ACS electrochemistry最新文献

{"title":"Paper-Based Electroanalysis for Emerging Pollutant Detection.","authors":"Sima Singh, Alessandra Glovi, Gabriella Iula, Stefano Cinti","doi":"10.1021/acselectrochem.5c00332","DOIUrl":"10.1021/acselectrochem.5c00332","url":null,"abstract":"<p><p>Over the past two decades, the pollution lexicon has expanded beyond nutrients, hydrocarbons, and heavy metals to include emerging pollutants (EPs) and emerging contaminants (ECs), which now pose a critical challenge to environmental monitoring. Although, the conventional techniques are accurate and sensitive but often impractical for rapid, on-site monitoring. In response, a new wave of innovation has emerged to redefine environmental sensing through the development of paper-based electrochemical analytical devices (ePADs) which is a convergence of green chemistry, flexible electronics, and smart design. At the heart of their effectiveness lies in cellulose materials which depends on renewability, biodegradability, capillarity, and flexibility enable effective, low impact ePADs for passive fluid handling and microfluidics. Advances in 3D origami-based ePADs enable multi-analyte sensing, and, when paired with green manufacturing and smartphone-linked, low-power electronics, deliver real-time, cloud-ready data. Achieving widespread, sustainable deployment for decentralized pollution monitoring will require standardized validation, scalable manufacturing, and collaboration across scientific, technological, and policy domains. Looking forward, more than a replacement for conventional techniques, ePADs invite us to rethink our relationship with the environment. It signals a new contract between innovation and the planet-one in which analytical performance is inseparable from ecological responsibility. Each cellulose channel and fold demonstrates that high-precision sensing can be lightweight, biodegradable, and accessible. In this vision, smarter technology is also gentler, delivering cleaner water, healthier communities, and a more resilient Earth.</p>","PeriodicalId":520400,"journal":{"name":"ACS electrochemistry","volume":"1 12","pages":"2630-2647"},"PeriodicalIF":0.0,"publicationDate":"2025-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12683636/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145717175","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Comparative Study of Conductive 3D Printing Filaments for Electrochemical Sensing Applications Pretreated by Alumina Polishing, Electrochemical Activation, and Electrodeposition of Au Nanoparticles.","authors":"Shakir Ahmed, Enock G Arthur, Tanner Obrzut, Ricoveer Shergill, Alexa Williams, Kelvin Wamalwa, Zackary D Epright, Cameron Darvish, Yousef Khatib, Wanlu Li, Bhavik A Patel, Glen D O'Neil","doi":"10.1021/acselectrochem.5c00240","DOIUrl":"10.1021/acselectrochem.5c00240","url":null,"abstract":"<p><p>3D-printed electrochemical devices have gained tremendous attention recently because they are highly customizable platforms for analysis and energy storage that can be produced using simple, inexpensive components in a wide variety of settings. 3D-printed electrochemical sensors, fabricated from carbon-loaded conductive thermoplastics, enable decentralized production of electrochemical devices that, if optimized, could be widely distributed. Achieving this goal requires a comprehensive understanding of the electrochemical behavior of these filaments. Here, we investigated how the electrochemical behavior of three commercial filaments was affected by alumina polishing, electrochemical activation in 0.5 M NaOH, and electrodepositing Au nanoparticles (NPs). The goal of this study is to characterize if/how these commonly used pretreatments affect different filaments. The study is not an exhaustive combination of all filaments and pretreatment options. We characterized the physical properties of each filament/pretreatment using thermogravimetric analysis, scanning electron microscopy, and Raman microscopy measurements. We then benchmarked the background electrochemical processes (capacitance and solvent window), the peak current response versus scan rate, and the peak potential separation of two common outer-sphere redox species (ruthenium hexamine and ferrocene methanol) for each filament under each pretreatment (<i>i.e.</i>, nine total conditions). We subsequently investigated how the filaments responded to inner-sphere redox couples that were surface sensitive (ferrocyanide oxidation), dependent on surface adsorption (dopamine oxidation), and sensitive to surface oxides (Fe²⁺ oxidation). The data collectively underline the complexity of electrodes fabricated from conductive 3D printing filaments and highlight several important considerations that should be addressed when interpreting the electrochemistry of such materials. First, we present evidence that these materials behave as partially blocked electrodes, which complicates interpretations of electrochemical data. We also found that the outer-sphere electrochemical reactivity on a given filament was largely consistent regardless of pretreatment. The important variable for assessing outer-sphere electron transfer was the uncompensated resistance (<i>R</i> _u), which varies depending on the filament material, electrode size, and contact method. Finally, we observed that the selected filaments do not respond to pretreatments identically when tested against inner-sphere redox species, suggesting that a variety of treatments should be evaluated when assessing conductive 3D-printed filament electrodes.</p>","PeriodicalId":520400,"journal":{"name":"ACS electrochemistry","volume":"1 11","pages":"2386-2401"},"PeriodicalIF":0.0,"publicationDate":"2025-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12598703/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145497789","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Highly Corrugated Ni Films Electrodeposited onto Boron Doped Diamond Electrodes for Alkaline Water Electrolysis.","authors":"Alexander W Black, Paul W May, David J Fermin","doi":"10.1021/acselectrochem.5c00319","DOIUrl":"10.1021/acselectrochem.5c00319","url":null,"abstract":"<p><p>Ni-based electrocatalysts are among the most active materials for the hydrogen evolution reaction (HER) in alkaline media. In this work, we demonstrate the ability to use films of boron-doped diamond (BDD), a stable and corrosion-resistant electrode material, as a support for highly textured Ni films. Our approach is based on the electrodeposition of NiCu alloy thin-films, followed by electrochemical dealloying. The structure and composition of the electrocatalysts were characterized using scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. In pH 13 KOH, a dealloyed Ni catalyst corresponding to an initial NiCu composition of 68% Ni, gave a HER overpotential at 10 mA cm^-2 of 152 mV. With further analysis, we show that the rate of HER is 2^nd order with respect to the number of Ni active sites, and that the kinetics are limited by the surface diffusion of adsorbed intermediates. Two Tafel slopes are additionally observed, suggesting a change in HER mechanism and intrinsic activity at dealloyed Ni catalysts.</p>","PeriodicalId":520400,"journal":{"name":"ACS electrochemistry","volume":"1 11","pages":"2591-2601"},"PeriodicalIF":0.0,"publicationDate":"2025-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12598865/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145497902","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Operando Impedance Spectroscopy Informed Dynamic Internal Resistance Compensation Mitigates Bubble-Induced Distortions of the Applied Potential.","authors":"Blaž Tomc, Miha Hotko, Aleš Marsel, Nik Maselj, Maja Svete, Luka Suhadolnik, Marjan Bele, Pedro Farinazzo Bergamo Dias Martins, Dušan Strmčnik, Miran Gaberšček, Nejc Hodnik","doi":"10.1021/acselectrochem.5c00368","DOIUrl":"10.1021/acselectrochem.5c00368","url":null,"abstract":"<p><p>Bubble formation during gas-evolving electrochemical reactions disrupts potential control and obscures intrinsic catalyst-performance relationships. While conventional strategies to mitigate this issue have relied on surface engineering or cell design, here we introduce a dynamic internal resistance (IR) compensation approach that adapts to bubble-induced fluctuations in real time. This was achieved by employing (i) operando electrochemical impedance spectroscopy (EIS), which provided the electrolyte resistance (<i>R</i> _Ohm) parameter continuously, and (ii) a Python control loop to extract EIS data and dynamically adjust the IR compensation. This self-correcting approach effectively suppressed bubble-induced artifacts during prolonged electrochemical CO₂ reduction (ECO₂R) on copper, enabling accurate performance evaluation and reliable assessment of catalyst instability under realistic operating conditions. We argue that such control is essential in ECO₂R stability studies, where even minor potential shifts can obscure intrinsic catalyst-performance relationships and hinder mechanistic insight into degradation.</p>","PeriodicalId":520400,"journal":{"name":"ACS electrochemistry","volume":"1 12","pages":"2823-2830"},"PeriodicalIF":0.0,"publicationDate":"2025-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12683638/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145717170","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"H₂O₂ Synthesis with Molecular Electrocatalysts Enables Substantial Current Densities in a Flow Cell Using Gas Diffusion Electrodes.","authors":"Phebe H van Langevelde, Nathalie E G Ligthart, Pim G J van Duren, David A Vermaas, Dennis G H Hetterscheid","doi":"10.1021/acselectrochem.5c00179","DOIUrl":"10.1021/acselectrochem.5c00179","url":null,"abstract":"<p><p>The development of catalysts for the two-electron oxygen reduction reaction (ORR) toward H₂O₂ generation has gained substantial interest, as well as studying their activity in advanced electrochemical cell configurations. However, molecular ORR catalysts are seldom studied outside of the idealized environment of a rotating disk electrode (RDE) setup. Consequently, the catalytic currents reported for all molecular catalysts are limited by the mass transport of oxygen, and their properties in industrially relevant reactor configurations have remained unexplored. To assess their full potential, we report herein the application of a molecular, copper-based ORR catalyst, Cu-(tmpa) (tmpa = tris-(2-pyridylmethyl)-amine), in a cell configuration with gas diffusion electrodes (GDEs) to enhance mass transfer and thereby catalytic currents. We have identified the factors that control the catalytic current, such as buffer and catalyst concentration and GDE composition, using a readily assembled GDE cell, and we demonstrate that Cu-(tmpa) can generate H₂O₂ over multiple hours in a GDE flow cell. Under these conditions, a Faradaic efficiency of 50% can be maintained and H₂O₂ can be generated at a rate of 0.11 mmol cm^-2 h^-1 at a current density of -20 mA/cm². The current density is increased by almost 10 times in a GDE configuration compared to a conventional RDE setup, and the selectivity trends of the GDE system differ from the results obtained in an RDE setup, as a higher current density generates a higher selectivity toward H₂O₂ in a GDE setup. Overall, this work shows that the full potential of molecular catalysts can be assessed upon their implementation in a GDE setup and that their well-defined active sites can contribute to the emerging field of H₂O₂-generating catalysts.</p>","PeriodicalId":520400,"journal":{"name":"ACS electrochemistry","volume":"1 11","pages":"2326-2337"},"PeriodicalIF":0.0,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12598710/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145497954","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Activating C-C Coupling on Copper during CO₂RR: Charge-Controlled Design of Alloy Catalysts.","authors":"Wei Wang, Mattia Salomone, Michele Re Fiorentin, Francesca Risplendi, Giancarlo Cicero","doi":"10.1021/acselectrochem.5c00297","DOIUrl":"10.1021/acselectrochem.5c00297","url":null,"abstract":"<p><p>CO dimerization is a key step in the electrochemical reduction of CO₂ to multicarbon (C₂₊) products at low overpotentials. Although Cu(100) is uniquely active for this process, its performance remains limited, and the mechanisms behind improved activity and selectivity through alloying are not fully understood. Here, we combine machine-learning screening with constant-potential density functional theory simulations to systematically investigate CO dimerization on dilute CuM(100) alloys. p-block metals, particularly Al and Ga, make the reaction exothermic and lower the activation barrier relative to pure Cu, with Al showing the highest activity. Charge analysis along the reaction path reveals that electron donation from these heteroatoms stabilizes the CO dimer intermediate, enabling efficient C-C coupling under operating conditions. This behavior is captured by a strong linear correlation between reaction energy and excess surface charge at fixed potential, introducing a physically grounded descriptor that integrates covalent and electrostatic contributions to reaction energetics. Our findings reveal that excess surface charge can serve as a practical reactivity descriptor that directly correlates with C-C coupling activity and guides the rational design of more efficient CO₂RR electrocatalysts.</p>","PeriodicalId":520400,"journal":{"name":"ACS electrochemistry","volume":"1 11","pages":"2512-2520"},"PeriodicalIF":0.0,"publicationDate":"2025-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12598899/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145497841","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Anion Exchange Membrane Water Electrolysis Using a Catalyst-Coated Membrane Cathode.","authors":"Habin Park, Shane Harris, Paul A Kohl","doi":"10.1021/acselectrochem.5c00280","DOIUrl":"10.1021/acselectrochem.5c00280","url":null,"abstract":"<p><p>A catalyst-coated membrane (CCM) approach to electrode fabrication for high pH water electrolysis offers enhanced interfacial contact between the catalyst layer and the membrane surface in comparison to the catalyst-coated substrate (CCS) electrode configuration. The CCM facilitates enhanced ionic and water transport between the cathode and the anion exchange membrane (AEM). This advantage is particularly significant with AEM water electrolysis (compared to proton exchange membrane water electrolysis) because the cathode typically operates under dry conditions and relies solely on diffusive water transport across the AEM from the liquid-fed anode. This study presents a direct performance comparison between CCS and CCM cathode configurations using identical hydrogen evolution reaction (HER) catalysts and other components. The use of a pseudo-reference electrode integrated into the membrane electrode assembly enabled detailed analysis of the CCM cathode polarization behavior. Surface characterization provided insight into the degradation mechanisms associated with the CCM configuration. Optimization of the cathode ionomer cross-link density improved both the cathode polarization performance and the electrolysis device durability. Further optimization of the HER catalyst loading in the CCM cathode resulted in additional gains in the electrolysis efficiency. Collectively, these findings offer valuable guidance for the design and fabrication of high-performance, durable AEM electrolysis CCMs.</p>","PeriodicalId":520400,"journal":{"name":"ACS electrochemistry","volume":"1 11","pages":"2495-2502"},"PeriodicalIF":0.0,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12598701/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145497947","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Coupled Benchtop NMR and EPR Spectroscopy Reveals the Electronic Structure of Viologen Radicals in a Redox Flow Battery.","authors":"Giu A Silva Testa, Mathijs A Damhuis, Tom Speelman, Kim Baas, Johannes A A W Elemans, Evan Wenbo Zhao","doi":"10.1021/acselectrochem.5c00194","DOIUrl":"10.1021/acselectrochem.5c00194","url":null,"abstract":"<p><p>Viologens are a class of organic molecules with promising properties for redox flow battery applications. However, their molecular-level mechanisms remain challenging to fully probe and understand. In particular, the role of π-dimerization of singly reduced radicals is still debated, with conflicting views on its impact on battery performance. The electronic structure of a viologen radical in a working redox flow battery has remained elusive. Magnetic resonance spectroscopies offer powerful methods for studying flow batteries in <i>operando</i>, but their high cost and maintenance requirements make them less accessible to many researchers in the community. In this study, we introduce a novel dual benchtop nuclear magnetic resonance and electron paramagnetic resonance methodology to investigate viologen-based redox flow batteries. We revealed the electron spin density of in situ generated radicals via the hyperfine coupling interactions measured by EPR, aided by DFT calculations. Notably, the relatively low radical concentration observed during battery cycling suggests that π-dimers form even at a low concentration of 10 mM. Stability of the viologen radicals was also monitored. This study highlights the strength of the dual benchtop approach in uncovering molecular-scale processes in a redox flow battery. Moreover, its flexible and accessible design makes this coupled benchtop technique a versatile tool for investigating a wide range of flow electrochemical systems.</p>","PeriodicalId":520400,"journal":{"name":"ACS electrochemistry","volume":"1 10","pages":"1977-1982"},"PeriodicalIF":0.0,"publicationDate":"2025-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12498384/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145246258","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Unblocking a Path for Single Entity Electrochemistry in Digital Sensing.","authors":"Audrey Pumford, Ruixuan Wan, Wenyu Huang, Bo Zhang, Ryan J White","doi":"10.1021/acselectrochem.5c00188","DOIUrl":"10.1021/acselectrochem.5c00188","url":null,"abstract":"<p><p>Traditionally, single nanoparticle collision experiments have been used to understand fundamental properties about nanoparticles at the highest resolution-one at a time. However, this technique shows great promise in being used for future applications such as a digital sensing platform. For this technique to translate into an ultrasensitive sensing method, two main challenges must be addressed: (1) achieving sufficient sensitivity (signal-to-noise ratio) when there are modifications to the particle or electrode to impart biospecificity or chemical specificity and (2) improving the reproducibility and standardization of data analysis across experiments. In this perspective, we discuss the state of the field of nanoparticle collision experiments, common challenges researchers may face, and suggestions on what it will take to move this technique forward into important and ultrasensitive applications.</p>","PeriodicalId":520400,"journal":{"name":"ACS electrochemistry","volume":"1 9","pages":"1545-1554"},"PeriodicalIF":0.0,"publicationDate":"2025-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13502092/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148815416","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Revealing and Mitigating Crossover-Driven Side Reactions in Ferrocyanide-Based Redox Flow Batteries.","authors":"Emma J Latchem, Thomas Kress, Muireann Anna de H-Óra, Anqi Wang, Qilei Song, Alexander C Forse","doi":"10.1021/acselectrochem.5c00178","DOIUrl":"10.1021/acselectrochem.5c00178","url":null,"abstract":"<p><p>There is an urgent need for new energy storage solutions that will support the decarbonization of the electricity grid. Aqueous organic redox flow batteries are low-cost, long-duration energy storage devices that are in the process of being commercialized for this application; however, their operational lifetime is limited by electrolyte decomposition and crossover. These degradation processes are generally studied separately, so the relationship between the two is poorly understood. Previously, it had been assumed that the main contribution to battery capacity fade was electrochemical degradation of the electrolytes. Using the on-line ¹H NMR crossover characterization method we developed previously, we reveal the first experimental evidence for crossover-driven side reactions in redox flow batteries. If the impact of these side reactions is not considered, it will lead to an underestimation of crossover and its impacts on battery lifetime. We further introduce simple 'simulated-crossover' experiments to identify anolyte-catholyte combinations where these processes are occurring. Using these simulated-crossover experiments, we find that crossover-driven side reactions can be mitigated by avoiding the use of anolytes with hydroxyl functional groups when using ferrocyanide electrolytes. These insights should be used to assist the design of new anolytes and catholytes, which will facilitate the development of longer-lasting redox flow batteries.</p>","PeriodicalId":520400,"journal":{"name":"ACS electrochemistry","volume":"1 10","pages":"2071-2084"},"PeriodicalIF":0.0,"publicationDate":"2025-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12498410/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145246319","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}