Pub Date : 2025-12-02DOI: 10.1016/j.electacta.2025.147925
Evgenia Dmitrieva , Alexey Popov , Horst Hartmann
A series of amino-substituted mono- and bis-thienyl ketones were characterized by means of cyclic voltammetry, ultraviolet−visible−near infrared (UV−Vis−NIR) absorption spectroscopy, and in situ electron paramagnetic resonance (EPR)/UV−Vis−NIR spectroelectrochemistry. The molecular structures of bis-thienyl ketones contain morpholine (3a–c) or N,N´-disubstituted amino (3d–f) groups. The electrochemical reduction of the ketones leads to the formation of stable radical anions, and their EPR and UV−Vis−NIR spectral features were analyzed in detail. In contrast, the radical cations are not stable and undergo follow-up chemical reactions with formation of redox-active dimers. The EPR data and DFT calculations provide information about the charge/spin localization in the electrochemically generated radical ions.
采用循环伏安法、紫外-可见-近红外（UV - Vis - NIR）吸收光谱和原位电子顺磁共振(EPR)/紫外-可见-近红外（UV - Vis - NIR）光谱电化学对一系列氨基取代的单噻吩酮和双噻吩酮进行了表征。双噻吩基酮的分子结构中含有啉（3a-c）或N，N′-二取代氨基（3d-f）基团。酮类化合物的电化学还原生成了稳定的自由基阴离子，并对其EPR和UV - Vis - NIR光谱特征进行了详细分析。相反，自由基阳离子不稳定，并发生后续化学反应，形成氧化还原活性二聚体。EPR数据和DFT计算提供了电化学生成的自由基离子中电荷/自旋定位的信息。
{"title":"EPR and UV−Vis−NIR spectroscopic features of radical ions of amino substituted thienyl ketones","authors":"Evgenia Dmitrieva , Alexey Popov , Horst Hartmann","doi":"10.1016/j.electacta.2025.147925","DOIUrl":"10.1016/j.electacta.2025.147925","url":null,"abstract":"<div><div>A series of amino-substituted mono- and bis-thienyl ketones were characterized by means of cyclic voltammetry, ultraviolet−visible−near infrared (UV−Vis−NIR) absorption spectroscopy, and in situ electron paramagnetic resonance (EPR)/UV−Vis−NIR spectroelectrochemistry. The molecular structures of bis-thienyl ketones contain morpholine (<strong>3a–c</strong>) or <em>N,N</em>´-disubstituted amino (<strong>3d–f</strong>) groups. The electrochemical reduction of the ketones leads to the formation of stable radical anions, and their EPR and UV−Vis−NIR spectral features were analyzed in detail. In contrast, the radical cations are not stable and undergo follow-up chemical reactions with formation of redox-active dimers. The EPR data and DFT calculations provide information about the charge/spin localization in the electrochemically generated radical ions.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"548 ","pages":"Article 147925"},"PeriodicalIF":5.6,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145651201","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}
Supercritical CO2 corrosion represents a significant technological bottleneck for pipeline-scale applications, posing serious risks to the safe operation of carbon capture, utilization, and storage (CCUS) systems. However, the influence of the synergistic effects of temperature, pressure, and flow rate on the corrosion mechanism remains poorly understood. Notably, studies investigating the optimal temperature-pressure interval across varying flow rates are scarce, which hinders the development of effective corrosion control strategies. The findings reveal a pronounced "optimal temperature-pressure-flow rate combination" effect in supercritical CO2 corrosion; this specific combination yields the lowest corrosion rate while deviations from it result in significantly elevated rates. To address potential misjudgments arising from reliance on a single electrochemical parameter, we propose a closed-loop validation method that integrates "electrochemical parameters - corrosion mechanism - morphological features." This study demonstrates for the first time that temperature, pressure, and flow rate regulate the nucleation-growth-sedimentation kinetic processes of FeCO3. These factors directly impact film layer densification and consequently control the overall corrosion rate. The results not only support safe applications of supercritical CO2 technology but also provide an essential experimental foundation for developing robust corrosion control strategies within CCUS systems.
{"title":"Temperature-pressure-flow rate synergy effect on corrosion behavior of supercritical CO2 pipelines: Optimal conditions and FeCO₃ film mechanism","authors":"Zihong Liu, Jiazhu Bao, Jie Wang, Jiguang Wang, Yu Liu, Yongchen Song, Lunxiang Zhang","doi":"10.1016/j.electacta.2025.147943","DOIUrl":"10.1016/j.electacta.2025.147943","url":null,"abstract":"<div><div>Supercritical CO<sub>2</sub> corrosion represents a significant technological bottleneck for pipeline-scale applications, posing serious risks to the safe operation of carbon capture, utilization, and storage (CCUS) systems. However, the influence of the synergistic effects of temperature, pressure, and flow rate on the corrosion mechanism remains poorly understood. Notably, studies investigating the optimal temperature-pressure interval across varying flow rates are scarce, which hinders the development of effective corrosion control strategies. The findings reveal a pronounced \"optimal temperature-pressure-flow rate combination\" effect in supercritical CO<sub>2</sub> corrosion; this specific combination yields the lowest corrosion rate while deviations from it result in significantly elevated rates. To address potential misjudgments arising from reliance on a single electrochemical parameter, we propose a closed-loop validation method that integrates \"electrochemical parameters - corrosion mechanism - morphological features.\" This study demonstrates for the first time that temperature, pressure, and flow rate regulate the nucleation-growth-sedimentation kinetic processes of FeCO<sub>3</sub>. These factors directly impact film layer densification and consequently control the overall corrosion rate. The results not only support safe applications of supercritical CO<sub>2</sub> technology but also provide an essential experimental foundation for developing robust corrosion control strategies within CCUS systems.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"548 ","pages":"Article 147943"},"PeriodicalIF":5.6,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145657558","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 : 2025-12-02DOI: 10.1016/j.electacta.2025.147944
Xiutao Yang , Zhijie Luo , Yuying Wang , Shaoqin Zhang , Guopeng Zhu , Chunhui Wang , Quanying Wang , Hongwen Yu
The sensitive and accurate detection of 17β-estradiol (E2) is crucial for assessing environmental and food safety risks. To this end, we developed a novel electrochemical hybrid sensor by integrating an aptamer (Apt) with molecularly imprinted polymers (MIP) on a glassy carbon electrode (GCE) modified with AgNPs/NiMOF-Ni composites. This unique design leverages the large conductive surface of AgNPs/NiMOF-Ni to immobilize the recognition elements, while the Apt-MIP dual-recognition system ensures exceptional target specificity. The fabricated sensor demonstrated high sensitivity, excellent selectivity, and satisfactory stability for E2 detection. It achieved a broad linear range from 1.0 × 10⁻¹⁵ M to 1.0 × 10⁻⁶ M and an ultra-low detection limit of 0.44 fM (S/N = 3). When applied to spiked water and milk samples, the sensor delivered reliable recoveries of 95.2 % - 109 % with a relative standard deviation (RSD) ≤ 4.8 %. These results affirm the strong potential of our hybrid sensor for the practical monitoring of trace E2 contamination.
{"title":"Hybrid sensor with aptamer and molecularly imprinted polymers based on AgNPs/NiMOF-Ni for ultra-trace recognition of 17β-estradiol","authors":"Xiutao Yang , Zhijie Luo , Yuying Wang , Shaoqin Zhang , Guopeng Zhu , Chunhui Wang , Quanying Wang , Hongwen Yu","doi":"10.1016/j.electacta.2025.147944","DOIUrl":"10.1016/j.electacta.2025.147944","url":null,"abstract":"<div><div>The sensitive and accurate detection of 17β-estradiol (E2) is crucial for assessing environmental and food safety risks. To this end, we developed a novel electrochemical hybrid sensor by integrating an aptamer (Apt) with molecularly imprinted polymers (MIP) on a glassy carbon electrode (GCE) modified with AgNPs/NiMOF-Ni composites. This unique design leverages the large conductive surface of AgNPs/NiMOF-Ni to immobilize the recognition elements, while the Apt-MIP dual-recognition system ensures exceptional target specificity. The fabricated sensor demonstrated high sensitivity, excellent selectivity, and satisfactory stability for E2 detection. It achieved a broad linear range from 1.0 × 10⁻¹⁵ M to 1.0 × 10⁻⁶ M and an ultra-low detection limit of 0.44 fM (S/<em>N</em> = 3). When applied to spiked water and milk samples, the sensor delivered reliable recoveries of 95.2 % - 109 % with a relative standard deviation (RSD) ≤ 4.8 %. These results affirm the strong potential of our hybrid sensor for the practical monitoring of trace E2 contamination.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"548 ","pages":"Article 147944"},"PeriodicalIF":5.6,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145651199","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 : 2025-12-02DOI: 10.1016/j.electacta.2025.147945
Feixuan Li , Yu Xiong , Dongping Zhan , Xinxin Xiao , Shizhen Wang
This study presents a hybrid system combining MIP-202 (Zr⁴⁺-Asp-coordinated framework) immobilized L-phenylalanine dehydrogenase with polymerized methylene blue (PMB) based electrodes. MIP-202 acted as a biocompatible framework that preserved enzymatic activity. PMB modulated the oxidation of the enzyme cofactor NADH into NAD+ via proton-coupled electron transfer (PCET), reducing overpotentials. Such a biohybrid, operated at a relatively low potential of +0.15 V vs. SCE, enables proof-of-concept electrochemical biosensing of L-phenylalanine (L-Phe) and bioelectrosynthesis of phenylpyruvate (PPA). Both applications are of great significance, as L-Phe is an important biomarker for the diagnostics of phenylketonuria, while PPA is a common α-keto acid. It demonstrated a limit of detection (LOD) of 17.03 μM for sensing L-phe and a ca. two-fold increase in PPA production compared to the biocatalysis system without using cofactor regeneration.
{"title":"Electrochemical biosensing of L-phenylalanine and bioelectrosynthesis of phenylpyruvate based on an efficient cofactor regeneration electrode","authors":"Feixuan Li , Yu Xiong , Dongping Zhan , Xinxin Xiao , Shizhen Wang","doi":"10.1016/j.electacta.2025.147945","DOIUrl":"10.1016/j.electacta.2025.147945","url":null,"abstract":"<div><div>This study presents a hybrid system combining MIP-202 (Zr⁴⁺-Asp-coordinated framework) immobilized L-phenylalanine dehydrogenase with polymerized methylene blue (PMB) based electrodes. MIP-202 acted as a biocompatible framework that preserved enzymatic activity. PMB modulated the oxidation of the enzyme cofactor NADH into NAD<sup>+</sup> via proton-coupled electron transfer (PCET), reducing overpotentials. Such a biohybrid, operated at a relatively low potential of +0.15 V vs. SCE, enables proof-of-concept electrochemical biosensing of L-phenylalanine (L-Phe) and bioelectrosynthesis of phenylpyruvate (PPA). Both applications are of great significance, as L-Phe is an important biomarker for the diagnostics of phenylketonuria, while PPA is a common α-keto acid. It demonstrated a limit of detection (LOD) of 17.03 μM for sensing L-phe and a ca. two-fold increase in PPA production compared to the biocatalysis system without using cofactor regeneration.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"548 ","pages":"Article 147945"},"PeriodicalIF":5.6,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145651200","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 : 2025-12-02DOI: 10.1016/j.electacta.2025.147946
Xueqi Zhang , Shichao Chen , Kang Wang , Zhongli Tang , Xitao Wang
The preparation of non-precious metal catalysts employed in oxygen evolution reaction (OER) is of great important for hydrogen production via electrocatalytic water splitting. In this work, a 2D/2D CoFe LDH/MOF heterostructure was constructed on nickel foam (NF) by in-situ partial conversion of CoFe MOF to CoFe LDH, and evaluated as an effective OER catalyst. Owing to the unique 2D/2D heterostructure, substantial electrochemical active surface area (ECSA), superior electron conductivity, accelerated mass/charge transfer kinetics and synergistic effect between the two materials, LDH/MOF-6 h sample combining structural features of both MOF and LDH exhibited a lowest overpotential of 257 mV, a small Tafel slope of 50.71 mV·dec‑1 at 20 mA cm-2 current density, along with a highest ECSA of 108 cm2(27,000 cm2 g-1). Moreover, LDH/MOF-6 h sample demonstrated superior stability over 100 h of continuous reaction in alkaline electrolyte, which indicates that 2D/2D CoFe LDH/MOF heterostructure is a highly future-oriented material for OER applications.
{"title":"The In-situ preparation of CoFe LDH/MOF electrocatalysts with 2D/2D structure and its enhanced electrocatalytic performance for OER","authors":"Xueqi Zhang , Shichao Chen , Kang Wang , Zhongli Tang , Xitao Wang","doi":"10.1016/j.electacta.2025.147946","DOIUrl":"10.1016/j.electacta.2025.147946","url":null,"abstract":"<div><div>The preparation of non-precious metal catalysts employed in oxygen evolution reaction (OER) is of great important for hydrogen production via electrocatalytic water splitting. In this work, a 2D/2D CoFe LDH/MOF heterostructure was constructed on nickel foam (NF) by in-situ partial conversion of CoFe MOF to CoFe LDH, and evaluated as an effective OER catalyst. Owing to the unique 2D/2D heterostructure, substantial electrochemical active surface area (ECSA), superior electron conductivity, accelerated mass/charge transfer kinetics and synergistic effect between the two materials, LDH/MOF-6 h sample combining structural features of both MOF and LDH exhibited a lowest overpotential of 257 mV, a small Tafel slope of 50.71 mV·dec<sup>‑1</sup> at 20 mA cm<sup>-2</sup> current density, along with a highest ECSA of 108 cm<sup>2</sup>(27,000 cm<sup>2</sup> g<sup>-1</sup>). Moreover, LDH/MOF-6 h sample demonstrated superior stability over 100 h of continuous reaction in alkaline electrolyte, which indicates that 2D/2D CoFe LDH/MOF heterostructure is a highly future-oriented material for OER applications.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"548 ","pages":"Article 147946"},"PeriodicalIF":5.6,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145657559","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 : 2025-12-02DOI: 10.1016/j.electacta.2025.147922
Gabriel M. Silva , Heitor F. Trevizan , Yuri A. Oliveira , Silvania Lanfredi , Marcos F.S. Teixeira
This work reports the rational design and in-depth characterization of a photo-active anode for the oxygen evolution reaction (OER), fabricated by the alternating electrochemical deposition of a p-type poly[Pd(salen)] metallopolymer and n-type reduced graphene oxide (rGO). The resulting layered architecture forms a well-defined p-n heterojunction, as confirmed by Mott-Schottky analysis, which is fundamental to its high performance. Under illumination, the poly[Pd(salen)]/rGO platform demonstrates a remarkable reduction in the OER overpotential of 241 mV, driven by the photovoltage generated at the interface. A comprehensive investigation combining electrochemical impedance spectroscopy, Tafel analysis, and direct oxygen monitoring revealed a complex, light-dependent mechanism. The reaction follows pseudo-first-order kinetics and its rate is directly proportional to the incident photon flux. Notably, the analysis suggests a light-induced shift in the rate-determining step, while Turnover Frequency (TOF) calculations show a dramatic enhancement of the intrinsic catalytic activity of each palladium site, reaching 35 s⁻¹ under 30 W illumination. Based on these results, a band-alignment diagram of the stepped-gap heterojunction is proposed to explain how efficient spatial separation of photogenerated charge carriers at the p–n interface drives the enhanced catalytic activity. This study not only presents an efficient photoanode but also provides a deep mechanistic understanding of the synergy between molecular catalysts and graphene materials, paving the way for the design of advanced materials for solar-to-fuel conversion.
{"title":"Light-driven, low-overpotential water oxidation on an alternating-layer architecture of palladium-salen/reduced graphene oxide p-n heterojunction","authors":"Gabriel M. Silva , Heitor F. Trevizan , Yuri A. Oliveira , Silvania Lanfredi , Marcos F.S. Teixeira","doi":"10.1016/j.electacta.2025.147922","DOIUrl":"10.1016/j.electacta.2025.147922","url":null,"abstract":"<div><div>This work reports the rational design and in-depth characterization of a photo-active anode for the oxygen evolution reaction (OER), fabricated by the alternating electrochemical deposition of a p-type poly[Pd(salen)] metallopolymer and n-type reduced graphene oxide (rGO). The resulting layered architecture forms a well-defined p-n heterojunction, as confirmed by Mott-Schottky analysis, which is fundamental to its high performance. Under illumination, the poly[Pd(salen)]/rGO platform demonstrates a remarkable reduction in the OER overpotential of 241 mV, driven by the photovoltage generated at the interface. A comprehensive investigation combining electrochemical impedance spectroscopy, Tafel analysis, and direct oxygen monitoring revealed a complex, light-dependent mechanism. The reaction follows pseudo-first-order kinetics and its rate is directly proportional to the incident photon flux. Notably, the analysis suggests a light-induced shift in the rate-determining step, while Turnover Frequency (TOF) calculations show a dramatic enhancement of the intrinsic catalytic activity of each palladium site, reaching 35 s⁻¹ under 30 W illumination. Based on these results, a band-alignment diagram of the stepped-gap heterojunction is proposed to explain how efficient spatial separation of photogenerated charge carriers at the p–n interface drives the enhanced catalytic activity. This study not only presents an efficient photoanode but also provides a deep mechanistic understanding of the synergy between molecular catalysts and graphene materials, paving the way for the design of advanced materials for solar-to-fuel conversion.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"548 ","pages":"Article 147922"},"PeriodicalIF":5.6,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145651242","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 : 2025-12-01DOI: 10.1016/j.electacta.2025.147932
Quanxing Liu , Mei Li , Rugeng Liu , Meng Zhang , Yubao Liu , Wei Han
To investigate the effect of cathode material on the electrochemical formation of UO2, in this work, ITO, Pt, and graphite were employed as working electrode to study the electrochemical behaviors of UO22+ and the electrochemical formation of UO2 in LiCl-KCl eutectic. The results of CV, SWV and CP indicated that on the three electrodes, the reduction of UO22+ to UO2 was a one-step process with a two-electron transfer, which is different from the electrochemical behavior of inert electrodes such as Mo and W. The exchange current densities j0 of UO22+/UO2 and diffusion coefficient D of UO22+ were measured by LP and semi-integral methods, respectively. The values of j0 on Pt electrode is much larger than those on ITO and graphite electrodes, and the values of D on the three electrodes were in the same order of magnitude (10–5 cm2/s). UO2 was prepared by potentiostatic electrolysis at η=150 mV on the three electrodes and characterized by XRD and SEM-EDS. The morphology of UO2 was found to be like-dendrite structure on Pt and graphite electrodes, and particles on ITO electrode with good adhesion. In addition, potentiostatic electrolysis was conducted on ITO electrode for different times, and the products were analyzed by XRD, AFM and SEM. The morphology of UO2 changed with time, from the small particles, octahedron, truncated octahedron, cuboctahedron to cubic. The texture coefficient Tc of (111) and (200) crystal plane were calculated. With increasing the electrolysis time, Tc(111) first increased and then decreased, while Tc(200) first decreased and then increased.
{"title":"Electrochemical behavior and formation of UO2 on different electrodes (ITO, Pt and graphite) in LiCl-KCl eutectic","authors":"Quanxing Liu , Mei Li , Rugeng Liu , Meng Zhang , Yubao Liu , Wei Han","doi":"10.1016/j.electacta.2025.147932","DOIUrl":"10.1016/j.electacta.2025.147932","url":null,"abstract":"<div><div>To investigate the effect of cathode material on the electrochemical formation of UO<sub>2</sub>, in this work, ITO, Pt, and graphite were employed as working electrode to study the electrochemical behaviors of UO<sub>2</sub><sup>2+</sup> and the electrochemical formation of UO<sub>2</sub> in LiCl-KCl eutectic. The results of CV, SWV and CP indicated that on the three electrodes, the reduction of UO<sub>2</sub><sup>2+</sup> to UO<sub>2</sub> was a one-step process with a two-electron transfer, which is different from the electrochemical behavior of inert electrodes such as Mo and W. The exchange current densities <em>j<sub>0</sub></em> of UO<sub>2</sub><sup>2+</sup>/UO<sub>2</sub> and diffusion coefficient <em>D</em> of UO<sub>2</sub><sup>2+</sup> were measured by LP and semi-integral methods, respectively. The values of <em>j<sub>0</sub></em> on Pt electrode is much larger than those on ITO and graphite electrodes, and the values of <em>D</em> on the three electrodes were in the same order of magnitude (10<sup>–5</sup> cm<sup>2</sup>/s). UO<sub>2</sub> was prepared by potentiostatic electrolysis at <em>η</em>=150 mV on the three electrodes and characterized by XRD and SEM-EDS. The morphology of UO<sub>2</sub> was found to be like-dendrite structure on Pt and graphite electrodes, and particles on ITO electrode with good adhesion. In addition, potentiostatic electrolysis was conducted on ITO electrode for different times, and the products were analyzed by XRD, AFM and SEM. The morphology of UO<sub>2</sub> changed with time, from the small particles, octahedron, truncated octahedron, cuboctahedron to cubic. The texture coefficient <em>T</em><sub>c</sub> of (111) and (200) crystal plane were calculated. With increasing the electrolysis time, <em>T</em><sub>c(111)</sub> first increased and then decreased, while <em>T</em><sub>c(200)</sub> first decreased and then increased.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"548 ","pages":"Article 147932"},"PeriodicalIF":5.6,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145658150","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 : 2025-12-01DOI: 10.1016/j.electacta.2025.147929
Hongxuan Xing , Zhongning Shi , Jidong Li , Renyun Zhang
AA6061 is pivotal for marine lightweight structures but suffers from severe corrosion in chloride-rich environments. To address this, a novel hydrophobic TiO2@Co-Mo-Ce coating was fabricated on AA6061 via synergistie co-deposition, and investigated role of nano-TiO2 in regulating metal ion co-deposition kinetics. Electrochemical analyses revealed that TiO2 nanoparticles induce a cathodic shift in deposition potential, suppress hydrogen evolution, and transform metal ion nucleation from progressive to instantaneous mode by providing additional nucleation sites. TiO2@Co-Mo-Ce hydrophobic coating generated micro/nano-roughness (Ra increased by 60%) and grafted low-surface-energy groups, achieving a static water contact angle of 133.21°. The composite coating exhibited exceptional corrosion resistance (corrosion rate: 0.00862 mm·a-1 98.4% lower than bare AA6061) and high microhardness (>300 HV0.2). This work elucidates the dynamic coupling mechanism of nano-TiO2 in multi-ion systems, providing a pathway for designing robust hydrophobic coatings for marine applications.
{"title":"Interfacial engineering of TiO2@Co-Mo-Ce hydrophobic coatings on AA6061 via synergistic Co-deposition: Role of nano-TiO2 in regulating metal ion Co-deposition kinetics","authors":"Hongxuan Xing , Zhongning Shi , Jidong Li , Renyun Zhang","doi":"10.1016/j.electacta.2025.147929","DOIUrl":"10.1016/j.electacta.2025.147929","url":null,"abstract":"<div><div>AA6061 is pivotal for marine lightweight structures but suffers from severe corrosion in chloride-rich environments. To address this, a novel hydrophobic TiO<sub>2</sub>@Co-Mo-Ce coating was fabricated on AA6061 via synergistie co-deposition, and investigated role of nano-TiO<sub>2</sub> in regulating metal ion co-deposition kinetics. Electrochemical analyses revealed that TiO<sub>2</sub> nanoparticles induce a cathodic shift in deposition potential, suppress hydrogen evolution, and transform metal ion nucleation from progressive to instantaneous mode by providing additional nucleation sites. TiO<sub>2</sub>@Co-Mo-Ce hydrophobic coating generated micro/nano-roughness (R<sub>a</sub> increased by 60%) and grafted low-surface-energy groups, achieving a static water contact angle of 133.21°. The composite coating exhibited exceptional corrosion resistance (corrosion rate: 0.00862 mm·a<sup>-1</sup> 98.4% lower than bare AA6061) and high microhardness (>300 HV0.2). This work elucidates the dynamic coupling mechanism of nano-TiO<sub>2</sub> in multi-ion systems, providing a pathway for designing robust hydrophobic coatings for marine applications.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"548 ","pages":"Article 147929"},"PeriodicalIF":5.6,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145651202","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 : 2025-12-01DOI: 10.1016/j.electacta.2025.147930
Haofeng Lu , Junping Tang , Zhenghu Zhu , Xunwang Duan , Xinyu Li , Cheng Chen , Xinfeng Wu , Yonghou Xiao , Lexing You , Xinzhou Ma , Xue Zhang , Weiheng Shih , Donghai Lin
Engineering the surface electronic structure of Pd-based catalysts is crucial for enhancing ethanol oxidation reaction (EOR) kinetics and durability in alkaline direct ethanol fuel cells. Herein, we report a high-performance PdBi alloy electrocatalyst supported on nitrogen-doped carbon monolith foam (CMF) derived from zeolitic imidazolate framework-8 (ZIF-8) pyrolysis and denoted as Pd₃Bi₁@CMF. The catalyst exhibits a mass activity of 1920 mA mg⁻¹Pd—2.8-fold higher than commercial Pd/C—attributed to its high electrochemical surface area (51.2 m² g⁻¹Pd) and uniform dispersion of ∼5.7 nm nanoparticles. X-ray photoelectron spectroscopy (XPS) confirms Bi-induced downshift of Pd 3d binding energy, weakening COads adsorption, while Bi promotes OH⁻ activation for oxidative removal of intermediates via a bifunctional mechanism. Strong metal–support interaction with N-doped CMF enhances structural stability, enabling 65.6 % activity retention after 300 CV cycles. Rotating disk electrode (RDE) analysis reveals a 5.2-electron transfer pathway, approaching the theoretical five-electron pathway for complete ethanol-to-acetate conversion. This study demonstrates that synergistic modulation of the surface electronic structure through alloying and rational support design offers a powerful strategy for developing advanced, durable, and highly active Pd-based EOR electrocatalysts.
{"title":"Engineering the surface electronic structure of Pd via Bi alloying and N-doped carbon support for enhanced ethanol oxidation","authors":"Haofeng Lu , Junping Tang , Zhenghu Zhu , Xunwang Duan , Xinyu Li , Cheng Chen , Xinfeng Wu , Yonghou Xiao , Lexing You , Xinzhou Ma , Xue Zhang , Weiheng Shih , Donghai Lin","doi":"10.1016/j.electacta.2025.147930","DOIUrl":"10.1016/j.electacta.2025.147930","url":null,"abstract":"<div><div>Engineering the surface electronic structure of Pd-based catalysts is crucial for enhancing ethanol oxidation reaction (EOR) kinetics and durability in alkaline direct ethanol fuel cells. Herein, we report a high-performance PdBi alloy electrocatalyst supported on nitrogen-doped carbon monolith foam (CMF) derived from zeolitic imidazolate framework-8 (ZIF-8) pyrolysis and denoted as Pd₃Bi₁@CMF. The catalyst exhibits a mass activity of 1920 mA mg⁻¹Pd—2.8-fold higher than commercial Pd/C—attributed to its high electrochemical surface area (51.2 m² g⁻¹Pd) and uniform dispersion of ∼5.7 nm nanoparticles. X-ray photoelectron spectroscopy (XPS) confirms Bi-induced downshift of Pd 3d binding energy, weakening CO<sub>ads</sub> adsorption, while Bi promotes OH⁻ activation for oxidative removal of intermediates via a bifunctional mechanism. Strong metal–support interaction with N-doped CMF enhances structural stability, enabling 65.6 % activity retention after 300 CV cycles. Rotating disk electrode (RDE) analysis reveals a 5.2-electron transfer pathway, approaching the theoretical five-electron pathway for complete ethanol-to-acetate conversion. This study demonstrates that synergistic modulation of the surface electronic structure through alloying and rational support design offers a powerful strategy for developing advanced, durable, and highly active Pd-based EOR electrocatalysts.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"548 ","pages":"Article 147930"},"PeriodicalIF":5.6,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145651114","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 : 2025-12-01DOI: 10.1016/j.electacta.2025.147931
Seyed Hamid Safiabadi Tali, Rozhin Saebi, Abdolali Mehrjou, Farzad Mirzaie, Zubi Sadiq, Marc-Antoni Goulet, Sana Jahanshahi-Anbuhi
Electrochemical paper-based analytical devices (ePADs) provide a low-cost, portable, and sensitive platform for diverse analytical applications. While screen printing is widely used for electrode fabrication, it often depends on specialized equipment and outsourced mask production, limiting accessibility in laboratories and resource-limited settings. Another key yet under-addressed challenge is the presence of hydrophobic ink components, which impede paper’s natural capillary flow and reduce the device’s electrochemical performance. In this study, we present a do-it-yourself (DIY) screen-printing method using a portable table with a mesh screen costing under USD 50 and CO2 laser-cut adhesive vinyl masks. This approach enables rapid, on-demand mask production and achieves electrode resolution of 286 ± 31 μm. Additionally, we introduce a simple yet highly effective post-printing water treatment to mitigate ink hydrophobicity. This method has led to a remarkable increase in oxidation peak currents, from 4 ± 2 μA to 305 ± 18 μA, when measuring 10 mM ferricyanide/ferrocyanide by cyclic voltammetry (-1 to 1 V, 0.1 V/s), corresponding to more than a 75-fold enhancement. We further developed a novel “sandwiched” electrode configuration, enclosing electrodes between two paper layers, which achieved a 1.96-fold increase in electroactive surface area over conventional single-layer designs. Applied to bienzymatic glucose detection as a proof-of-concept, these sandwiched ePADs showed a ∼1.8-fold increase in sensitivity. Finally, we have validated the ePADs for glucose sensing in cell culture media, demonstrating practical applicability. Collectively, these strategies provide a scalable, low-cost fabrication method and design enhancements that improve ePAD performance and usability, particularly in low-resource settings.
{"title":"Do-it-yourself screen printing of electrochemical paper-based analytical devices with water treatment and sandwiched electrodes for amplified signal","authors":"Seyed Hamid Safiabadi Tali, Rozhin Saebi, Abdolali Mehrjou, Farzad Mirzaie, Zubi Sadiq, Marc-Antoni Goulet, Sana Jahanshahi-Anbuhi","doi":"10.1016/j.electacta.2025.147931","DOIUrl":"10.1016/j.electacta.2025.147931","url":null,"abstract":"<div><div>Electrochemical paper-based analytical devices (ePADs) provide a low-cost, portable, and sensitive platform for diverse analytical applications. While screen printing is widely used for electrode fabrication, it often depends on specialized equipment and outsourced mask production, limiting accessibility in laboratories and resource-limited settings. Another key yet under-addressed challenge is the presence of hydrophobic ink components, which impede paper’s natural capillary flow and reduce the device’s electrochemical performance. In this study, we present a do-it-yourself (DIY) screen-printing method using a portable table with a mesh screen costing under USD 50 and CO<sub>2</sub> laser-cut adhesive vinyl masks. This approach enables rapid, on-demand mask production and achieves electrode resolution of 286 ± 31 μm. Additionally, we introduce a simple yet highly effective post-printing water treatment to mitigate ink hydrophobicity. This method has led to a remarkable increase in oxidation peak currents, from 4 ± 2 μA to 305 ± 18 μA, when measuring 10 mM ferricyanide/ferrocyanide by cyclic voltammetry (-1 to 1 V, 0.1 V/s), corresponding to more than a 75-fold enhancement. We further developed a novel “sandwiched” electrode configuration, enclosing electrodes between two paper layers, which achieved a 1.96-fold increase in electroactive surface area over conventional single-layer designs. Applied to bienzymatic glucose detection as a proof-of-concept, these sandwiched ePADs showed a ∼1.8-fold increase in sensitivity. Finally, we have validated the ePADs for glucose sensing in cell culture media, demonstrating practical applicability. Collectively, these strategies provide a scalable, low-cost fabrication method and design enhancements that improve ePAD performance and usability, particularly in low-resource settings.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"548 ","pages":"Article 147931"},"PeriodicalIF":5.6,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145651241","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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