Electrochimica Acta最新文献_第10页

Contact impedance during fretting corrosion of metallic biomaterials as a non-destructive evaluation of damage accumulation: Theory and experiment 金属生物材料微动腐蚀过程中的接触阻抗作为损伤积累的无损评价：理论与实验

IF 5.6 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2026-01-05 DOI: 10.1016/j.electacta.2026.148135

Dinghe (Larry) Liu , Amandine Impergre , Jeremy L. Gilbert

Fretting crevice corrosion, or mechanically assisted crevice corrosion (MACC), typically arises when two alloys covered by passive oxide film experience small scale reciprocal sliding (fretting) in the presence of an electrolyte. Several models describing the mechanical and electrochemical behavior in MACC have been explored. A gap in our understanding is the evolution of the damage state within the contact regions as the fretting corrosion progresses. In this work, a method was used to measure the high frequency (5 kHz) impedance across the contacting junction of Ti-6Al-4 V and CoCrMo alloys to study the progression of changes within the contact region by capturing the impedance response over the course of fretting corrosion. We discovered a systematic progression of increasing real and imaginary impedances with increased fretting corrosion damage that gives rise to a semicircular arc centered on the imaginary impedance axis of a Complex Plane plot (i.e., Nyquist plot). The impedance starts near zero (0.1 Ω) and rises along this circular path. Higher concentrations resulting in smaller maximum impedance values and smaller radii of the arcs (p < 0.001). An electrical circuit model of parallel resistances and capacitances that depend on the coupled area fraction of metal-metal junctions and oxide-covered areas, and their change during degradation, is presented to describe how impedance variations arise. The proposed model fits the observed response and provides deeper insight into the progression of damage. The single frequency contact impedance method can non-destructively monitor the damage of any fretting corrosion junctions.

微动缝隙腐蚀，或机械辅助缝隙腐蚀（MACC），通常发生在两种被钝化氧化膜覆盖的合金在电解质存在下经历小规模的互滑（微动）时。一些描述MACC力学和电化学行为的模型已经被探索。随着微动腐蚀的进行，接触区域内损伤状态的演变是我们认识上的一个空白。在这项工作中，采用了一种方法来测量ti - 6al - 4v和CoCrMo合金接触结的高频（5 kHz）阻抗，通过捕捉微动腐蚀过程中的阻抗响应来研究接触区域内变化的进展。我们发现，随着微动腐蚀损伤的增加，实阻抗和虚阻抗呈系统的增长，从而产生以复平面图（即奈奎斯特图）的虚阻抗轴为中心的半圆弧。阻抗开始接近零（0.1 Ω），并沿着这个圆形路径上升。浓度越高，最大阻抗值越小，弧线半径越小（p < 0.001）。并联电阻和电容的电路模型依赖于金属-金属结和氧化物覆盖区域的耦合面积分数，以及它们在退化过程中的变化，提出了阻抗变化是如何产生的。提出的模型拟合观察到的响应，并提供了更深入的了解损伤的进展。单频接触阻抗法可以无损地监测任意微动腐蚀结的损伤情况。

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引用次数: 0

Mechanistic insights into anodic oxidation and FA-ECMP of 4H-SiC in inorganic salt electrolytes 无机盐电解质中4H-SiC阳极氧化和FA-ECMP的机理研究

IF 5.6 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2026-01-05 DOI: 10.1016/j.electacta.2026.148133

Hao Guo , Shenglong Zhang , Xiaozhe Yang , Xu Yang , Kazuya Yamamura , Zhuangde Jiang

Fixed-abrasive electrochemical mechanical polishing (FA-ECMP) has emerged as a promising, green, and cost-effective technique for achieving high-quality finishing of silicon carbide (SiC). To further enhance its performance, this study systematically investigates the anodic oxidation behavior and FA-ECMP mechanisms of 4H-SiC (0001) in five non-polluting inorganic salt electrolytes (0.1 mol/L K₂SO₄, KCl, KNO₃, KHCO₃, and K₂CO₃ aqueous solutions). Comprehensive characterization—including nanoindentation, Raman spectroscopy, XRD, AFM, and cross-sectional SEM—reveals pronounced electrolyte-dependent differences in oxide-layer properties. Among all conditions, the K₂CO₃ electrolyte produces an oxide layer that is smoother, denser, harder, and exhibits a slight degree of crystallinity, yielding the highest interfacial uniformity. However, the compact layer significantly suppresses further oxidation, resulting in the lowest anodic current and the thinnest oxide layer. FA-ECMP experiments on 4-inch 4H-SiC wafers demonstrate that K₂CO₃ uniquely enables both a high oxide-generation rate and a high oxide-removal rate during polishing. Consequently, superior post-polishing performance is achieved, with surface roughness (Sa) reduced from 26.033 nm to 0.238 nm and a material removal rate of 3.588 μm/h. The material removal mechanisms in different electrolytes were revealed through nanoscratch experiments and the quartz FA-CMP results. This study establishes a non-polluting electrolyte strategy that significantly improves the FA-ECMP performance of 4H-SiC, providing systematic theoretical and practical support for developing green, high-efficiency ultra-precision SiC polishing and accelerating the industrial adoption of ECMP technologies.

固定磨料电化学机械抛光（FA-ECMP）已成为一种有前途的、绿色的、经济高效的技术，用于实现高质量的碳化硅（SiC）精加工。为了进一步提高其性能，本研究系统地研究了4H-SiC（0001）在5种无污染无机盐电解质（0.1 mol/L K₂SO₄、KCl、KNO₃、KHCO₃和K₂CO₃水溶液）中的阳极氧化行为和FA-ECMP机理。综合表征-包括纳米压痕，拉曼光谱，XRD， AFM和横截面sem -揭示了明显的电解质依赖于氧化层性质的差异。在所有条件下，K₂CO₃电解质产生的氧化层更光滑、更致密、更硬，并表现出轻微的结晶度，产生最高的界面均匀性。然而，致密层显著抑制进一步氧化，导致最低的阳极电流和最薄的氧化层。在4英寸4H-SiC晶圆上进行的FA-ECMP实验表明，K₂CO₃在抛光过程中具有独特的高氧化物生成率和高氧化物去除率。表面粗糙度（Sa）从26.033 nm降至0.238 nm，材料去除率为3.588 μm/h，获得了优异的抛光后性能。通过纳米划痕实验和石英FA-CMP结果揭示了材料在不同电解质中的去除机理。本研究建立了一种无污染的电解液策略，显著提高了4H-SiC的FA-ECMP性能，为发展绿色、高效的超精密SiC抛光和加速ECMP技术的工业应用提供了系统的理论和实践支持。

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引用次数: 0

Influence of CeO2MnOx heterostructure on hydrogen peroxide electrogeneration on carbon-based catalysts CeO2MnOx异质结构对碳基催化剂上过氧化氢发电的影响

IF 5.6 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2026-01-04 DOI: 10.1016/j.electacta.2026.148125

Caroline de O. Carrilho , Juliana M.S. de Jesus , João Paulo C. Moura , Dara Silva Santos , Aline B. Trench , Caio Machado Fernandes , Aila O. Santos , Odivaldo C. Alves , Júlio C.M. Silva , Mauro C. dos Santos

The sustainable electrogeneration of hydrogen peroxide (H₂O₂) via the two-electron oxygen reduction reaction (2e⁻ ORR) represents a promising alternative to conventional production methods. In this study, CeO₂ and CeO₂MnOx nanoparticles were synthesized and supported on Vulcan XC-72 carbon at varying loadings (1, 3, and 5%), aiming to assess the lowest metal loading and high H₂O₂ electrosynthesis. Physicochemical characterizations confirmed the successful formation of CeO₂ nanowires and the effectiveness of the MnOx surface modification. XRD, TEM, XPS, EPR, and contact angle analyses revealed that CeO₂ loading increased surface hydrophilicity due to oxygenated functional groups, thereby favoring electrochemical activity. On the other hand, all CeO₂MnO_x loadings were statistically equal to Vulcan XC-72 in terms of contact angle. Electrochemical evaluations using a rotating ring-disk electrode (RRDE) demonstrated enhanced ORR activity and high H₂O₂ selectivity for the 1% CeO₂MnOx/C and 3% CeO₂/C catalysts, achieving up to 90% selectivity and elevated ring currents. The results suggest that low metal loading and surface modification via MnOx improve the balance between active site exposure, oxygen adsorption, and intermediate stabilization, thus favoring the selective 2e⁻ pathway. These findings support the development of cost-effective, non-noble-metal catalysts for the electrosynthesis of green H₂O₂.

通过双电子氧还原反应（2e⁻ORR）可持续产生过氧化氢（H2O2）代表了传统生产方法的一种有前途的替代方法。在本研究中，在不同负载（1、3和5%）的Vulcan XC-72碳上合成了CeO2和CeO2MnOx纳米颗粒，旨在评估最低金属负载和高H2O2电合成。物理化学表征证实了CeO2纳米线的成功形成和MnOx表面改性的有效性。XRD， TEM， XPS， EPR和接触角分析表明，由于氧化官能团的存在，CeO2负载增加了表面亲水性，从而有利于电化学活性。另一方面，在接触角方面，所有的CeO2MnOx装载在统计上都等于Vulcan XC-72。使用旋转环盘电极（RRDE）进行的电化学评价表明，1% CeO2MnOx/C和3% CeO2/C催化剂的ORR活性增强，H2O2选择性高，可达到90%的选择性和更高的环电流。结果表明，低金属负载和通过MnOx进行的表面修饰改善了活性位点暴露、氧吸附和中间稳定之间的平衡，从而有利于2e的选择性发展。这些发现为电合成绿色H2O2的低成本、非贵金属催化剂的开发提供了支持。

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引用次数: 0

Efficient conversion of CO2 to formic acid at nanostructured CuBi catalyst: Electrochemical, spectroscopic and DFT studies 二氧化碳在纳米结构CuBi催化剂上高效转化为甲酸：电化学、光谱和DFT研究

IF 5.6 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2026-01-04 DOI: 10.1016/j.electacta.2026.148126

Negar Sabouhanian, Brendan J.R. Laframboise, Jonathan Quintal, Zhangfei Su, Leanne D. Chen, Jacek Lipkowski, Aicheng Chen

Bismuth-based catalysts have been recognized for their high efficiency as electrocatalysts for CO₂ reduction to formate. In this work, Bi-rich CuBi bimetallic catalysts are co-electrodeposited and evaluated for their performance towards CO₂ conversion to formate and formic acid. The optimized CuBi catalysts with a Cu/Bi ratio of 20.5/79.5 showed a high Faradaic efficiency of 92% for formate formation at –0.8 V vs. RHE in an H-type cell. In addition, pure formic acid was produced with a Faradaic efficiency of ∼98% at –90 mA cm^–2 using a three-compartment membrane electrode assembly (MEA) cell system with an acidic-ion exchange bead electrolyte. The in-situ electrochemical Raman spectroscopic measurements revealed the reduction of the initial bismuth oxides on the surface to metallic bismuth during the CO₂ reduction process. The in-situ electrochemical attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy was employed to study the kinetics of the CO₂ reduction, revealing that the formate generation predominantly occurred through the adsorbed *OCHO intermediate in a bidentate configuration. This has been further confirmed by the density functional theory (DFT) calculation. The high catalytic performance of the optimized CuBi catalyst was mainly due to Bi as the dominant component, which served as active sites, while additional Cu modified the electronic structure and facilitated the formation of *OCHO intermediate. This work demonstrates the effectiveness of the integration of electrochemical, in situ spectroscopic and DFT approaches to gain fundamental understanding of the reaction kinetics, which would greatly facilitate the design of advanced electrochemical processes for clean energy and environmental applications.

铋基催化剂作为一种高效的电催化剂，已被公认为是二氧化碳还原成甲酸盐的催化剂。在这项工作中，富bi的CuBi双金属催化剂被共电沉积，并评估了它们将CO2转化为甲酸和甲酸的性能。优化后的Cu/Bi比为20.5/79.5的CuBi催化剂在h型电池中-0.8 V相对于RHE条件下生成甲酸酯的法拉第效率高达92%。此外，在-90 mA cm-2下，使用具有酸性离子交换头电解质的三室膜电极组件（MEA）电池系统，以法拉第效率为~ 98%生产纯甲酸。原位电化学拉曼光谱测量显示，在CO2还原过程中，表面的初始铋氧化物还原为金属铋。利用原位电化学衰减全反射傅立叶变换红外光谱（ATR-FTIR）研究CO2还原动力学，发现甲酸酯主要通过吸附的*OCHO中间体以双齿构型生成。密度泛函理论（DFT）的计算进一步证实了这一点。优化后的CuBi催化剂具有较高的催化性能，主要是由于Bi为主导成分，充当活性位点，而Cu修饰了电子结构，促进了*OCHO中间体的形成。这项工作证明了电化学，原位光谱和DFT方法集成的有效性，以获得对反应动力学的基本理解，这将极大地促进清洁能源和环境应用的先进电化学过程的设计。

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引用次数: 0

First-principles investigation of the physical and hydrogen storage properties of novel octahydrides XCr3H8 (X = Mg, Ca, Sr) 新型八氢化物XCr3H8 （X = Mg, Ca, Sr）物理和储氢性能的第一性原理研究

IF 5.6 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2026-01-03 DOI: 10.1016/j.electacta.2026.148118

Yanxi Qin , Saifei Wang , Yan Chen , Shanjun Chen , Jie Hou , Weibin Zhang

The first-principles was employed to investigate the hydrogen storage, dynamic, thermodynamic, electronic, optical, structural, and mechanical properties of hydrides XCr₃H₈ (X = Mg, Ca, Sr) for the first time. Their negative formation energies of XCr₃H₈ supported their thermodynamic stability, while mechanical and dynamic stabilities were determined by elastic constants and phonon spectra analysis. The B/G ratio investigation indicated that MgCr₃H₈ and CaCr₃H₈ exhibit ductility, whereas SrCr₃H₈ is brittle. The calculated Poisson's ratios suggest that XCr₃H₈ compounds are ionic-bonded materials. The metallic behavior of these compounds was identified through the band structure analysis. Based on the calculated high magnetic moments of XCr₃H₈, these compounds exhibit excellent magnetic properties and have potential applications as permanent magnets or magnetic recording media. The optical properties of these hydrides showed their high dielectric constants, strong infrared reflectance, and significant ultraviolet absorption. As the mass of the X atom increases, both of the gravimetric and volumetric hydrogen storage capacities show a decreasing trend in the order of MgCr₃H₈ (4.38 wt%; 170.77 gH₂/L) > CaCr₃H₈ (3.95 wt%; 151.96 gH₂/L) > SrCr₃H₈ (3.21 wt%; 135.78 gH₂/L). In addition, they exhibit suitable hydrogen desorption temperatures of 250 K for MgCr₃H₈, 291 K for CaCr₃H₈, and 223 K for SrCr₃H₈. The thermal properties of these hydrides, including energy, heat capacity, entropy, and free energy, were also studied. These theoretical investigations suggest that the XCr₃H₈ hydrides studied possess excellent properties and contribute valuable data for the research on efficient hydrogen storage materials.

首次应用第一性原理研究了XCr3H8 （X = Mg, Ca, Sr）氢化物的储氢、动力学、热力学、电子、光学、结构和力学性能。XCr3H8的负形成能支持其热力学稳定性，而力学和动力学稳定性则由弹性常数和声子谱分析确定。B/G比研究表明，MgCr3H8和CaCr3H8具有延展性，而SrCr3H8具有脆性。计算得到的泊松比表明XCr3H8化合物是离子键材料。通过带结构分析确定了这些化合物的金属行为。基于计算得到的XCr3H8的高磁矩，这些化合物表现出优异的磁性能，具有作为永磁体或磁记录介质的潜在应用。这些氢化物具有较高的介电常数、较强的红外反射率和显著的紫外吸收。随着X原子质量的增加，重量储氢量和体积储氢量均呈下降趋势，依次为MgCr3H8 (4.38 wt%; 170.77 gH2/L) >、CaCr3H8 (3.95 wt%; 151.96 gH2/L) >、SrCr3H8 （3.21 wt%; 135.78 gH2/L）。此外，MgCr3H8的脱氢温度为250 K， CaCr3H8为291 K， SrCr3H8为223 K。研究了这些氢化物的热性能，包括能量、热容、熵和自由能。这些理论研究表明，所研究的XCr3H8氢化物具有优异的性能，为高效储氢材料的研究提供了有价值的数据。

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引用次数: 0

Strategic design of Ni(II)-dithiolate–1,10-phenanthroline complexes: Influence of isomeric methoxy substitutions on dihedral angle–Hammett interplay and oxygen evolution reaction performance Ni(II)-二硫代酸- 1,10-菲罗啉配合物的策略设计：异聚甲氧基取代对二面角-哈米特相互作用对析氧反应性能的影响

IF 5.6 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2026-01-03 DOI: 10.1016/j.electacta.2026.148120

Madhav Raj Jayswal , Daniel Omoding , Shreya Srivastava , Aparna Kushwaha , Xiang Li , Abhinav Kumar , Mohd. Muddassir

The strategic design of transition metal dithiolates, particularly Ni-based systems, is vital for advancing high-efficiency molecular electrocatalysts in water-splitting reactions. In this context, three new heteroleptic 1,10-Phenanthroline (Phen) appended Ni(II) complexes bearing positional isomeric methoxyphenylacetonitriledithiolates [Ni(L1)Phen] (2Ni-Phen), [Ni(L2)Phen] (3Ni-Phen), and [Ni(L3)Phen] (4Ni-Phen) (L1 = 2-methoxyphenylacetonitriledithiolate; L2 = 3-methoxyphenylacetonitriledithiolate; L3 = 4-methoxyphenylacetonitriledithiolate) have been synthesized and characterized. The geometry optimization reveals distorted square-planar coordination around Ni(II), defined by two sulfur atoms of the dithiolate and two nitrogen atoms of Phen. These complexes have been employed as heterogeneous electrocatalyst for oxygen evolution reaction and the study reveals that the electrocatalytic activity trends are strongly governed by both the Hammett electronic effect of the methoxy substituent and the dihedral angle between the NiS₂C₂ plane and the appended aromatic ring, which together modulate electron density and facilitate optimal orbital overlap during oxygen evolution. 3Ni-Phen displays the best OER performance with an onset potential of 1.56 V (vs. RHE), η⁰ of 327 mV, η⁵ of 385 mV, η¹⁰ of 410 mV, highest turnover frequency (TOF) of 283.6 ± 1.0 × 10^–3 s^-1 at η = 750, and a remarkably low Tafel slope of 53 mV·dec⁻¹. Post-OER FESEM analysis further confirms the retention of nanoscale morphological features in 3Ni-Phen relative to significant surface coarsening in 2Ni-Phen and 4Ni-Phen, underpinning its enhanced structural robustness and sustained activity. This study demonstrates that the synergistic interplay of substituent electronic effects, coordination dihedral angle, and morphological stability provides a rational framework for designing Ni–dithiolate molecular electrocatalysts for efficient oxygen evolution.

过渡金属二硫酯的战略性设计，特别是镍基体系，对于推进高效分子电催化剂在水分解反应中的应用至关重要。在此背景下，合成了三种新的杂电性1,10-菲罗啉（Phen）附加Ni（II）配合物，含有位置异构体甲氧基苯乙腈二硫酸盐[Ni(L1)Phen] (2Ni-Phen), [Ni(L2)Phen] （3Ni-Phen）和[Ni(L3)Phen] (4Ni-Phen) （L1 = 2-甲氧基苯乙腈二硫酸盐；L2 = 3-甲氧基苯乙腈二硫酸盐；L3 = 4-甲氧基苯乙腈二硫酸盐）。几何优化揭示了Ni（II）周围扭曲的方平面配位，由二硫酸盐的两个硫原子和Phen的两个氮原子定义。这些配合物被用作析氧反应的非均相电催化剂，研究表明，电催化活性的变化趋势受甲氧基取代基的哈米特电子效应和n2c2平面与附加芳环之间的二面角的强烈支配，它们共同调节析氧过程中的电子密度并促进最佳轨道重叠。3Ni-Phen表现出最好的OER性能，其起始电位为1.56 V（相对于RHE）， η0为327 mV， η5为385 mV， η10为410 mV， η = 750时的最高转换频率（TOF）为283.6±1.0 × 10-3 s-1， Tafel斜率为53 mV·dec⁻¹。oer后的FESEM分析进一步证实，相对于2Ni-Phen和4Ni-Phen中显著的表面粗化，3Ni-Phen中保留了纳米级的形态特征，支撑了其增强的结构坚固性和持续活性。本研究表明，取代基电子效应、配位二面角和形态稳定性的协同作用为设计高效析氧ni -二硫酯分子电催化剂提供了合理的框架。

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引用次数: 0

Electricity generation and energy storage in MFCs with carbon felt/multi-walled carbon nanotubes/bimetallic oxide/polyaniline capacitive anode 碳毡/多壁碳纳米管/双金属氧化物/聚苯胺电容阳极mfc的发电与储能

IF 5.6 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2026-01-03 DOI: 10.1016/j.electacta.2026.148122

Yuyang Wang , Zhijie Wang , Dongming Zhang , Xiangquan Kong , Su Ma , Ying Duan , Andrii Vyshnikin , Vitalii Palchykov

Microbial fuel cells (MFCs) represent an innovative biomass energy technology that harnesses microbial metabolism for the generation of electricity. In this study, a multilayer capacitive CF/MWCNTs/NiCo₂O₄/PANI electrode was developed by loading multi-walled carbon nanotubes (MWCNTs), NiCo₂O₄, and polyaniline (PANI) onto carbon fiber. The power density of the MFC equipped with the CF/MWCNTs/NiCo₂O₄/PANI bioanode (1458.0 mW/m²) was 4.3 times higher than that of the MFC equipped with the CF anode. Additionally, the Chronoamperometry test revealed that the storage capacity of the CF/MWCNTs/NiCo₂O₄/PANI composite anode was 4073.96 C/m², which indicated a 7.92-fold increase compared with that of the CF anode. In this study, the electrochemical, morphological, and chemical properties of the prepared anode were characterized via SEM, EDS, FTIR, XRD, CLSM and BET techniques. The EIS results indicated that PANI enhanced the attachment and growth of biofilms. Additionally, high-throughput sequencing revealed that electrogenic bacteria accounted for 88.9% of the total microbial population on the CF/MWCNTs/NiCo₂O₄/PANI electrode. This condition resulted in increased electrical charge generation, and a substantial amount of electricity was produced. This innovative approach significantly enhanced the current output and energy storage capacity of MFCs to effectively address the issue of low power generation.

微生物燃料电池（mfc）是一种利用微生物代谢发电的创新生物质能技术。在本研究中，通过在碳纤维上加载多壁碳纳米管（MWCNTs）、NiCo2O4和聚苯胺（PANI），制备了多层电容性CF/MWCNTs/NiCo2O4/PANI电极。配置CF/MWCNTs/NiCo2O4/PANI生物阳极的MFC功率密度（1458.0 mW/m2）比配置CF阳极的MFC高4.3倍。此外，Chronoamperometry测试表明，CF/MWCNTs/NiCo2O4/PANI复合阳极的存储容量为4073.96 C/m2，比CF阳极提高了7.92倍。通过SEM、EDS、FTIR、XRD、CLSM和BET等技术对制备的阳极进行了电化学、形貌和化学性能表征。EIS结果表明，聚苯胺促进了生物膜的附着和生长。此外，高通量测序显示，电致细菌占CF/MWCNTs/NiCo2O4/PANI电极上微生物总数的88.9%。这种情况导致电荷产生增加，产生了大量的电力。这一创新方法显著提高了mfc的电流输出和储能能力，有效解决了低发电量问题。

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引用次数: 0

Spiky self-supporting NiTe@CoFe-LDH/NF heterostructure electrocatalyst for stable and highly efficient seawater electrolysis 用于稳定高效海水电解的尖状自支撑型NiTe@CoFe-LDH/NF异质结构电催化剂

IF 5.6 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2026-01-03 DOI: 10.1016/j.electacta.2026.148121

Jie Yin , Mengzhao Liu , Weiji Wang , Chengjian Wang , Ping Geng

Seawater electrolysis for hydrogen production has become an indispensable component of future energy systems thanks to its great efficiency, cleanliness, and sustainability. Designing highly efficient and cost-effective bifunction electrocatalysts holds significant importance for the widespread application of seawater electrolysis technology, yet significant challenges remain. Herein, a heterogeneous NiTe@CoFe-LDH with spiky-like structure is synthesized directly on Ni foam through hydrothermal and electrochemical deposition techniques. Supported by strong intrinsic reactivity, high density of functional sites, minimal charge-transfer impedance, and promoted adsorption-desorption cycle of intermediates, the NiTe@CoFe-LDH/NF self-supported electrocatalyst demonstrates excellent catalytic performance toward both the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER), with low required overpotentials of 326 mV and 186 mV to reache the current density of 100 mA cm⁻², respectively, and further demonstrates strong durability over 100 h in alkaline natural seawater. Moreover, configured as both electrodes, the NiTe@CoFe-LDH catalyst enables overall seawater electrolysis at 100 mA cm⁻² with a low operational voltage of 1.661 V. This work not only provides an non-noble metal electrocatalyst with highly efficient overall seawater splitting activity, but also has a guiding significance for the rational design of heterojunction catalyst.

海水电解制氢因其高效、清洁和可持续性而成为未来能源系统不可或缺的组成部分。设计高效、经济的双功能电催化剂对海水电解技术的广泛应用具有重要意义，但仍存在重大挑战。本文通过水热沉积和电化学沉积技术，直接在泡沫镍上合成了具有尖刺状结构的异相NiTe@CoFe-LDH。NiTe@CoFe-LDH/NF自持型电催化剂具有较强的内在反应活性、较高的功能位点密度、极小的电荷转移阻抗以及促进中间体的吸附-解吸循环等特点，对析氧反应（OER）和析氢反应（HER）均表现出优异的催化性能，所需过电位分别为326 mV和186 mV，达到100 mA cm−2的电流密度。并进一步证明了在碱性天然海水中100小时以上的耐久性。此外，NiTe@CoFe-LDH催化剂配置为两个电极，可以在100ma cm（⁻²）下进行海水电解，工作电压低至1.661 V。本工作不仅提供了一种具有高效海水整体分裂活性的非贵金属电催化剂，而且对异质结催化剂的合理设计具有指导意义。

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引用次数: 0

Review: Electrochemical properties of chalcones: Experimental insights, theoretical correlations, and future perspectives 综述：查尔酮的电化学性质：实验见解、理论关联和未来展望

IF 5.6 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2026-01-03 DOI: 10.1016/j.electacta.2026.148117

Jeanet Conradie , Chiedozie Chukwuemeka Aralu , Kovo G. Akpomie , Chinemerem Ruth Ohoro , Nnabuk Okon Eddy

Chalcones are versatile α,β-unsaturated carbonyl compounds with a wide range of chemical and functional properties, and their electrochemical behavior offers valuable insights into structure–property relationships relevant to materials science, catalysis, and molecular electronics. This review summarizes and critically evaluates the published electrochemical data on both non-metal-containing and metallocene-containing chalcones, highlighting key experimental findings and their correlation with theoretical predictions. For non-metallic chalcones, the reduction processes are strongly influenced by substituent effects and conjugation patterns, which can be interpreted using molecular descriptors, such as frontier orbital energies and electron affinities, that we obtain here from DFT calculations. Incorporation of metallocene units, particularly ferrocenyl and ruthenocenyl groups, introduces new redox-active sites and profoundly alters electron-transfer behavior. Substituent effects on oxidation potentials, diffusion-controlled one-electron processes, and the influence on the chalcone are discussed in detail, together with correlations between experimental redox potentials and theoretical parameters. The review also identifies key limitations of the current literature, including the restricted structural diversity studied, limited mechanistic insight, and insufficient linkage between electrochemical properties and functional applications. Finally, perspectives for future research are outlined, emphasizing the need for broader structural exploration, more advanced electrochemical and computational approaches, and integration of chalcone redox chemistry into emerging technological applications.

查尔酮是一种多功能的α，β-不饱和羰基化合物，具有广泛的化学和功能性质，其电化学行为为材料科学，催化和分子电子学相关的结构-性质关系提供了有价值的见解。本文总结并批判性地评价了已发表的关于非金属和含茂金属查尔酮的电化学数据，重点介绍了关键的实验结果及其与理论预测的相关性。对于非金属查尔酮，还原过程受到取代基效应和共轭模式的强烈影响，这可以用分子描述符来解释，例如我们从DFT计算中得到的前沿轨道能量和电子亲和。茂金属单元，特别是二茂铁基和钌茂基的结合，引入了新的氧化还原活性位点，并深刻地改变了电子转移行为。详细讨论了取代基对氧化电位的影响、扩散控制的单电子过程以及对查尔酮的影响，以及实验氧化还原电位与理论参数之间的相关性。该综述还指出了当前文献的主要局限性，包括研究的结构多样性有限，机制见解有限，电化学性质与功能应用之间的联系不足。最后，展望了未来研究的前景，强调需要更广泛的结构探索，更先进的电化学和计算方法，以及将查尔酮氧化还原化学融入新兴技术应用中。

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引用次数: 0

High selectivity and portable sensing of blood lead ions using dual input detection based on Schottky heterojunction 基于肖特基异质结的双输入检测的高选择性和便携式血铅离子传感

IF 5.6 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2026-01-03 DOI: 10.1016/j.electacta.2026.148119

Chenbo Hui , Gui-fang Li , Yue Tan , Jiezhang Luo , Yongyi Yang , Yongqian Du , Yinghao Chen , Shibin Liu

The on-site detection of trace blood lead ions (Pb²⁺) remains challenging due to insufficient selectivity and portability of existing sensors. Conventional methods struggle with complex biological matrices and co-existing interferents. To address this, a miniaturized Pt/Si Schottky heterojunction sensor functionalized with glutathione (GSH) was demonstrated in this work, leveraging its specific coordination with Pb²⁺ to modulate interfacial potential and enhance selectivity. A dual-input detection mode combining reverse Direct Current bias (DC) and Alternating Current excitation (AC) was designed to transduce Pb²⁺-GSH binding into measurable AC current changes. Device operation was optimized via Silvaco TCAD simulations and experiments (∣v_ac∣ < 200 mV, f < 18 kHz). In PBS, the sensor exhibited a wide linear detection range (10⁻⁸–10⁻³ mol/L, R² = 0.98) and high selectivity, with a Pb²⁺ response of 6.65 ± 0.16 μA at 10⁻³ mol/L—significantly exceeding interferents such as Cu²⁺ (< 2 μA). In anticoagulated bovine blood, it maintained excellent sensitivity (Δ∣i_ac∣ vs. log[Pb²⁺], R² = 0.98) and anti-interference ability, yielding a response of 1.48 ± 0.12 μA at 10⁻⁶ mol/L Pb²⁺. The integrated system, comprising a miniaturized device (1.5 mm × 4 mm) and portable detection circuit (80 mm × 60 mm of printed circuit board), enables portable and real-time detection. This work presents a robust, miniaturized sensing platform for highly selective and portable Pb²⁺ monitoring in blood. It offers a viable solution for on-site lead poisoning screening and holds potential for multiplexed heavy metal detection via adaptable surface modifications.

由于现有传感器的选择性和便携性不足，痕量血铅离子（Pb 2 +）的现场检测仍然具有挑战性。传统方法难以处理复杂的生物基质和共存的干扰物。为了解决这个问题，在这项工作中展示了一种用谷胱甘肽（GSH）功能化的小型化Pt/Si Schottky异质结传感器，利用其与Pb 2⁺的特定配合来调节界面电位并增强选择性。设计了一种结合反向直流偏置（DC）和交流励磁（AC）的双输入检测模式，将Pb 2 + -GSH结合转化为可测量的交流电流变化。通过Silvaco TCAD仿真和实验（∣vac∣< 200 mV, f < 18 kHz）对器件工作进行优化。在PBS中，该传感器具有宽的线性检测范围（10⁻⁸-10⁻³mol/L, R²= 0.98）和高选择性，Pb 2⁺在10⁻³mol/L时的响应为6.65±0.16 μA，显著超过Cu 2⁺（< 2 μA）等干扰物。在抗凝牛血液中，它保持了优异的灵敏度（Δ∣iac∣vs. log[Pb²+],R²= 0.98）和抗干扰能力，在10⁻26 mol/L时Pb²+的响应为1.48±0.12 μA。该集成系统由小型化器件（1.5 mm × 4 mm）和便携式检测电路（80 mm × 60 mm印刷电路板）组成，可实现便携式和实时检测。这项工作提出了一个强大的、小型化的传感平台，用于高选择性和便携式Pb 2 +在血液中的监测。它为现场铅中毒筛查提供了可行的解决方案，并具有通过适应性表面修饰进行多重重金属检测的潜力。

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引用次数: 0