ACS electrochemistry最新文献

{"title":"FRET-Enhanced Optical Imaging of Nanoparticle Collision on a Gold Ultramicroelectrode.","authors":"Wenyu Huang, Bo Zhang","doi":"10.1021/acselectrochem.6c00197","DOIUrl":"10.1021/acselectrochem.6c00197","url":null,"abstract":"<p><p>While optical imaging can help better study nanoparticle collision electrochemistry, it remains challenging to establish an optical signal that can directly reflect the redox state of individual particles during their transient collision process. Herein, we report a method based on the use of Förster resonance energy transfer (FRET) for enhancing the optical contrast of nanoparticle collision events on a gold ultramicroelectrode (UME). We first showed that methylene blue (MB), a redox-active fluorophore, exhibits fluorescence turn-off upon reduction on the electrode. To further amplify the optical signal, MB was used as a FRET acceptor and paired with Rhodamine 101 (R101) as the donor, such that MB quenches R101 emission via energy transfer, while reduced MB would disrupt this process, leading to the recovery of R101's fluorescence emission. Using polystyrene nanoparticles (PSNPs) labeled with both R101 and MB, we demonstrated fluorescence imaging of nanoparticle collision events on an Au UME, where individual particles exhibited fluorescence turn-on of R101 emission upon collision owing to the electrochemical reduction of surface-bound MB. Compared with direct imaging in the MB channel, the FRET readout provided substantially higher optical contrast and enabled clearer visualization of single-particle electrochemical processes. This work demonstrates a useful fluorescence transduction strategy for improving optical tracking in nanoparticle collision electrochemistry.</p>","PeriodicalId":520400,"journal":{"name":"ACS electrochemistry","volume":"2 8","pages":"2076-2085"},"PeriodicalIF":0.0,"publicationDate":"2026-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13496260/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148804995","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":"C(sp³)-F Adsorption Implicated for Reductive Activation at Ag Electrodes.","authors":"Ye Ji Kim, Ching-Nung Chen, Eva Devlin, Anna Wuttig","doi":"10.1021/acselectrochem.6c00101","DOIUrl":"10.1021/acselectrochem.6c00101","url":null,"abstract":"<p><p>The reductive activation of C-(sp³)-F bonds enables the derivatization of fluorinated motifs with medicinal value as well as the recycling of fluorochemicals. The electrochemical reductive activation of C-(sp³)-Cl, C-(sp³)-Br, and C-(sp³)-I bonds at Ag electrodes is well-documented and commonly attributed to inner-sphere, surface-mediated pathways. In contrast, experimental support for surface-mediated reductive C-(sp³)-F activation at Ag electrodes remains limited. Here, we report evidence for the adsorption of organic fluorides at polarized Ag electrodes. We compare spectroscopic and voltammetric data of nitrile-tagged benzylic bromide, chloride, and fluoride substrate with their non-halogenated congener. Surface-sensitive and in situ spectroscopic data are consistent with their adsorption on polarized Ag surfaces, including the organic fluoride, prior to Faradaic charge transfer. Voltammetric data demonstrate enhanced reductive activation of organic halides at Ag, including the organic fluoride, compared to glassy carbon. Exposing organic fluoride adsorption at electrified surfaces motivates electrode designs that can exploit surface interactions for the development of electroorganic methods beyond outer-sphere modalities.</p>","PeriodicalId":520400,"journal":{"name":"ACS electrochemistry","volume":"2 7","pages":"1551-1561"},"PeriodicalIF":0.0,"publicationDate":"2026-05-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13339136/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148407775","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":"Size-Dependent Oxidation of Copper Nanostructured Electrocatalysts Produced by Spark Ablation.","authors":"Johannes Sterzinger, Bogdan Gulie, Vincenz Maier, Tim Steeger, Carsten Peters, Nikolaos Patelis, Elena Gubanova, Marc Willinger, Aliaksandr S Bandarenka","doi":"10.1021/acselectrochem.6c00062","DOIUrl":"10.1021/acselectrochem.6c00062","url":null,"abstract":"<p><p>Nanostructured materials play a crucial role in today's society and are widely used across a range of fields, from catalysis to energy storage systems. However, their synthesis and characterization are often time-, cost-, and energy-consuming. This study aims to develop relatively simple approaches for upscaling size-selected nanoparticle synthesis via a plasma-based physical strategy and for determining particle sizes using electrochemical methods. We present a scalable, cost-effective spark ablation synthesis strategy that enables the production of high-purity, non-agglomerated copper (Cu) nanoparticles, directly immobilized on a carbon support, without the use of reducing agents or surfactants. This approach achieves high collection efficiency and imposes no limitations on attainable mass loading. To address challenges in nanoparticle size characterization, we introduce a simple electrochemical approach, namely anodic potential sweep oxidation, for determining particle size based on the size-dependent oxidation potential. For the produced Cu nanoparticles, a strong linear correlation (<i>R</i> ² = 0.99) was observed between particle radius and oxidation peak potential. This study demonstrates that the size of approximately spherical Cu nanoparticles can be estimated by simple, cost-effective electrochemical measurements, without the need for complex microscopy techniques. That opens a perspective for the express-assessment of particle size changes during various physicochemical processes, e.g., catalytic reactions.</p>","PeriodicalId":520400,"journal":{"name":"ACS electrochemistry","volume":"2 6","pages":"1397-1405"},"PeriodicalIF":0.0,"publicationDate":"2026-05-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13244637/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148214214","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":"Oxidative Stability and Redox Coupling in 3,4,3-LI(1,2-HOPO) <i>f</i>‑Element Complexes under Acidic Conditions.","authors":"Jeffrey R McLachlan, Amanda K Fellinge, Andrae A Tabbs, Nolwenn Mahieu, Alexander M Brown, Parker R Stow, Joshua J Woods, Rebecca J Abergel","doi":"10.1021/acselectrochem.6c00042","DOIUrl":"10.1021/acselectrochem.6c00042","url":null,"abstract":"<p><p>3,4,3-LI-(1,2-HOPO) is an octadentate hydroxypyridinone chelator that forms exceptionally stable complexes with tri- and tetravalent <i>f</i>-element ions and has been widely explored in radiopharmaceutical development, actinide decorporation, and metal separations. Despite a broad range of applications under highly acidic, oxidative, and radiolytic conditions, the intrinsic ligand-centered redox chemistry of 3,4,3-LI-(1,2-HOPO), and the influence of metal coordination on this behavior, remain poorly defined. Here, we present the first systematic electrochemical investigation of uncoordinated 3,4,3-LI-(1,2-HOPO) and its La-(III), Th-(IV), Zr-(IV), and Ce-(IV/III) complexes in acidic aqueous media. Cyclic voltammetry reveals that the free ligand undergoes a single, irreversible, pH- and protonation-state-dependent oxidation assigned to the 1-electron oxidation of the hydroxypyridinone moieties, proceeding through either an electron transfer or proton-coupled electron transfer mechanism. Coordination to redox-inactive metal ions significantly suppresses ligand oxidation, shifting oxidation potentials anodically by 0.2 to 0.5 V, depending on metal identity and speciation. Density functional theory calculations demonstrate strong sensitivity of ligand redox potentials to hydration state, coordination mode, and metal-ligand interactions. A pH-dependent reduction mechanism governed by coupled electron-transfer and protonation equilibria is evidenced in the Ce-(IV/III) system, enabling clear distinction between ligand-centered and metal-centered redox processes. Notably, oxygen is determined to be the chemical oxidant responsible for the spontaneous oxidation of Ce-(III), and likely Bk-(III), complexes, resolving a long-standing mechanistic ambiguity. Combined, these results establish quantitative design principles for predicting ligand oxidative stability in <i>f</i>-element complexes, as well as a general experimental framework for disentangling their ligand- and metal-centered redox chemistry using trivalent and tetravalent <i>f</i>-element-3,4,3-LI-(1,2-HOPO) systems as an example.</p>","PeriodicalId":520400,"journal":{"name":"ACS electrochemistry","volume":"2 6","pages":"1361-1371"},"PeriodicalIF":0.0,"publicationDate":"2026-05-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13245542/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148214230","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":"Mechanistic Insights into the Suppression of Proton Intercalation and the Hydrogen Evolution Reaction through Phosphorus Doping in Tungsten Oxide.","authors":"Oguz Kaan Kucukosman, Hengfei Gu, Xueyuan Zhang, Jacob Smith, Zhiyuan Zhang, Elizabeth Desmet, Yiguang Ju, Eric Garfunkel, Miaofang Chi, Aditya Dilip Lele, Huixin He","doi":"10.1021/acselectrochem.6c00059","DOIUrl":"10.1021/acselectrochem.6c00059","url":null,"abstract":"<p><p>The hydrogen evolution reaction (HER) is an inevitable parasitic process that limits the efficiency and selectivity of electrochemical hydrogenation reactions using water as the hydrogen source. Although introducing oxygen vacancies and heteroatom dopants into transition-metal oxides is widely employed to enhance hydrogenation activity, such modifications often inadvertently promote HER. Here, we demonstrate a counterintuitive suppression of proton intercalation and HER in metalloid phosphorus (P)-doped WO₃ catalysts, with progressively stronger suppression at higher P-doping levels. Electrochemical impedance spectroscopy, Mott-Schottky analysis, and hydrogen bond dissociation free energy (H-BDFE) measurement reveal that, despite enhanced electronic conductivity, improved interfacial charge transfer, and decreased H-BDFE, phosphorus doping significantly increases the adsorption resistance associated with W-H* intermediate formation and reduces H* surface coverage, thereby suppressing HER kinetics. Density functional theory calculations further show that even though the W d-band center was downshifted toward its Fermi level, P-doping broadens the distribution of hydrogen binding strengths across oxygen sites of the WO₃ catalysts, such that many sites bind hydrogen too weakly to support efficient proton intercalation. These insights reveal an alternative HER suppression mechanism whereby heteroatom doping enables local control of proton intercalation and hydrogen adsorption kinetics beyond conventional d-band tuning, proton/electron supply, or charge-transport limitations.</p>","PeriodicalId":520400,"journal":{"name":"ACS electrochemistry","volume":"2 6","pages":"1383-1396"},"PeriodicalIF":0.0,"publicationDate":"2026-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13244369/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148214231","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":"Heterogeneous PFAS Defluorination and Fluoride Upcycling into Medicinal Agents in Aqueous Electrolytes.","authors":"Pramod Tiwari, Nabin Pandey, Soumalya Sinha, Jianbing Jimmy Jiang","doi":"10.1021/acselectrochem.6c00070","DOIUrl":"10.1021/acselectrochem.6c00070","url":null,"abstract":"<p><p>Per- and polyfluoroalkyl substances (PFASs) mineralization and the upcycling of released fluoride (F^-) are desired for closing the fluorine cycle. While PFAS filtration and degradation are ongoing research, comprehensive PFAS mineralization followed by immediate valorization of the released F^- remains rare. Herein, we report a heterogenized copper-(I) electrocatalyst that fully (100%) decomposes 0.5 mM perfluorooctanoic acid (PFOA), a common groundwater PFAS contaminant, in aqueous KHCO₃ electrolyte at an anodic current of 5 mA over 18 h. Up to 84% PFOA degradation was achieved at the maximum tested concentration (2 mM) under identical electrochemical conditions, along with a corresponding 91% F^- recovery rate. Interestingly, KHCO₃ acts beyond a supporting electrolyte, influencing the rate-limiting step involved in PFOA defluorination, as revealed by the detection of ¹³CO₂H-incorporated PFOA under ¹³CO₂. In addition, we examined the degradation and defluorination rates of 11 PFASs with different chain lengths and configurations, and also valorized the produced F^- for the <i>in-situ</i> syntheses of medicinally relevant alkyl/arylsulfonyl fluorides (R-SO₂F, R = -Me, -(CH₂)₂Cl, and benzyl), without extracting F^- from the post-electrolysis solution and applying current/potential during the fluorination event. This report showcases a rare heterogenized molecular Cu-(I)-electrocatalyst for mineralizing PFASs and the subsequent room temperature F^- valorization.</p>","PeriodicalId":520400,"journal":{"name":"ACS electrochemistry","volume":"2 6","pages":"1422-1432"},"PeriodicalIF":0.0,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13244370/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148214202","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":"An Automated Electrochemistry Platform for Accelerating the Characterization of Enzymatic Electrochemistry.","authors":"Michael A Pence, Zachary A Nguyen, Luke G Kays, Dylan G Boucher, Joaquín Rodríguez-López, Shelley D Minteer","doi":"10.1021/acselectrochem.6c00095","DOIUrl":"10.1021/acselectrochem.6c00095","url":null,"abstract":"<p><p>Enzymatic electrochemistry harnesses the selectivity of enzymes to enable electrochemical applications spanning sensing, synthesis, and energy conversion. However, the sequential nature of electroanalytical experiments limits throughput, restricting the scale at which enzyme-electrode systems can be screened. Here we demonstrate the capabilities of an automated electrochemistry platform, eLab, to increase the throughput of enzymatic electrochemistry investigations. We used the eLab to collect over 10,000 cyclic voltammograms across a large parameter space consisting of two enzyme variants (promiscuous and wild-type glucose oxidase), 20 saccharide substrates, 21 concentrations, and four scan rates, with measurements being made all in triplicate. The expansive dataset enabled rapid identification of apparent outlier behavior of wild-type glucose oxidase toward glucose, which was confirmed to arise from oxygen sensitivity through targeted manual experiments. The promiscuous variant showed negligible oxygen sensitivity, a critical advantage for applications, such as enzymatic sensors, bioelectrosynthesis, and biofuel cells. Overall, this work demonstrates how automation can be applied to accelerate discovery in bioelectrochemistry.</p>","PeriodicalId":520400,"journal":{"name":"ACS electrochemistry","volume":"2 7","pages":"1519-1526"},"PeriodicalIF":0.0,"publicationDate":"2026-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13339139/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148407710","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":"Non-enzymatic Glucose Detection Mechanism on Pt: A Surface Interrogation Scanning Electrochemical Microscopy Investigation.","authors":"Nazario Martino, Francesco Panico, Frank Marken, Alberto Vertova, Alessandro Minguzzi","doi":"10.1021/acselectrochem.5c00464","DOIUrl":"10.1021/acselectrochem.5c00464","url":null,"abstract":"<p><p>Understanding the surface-state dependence of glucose electrooxidation on platinum is essential for advancing non-enzymatic glucose sensing. Mechanistic assignment based on classical cyclic voltammetry (CV) remains ambiguous because CV convolves glucose adsorption-dehydrogenation with the simultaneous formation and removal of Pt-oxygenated species. Here, we investigate glucose electrooxidation on polycrystalline Pt in phosphate buffer solution (pH 7.3) by combining conventional voltammetry with surface interrogation scanning electrochemical microscopy (SI-SECM), which enables quantitative titration of surface-bound oxidizing equivalents. Using the [Ru-(NH₃)₆]^3+/2+ redox couple as a mediator, the Pt substrate was pre-polarized for 30 s at controlled potentials, then switched to open circuit while tip voltammetry generated Ru²⁺ to titrate oxidising species (PtOx_ads) formed on the substrate. SI-SECM reveals that titratable PtOx_ads begins to form at ∼0.61 V vs RHE and increases with the increase of the pre-polarizing potential. Results evidence how, in the 0.61-0.81 V potential range, commonly associated with incipient hydroxide/OH, these oxidizing species are not consumed by glucose. In contrast, at more anodic potentials (≥0.9 V), the PtOx_ads amount is significantly reduced in the presence of glucose, indicating direct involvement of higher-potential Pt-oxide species in glucose oxidation. These outcomes clarify the potential-dependent reactivity of Pt-oxygenated layers in neutral media and demonstrate SI-SECM as a powerful approach to decoupling and quantifying surface oxidants that cannot be resolved by CV alone.</p>","PeriodicalId":520400,"journal":{"name":"ACS electrochemistry","volume":"2 5","pages":"1138-1147"},"PeriodicalIF":0.0,"publicationDate":"2026-04-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13159967/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147936784","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":"Exploring Improved Supercapacitor Electrodes for Electrochemical Carbon Dioxide Capture.","authors":"Zhen Xu, Angus Pedersen, Shunsuke Shimizu, Takeharu Yoshii, Hirotomo Nishihara, Maria-Magdalena Titirici, Jesús Barrio, Alexander C Forse","doi":"10.1021/acselectrochem.6c00086","DOIUrl":"10.1021/acselectrochem.6c00086","url":null,"abstract":"<p><p>This study introduces a new porous carbon for electrochemical CO₂ capture. Featuring both micro- and mesoporosity, it outperforms predominantly microporous YP80F (a commercial benchmark) by delivering faster CO₂ adsorption and lower energy consumption. This highlights the importance of mesoporosity in designing improved supercapacitor electrodes for rapid, energy-efficient electrochemical CO₂ capture.</p>","PeriodicalId":520400,"journal":{"name":"ACS electrochemistry","volume":"2 5","pages":"1115-1120"},"PeriodicalIF":0.0,"publicationDate":"2026-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13158909/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147936662","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":"Functionalized Metal-Organic Framework Thin Films for Stable and Efficient Electrochemical Water Oxidation under Near-Neutral Conditions.","authors":"Sumanta Basak, Arshia Sulaiman, Amanda J Morris","doi":"10.1021/acselectrochem.6c00031","DOIUrl":"10.1021/acselectrochem.6c00031","url":null,"abstract":"<p><p>The development of molecularly modified metal-organic frameworks (MOFs) for electrochemical water oxidation has emerged as a promising strategy for efficient artificial photosynthesis. In this study, a ruthenium-based water oxidation catalyst (WOC) was incorporated into the UiO-67 framework, forming RuM-UiO-67 films grown directly on conductive FTO substrates. These modified films demonstrate efficient water oxidation activity at near-neutral pH (pH 6), operating at a low overpotential of ∼600 mV. The catalyst exhibits a turnover frequency (TOF) of (0.32 ± 0.02) s^-1 at 1.5 V versus the normal hydrogen electrode (NHE) in buffered solution (pH 6) for the oxygen evolution reaction. Notably, incorporation into the MOF results in a 12-fold increase in electroactive surface coverage compared to a monolayer of the same catalyst on bare FTO. Faradaic efficiency analysis revealed incomplete conversion to O₂, and follow-up iodometric analysis confirmed the formation of H₂O₂ as a competing two-electron oxidation product during electrocatalysis. These results highlight the utility of MOF-based architectures for maximizing the catalyst accessibility and stability under electrochemical water oxidation conditions.</p>","PeriodicalId":520400,"journal":{"name":"ACS electrochemistry","volume":"2 5","pages":"1282-1292"},"PeriodicalIF":0.0,"publicationDate":"2026-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13158918/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147936757","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}