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The polarization response of a coplanar electrochemical capacitor covered with an ionic liquid as the electrolyte has been examined using a combination of two powerful analytic techniques, X-ray photoelectron spectroscopy (XPS) and scanning electron microcopy (SEM). Spatiotemporal distribution of the ionic liquid surface potential, upon DC or AC (square wave) biasing, has been monitored chemical element binding energy shifts using XPS and secondary electron intensity variations using SEM. SEM's high spatial resolution and speedy imaging together with application of a data mining algorithm made mapping of the surface potential distribution across the capacitor possible. Interestingly, despite the differences in the detection principles, both techniques yield similar polarization relaxation time constants. The results demonstrate the power of a synergistic combination of the two techniques with complementary capabilities and pave the way to a deeper understanding of liquid/solid interfaces and for performance evaluation and diagnostics of electrochemical devices.
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http://dx.doi.org/10.1021/acs.analchem.1c02779 | DOI Listing |
J Mass Spectrom
October 2025
Department of Chemistry and Technology of Drugs, "Sapienza" University of Rome, Rome, Italy.
Ionic liquids (ILs) are a class of organic salts with melting points below 100°C. Owing to their unique chemical and physical properties, they are used as solvents and catalysts in various chemical transformations, progressively replacing common volatile organic solvents (VOCs) in green synthetic applications. However, their intrinsic ionic nature can restrict the use of mass spectrometric techniques to monitor the time progress of a reaction occurring in an IL medium, thus preventing one from following the formation of the reaction products or intercepting the reaction intermediates.
View Article and Find Full Text PDFACS Electrochem
September 2025
School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, UK.
The study of electrochemical oxidations has wide-ranging implications, from the development of new electrocatalysts for fuel cells for energy conversion, to the synthesis of fine chemicals. 2,2,6,6-Tetramethylpiperidine-1-oxyl (TEMPO) has been used for decades as a sustainable, metal-free mediator for chemical oxidations and is now being used for electrochemical oxidations. We describe here a novel approach to TEMPO-mediated electrooxidations, in which the chemical input and waste generated during electrooxidations of alcohols are minimized by using a multifunctional room temperature ionic liquid (RTIL) to facilitate flow electrosynthesis.
View Article and Find Full Text PDFNanoscale Adv
July 2025
University of Kentucky, Department of Chemical and Materials Engineering 177 F.P. Anderson Tower Lexington Kentucky 40506-0046 USA
The crystallization behavior of ionic liquids (ILs) 1-butyl-3-methylimidazolium [BMIM] hexafluorophosphate [PF] and chloride [Cl] is investigated upon confinement in 2.3 or 8.2 nm diameter silica nanopore arrays, along with the effects of covalently modifying the pore walls with 1-(3-trimethoxysilylpropyl)3-methylimidazolium [TMS-MIM] groups.
View Article and Find Full Text PDFChem Commun (Camb)
September 2025
School of Chemistry and Life Resources, Renmin University of China, Beijing, 100872, China.
Through molecular dynamics simulations of imidazolium-based ionic liquid-water mixtures, it was found that the trace water leads to an anomalous non-monotonic change in the diffusion coefficients of ionic liquid, characterized by an initial decrease followed by an increase. Hydrogen bond analysis revealed that this unusual trend is governed by the weighted hydrogen bond lifetime, reflecting the stability of the hydrogen-bond network, rather than simply the number or energy of hydrogen bonds.
View Article and Find Full Text PDFACS Appl Mater Interfaces
September 2025
Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Institute of New Energy, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), Fudan University, Shanghai 200433, China.
Li-metal batteries promise ultrahigh energy density, but their application is limited by Li-dendrite growth. Theoretically, fluorine-containing anions such as bis(fluorosulfonyl)imide (FSI) in electrolytes can be reduced to form LiF-rich solid-electrolyte interphases (SEIs) with high Young's modulus and ionic conductivity that can suppress dendrites. However, the anions migrate toward the cathode during the charging process, accompanied by a decrease in the concentration of interfacial anions near the anode surface.
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