen vacancies (WO3-x) was synthesized via the defect engineering strategy. The experiment results illustrate that, compared with pure WO3 (120.43 mmol m−2 h−1), the optimal WO3-x catalyst (WO3-x-20) shows improved production rate of glyoxylic acid of 253.93 mmol m−2 h−1 at 1.4 V vs. RHE with excellent selectivity (83.4 %) and faradaic efficiency (86.1 %) of glyoxylic acid. This superior performance of WO3-x-20 can be attributed to expanding the range of light absorption, promote the separation and transmission of photogenerated charges, and enhance charge lifetime caused by the adjusted electronic structure on the surface. Moreover, theoretical calculation confirms the important role of oxygen vacancies for enhancing adsorption of glyoxal and decreasing the free energy of desorption of glyoxylic acid, thus facilitating the surface reaction kinetics. This work provides an efficient strategy for improvement of PEC glyoxal oxidation property.
{"title":"Defect engineering of WO3 for selective photoelectrochemical glyoxal oxidation to glyoxylic acid","authors":"Xinping Wang , Hongchao Wang , Qing Xiao , Lipeng Guo , Liangjun Hong , Zhefei Zhao , Huajun Zheng","doi":"10.1016/j.electacta.2026.148392","DOIUrl":"10.1016/j.electacta.2026.148392","url":null,"abstract":"<div><div>Photoelectrochemical (PEC) glyoxal oxidation to highly valuable glyoxylic acid is a promising avenue for alleviating the strict reaction conditions and environmental pollution caused by the current chemical method. However, constructing efficient photoanode to achieve production of glyoxylic acid with high selectivity remains a challenge. In this study, the uniformly grown WO<sub>3</sub> nanoplates array with oxygen vacancies (WO<sub>3-x</sub>) was synthesized via the defect engineering strategy. The experiment results illustrate that, compared with pure WO<sub>3</sub> (120.43 mmol m<sup>−2</sup> h<sup>−1</sup>), the optimal WO<sub>3-x</sub> catalyst (WO<sub>3-x</sub>-20) shows improved production rate of glyoxylic acid of 253.93 mmol m<sup>−2</sup> h<sup>−1</sup> at 1.4 V vs. RHE with excellent selectivity (83.4 %) and faradaic efficiency (86.1 %) of glyoxylic acid. This superior performance of WO<sub>3-x</sub>-20 can be attributed to expanding the range of light absorption, promote the separation and transmission of photogenerated charges, and enhance charge lifetime caused by the adjusted electronic structure on the surface. Moreover, theoretical calculation confirms the important role of oxygen vacancies for enhancing adsorption of glyoxal and decreasing the free energy of desorption of glyoxylic acid, thus facilitating the surface reaction kinetics. This work provides an efficient strategy for improvement of PEC glyoxal oxidation property.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"555 ","pages":"Article 148392"},"PeriodicalIF":5.6,"publicationDate":"2026-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135112","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: 2026-02-02DOI: 10.1016/j.electacta.2026.148355
Ahmet Cetinkaya , Ensar Piskin , Leena Regi Saleth , M. Altay Unal , Acelya Yılmazer , Esen Bellur Atici , Sanjiv Dhingra , Sibel A. Ozkan
Vericiguat (VER) is an innovative orally administered pharmacological agent that directly activates the enzyme soluble guanylate cyclase (sGC). This compound was developed for the treatment of individuals with symptomatic chronic heart failure and is prescribed to reduce mortality, minimize heart failure-related hospitalizations, and reduce the need for outpatient intravenous (IV) diuretics. This study aimed to develop a nanomaterial-supported, porous, and functional sensor interface using molecular imprinting to enable selective, sensitive, and reliable detection of the VER. For this purpose, the sensor platform was synthesized on the surface of a glassy carbon electrode (GCE) via photopolymerization, with the target analyte VER as a template molecule and 3-aminophenyl boronic acid (3-APBA) as a functional monomer. The photopolymerization (PP) process enabled the formation of a three-dimensional polymer matrix with selective recognition sites, thereby creating cavities tailored to the unique chemical and structural properties of the VER molecule. Titanium carbide MXene quantum dots (Ti₃C₂ MQDS) integrated onto the electrode surface also increased the electroactive surface area of the sensor, facilitating electron transfer and significantly improving overall sensor performance (sensitivity, selectivity, and stability). The surface of the developed VER/3-APBA@Ti₃C₂ MQDS/MIP-GCE sensor was characterized using a scanning electron microscope (SEM), and its electrochemical properties were evaluated using cyclic voltammetry (CV) and impedance spectroscopy (EIS). These measurements were carried out indirectly in a 5.0 mM [Fe(CN)6]3–/4– solution. For both standard and commercial serum samples, the computed limits of detection (LODs) were 4.38 × 10−13 M and 4.67 × 10−14 M, respectively. The recovery values for the MIP-based sensors ranged from 99.43% to 101.22% for commercial serum samples. The sensor's selectivity for VER was validated by the relative k' values obtained from the imprinting factor (k) analysis of a few drugs that are structurally similar to VER. Computations using density functional theory were employed to gain a deeper understanding of the interactions between the template and the functional monomer. Moreover, the greenness metric of the developed sensor, calculated using green chemistry approaches, was achieved through a production method that utilizes environmentally friendly solvents, requires low energy, and minimizes waste generation.
{"title":"Next-generation electrochemical sensing of vericiguat at ultra-trace levels using mxene-supported molecularly imprinted polymer nanohybrid platform","authors":"Ahmet Cetinkaya , Ensar Piskin , Leena Regi Saleth , M. Altay Unal , Acelya Yılmazer , Esen Bellur Atici , Sanjiv Dhingra , Sibel A. Ozkan","doi":"10.1016/j.electacta.2026.148355","DOIUrl":"10.1016/j.electacta.2026.148355","url":null,"abstract":"<div><div>Vericiguat (VER) is an innovative orally administered pharmacological agent that directly activates the enzyme soluble guanylate cyclase (sGC). This compound was developed for the treatment of individuals with symptomatic chronic heart failure and is prescribed to reduce mortality, minimize heart failure-related hospitalizations, and reduce the need for outpatient intravenous (IV) diuretics. This study aimed to develop a nanomaterial-supported, porous, and functional sensor interface using molecular imprinting to enable selective, sensitive, and reliable detection of the VER. For this purpose, the sensor platform was synthesized on the surface of a glassy carbon electrode (GCE) via photopolymerization, with the target analyte VER as a template molecule and 3-aminophenyl boronic acid (3-APBA) as a functional monomer. The photopolymerization (PP) process enabled the formation of a three-dimensional polymer matrix with selective recognition sites, thereby creating cavities tailored to the unique chemical and structural properties of the VER molecule. Titanium carbide MXene quantum dots (Ti₃C₂ MQDS) integrated onto the electrode surface also increased the electroactive surface area of the sensor, facilitating electron transfer and significantly improving overall sensor performance (sensitivity, selectivity, and stability). The surface of the developed VER/3-APBA@Ti₃C₂ MQDS/MIP-GCE sensor was characterized using a scanning electron microscope (SEM), and its electrochemical properties were evaluated using cyclic voltammetry (CV) and impedance spectroscopy (EIS). These measurements were carried out indirectly in a 5.0 mM [Fe(CN)<sub>6</sub>]<sup>3–/4–</sup> solution. For both standard and commercial serum samples, the computed limits of detection (LODs) were 4.38 × 10<sup>−13</sup> M and 4.67 × 10<sup>−14</sup> M, respectively. The recovery values for the MIP-based sensors ranged from 99.43% to 101.22% for commercial serum samples. The sensor's selectivity for VER was validated by the relative k' values obtained from the imprinting factor (k) analysis of a few drugs that are structurally similar to VER. Computations using density functional theory were employed to gain a deeper understanding of the interactions between the template and the functional monomer. Moreover, the greenness metric of the developed sensor, calculated using green chemistry approaches, was achieved through a production method that utilizes environmentally friendly solvents, requires low energy, and minimizes waste generation.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"555 ","pages":"Article 148355"},"PeriodicalIF":5.6,"publicationDate":"2026-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101899","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: 2026-02-03DOI: 10.1016/j.electacta.2026.148374
Haiyan Wang , Dan Li , Weiwei Yu , Yu Liu , Jiajun Zhu , Wenxi Chen , Qianku Hu , Aiguo Zhou , Xusheng Li
Two-dimensional transition metal borides (MBenes) have garnered great attention in electrochemical energy storage, thanks to their unique layered structure, exceptional stability, high Young’s modulus, superior conductivity and prominent surface activity. Group VB elements V and Ta, with analogous electronic configurations and stable multivalence, yield superconducting compounds. Experimentally synthesized 2D materials suffer from functional groups and restacking, impairing conductivity and cyclability. Although O/S-modified MXenes are promising high-performance LIB electrodes, it remains unclear whether functionalized MBenes can similarly boost electrochemical performance. This work demonstrates that VBT and TaBT (T=bare, O, S, Se) exhibit excellent kinetic/thermodynamic stability and conductivity as electrodes. Based on the most stable Li adsorption sites, the Li-ion diffusion energy barriers are found to follow the order: VB (0.017 eV) < VBO (0.17 eV) < VBSe (0.21 eV) < VBS (0.23 eV); TaB (0.049 eV) < TaBO (0.21 eV) < TaBSe (0.25 eV) < TaBS (0.27 eV). With the progressive increase in the concentration of Li adsorbed on VBT and TaBT monolayers, the introduction of S and Se functional groups results in a negative open circuit voltage (OCV) during the adsorption process. In contrast, the introduction of O functional groups retains the maximum Li adsorption capacity, although the lithium storage capacity (345 mAh/g for VBO and 129 mAh/g for TaBO) is slightly lower than that of bare VB and TaB. Notably, the incorporation of the O functional group serves to modulate the voltage, thereby increasing the average OCV of VB from 0.72 V to 1.55 V, while decreasing the average OCV of TaB from 0.66 V to 0.62 V. This research offers novel insights into the exploration of suitable surface functional groups to improve the performance of anode materials in ion batteries.
{"title":"Theoretical investigation of VBT and TaBT (T=bare, O, S and Se) as electrode materials for Li-ion batteries","authors":"Haiyan Wang , Dan Li , Weiwei Yu , Yu Liu , Jiajun Zhu , Wenxi Chen , Qianku Hu , Aiguo Zhou , Xusheng Li","doi":"10.1016/j.electacta.2026.148374","DOIUrl":"10.1016/j.electacta.2026.148374","url":null,"abstract":"<div><div>Two-dimensional transition metal borides (MBenes) have garnered great attention in electrochemical energy storage, thanks to their unique layered structure, exceptional stability, high Young’s modulus, superior conductivity and prominent surface activity. Group VB elements V and Ta, with analogous electronic configurations and stable multivalence, yield superconducting compounds. Experimentally synthesized 2D materials suffer from functional groups and restacking, impairing conductivity and cyclability. Although O/S-modified MXenes are promising high-performance LIB electrodes, it remains unclear whether functionalized MBenes can similarly boost electrochemical performance. This work demonstrates that VBT and TaBT (<em>T</em>=bare, O, S, Se) exhibit excellent kinetic/thermodynamic stability and conductivity as electrodes. Based on the most stable Li adsorption sites, the Li-ion diffusion energy barriers are found to follow the order: VB (0.017 eV) < VBO (0.17 eV) < VBSe (0.21 eV) < VBS (0.23 eV); TaB (0.049 eV) < TaBO (0.21 eV) < TaBSe (0.25 eV) < TaBS (0.27 eV). With the progressive increase in the concentration of Li adsorbed on VBT and TaBT monolayers, the introduction of S and Se functional groups results in a negative open circuit voltage (OCV) during the adsorption process. In contrast, the introduction of O functional groups retains the maximum Li adsorption capacity, although the lithium storage capacity (345 mAh/g for VBO and 129 mAh/g for TaBO) is slightly lower than that of bare VB and TaB. Notably, the incorporation of the O functional group serves to modulate the voltage, thereby increasing the average OCV of VB from 0.72 V to 1.55 V, while decreasing the average OCV of TaB from 0.66 V to 0.62 V. This research offers novel insights into the exploration of suitable surface functional groups to improve the performance of anode materials in ion batteries.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"555 ","pages":"Article 148374"},"PeriodicalIF":5.6,"publicationDate":"2026-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101898","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}
All-solid-state batteries (ASSBs) have emerged as a key focus in next-generation energy storage technologies due to their high energy density, high power density, and superior safety performance. However, the significant volume expansion of Si-based anodes during charging and discharging severely restricts their commercial application, and the internal electrochemical-mechanical coupling mechanisms remain poorly understood. This study develops a multiphysics coupling model for Si-based ASSBs based on a three-dimensional heterogeneous electrode structure, integrating electrochemical kinetics, lithium-ion diffusion, and mechanical deformation. The electrode microstructure is reconstructed using X-ray tomography data, and simulated voltage profiles during charge and discharge are validated against experimental results. Results reveal that lithium-ion concentration, strain, and stress distribute nonuniformly within the electrode. The effects of C-rates and solid electrolyte conductivity on battery performance are systematically investigated. High C-rates and low electrolyte conductivity exacerbate concentration gradients and mechanical stress within the electrode, resulting in capacity decay and an increased risk of mechanical failure. This study provides a theoretical foundation and simulation framework for the design of reliable and robust Si-based ASSBs.
{"title":"Three-dimensional electrochemical-mechanical coupled modeling and performance evaluation of Si-based all-solid-state batteries with heterogeneous structure","authors":"Jing Wu, Yihan Liu, Xiaotong Wang, Wenjing Zhang, Chunhao Yuan","doi":"10.1016/j.electacta.2026.148380","DOIUrl":"10.1016/j.electacta.2026.148380","url":null,"abstract":"<div><div>All-solid-state batteries (ASSBs) have emerged as a key focus in next-generation energy storage technologies due to their high energy density, high power density, and superior safety performance. However, the significant volume expansion of Si-based anodes during charging and discharging severely restricts their commercial application, and the internal electrochemical-mechanical coupling mechanisms remain poorly understood. This study develops a multiphysics coupling model for Si-based ASSBs based on a three-dimensional heterogeneous electrode structure, integrating electrochemical kinetics, lithium-ion diffusion, and mechanical deformation. The electrode microstructure is reconstructed using X-ray tomography data, and simulated voltage profiles during charge and discharge are validated against experimental results. Results reveal that lithium-ion concentration, strain, and stress distribute nonuniformly within the electrode. The effects of C-rates and solid electrolyte conductivity on battery performance are systematically investigated. High C-rates and low electrolyte conductivity exacerbate concentration gradients and mechanical stress within the electrode, resulting in capacity decay and an increased risk of mechanical failure. This study provides a theoretical foundation and simulation framework for the design of reliable and robust Si-based ASSBs.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"555 ","pages":"Article 148380"},"PeriodicalIF":5.6,"publicationDate":"2026-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135491","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: 2026-01-31DOI: 10.1016/j.electacta.2026.148348
Filipe C.D.A. Lima , Frank N. Crespilho
Electron transport in proteins has traditionally been described within Marcus theory, where localized hopping events between redox centers are modulated by nuclear reorganization. Recent advances in scanning tunneling microscopy (STM) and single-protein junction measurements, however, reveal measurable conductance values and resonant tunneling features that suggest delocalized quantum contributions. In this work, we present a unified theoretical model that combines Landauer transmission with Marcus heterogeneous kinetics to rationalize enzymatic electron transport. Within the Landauer–Büttiker formalism, STM conductance maps provide access to local transmission probabilities and electrode–protein couplings, which can be recast into effective electronic coupling parameters. These couplings, when introduced into Marcus theory, yield spatially resolved heterogeneous rate constants (), bridging quantum conductance channels with classical ET kinetics. We illustrate this connection with model calculations, including Breit–Wigner transmission functions, Marcus parabolas across conductance ranges of 1–100 nS, and simulated STM conductance maps for enzymes with multiple hotspots. The results demonstrate that nanoscale conductance variations translate into orders-of-magnitude differences in , emphasizing the dual roles of electronic coupling and reorganization energy in shaping enzymatic ET landscapes. The Landauer–Marcus approach establishes a rigorous methodology for connecting experimental conductance measurements with kinetic predictions, offering a general route for interpreting and designing enzyme-based electron transport systems.
{"title":"Protein local conductance in quantum bioelectrochemistry via Landauer–Marcus kinetics","authors":"Filipe C.D.A. Lima , Frank N. Crespilho","doi":"10.1016/j.electacta.2026.148348","DOIUrl":"10.1016/j.electacta.2026.148348","url":null,"abstract":"<div><div>Electron transport in proteins has traditionally been described within Marcus theory, where localized hopping events between redox centers are modulated by nuclear reorganization. Recent advances in scanning tunneling microscopy (STM) and single-protein junction measurements, however, reveal measurable conductance values and resonant tunneling features that suggest delocalized quantum contributions. In this work, we present a unified theoretical model that combines Landauer transmission with Marcus heterogeneous kinetics to rationalize enzymatic electron transport. Within the Landauer–Büttiker formalism, STM conductance maps provide access to local transmission probabilities and electrode–protein couplings, which can be recast into effective electronic coupling parameters. These couplings, when introduced into Marcus theory, yield spatially resolved heterogeneous rate constants (<span><math><msub><mi>k</mi><mtext>het</mtext></msub></math></span>), bridging quantum conductance channels with classical ET kinetics. We illustrate this connection with model calculations, including Breit–Wigner transmission functions, Marcus parabolas across conductance ranges of 1–100 nS, and simulated STM conductance maps for enzymes with multiple hotspots. The results demonstrate that nanoscale conductance variations translate into orders-of-magnitude differences in <span><math><msub><mi>k</mi><mtext>het</mtext></msub></math></span>, emphasizing the dual roles of electronic coupling and reorganization energy in shaping enzymatic ET landscapes. The Landauer–Marcus approach establishes a rigorous methodology for connecting experimental conductance measurements with kinetic predictions, offering a general route for interpreting and designing enzyme-based electron transport systems.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"555 ","pages":"Article 148348"},"PeriodicalIF":5.6,"publicationDate":"2026-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146095522","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: 2026-02-07DOI: 10.1016/j.electacta.2026.148403
Qiao Wan , Yajun Li , Yahong Su , Wenqing Jia , Jiang Zhu , Qiang Yu , Zhen Chen , Lingli Lei , Yuanyuan Zhang
This study aims to develop a high-performance, low-cost non-enzymatic electrochemical sensing materials for glucose detection, addressing the limitations of existing technologies. A three-dimensional porous hierarchical layered-nanoflower heterostructured CuCoP/MXene composite was synthesized through in situ growth of CuCo-MOF nanoflowers on Ti3C2−MXene via a one-step hydrothermal method, followed by oxidation and phosphidation treatments. This unique architecture significantly increases the specific reactive surface area, exposes abundant active sites, and provides sufficient interfacial regions for glucose oxidation. The synergistic effect between copper (Cu) and cobalt (Co) further enhances the electrocatalytic performance. Meanwhile, MXene serves as a conductive scaffold that not only facilitates electron transfer but also promotes the diffusion and adsorption of glucose molecules, owing to its excellent conductivity and continuous interlayer channels. The fabricated sensor exhibits an extensive linear detection range (0.5–6000 μM), high sensitivity (1408.49 μA mM-1·cm-2), a low detection limit (0.14 μM, S/N = 3), along with excellent selectivity, reproducibility, and stability, together with a swift response time (3 s). Moreover, the sensor has been successfully applied to the accurate detection of glucosein samples of serum, showing high reliability and promising practical value.
{"title":"3D porous layered CuCoP/MXene nanoflowers via MXene-assisted in situ growth for non-enzymatic glucose biosensing","authors":"Qiao Wan , Yajun Li , Yahong Su , Wenqing Jia , Jiang Zhu , Qiang Yu , Zhen Chen , Lingli Lei , Yuanyuan Zhang","doi":"10.1016/j.electacta.2026.148403","DOIUrl":"10.1016/j.electacta.2026.148403","url":null,"abstract":"<div><div>This study aims to develop a high-performance, low-cost non-enzymatic electrochemical sensing materials for glucose detection, addressing the limitations of existing technologies. A three-dimensional porous hierarchical layered-nanoflower heterostructured CuCoP/MXene composite was synthesized through <em>in situ</em> growth of CuCo-MOF nanoflowers on Ti<sub>3</sub>C<sub>2</sub>−MXene <em>via</em> a one-step hydrothermal method, followed by oxidation and phosphidation treatments. This unique architecture significantly increases the specific reactive surface area, exposes abundant active sites, and provides sufficient interfacial regions for glucose oxidation. The synergistic effect between copper (Cu) and cobalt (Co) further enhances the electrocatalytic performance. Meanwhile, MXene serves as a conductive scaffold that not only facilitates electron transfer but also promotes the diffusion and adsorption of glucose molecules, owing to its excellent conductivity and continuous interlayer channels. The fabricated sensor exhibits an extensive linear detection range (0.5–6000 μM), high sensitivity (1408.49 μA mM<sup>-1</sup>·cm<sup>-2</sup>), a low detection limit (0.14 μM, S/<em>N</em> = 3), along with excellent selectivity, reproducibility, and stability, together with a swift response time (3 s). Moreover, the sensor has been successfully applied to the accurate detection of glucosein samples of serum, showing high reliability and promising practical value.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"555 ","pages":"Article 148403"},"PeriodicalIF":5.6,"publicationDate":"2026-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135095","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-04-10Epub Date: 2026-02-02DOI: 10.1016/j.electacta.2026.148359
Nina Plankensteiner , Anupam Ruturaj Tripathy , Tibor Kuna , Philippe M. Vereecken
The electrochemical reduction of CO2 to hydrocarbons offers a promising solution to transform greenhouse emissions into valuable chemicals. Copper is a promising catalyst, but the electrocatalytic formation of C2+ products requires simultaneous adsorption of various intermediates and charge transfer steps for C-C bond formation. As such, a large portion of the surface is constantly occupied by multiple species and the supply of fresh reaction intermediates becomes a limitation. Therefore, a strategy for CO2R on Cu is adding a second catalyst in close proximity that supplies specific reaction intermediates to the Cu sites where they are converted to higher hydrocarbons. Ag is especially opportune as a co-catalyst, since it has a high selectivity to form CO, a key reaction intermediate in the pathway to C2+ products. In this work the synergistic electrocatalytic behavior of Ag with Cu is investigated using regularly nanopatterned Ag lines as co-catalyst on planar Cu electrodes. UV nano-imprint lithography allowed to systematically vary pattern dimensions, distance between Ag and Cu as well as the Ag-Cu contact points, while keeping the total Ag:Cu area constant at ∼50:50%. With decreasing distance between two Ag lines from 400 to 200nm and doubling Ag-Cu contact interface, the synergistic effect between Ag and Cu was shown by an increased product selectivity to C2H4. Larger Ag line distance resulted in increased CH4 and H2 formation. This work shows how nanopatterning can guide fundamental investigations leading to the deterministic design of electrodes with two (or more) catalysts for CO2 electroreduction with tailored product selectivity.
{"title":"Deterministically designed regular Ag nanopatterns as co-catalysts on Cu to elucidate the role of Ag-Cu contact interface in electrocatalytic CO2 reduction reaction","authors":"Nina Plankensteiner , Anupam Ruturaj Tripathy , Tibor Kuna , Philippe M. Vereecken","doi":"10.1016/j.electacta.2026.148359","DOIUrl":"10.1016/j.electacta.2026.148359","url":null,"abstract":"<div><div>The electrochemical reduction of CO<sub>2</sub> to hydrocarbons offers a promising solution to transform greenhouse emissions into valuable chemicals. Copper is a promising catalyst, but the electrocatalytic formation of C<sub>2+</sub> products requires simultaneous adsorption of various intermediates and charge transfer steps for C-C bond formation. As such, a large portion of the surface is constantly occupied by multiple species and the supply of fresh reaction intermediates becomes a limitation. Therefore, a strategy for CO<sub>2</sub>R on Cu is adding a second catalyst in close proximity that supplies specific reaction intermediates to the Cu sites where they are converted to higher hydrocarbons. Ag is especially opportune as a co-catalyst, since it has a high selectivity to form CO, a key reaction intermediate in the pathway to C<sub>2+</sub> products. In this work the synergistic electrocatalytic behavior of Ag with Cu is investigated using regularly nanopatterned Ag lines as co-catalyst on planar Cu electrodes. UV nano-imprint lithography allowed to systematically vary pattern dimensions, distance between Ag and Cu as well as the Ag-Cu contact points, while keeping the total Ag:Cu area constant at ∼50:50%. With decreasing distance between two Ag lines from 400 to 200nm and doubling Ag-Cu contact interface, the synergistic effect between Ag and Cu was shown by an increased product selectivity to C<sub>2</sub>H<sub>4</sub>. Larger Ag line distance resulted in increased CH<sub>4</sub> and H<sub>2</sub> formation. This work shows how nanopatterning can guide fundamental investigations leading to the deterministic design of electrodes with two (or more) catalysts for CO<sub>2</sub> electroreduction with tailored product selectivity.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"555 ","pages":"Article 148359"},"PeriodicalIF":5.6,"publicationDate":"2026-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146109844","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 : 2026-04-01Epub Date: 2026-01-27DOI: 10.1016/j.electacta.2026.148322
Jinxu Song , Jiangwen Xu , Haotian Li , Hui Song , Hongyi Li , Jinshu Wang
The corrosion protection performance differences between TiO2 nanotubes of varying diameters combined with the same corrosion inhibitor were investigated. TiO2 nanotube arrays with distinct diameters were grown in-situ on a titanium substrate by adjusting the anodic oxidation voltage. Subsequently, a stearic acid composite coating was formed on the array surface via a chemical bath process. The electrochemical corrosion resistance, fouling resistance, and self-healing behavior of this superhydrophobic composite coating were comprehensively evaluated in both air and solution environments. In-situ monitoring of surface corrosion evolution at different interfaces in 7 days was performed using scanning vibrating electrode technology. Results indicate that, under identical corrosion inhibitor loading, the coating's corrosion protection performance is significantly influenced by TiO2 nanotube diameter. Furthermore, the nanotube array exhibits the capacity to store stearic acid, which is released upon coating damage, conferring self-healing properties to the interface in both air and solution environments. This study provides novel insights for the design of corrosion inhibitor carrier structures and self-healing anti-corrosion coatings.
{"title":"Self-healing behavior of TiO2 nanotube array-stearic acid composite coatings in 0.6M NaCl solution environment","authors":"Jinxu Song , Jiangwen Xu , Haotian Li , Hui Song , Hongyi Li , Jinshu Wang","doi":"10.1016/j.electacta.2026.148322","DOIUrl":"10.1016/j.electacta.2026.148322","url":null,"abstract":"<div><div>The corrosion protection performance differences between TiO<sub>2</sub> nanotubes of varying diameters combined with the same corrosion inhibitor were investigated. TiO<sub>2</sub> nanotube arrays with distinct diameters were grown in-situ on a titanium substrate by adjusting the anodic oxidation voltage. Subsequently, a stearic acid composite coating was formed on the array surface via a chemical bath process. The electrochemical corrosion resistance, fouling resistance, and self-healing behavior of this superhydrophobic composite coating were comprehensively evaluated in both air and solution environments. In-situ monitoring of surface corrosion evolution at different interfaces in 7 days was performed using scanning vibrating electrode technology. Results indicate that, under identical corrosion inhibitor loading, the coating's corrosion protection performance is significantly influenced by TiO<sub>2</sub> nanotube diameter. Furthermore, the nanotube array exhibits the capacity to store stearic acid, which is released upon coating damage, conferring self-healing properties to the interface in both air and solution environments. This study provides novel insights for the design of corrosion inhibitor carrier structures and self-healing anti-corrosion coatings.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"554 ","pages":"Article 148322"},"PeriodicalIF":5.6,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070511","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 : 2026-04-01Epub Date: 2026-01-27DOI: 10.1016/j.electacta.2026.148321
Xuchun Li , Hongjie Zhang , Yingying Lei , Kai Fu , Yu Zhou , Shu-Biao Xia , Panpan Zhang , Mingru Su , Yunjian Liu
Niobium-based Wadsley–Roth (ReO3-type shear) oxides are promising intercalation anodes for fast-charging and safe lithium-ion batteries owing to their open frameworks and relatively high operating potentials; however, their practical use is still hindered by limited electron/ion transport and insufficient reversible capacity. Herein, we synthesize In3+-doped In0.5Nb24.5O62 via a solvothermal–calcination route and demonstrate that In3+ doping triggers a defect-rich ReO3-type shear structure with expanded lattice parameters and abundant cation-vacancy/defect features. Such a structural modulation widens Li+ migration channels and creates additional electrochemically active sites, thereby accelerating charge transport and Li+ diffusion kinetics. Importantly, we systematically correlate calcination temperature and duration with phase evolution, defect/crystallite development, and rate/cycling behavior, identifying 1000°C for 6 h as an optimal condition that balances moderate crystallinity and high defect density for fast yet stable lithiation/delithiation. As a result, the optimized anode delivers a high initial charge capacity of 359.24 mAh g-1 at 0.1 C, retains 157.33 mAh g-1 at 20 C, and maintains 210.49 mAh g-1after 500 cycles at 10 C with a capacity retention of 97.5 %. Density functional theory further reveals that In3+ doping reduces the band gap and decreases Li adsorption/formation energies, while providing more favorable adsorption sites and additional diffusion pathways with reduced barriers, rationalizing the enhanced fast-charging performance. This work highlights a general strategy of dopant-induced defect shear engineering combined with precise thermal-treatment control for designing high-rate and long-life niobium-based intercalation anodes.
铌基Wadsley-Roth （reo3型剪切）氧化物由于其开放的结构和相对较高的工作电位，是快速充电和安全锂离子电池的有前途的插层阳极；然而，它们的实际应用仍然受到有限的电子/离子传输和不充分的可逆容量的阻碍。本文采用溶剂热煅烧的方法合成了In3+掺杂的In0.5Nb24.5O62，并证明了In3+掺杂引发了一个富含缺陷的reo3型剪切结构，具有扩展的晶格参数和丰富的阳离子空位/缺陷特征。这种结构调制拓宽了Li+迁移通道，创造了额外的电化学活性位点，从而加速了电荷传输和Li+扩散动力学。重要的是，我们系统地将煅烧温度和持续时间与相演变，缺陷/晶体发育和速率/循环行为联系起来，确定1000°C 6小时是平衡中等结晶度和高缺陷密度的最佳条件，以实现快速而稳定的锂化/去硫化。结果表明，优化后的阳极在0.1℃时的初始充电容量为359.24 mAh g-1，在20℃时保持157.33 mAh g-1，在10℃下循环500次后保持210.49 mAh g-1，容量保持率为97.5%。密度泛函理论进一步揭示了In3+的掺杂减小了带隙，降低了Li的吸附/形成能，同时提供了更多有利的吸附位点和附加的具有更低障碍的扩散途径，使快速充电性能的增强合理化。这项工作强调了掺杂诱导缺陷剪切工程与精确热处理控制相结合的一般策略，以设计高速率和长寿命的铌基插入阳极。
{"title":"Calcination-regulated defective shear ReO3-type In0.5Nb24.5O62 anodes enabling ultrafast and durable lithium storage","authors":"Xuchun Li , Hongjie Zhang , Yingying Lei , Kai Fu , Yu Zhou , Shu-Biao Xia , Panpan Zhang , Mingru Su , Yunjian Liu","doi":"10.1016/j.electacta.2026.148321","DOIUrl":"10.1016/j.electacta.2026.148321","url":null,"abstract":"<div><div>Niobium-based Wadsley–Roth (ReO<sub>3</sub>-type shear) oxides are promising intercalation anodes for fast-charging and safe lithium-ion batteries owing to their open frameworks and relatively high operating potentials; however, their practical use is still hindered by limited electron/ion transport and insufficient reversible capacity. Herein, we synthesize In<sup>3+</sup>-doped In<sub>0.5</sub>Nb<sub>24.5</sub>O<sub>62</sub> via a solvothermal–calcination route and demonstrate that In<sup>3+</sup> doping triggers a defect-rich ReO<sub>3</sub>-type shear structure with expanded lattice parameters and abundant cation-vacancy/defect features. Such a structural modulation widens Li<sup>+</sup> migration channels and creates additional electrochemically active sites, thereby accelerating charge transport and Li<sup>+</sup> diffusion kinetics. Importantly, we systematically correlate calcination temperature and duration with phase evolution, defect/crystallite development, and rate/cycling behavior, identifying 1000°C for 6 h as an optimal condition that balances moderate crystallinity and high defect density for fast yet stable lithiation/delithiation. As a result, the optimized anode delivers a high initial charge capacity of 359.24 mAh g<sup>-1</sup> at 0.1 C, retains 157.33 mAh g<sup>-1</sup> at 20 C, and maintains 210.49 mAh g<sup>-1</sup>after 500 cycles at 10 C with a capacity retention of 97.5 %. Density functional theory further reveals that In<sup>3+</sup> doping reduces the band gap and decreases Li adsorption/formation energies, while providing more favorable adsorption sites and additional diffusion pathways with reduced barriers, rationalizing the enhanced fast-charging performance. This work highlights a general strategy of dopant-induced defect shear engineering combined with precise thermal-treatment control for designing high-rate and long-life niobium-based intercalation anodes.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"554 ","pages":"Article 148321"},"PeriodicalIF":5.6,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146071050","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}
Aqueous zinc-ion batteries (AZIBs) have arisen as competitive prospects for grid-scale energy storage applications, primarily driven by their natural security advantages, economic viability, and ecological sustainability. Nevertheless, practical deployment of AZIBs faces severe constraints due to anode instability, manifested through uncontrolled dendritic growth, hydrogen evolution reaction (HER), and corrosive side reactions. This work introduces maleamic acid (MAA) as a zwitterionic electrolyte additive that concurrently regulates Zn2+ solvation chemistry and anode-electrolyte interface. The anionic COO− moiety displaces water molecules in the primary solvation sheath via Zn2+ coordination, effectively mitigating HER and corrosion. Simultaneously, the cationic NH3+ group forms an electrochemically adaptive interfacial layer through selective anode adsorption, which blocks aqueous species while enabling homogeneous Zn2+ nucleation to suppress dendrites. Such multifunctional modulation facilitates dendrite-free Zn plating, endowing Zn||Zn symmetric cells with exceptional cyclability exceeding 5000 h at 1 mA cm−2. When integrated into Zn||NaV3O8·1·5H2O full cells, the MAA-modified electrolyte delivers 89.1% capacity retention after 2000 cycles at 2 A g−1, with performance robustness further verified in flexible pouch cells. Our findings highlight molecular engineering of multifunctional additives as a pivotal strategy for advancing zinc-based energy storage technologies.
由于其天然安全优势、经济可行性和生态可持续性，水性锌离子电池（azib）已成为电网规模储能应用的竞争前景。然而，由于阳极不稳定性，azib的实际部署面临着严重的限制，表现为不受控制的枝晶生长、析氢反应（HER）和腐蚀性副反应。本文介绍了马来酸（MAA）作为一种两性离子电解质添加剂，同时调节Zn2+的溶剂化化学和阳极-电解质界面。阴离子COO -部分通过Zn2+配位取代了初级溶剂化鞘中的水分子，有效地减轻了HER和腐蚀。同时，阳离子NH3+基团通过选择性阳极吸附形成电化学自适应界面层，阻断含水物质，同时使Zn2+均质成核抑制枝晶。这种多功能调制有利于无枝晶Zn电镀，赋予Zn||Zn对称电池在1ma cm - 2下具有超过5000小时的卓越循环能力。当集成到Zn||NaV3O8·1·5H2O全电池中时，maa修饰的电解质在2 A g−1下循环2000次后可提供89.1%的容量保持率，其性能稳健性在柔性袋状电池中得到进一步验证。我们的研究结果强调了多功能添加剂的分子工程是推进锌基储能技术的关键策略。
{"title":"Dendrite-free Zn anodes enabled by interfacial shielding coupled with solvation structure regulation for stable aqueous zinc-ion batteries","authors":"Qian Li, Fang Yuan, Haojun Liu, Jiuer Yu, Yuanmeng Fan, Dengji Xiao, Jian Yang","doi":"10.1016/j.electacta.2026.148336","DOIUrl":"10.1016/j.electacta.2026.148336","url":null,"abstract":"<div><div>Aqueous zinc-ion batteries (AZIBs) have arisen as competitive prospects for grid-scale energy storage applications, primarily driven by their natural security advantages, economic viability, and ecological sustainability. Nevertheless, practical deployment of AZIBs faces severe constraints due to anode instability, manifested through uncontrolled dendritic growth, hydrogen evolution reaction (HER), and corrosive side reactions. This work introduces maleamic acid (MAA) as a zwitterionic electrolyte additive that concurrently regulates Zn<sup>2+</sup> solvation chemistry and anode-electrolyte interface. The anionic COO<sup>−</sup> moiety displaces water molecules in the primary solvation sheath via Zn<sup>2+</sup> coordination, effectively mitigating HER and corrosion. Simultaneously, the cationic NH<sub>3</sub><sup>+</sup> group forms an electrochemically adaptive interfacial layer through selective anode adsorption, which blocks aqueous species while enabling homogeneous Zn<sup>2+</sup> nucleation to suppress dendrites. Such multifunctional modulation facilitates dendrite-free Zn plating, endowing Zn||Zn symmetric cells with exceptional cyclability exceeding 5000 h at 1 mA cm<sup>−2</sup>. When integrated into Zn||NaV<sub>3</sub>O<sub>8</sub>·1·5H<sub>2</sub>O full cells, the MAA-modified electrolyte delivers 89.1% capacity retention after 2000 cycles at 2 A g<sup>−1</sup>, with performance robustness further verified in flexible pouch cells. Our findings highlight molecular engineering of multifunctional additives as a pivotal strategy for advancing zinc-based energy storage technologies.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"554 ","pages":"Article 148336"},"PeriodicalIF":5.6,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146071643","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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