Electrochimica Acta最新文献

{"title":"Development of Bimetallic MOF with reduced bandgap for high-performance asymmetric supercapacitors","authors":"Usama Zahid ,&nbsp;Muhammad Ramzan Khawar ,&nbsp;Sunmin Jang ,&nbsp;Yasir Javed ,&nbsp;Naveed Akhtar Shad ,&nbsp;Dongwhi Choi ,&nbsp;Awais Ahmad ,&nbsp;Munirah D. Albaqami","doi":"10.1016/j.electacta.2025.146103","DOIUrl":"10.1016/j.electacta.2025.146103","url":null,"abstract":"<div><div>Metal-organic framework (MOF) is a novel class of active material, a probable candidate for high-performance electrochemical energy storage devices due to their porous structure, enormous surface area, versatility, and structural tunability. Herein, we synthesized bimetallic MOFs with different concentrations of Ni or Co in Ag-MOF via a facile one-pot synthesis method and utilized it as a battery-type electrode in a hybrid supercapacitor. The flake-like synthesized materials exhibit outstanding electrochemical properties, specifically, Co₁Ag₃-MOF demonstrates the highest specific capacity/capacitance of 1323 C g⁻¹ (2646 F g⁻¹) at a current density of 1 A g⁻¹ and maintained 79.5 % of initial capacity even at higher current density. Moreover, the assembled asymmetric supercapacitor device (Co₁Ag₃-MOF//AC) achieves the highest energy density of 75.63 W h kg⁻¹ with a power density of 566.4 W kg⁻¹ at 1 A g⁻¹, manifesting reliable cyclic durability by retaining 88.35 % of its initial capacity and 92.45 % coulombic efficiency after 12,000 cycles. Moreover, the assembled hybrid coin cell can operate the commercially available calculator for 96 min. Based on both experimental and theoretical calculations, the optimized electronic structure of the Co₁Ag₃-MOF interface promotes electron transmission pathways and synergizes high redox activity, resulting in improved electrochemical performance. This study provides new insights into π-π conjugated materials with reduced band gap for further use in next-generation electronics for power supply.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"525 ","pages":"Article 146103"},"PeriodicalIF":5.5,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695326","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}

{"title":"UV-crosslinked glyoxal-methacrylate electrolytes for quasi-solid electric double layer capacitors","authors":"Silvia Porporato ,&nbsp;Juan Luis Gómez-Urbano ,&nbsp;Alessandro Piovano ,&nbsp;Giuseppe A. Elia ,&nbsp;Claudio Gerbaldi ,&nbsp;Andrea Balducci","doi":"10.1016/j.electacta.2025.146096","DOIUrl":"10.1016/j.electacta.2025.146096","url":null,"abstract":"<div><div>In this paper, the difunctional oligomer bisphenol A ethoxylate dimethacrylate (BEMA), known for readily undergo UV-induced polymerisation, is employed to produce a highly crosslinked polymer network, in combination with poly(ethylene glycol) methyl ether methacrylate (PEGMEMA) as a reactive diluent. The methacrylate-based membranes are soaked with a low-volatile glyoxal-based electrolyte, namely 1 M sodium bis(trifluoromethanesulfonil)imide (NaTFSI) in a 3:7 mixture of tetraethoxyglyoxal (TEG) and propylene carbonate (PC), respectively. The resulting gel polymer electrolytes are successfully employed for the fabrication of laboratory-scale quasi-solid electric double layer capacitors (EDLCs), showing sufficient thermal stability, high ionic conductivity at different temperatures, suitable electrochemical stability window and stable prolonged constant-current cycling (high capacitance up to 21 F <em>g</em>⁻¹ at 0.2 A <em>g</em>⁻¹ with excellent efficiency for thousands of cycles and &gt;85 % of capacitance retention after a rate capability test and 9500 reversible cycles), thus paving the way for further detailed studies and optimizations.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"525 ","pages":"Article 146096"},"PeriodicalIF":5.5,"publicationDate":"2025-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675431","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrospun graphene-cellulose acetate/Paulschulzia pseudovolvox (Algae) modified photoelectrodes generating electricity via harnessing solar energy: A novel biosensing design for photoelectrochemical pesticide detection via photosynthesis inhibition","authors":"Mustafa Buyukharman ,&nbsp;Nurbek Ashurov ,&nbsp;Abdumutolib Atakhanov ,&nbsp;Deniz Ozkan Vardar ,&nbsp;Hacer Azak ,&nbsp;Huseyin Bekir Yildiz","doi":"10.1016/j.electacta.2025.146099","DOIUrl":"10.1016/j.electacta.2025.146099","url":null,"abstract":"<div><div>This article explores the possibility of biophotovoltaic devices (BPVs) as a sustainable solution to the global energy issue and climate change mitigation. BPVs produce renewable power by harnessing sunshine and water, employing the photosynthetic processes of biological photocatalysts such as green algae and cyanobacteria. Carbon-based electrodes, particularly graphene (Gr), are distinguished as advantageous alternatives owing to their affordability, electrical conductivity, and mechanical robustness. While reduced graphene oxide is frequently utilized, non-oxidized graphene has not been extensively studied until recent researches emphasized its remarkable current-harvesting abilities. Moreover, one-dimensional structured nanomaterials, such as electrospun <em>nanofibers</em>, present opportunities for enhancing electron transit and augmenting charge collecting efficiency. A novel photoanode design has been developed, using <em>Paulschulzia pseudovolvox</em> sp. (green algae) immobilized on a graphene-cellulose acetate electrospun matrix. This mat offers a porous structure that facilitates suitable algal attachment and effective electron transfer. The cathode is linked to a gold electrode surface coated with Poly (4-(2,5-di(thiophen-2-yl)-1H-pyrrol-1-yl)benzamine), P(SNS-NH₂) electrochemically, on which the bilirubin oxidase (BOx) enzyme gets immobilized via glutaraldehyde activation. The algae-based system employs light to oxidize and dissociate water at the photoanode, producing oxygen. At the same time oxygen is converted to water at the cathode through bioelectrocatalysis. Optimizations were carried out to improve electron transport and promote electron transfer, hence achieving high photocurrent. Under optimal conditions, the BPV attained a peak power output of 55.2 mW/m² at a steady state with a current density of 125 mA/m². In addition to conversion of light energy to electricity, the system was applied as a pesticide biosensor. The BPV system effectively detected atrazine and diuron, with analytical characterisation performed for atrazine within the 0.1–1.2 μM range and diuron within the 0.01–0.15 μM range. The detection limits were significantly low, measuring 7.5 nM for atrazine and 0.29 nM for diuron. Furthermore, recovery studies were also performed to evaluate the pesticide biosensor capabilities of BPV.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"525 ","pages":"Article 146099"},"PeriodicalIF":5.5,"publicationDate":"2025-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675433","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}

{"title":"Optimizing self-assembled monolayer construction for aptasensors and preventing false signals. The case of erythromycin detection","authors":"Teodora Lupoi ,&nbsp;Sarah Baccara ,&nbsp;Yann R. Leroux ,&nbsp;Bogdan Feier ,&nbsp;Mathieu Pasturel ,&nbsp;Jean-Luc Cercus ,&nbsp;Cecilia Cristea ,&nbsp;Florence Geneste","doi":"10.1016/j.electacta.2025.146097","DOIUrl":"10.1016/j.electacta.2025.146097","url":null,"abstract":"<div><div>Although an aptamer selected for erythromycin (ERY) was synthesized and characterized, no electrochemical sensor has been reported yet. This study is the first development of an aptamer-based electrochemical sensor for ERY detection. Two immobilization platforms of the thiol-modified aptamer were evaluated: a gold-coated carbon screen-printed electrode (C-SPE) and a pure [111] gold electrode. Label-free ERY detection was performed by differential pulsed voltammetry (DPV) with K₄[Fe(CN)₆]/K₃[Fe(CN)₆] as a redox probe. Instability in surface chemistry initially led to a false signal on the C-SPE in the presence of ERY. To address this, we examined the stability of the mixed self-assembled monolayer (SAM) formed by the aptamer and a blocking agent. Extended thiol immobilization times enhanced the mixed SAM stability but did not improve the sensor analytical performance. Applying the optimized SAM construction to the pure gold electrode resulted in a stable aptasensor with a stable electrochemical signal during blank incubation. A calibration curve was obtained on the pure gold platform in an ERY concentration range of 1 × 10^–6 M to 2 × 10^–4 M with a limit of detection of 3.2 × 10^–7 M. In addition to the advancements made in the electrochemical detection of ERY using an aptamer-based sensor, this work provides insights into the stability of MCH/aptamer layers depending on their construction method.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"525 ","pages":"Article 146097"},"PeriodicalIF":5.5,"publicationDate":"2025-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675435","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}

{"title":"Effect of formamide and DMSO additives on the electrolyte properties of a lithium-ion battery: Experimental and theoretical study","authors":"Abdo Mohammed Al-Fakih,&nbsp;Jackson Tan,&nbsp;Madzlan Aziz,&nbsp;Muhammad Amirul Aizat Mohd Abdah,&nbsp;Hasmerya Maarof,&nbsp;Che Rozid Mamat,&nbsp;Mohamad Hamdi Zainal-Abidin,&nbsp;Juan Matmin","doi":"10.1016/j.electacta.2025.146095","DOIUrl":"10.1016/j.electacta.2025.146095","url":null,"abstract":"<div><div>Electrolytes play a vital role in the performance of lithium-ion batteries by enabling efficient ion transport and energy storage. To improve battery efficiency, additives are often incorporated into electrolytes. This study investigates the impact of formamide and dimethyl sulfoxide (DMSO) as additives in a typical lithium-ion battery electrolyte, ethylene carbonate/diethyl carbonate (EC/DEC). Formamide and DMSO were individually added to EC/DEC, and the electrochemical properties of the resulting electrolytes EC/DEC, EC/DEC in formamide, and EC/DEC in DMSO were assessed using linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS). The EC/DEC typical electrolyte and EC/DEC in DMSO were further analyzed using cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD) testing. Density functional theory (DFT) calculations were also performed to theoretically assess the electrolyte behavior and lithium-ion (Li⁺) solvation in the studied electrolytes. The findings exhibit enhanced conductivity and ion transference numbers of the electrolytes with formamide and DMSO compared to the typical EC/DEC electrolyte. The EC/DEC in formamide and DMSO electrolytes demonstrated better electrochemical stability under high voltage conditions. DFT results revealed that the HOMO-LUMO energy gap (∆<em>E</em>) for the EC/DEC electrolyte (8.3604 eV) increases when EC/DEC is combined with DMSO (8.6680 eV) or formamide (8.6663 eV), suggesting improved electrochemical stability. DFT calculations revealed that the addition of formamide and DMSO enhances the stability of the interaction between Li⁺ and EC/DEC, facilitating Li⁺ dissociation and improving its transport within the electrolyte. However, electrochemical cycling performance testing for the EC/DEC in DMSO electrolyte shows a decline in the later stages, indicating reduced electrochemical reversibility, likely due to solid electrolyte interphase (SEI) degradation in the presence of DMSO. This highlights the need to optimize the additive concentration in the EC/DEC electrolyte to achieve optimal electrochemical performance and extended cycle life.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"525 ","pages":"Article 146095"},"PeriodicalIF":5.5,"publicationDate":"2025-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675434","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}

{"title":"Nanoneedle array structure optimization-induced mass transfer in all-vanadium flow batteries","authors":"Yuan Liu ,&nbsp;Haoming Meng ,&nbsp;Kai Wan ,&nbsp;Sen Yao ,&nbsp;Yuxiang Miao ,&nbsp;Jinghua Li ,&nbsp;Jiaxi Xia ,&nbsp;Hai Li ,&nbsp;Mingfeng Du ,&nbsp;Tao Xie ,&nbsp;Chong Li ,&nbsp;Jianjun Hu","doi":"10.1016/j.electacta.2025.146089","DOIUrl":"10.1016/j.electacta.2025.146089","url":null,"abstract":"<div><div>This paper employs a robust acid pretreatment to activate the graphite felt electrode, subsequently facilitating the generation of nickel cobalt oxide (NiCoO₂) nano-needle arrays on the surface of the graphite felt electrode through a hydrothermal method. Additionally, the paper demonstrates the successful doping of the NiCoO₂ structure with nitrogen through the utilization of an ammonia annealing process. The experimental results reveal that this modification initiative enlarges the BET specific surface area of the electrode by a factor of sixteen. Furthermore, the needle array structure not only increases the delivery of active substances but also greatly facilitates the electrochemical reaction. The electrochemical performance of the modified graphite felts was markedly enhanced in comparison to that of the pristine graphite felts, due to the combined effect of the Ni-Co oxides' efficient electrocatalytic ability and the improvement of the mass transfer ability of the electrode resulting from the alteration of the electrode surface structure. The doping of the metal oxides with nitrogen can further increase their conductivity, thereby enhancing their catalytic performance for redox reactions. The Multiphysics simulation results on the electrode surface demonstrate that the upright channels between the needle arrays facilitate the full and rapid reaction of vanadium ions on the electrode surface, enabling the products to be detached from the electrode in a timely manner, which in turn reduces the concentration polarization on the electrode surface.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"525 ","pages":"Article 146089"},"PeriodicalIF":5.5,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675437","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}

{"title":"Performance Evaluation of Hydrothermally Prepared Ce-doped SrSnO3 for Electrochemical Energy Storage","authors":"Shahzaib Khan, Soumaya Gouadria, Abdullah G. Al-Sehemi, Abhinav Kumar","doi":"10.1016/j.electacta.2025.146091","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.146091","url":null,"abstract":"Perovskite-based nanostructures have been widely researched for supercapacitors, resulting in their outstanding conductivity, electrochemical features, minimal cost, and eco-friendliness. However, this study aims to compare the electrochemical activity of strontium tin oxide (SrSnO₃) and Ce-doped SrSnO₃ created by a one-pot hydrothermal procedure. The as-prepared materials were thoroughly analysed for their structure, chemical composition, and capacitive performance. The X-ray diffraction analysis indicated that the SrSnO₃ phase had a cubic crystal system. The capacitance, charge/discharge rate, and rate capability of SrSnO₃ were improved by cerium doping. The Ce-doped SrSnO₃ showed exceptional super-capacitive activity with a specific capacitance (C_sp) of 1155 F/g, specific energy (S_E) of 48 Wh/kg, and specific power (S_P) of 308 W/kg at a 1 A/g current density (j). Additionally, the doped material exhibited lower internal resistance than the undoped sample. The remarkable performance of the doped material was accredited to increased active sites, conductivity, electroactive surface, and a high ion diffusion rate. The advantageous characteristics of Ce-doped SrSnO₃ render it a potential material for electrochemical devices. However, the results provide a solid basis for creating advanced supercapacitor electrodes with more remarkable performance. Therefore, this work enhances our understanding of perovskites and demonstrates their potential use in electrochemistry, particularly for energy storage.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"18 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675438","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}

{"title":"CuO doping SiO2 for enhancing electron transfer to product C2H4 in electrocatalytic CO2 reduction","authors":"Xu Ji, Weicong Xu, Chao Liu, Xing Wang","doi":"10.1016/j.electacta.2025.146090","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.146090","url":null,"abstract":"The electrocatalytic CO₂ reduction reaction (CO₂RR) offers a promising pathway for carbon cycling and high-value fuel synthesis. However, the efficient production of ethylene (C₂H₄), a critical multicarbon product, remains constrained by insufficient catalyst activity and selectivity. Although copper-based materials enable C–C coupling, conventional CuO catalysts suffer from imbalanced *CO intermediate adsorption strength and sluggish charge transfer kinetics‌.In this study, a silica (SiO₂) doping strategy was employed to synergistically modulate the electronic structure and surface active site distribution of CuO, significantly enhancing CO₂-to-C₂H₄ conversion efficiency. Experimental results demonstrate that SiO₂ incorporation induces local electronic density rearrangement around Cu²⁺, stabilizing *CO adsorption, while the constructed Cu-O-Si interfaces accelerate charge transfer, enhances electron transfer and reduce the energy barrier for *COCHO formation. The optimized SiO₂-10%/CuO catalyst achieves a C₂H₄ Faraday efficiency of 42% and a partial current density of 6.3 mA/cm² at −1.4 V (vs. RHE), representing a threefold improvement over pristine CuO. Notably, the catalyst exhibits exceptional stability over 4 hours‌.Structural characterization and theoretical calculations reveal that SiO₂ doping promotes the self-assembly of CuO nanosheets into flower-like architectures with a high specific surface area and exposes synergistic (111)/(002) facets, which collectively enhance *CO intermediate enrichment and directional coupling‌. This work provides novel insights into designing high-performance CO₂RR catalysts through multidimensional modulation strategies.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"70 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675466","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}

{"title":"Correction to the conventional Klingler-Kochi method for accurate assessment of electrochemical kinetic parameters utilizing cyclic voltammetry","authors":"Rahul Agarwal","doi":"10.1016/j.electacta.2025.146081","DOIUrl":"10.1016/j.electacta.2025.146081","url":null,"abstract":"&lt;div&gt;&lt;div&gt;The conventional Klingler-Kochi method has been utilized for several decades and has recently gained significant traction in the estimation of electrochemical kinetic parameters. This includes the determination of formal electrode potential (&lt;span&gt;&lt;math&gt;&lt;msubsup&gt;&lt;mi&gt;E&lt;/mi&gt;&lt;mrow&gt;&lt;mi&gt;f&lt;/mi&gt;&lt;/mrow&gt;&lt;mn&gt;0&lt;/mn&gt;&lt;/msubsup&gt;&lt;/math&gt;&lt;/span&gt;), standard rate constant (&lt;span&gt;&lt;math&gt;&lt;msup&gt;&lt;mrow&gt;&lt;mi&gt;k&lt;/mi&gt;&lt;/mrow&gt;&lt;mn&gt;0&lt;/mn&gt;&lt;/msup&gt;&lt;/math&gt;&lt;/span&gt;) and dimensionless kinetic parameter (ψ) through the technique of cyclic voltammetry. However, the values obtained through this method occasionally exhibit significant discrepancies when compared to those derived from alternative techniques. The validation of the analytically derived Klingler-Kochi equations through alternate theoretical approach namely numerical methods (digital simulations) has revealed inaccuracies, resulting in misleading interpretations of kinetic data. Consequently, the original equations proposed by Klingler-Kochi have been re-derived, resulting in the refinement of the previous equations. This revised approach is referred to as the corrected Klingler-Kochi method, which should be employed for the accurate estimation of &lt;span&gt;&lt;math&gt;&lt;msubsup&gt;&lt;mi&gt;E&lt;/mi&gt;&lt;mrow&gt;&lt;mi&gt;f&lt;/mi&gt;&lt;/mrow&gt;&lt;mn&gt;0&lt;/mn&gt;&lt;/msubsup&gt;&lt;/math&gt;&lt;/span&gt;, &lt;span&gt;&lt;math&gt;&lt;msup&gt;&lt;mrow&gt;&lt;mi&gt;k&lt;/mi&gt;&lt;/mrow&gt;&lt;mn&gt;0&lt;/mn&gt;&lt;/msup&gt;&lt;/math&gt;&lt;/span&gt; and ψ for redox couples that adhere to the Butler-Volmer kinetic model, particularly those with a peak potential difference greater than 150 mV and a cathodic charge transfer coefficient (&lt;span&gt;&lt;math&gt;&lt;msub&gt;&lt;mi&gt;α&lt;/mi&gt;&lt;mi&gt;c&lt;/mi&gt;&lt;/msub&gt;&lt;/math&gt;&lt;/span&gt;) within the range of 0.3 &lt; &lt;span&gt;&lt;math&gt;&lt;msub&gt;&lt;mi&gt;α&lt;/mi&gt;&lt;mi&gt;c&lt;/mi&gt;&lt;/msub&gt;&lt;/math&gt;&lt;/span&gt; &lt; 0.7. The assertions are additionally substantiated by experimental validation through voltammetric analysis of the redox couples &lt;span&gt;&lt;math&gt;&lt;mrow&gt;&lt;mspace&gt;&lt;/mspace&gt;&lt;msup&gt;&lt;mrow&gt;&lt;mo&gt;[&lt;/mo&gt;&lt;mrow&gt;&lt;mi&gt;U&lt;/mi&gt;&lt;msub&gt;&lt;mi&gt;O&lt;/mi&gt;&lt;mn&gt;2&lt;/mn&gt;&lt;/msub&gt;&lt;msub&gt;&lt;mrow&gt;&lt;mo&gt;(&lt;/mo&gt;&lt;mrow&gt;&lt;mi&gt;C&lt;/mi&gt;&lt;msub&gt;&lt;mi&gt;O&lt;/mi&gt;&lt;mn&gt;3&lt;/mn&gt;&lt;/msub&gt;&lt;/mrow&gt;&lt;mo&gt;)&lt;/mo&gt;&lt;/mrow&gt;&lt;mn&gt;3&lt;/mn&gt;&lt;/msub&gt;&lt;/mrow&gt;&lt;mo&gt;]&lt;/mo&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mn&gt;4&lt;/mn&gt;&lt;mo&gt;−&lt;/mo&gt;&lt;/mrow&gt;&lt;/msup&gt;&lt;mo&gt;/&lt;/mo&gt;&lt;msup&gt;&lt;mrow&gt;&lt;mo&gt;[&lt;/mo&gt;&lt;mrow&gt;&lt;mi&gt;U&lt;/mi&gt;&lt;msub&gt;&lt;mi&gt;O&lt;/mi&gt;&lt;mn&gt;2&lt;/mn&gt;&lt;/msub&gt;&lt;msub&gt;&lt;mrow&gt;&lt;mo&gt;(&lt;/mo&gt;&lt;mrow&gt;&lt;mi&gt;C&lt;/mi&gt;&lt;msub&gt;&lt;mi&gt;O&lt;/mi&gt;&lt;mn&gt;3&lt;/mn&gt;&lt;/msub&gt;&lt;/mrow&gt;&lt;mo&gt;)&lt;/mo&gt;&lt;/mrow&gt;&lt;mn&gt;3&lt;/mn&gt;&lt;/msub&gt;&lt;/mrow&gt;&lt;mo&gt;]&lt;/mo&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mn&gt;5&lt;/mn&gt;&lt;mo&gt;−&lt;/mo&gt;&lt;/mrow&gt;&lt;/msup&gt;&lt;/mrow&gt;&lt;/math&gt;&lt;/span&gt;, &lt;span&gt;&lt;math&gt;&lt;mrow&gt;&lt;msup&gt;&lt;mrow&gt;&lt;mo&gt;[&lt;/mo&gt;&lt;mrow&gt;&lt;mtext&gt;Pu&lt;/mtext&gt;&lt;msub&gt;&lt;mi&gt;O&lt;/mi&gt;&lt;mn&gt;2&lt;/mn&gt;&lt;/msub&gt;&lt;msub&gt;&lt;mrow&gt;&lt;mo&gt;(&lt;/mo&gt;&lt;mrow&gt;&lt;mi&gt;C&lt;/mi&gt;&lt;msub&gt;&lt;mi&gt;O&lt;/mi&gt;&lt;mn&gt;3&lt;/mn&gt;&lt;/msub&gt;&lt;/mrow&gt;&lt;mo&gt;)&lt;/mo&gt;&lt;/mrow&gt;&lt;mn&gt;3&lt;/mn&gt;&lt;/msub&gt;&lt;/mrow&gt;&lt;mo&gt;]&lt;/mo&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mn&gt;4&lt;/mn&gt;&lt;mo&gt;−&lt;/mo&gt;&lt;/mrow&gt;&lt;/msup&gt;&lt;mo&gt;/&lt;/mo&gt;&lt;msup&gt;&lt;mrow&gt;&lt;mo&gt;[&lt;/mo&gt;&lt;mrow&gt;&lt;mtext&gt;Pu&lt;/mtext&gt;&lt;msub&gt;&lt;mi&gt;O&lt;/mi&gt;&lt;mn&gt;2&lt;/mn&gt;&lt;/msub&gt;&lt;msub&gt;&lt;mrow&gt;&lt;mo&gt;(&lt;/mo&gt;&lt;mrow&gt;&lt;mi&gt;C&lt;/mi&gt;&lt;msub&gt;&lt;mi&gt;O&lt;/mi&gt;&lt;mn&gt;3&lt;/mn&gt;&lt;/msub&gt;&lt;/mrow&gt;&lt;mo&gt;)&lt;/mo&gt;&lt;/mrow&gt;&lt;mn&gt;3&lt;/mn&gt;&lt;/msub&gt;&lt;/mrow&gt;&lt;mo&gt;]&lt;/mo&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mn&gt;5&lt;/mn&gt;&lt;mo&gt;−&lt;/mo&gt;&lt;/mrow&gt;&lt;/msup&gt;&lt;/mrow&gt;&lt;/math&gt;&lt;/span&gt;, &lt;span&gt;&lt;math&gt;&lt;mrow&gt;&lt;mi&gt;F&lt;/mi&gt;&lt;msup&gt;&lt;mrow&gt;&lt;mi&gt;e&lt;/mi&gt;","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"525 ","pages":"Article 146081"},"PeriodicalIF":5.5,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675436","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}

{"title":"Recombination layers for effective hydrogen crossover mitigation in proton exchange membrane water electrolyzers: Fabrication, characterization, and fundamental principles of operation","authors":"Alanna M. Gado ,&nbsp;Ryan J. Ouimet ,&nbsp;Leonard Bonville ,&nbsp;Radenka Maric ,&nbsp;Stoyan Bliznakov","doi":"10.1016/j.electacta.2025.146092","DOIUrl":"10.1016/j.electacta.2025.146092","url":null,"abstract":"<div><div>One major challenge that proton exchange membrane water electrolyzers (PEMWEs) face is hydrogen (H₂) gas crossover. If left unmitigated, H₂ crossover impacts the cell durability and becomes a safety issue. Fabrication of a catalytic recombination layer (RL) within the volume of the proton exchange membrane that provides active catalytic sites for recombination of hydrogen and oxygen gas molecules to water, is a viable strategy for H₂ crossover mitigation. This paper reports on designing, fabrication, and testing of membrane electrode assemblies (MEAs) for PEMWEs with two RLs. The recombination layers are incorporated into the volume of the membrane of a MEA fabricated by the reactive spray deposition technology (RSDT) method. As fabricated MEAs with an active area of 25 cm² and low catalyst loadings (0.3 mg_Ir cm^-2 on the anode and 0.2 mg_Pt cm^-2 on the cathode) demonstrated excellent performance. The RSDT-fabricated RLs demonstrated effective reduction of the H₂ crossover from about 50% of the lower flammability limit (LFL) to below 10% of the LFL, when operating at current densities between 0.58 A cm^-2 and 1.86 A cm^-2. Electrochemical impedance spectroscopy and distribution of relaxation times analysis are used to study the mechanism of the recombination reaction for both RLs. The analysis of the results provides for the first-time insights into the fundamental mechanism of the H₂ and O₂ recombination reaction on the Pt active catalytic sites in the RLs integrated in the membrane of PEMWEs.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"525 ","pages":"Article 146092"},"PeriodicalIF":5.5,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675467","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}