ACS electrochemistry最新文献

{"title":"Electrolyte Effects on Disorder-Enhanced Capacitance in Nanoporous Carbons.","authors":"Xinyu Liu, Kara Fong, Zhaohan Shen, Wei Yu, Hirotomo Nishihara, Clare P Grey, Alexander C Forse","doi":"10.1021/acselectrochem.5c00472","DOIUrl":"10.1021/acselectrochem.5c00472","url":null,"abstract":"<p><p>The impact of pore structure and surface functionality on the capacitance of nanoporous carbons has been widely studied across different electrolytes, yet the role of electrolyte chemistry in structural disorder-driven and ion adsorption capacity-related capacitance remains largely unexplored. In this study, we investigate the relationship between capacitance and the degree of structural order in 20 nanoporous carbons using ionic liquid electrolytes, aiming to establish the generality of disorder-driven capacitance and explore its underlying mechanisms. Our results demonstrate that carbons with smaller graphene-like domains and larger ion adsorption capacities exhibit higher capacitance in 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF₄) ionic liquid, consistent with our previous findings in 1 M tetraethylammonium tetrafluoroborate (TEABF₄) in acetonitrile (ACN). More generally, we find that the capacitance of a given carbon remains similar across different ionic liquid and organic electrolytes, provided that the pores are accessible to the electrolyte ions. This study shows the generality of disorder-driven and adsorption-dependent capacitance in nanoporous carbons in organic and ionic liquid systems and suggests that factors such as the nature of the defects and how they affect quantum capacitance may play an important role in disorder-driven capacitance, ultimately providing insights for designing high-performance supercapacitor electrodes.</p>","PeriodicalId":520400,"journal":{"name":"ACS electrochemistry","volume":"2 2","pages":"510-518"},"PeriodicalIF":0.0,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12884468/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146159844","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":"Electrochemical Insight into the Copper Redox Chemistry and H₂O₂ and O₂ Reducing Capability of Two AA10 Lytic Polysaccharide Monooxygenases.","authors":"Ella K Reid, Connor G Miles, Henry O Lloyd-Laney, Alison K Nairn, Jessie Branch, Nicholas Garland, Nicholas D J Yates, Alex Ascham, Paul H Walton, Glyn Hemsworth, Alison Parkin","doi":"10.1021/acselectrochem.5c00266","DOIUrl":"10.1021/acselectrochem.5c00266","url":null,"abstract":"<p><p>Lytic polysaccharide monooxygenases ([L]-PMOs) are copper-containing enzymes that catalyse cleavage of the glycosidic bond, a process central to microbial biomass degradation. Here, we describe electrochemical methods used to investigate the Cu^2+/1+ redox chemistry and the polysaccharide-free catalytic activity of two AA10 LPMOs: <i>Cj</i>AA10B from <i>Cellvibrio japonicus</i> and <i>Cf</i>AA10 from <i>Cellulomonas fimi</i>. Immobilisation of these enzymes on the surface of a graphite electrode allows for direct electrochemical measurements of Cu^2+/1+ redox cycling as well as the ability of both LPMOs to reduce H₂O₂ vs O₂. These measurements can be advantageous when compared to biological dye assays as they provide direct kinetic measurements and allow for investigation over a wider range of environmental conditions. Values of <i>k</i> _cat and <i>K</i> _M- are reported for H₂O₂ and O₂ reduction by <i>Cj</i>AA10B and <i>Cf</i>AA10 from pH 5-7, with <i>Cf</i>AA10 consistently outperforming <i>Cj</i>AA10B. Both enzymes perform faster catalysis with H₂O₂ but when comparing the affinity-coupled specificity constant (<i>k</i> _cat/<i>K</i> _M), the LPMOs perform similarly with both H₂O₂ and O₂, suggesting both substrates are viable. We also note an increase in redox signals as pH is decreased that correlates with EPR data suggesting a second species is formed <pH 5, postulated to occur due to the protonation of a glutamate residue (p<i>K</i> _a ∼ 4.6). The increase in signal size with decreasing pH that is seen for the non-catalytic Cu^2+/1+ transition is interpreted in light of an increasing proportion of electroactive species at low pH; such a change in activity with pH is notably not observed in the presence of substrate (H₂O₂ or O₂). This suggests that substrate binding modulates the active site, disrupting the effect of protonation. These findings establish electrochemistry as a powerful tool for probing LPMO activity.</p>","PeriodicalId":520400,"journal":{"name":"ACS electrochemistry","volume":"2 2","pages":"239-257"},"PeriodicalIF":0.0,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12884475/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146159895","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":"Compositional and Structural Impact on the Hydrogen Evolution Reaction Activity across Noble-Metal-Based Compositionally Complex Solid Solutions Thin Film Libraries.","authors":"Natalia Pukhareva, Moonjoo Kim, Felix Thelen, Geovane Arruda de Oliveira, Rico Zehl, Wolfgang Schuhmann, Alfred Ludwig","doi":"10.1021/acselectrochem.5c00406","DOIUrl":"10.1021/acselectrochem.5c00406","url":null,"abstract":"<p><p>Compositionally complex solid solutions (CCSS), often called high-entropy alloys (HEA) have emerged as a promising platform for electrocatalysts for the hydrogen evolution reaction (HER). However, due to their complexity, the interplay among surface composition, structure, and catalytic activity remains insufficiently understood. Herein, noble-metal-based CCSS thin-film materials libraries, prepared by combinatorial magnetron sputtering, are employed as a platform to elucidate how HER activities of CCSS electrocatalysts are linked to their volume composition through surface segregation and crystal structure. High-throughput investigations of three CCSS material libraries, Ir-Pd-Pt-Rh-Ru, Ag-Au-Pd-Pt-Ru, and Ag-Au-Cu-Pd-Pt, were conducted to assess their structural, compositional, and electrochemical properties, using high-throughput X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS) coupled with Gaussian process regression, and long-range scanning electrochemical cell microscopy (SECCM). Correlative data analysis revealed that the composition-dependent surface segregation, driven by surface energy differences, modulates the distribution of active sites on the surface. We identified Ir₁₀Pd₁₅Pt₄₆Rh₁₂Ru₁₇ as the most active volume composition for HER which corresponds to a surface composition of Ir₆Pd₁₇Pt₅₀Rh₁₁Ru₁₆. Moreover, the HER trends were governed not only by the intrinsic activity of the constituent elements but also by unexpected synergetic effects between them. The findings offer direct insights into composition-structure-activity relationships in compositionally complex electrocatalysts.</p>","PeriodicalId":520400,"journal":{"name":"ACS electrochemistry","volume":"2 2","pages":"364-373"},"PeriodicalIF":0.0,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12884461/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146159839","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":"From Pure to Seawater Electrolysis: Unveiling the Impact of Ionic Species and Contaminants on Electrocatalysis.","authors":"Sahanaz Parvin, Emmanuel Aransiola, Sonakshi Saini, Matthew T McDowell, Seunghoon Lee, Juliane Weber, Yiqing Wu, Yuanyuan Li, Chang Liu, Zili Wu, Jonas Baltrusaitis","doi":"10.1021/acselectrochem.5c00381","DOIUrl":"10.1021/acselectrochem.5c00381","url":null,"abstract":"<p><p>Water electrolysis, including seawater splitting to produce hydrogen and oxygen, stands as a promising approach for the efficient storage of intermittent energy. However, the half-reactions of water splitting, the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), are known to be very sensitive toward the quality of water employed and are susceptible to contaminants originating from various sources, including the electrolyte or the electrodes. Those contaminants have a profound impact on the activity of these reactions of water splitting by modifying the electronic and physical structures of electrocatalysts as well as electrode-electrolyte interfaces. For seawater electrolysis, the unintentional presence of impurities, such as anions, cations, and organic compounds, affects the catalyst stability, selectivity, and activity. Despite the existence of numerous comprehensive reviews that delve into various aspects of catalysts and their structure-property relationships for several electrocatalytic reactions, the impact of contaminants has often been ignored. This critical review endeavors to address this issue by providing an overview of the diverse sources of contaminants influencing electrocatalytic water splitting and seawater splitting reactions, delineating the trends in electrochemical parameters and detailing different characterization methods for elucidating the physical and electronic changes of the electrode and electrolyte.</p>","PeriodicalId":520400,"journal":{"name":"ACS electrochemistry","volume":"2 1","pages":"43-67"},"PeriodicalIF":0.0,"publicationDate":"2025-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12766682/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145914535","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":"Quaternary Ammonium Additives as Dual Inhibitors of Hydrogen Evolution and Cathodic Corrosion in Aqueous Electrosynthesis.","authors":"Achanta K S Koushik, Pietro Vannini, Eva Plut, Wiebke Jansen, Siegfried R Waldvogel, Jean-Philippe Tessonnier","doi":"10.1021/acselectrochem.5c00398","DOIUrl":"10.1021/acselectrochem.5c00398","url":null,"abstract":"<p><p>In organic electrosynthesis, the hydrogen evolution reaction (HER) is a parasitic process that significantly diminishes the faradaic efficiency (FE) of aqueous electrochemical reductions and contributes to the cathodic corrosion of widely used metals such as lead and tin. Developing strategies that selectively suppress HER without hindering desired electrochemical transformations is therefore crucial. In this study, we demonstrate that various quaternary ammonium salts (QAS) suppress HER on lead cathodes even under acidic conditions (pH 1). These QAS electrostatically self-assemble at the negatively charged lead surface, forming a cationic barrier that hinders hydronium ion (H₃O⁺) diffusion to the surface, thereby mitigating HER. Chronoamperometry (CA) at -1.8 V vs Ag/AgCl for 1 h revealed stark differences in QAS performance depending on molecular structure. H12MS (<i>N</i>,<i>N</i>,<i>N</i>,<i>N'</i>,<i>N'</i>,<i>N'</i>-hexamethyl-1,12-dodecanediammonium methyl sulfate) was the most effective salt, suppressing hydrogen evolution from ∼0.76 to ∼0.11 mmol cm^-2 (an 85% decrease), even at concentrations as low as 1 μM. CA also showed that the monotonic increase in current over time for blank lead electrodes, which is due to corrosion and surface roughening, was also suppressed in the presence of QAS, underscoring their dual role as inhibitors of both HER and cathodic corrosion. Moreover, during the electrochemical hydrogenation of fumaric acid at -1.7 V vs Ag/AgCl, the addition of 1 mM H12MS enhanced the faradaic efficiency from 7.3% to 38.5% (a 5.3-fold increase) without affecting the yield of succinic acid. These findings highlight the effectiveness of QAS additives in tailoring the boundary layer to improve the efficiency and durability of electrochemical processes.</p>","PeriodicalId":520400,"journal":{"name":"ACS electrochemistry","volume":"2 1","pages":"175-187"},"PeriodicalIF":0.0,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12766671/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145914471","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 Look inside a Flexible Open-Source Scanning Electrochemical Probe Microscope.","authors":"Kim McKelvey, Martin Andrew Edwards, Minkyung Kang, Marc Brunet Cabré, Nicholas B Jones, Patrick R Unwin","doi":"10.1021/acselectrochem.5c00354","DOIUrl":"10.1021/acselectrochem.5c00354","url":null,"abstract":"<p><p>Scanning electrochemical probe microscopy (SEPM) maps and investigates the chemical and physical properties of surfaces and interfaces using a micro- or nanoscale electrochemical probe, e.g., a microelectrode or a nanopipette, positioned close to an interface of interest. SEPM instruments share a common general architecture but are distinct from each other through the choice of probe and in the different physicochemical properties of the sample that can be investigated, including, among others, interfacial charge transfer rates, topography, permeability, or surface charge. Thus, a single instrument, with an appropriately flexible control system, can facilitate widespread access to the family of SEPM techniquesscanning electrochemical microscopy (SECM), scanning ion conductance microscopy (SICM), scanning electrochemical cell microscopy (SECCM), the scanning micropipette contact method (SMCM), and hybrid varieties of these techniques. Herein, we describe in detail a <i>flexible open-source SEPM instrument</i> that can perform <i>common and widely applicable SEPM techniques and experimenter-defined methodologies, with minimal programming from the user.</i> The instrument makes use of a field programmable gate array (FPGA)-based data acquisition card, and this contribution further illustrates the benefits of adopting FPGA architecture generally in electrochemical instrumentation. We describe the software and hardware for the instrument, using examples from the literature to illustrate how common SEPM operation modes and hyphenated techniques are readily implemented. Additionally, to demonstrate the application of custom-developed scanning protocols, we briefly present some further experimental examples. This Tutorial seeks to serve the needs of expert users of SEPMs and encourage new entrants alike. To this end, to encourage those who are interested in either setting up their own instruments or making optimal use of commercially available instruments, we also briefly include some more basic and general information on SEPM techniques and uses, to put the more advanced work and instrumental aspects in context.</p>","PeriodicalId":520400,"journal":{"name":"ACS electrochemistry","volume":"2 1","pages":"78-91"},"PeriodicalIF":0.0,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12766686/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145914370","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":"Nanomaterial Modification of Ultramicroelectrodes Using Design-of-Experiments Principles.","authors":"Rachel A Bocking, Thomas M Dixon, Brenna Parke, Parastoo Hashemi, Richard A Bourne, Paolo Actis, Robert Menzel","doi":"10.1021/acselectrochem.5c00227","DOIUrl":"10.1021/acselectrochem.5c00227","url":null,"abstract":"<p><p>Modification of ultramicroelectrode sensors with electroactive nanomaterials is key to enhancing their microscale sensing performance for advanced applications in cellular biology, disease diagnostics, or scanning electrochemical microscopy (SECM). This work employs a modern design-of-experiment (DoE) approach to develop a systematic, multiple-parameter methodology for the development of robust ultramicroelectrode modification protocols. Specifically, platinum ultramicroelectrode sensors are coated with platinum/nanocarbon nanocomposites through electrophoretic deposition (EPD), using 2 ^<i>k</i> factorial screening designs to systematically investigate the ultramicroelectrode modification process. The steady state current is employed as a quantitative DoE target metric, enabling us to map and model optimum ultramicroelectrode modification conditions. DoE-optimized modification conditions are shown to achieve substantial improvements in coating quality and limit of detection in a model H₂O₂ sensing study. The DoE-optimized conditions are also successfully translated to the modification of carbon-fiber ultramicroelectrodes (CFM), achieving effective modification in a single experiment. This systematic DoE approach provides a versatile, robust, and highly effective method for developing ultramicroelectrode modification across multiple parameters through a minimal number of experiments. Importantly, the DoE methodology also readily identifies tolerances and limiting conditions for the modification process, vital for broader adoption and future technology translation of functionalized ultramicroelectrodes.</p>","PeriodicalId":520400,"journal":{"name":"ACS electrochemistry","volume":"2 1","pages":"101-112"},"PeriodicalIF":0.0,"publicationDate":"2025-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12766678/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145914455","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":"Electrochemical Impedance Spectroscopy Investigation of the SEI Formed on Lithium Metal Anodes.","authors":"Lorenz F Olbrich, Nicolò Pianta, Ben Jagger, Yiming Xu, Manav Kakkanat, Federico Scarpioni, Christopher Allen, Fabio La Mantia, Riccardo Ruffo, Mauro Pasta","doi":"10.1021/acselectrochem.5c00388","DOIUrl":"10.1021/acselectrochem.5c00388","url":null,"abstract":"<p><p>Electrochemical impedance spectroscopy (EIS) is widely used to probe the solid electrolyte interphase (SEI) under realistic conditions, without causing damage to its structure. However, the models and experimental conditions often raise concerns about the reliability of the results. In this work, we present an extensive EIS study of lithium metal in the model electrolyte lithium bis-(fluorosulfonyl)-imide in tetraglyme, analyzing the system at equilibrium as a function of time, temperature, and salt concentration using a setup designed to minimize artifacts. We apply information theory to determine the number of independent degrees of freedom and constrain the number of Voigt elements used in fitting. Our analysis reveals strong correlations among processes, warranting caution when assigning physical meaning. X-ray photoelectron spectroscopy and 4D-scanning transmission electron microscopy measurements are used to support the interpretation and provide complementary insights into the chemical nature of the interphase. The unique and extensive dataset we have collected, comprising over 12000 highly reproducible impedance spectra, will serve as a valuable resource to the community for further analysis and for supporting additional modeling and experimental efforts.</p>","PeriodicalId":520400,"journal":{"name":"ACS electrochemistry","volume":"2 1","pages":"166-174"},"PeriodicalIF":0.0,"publicationDate":"2025-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12766685/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145914378","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":"Debunking Pitfalls of Li-N₂ Cells for Ammonia Electroproduction: Is This Setup Affordable to Prove Nitro-Fixation before Lithium Plating?","authors":"Anna Mangini, Alberto Garbujo, Pierdomenico Biasi, Valentina Testa, Maria Concetta Bruzzoniti, Luca Rivoira, Sara Garcia-Ballesteros, Federico Bella","doi":"10.1021/acselectrochem.5c00402","DOIUrl":"10.1021/acselectrochem.5c00402","url":null,"abstract":"<p><p>The Li-N₂ cell represents a fascinating device that opens a new pathway for ammonia electrosynthesis. It combines the unique property of lithium, which can spontaneously react with N₂ under mild conditions, with an energy-efficient solution to the challenging N₂ fixation reaction. However, such a battery-inspired setup may be susceptible to false-positive results and present some pitfalls. This work elucidates some critical aspects of Li-N₂ cells, aiming at identifying a reliable methodology to assess the electrochemical reduction of N₂ at the cathodic surface, avoiding misleading pathways. Despite the spontaneous nature of the reaction between lithium and N₂, it remains uncertain whether it is feasible to promote the electrochemical fixation of N₂ before reaching the lithium plating potential. This would involve lithium as an ion in the electrolyte, which should activate and enable N₂ reduction on the carbonaceous surface before any Li⁺ reduction occurs, i.e., at a potential higher than the lithium plating potential (-3.04 V vs SHE). This study discusses this possibility, searching for setup limitations, such as the presence of metallic lithium at the anode, and pitfalls, such as the use of cyclic voltammetry in different testing environments as a methodology to evaluate the formation of Li₃N before lithium plating occurs.</p>","PeriodicalId":520400,"journal":{"name":"ACS electrochemistry","volume":"1 12","pages":"2866-2877"},"PeriodicalIF":0.0,"publicationDate":"2025-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12683635/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145717062","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":"Hydrophobic Diffusion Media via Electrografted Organosilicons Enable Competitive Performance in Polymer Electrolyte Fuel Cells.","authors":"Irene Sinisgalli, Adrian Mularczyk, Antoni Forner-Cuenca","doi":"10.1021/acselectrochem.5c00333","DOIUrl":"10.1021/acselectrochem.5c00333","url":null,"abstract":"<p><p>Hydrophobic surface modification of porous carbon materials is critical for the performance and durability of polymer electrolyte membrane fuel cells and many other electrochemical technologies. However, conventional treatments rely on dip coating approaches using polymer dispersions containing fluorinated compounds (i.e., polytetrafluoroethylene), which pose environmental hazards and yield heterogeneous surfaces with limited control over wetting behavior and poor durability. Here, we introduce a facile method that exploits the facile electroreduction of 4-nitrobenzodiazonium tetrafluoroborate to generate aryl radicals and initiate a radical chain reaction that enables the grafting of vinyl-terminated organosilicon compounds. This method proceeds under ambient conditions and at milder potentials than traditional vinylic electrografting. We investigate three organosilicon derivativesallyltriisopropylsilane, acryloxymethyl-trimethylsilane, and monomethacryl-oxypropyl-terminated polydimethylsiloxaneas electrografted coatings to tailor surface wettability. We perform microscopic, spectroscopic, and contact angle measurements and electrochemical characterization to correlate chemical moieties with the resulting wettability and electrochemical performance in fuel cells. We find that the electrografted coatings form a covalently bonded, thin layer that significantly reduces the solid surface energy of the carbonaceous substrate, reaching values close to those of polytetrafluoroethylene. Additionally, we find a correlation between surface energy and fuel cell performance, where the less hydrophobic coatings show cell flooding under more humid conditions. Polydimethylsiloxane-based coating outperforms the commercial baseline (polytetrafluoroethylene) in operando fuel cells, which paves a promising pathway for this class of materials. Importantly, this study highlights the potential of fluorine-free alternatives to traditional fluorinated hydrophobic treatments, offering a more sustainable and environmentally friendly approach without compromising performance.</p>","PeriodicalId":520400,"journal":{"name":"ACS electrochemistry","volume":"1 12","pages":"2723-2735"},"PeriodicalIF":0.0,"publicationDate":"2025-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12683640/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145717202","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}