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The double layer at the solid/electrolyte interface is a key concept in electrochemistry. Here, we present an experimental study combined with simulations, which provides a molecular picture of the double-layer formation under applied voltage. By THz spectroscopy we are able to follow the stripping away of the cation/anion hydration shells for an NaCl electrolyte at the Au surface when decreasing/increasing the bias potential. While Na is attracted toward the electrode at the smallest applied negative potentials, stripping of the Cl hydration shell is observed only at higher potential values. These phenomena are directly measured by THz spectroscopy with ultrabright synchrotron light as a source and rationalized by accompanying molecular dynamics simulations and electronic-structure calculations.
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http://dx.doi.org/10.1073/pnas.2108568118 | DOI Listing |
Langmuir
September 2025
School of Materials Science and Engineering, Sun Yat-sen University, Higher Education Megacenter, Guangzhou 510006, P. R. China.
The interface between grafted poly(-isopropylacrylamide) (PNIPAM) and fluid plays an important role in drug delivery, responsive nanomaterials, and separation technologies. However, under external shear, the transport at the interface is regulated by both the thermoresponsive behavior and grafting densities. This study combines equilibrium and nonequilibrium molecular dynamics simulations to investigate the synergistic effects of grafting density, temperature, and shear flow on the structural and dynamic properties of PNIPAM brushes in methanol-water solutions.
View Article and Find Full Text PDFJ Phys Chem B
August 2025
Department of Chemical Engineering, The Pennsylvania State University, University Park, Pennsylvania 16802, United States.
Sulfonated polystyrene membranes exhibit a nanostructure characterized by tortuous, interconnected hydrophilic pores enclosed by a hydrophobic polymer domain. The characteristic pore size plays a crucial role in determining the salt partition coefficients. To directly relate pore size to salt partitioning, we construct a simplified pore space confined between flat sulfonated polystyrene walls.
View Article and Find Full Text PDFAdv Mater
August 2025
Siyuan Laboratory, Guangzhou Key Laboratory of Vacuum Coating Technologies and New Energy Materials, Guangdong Provincial Engineering Technology Research Center of Vacuum Coating Technologies and New Energy Materials, Guangdong Provincial Key Laboratory of Nanophotonic Manipulation, Department of Ph
Ion transport property and water structure of electrolytes are two of the most important issues for aqueous batteries, especially when operated at extreme temperatures. To this end, a sepiolite-based clay electrolyte (SCYE) with nanoconfined channels as single-ion conductor is proposed. The inner Zn and anions solvation shells exhibit fascinating hydration-shell reconfiguration behavior compared to the conventional Zn(ClO) aqueous electrolytes.
View Article and Find Full Text PDFSmall
August 2025
Department of Chemical and Biological Engineering, Monash University, Clayton, Victoria, 3800, Australia.
2D nanochannels have drawn significant interest as a means to develop nanofluidic devices with great potential for future sensing. Target recognition in the 2D nanochannels of a sensing system has been verified to change the ionic passageways to obtain high sensitivity, but until recently, the signal mechanisms have rarely been investigated. Here, explicit hydrophobic interactions and charge effects on target-induced ionic signals are demonstrated by using hydrophobic 2D nanochannels and hydrophilic negatively charged DNA complex-functionalized nanochannels.
View Article and Find Full Text PDFChem Sci
August 2025
National Innovation Center for Industry-Education Integration of Energy Storage Technology, MOE Key Laboratory of Low-grade Energy Utilization Technologies and Systems, CQU-NUS Renewable Energy Materials & Devices Joint Laboratory, College of Energy & Power Engineering, Chongqing University Chongqin
The sluggish de-solvation reaction kinetics of hydrated ions and the occurrence of undesired water electrolysis on the electrode-electrolyte interface pose significant challenges to the practical deployment of aqueous supercapacitors. Interestingly, biological ion channels exhibit remarkable abilities to facilitate the de-solvation and low-energy transport of hydrated ions, and these are achieved through their size-limited confinement effects and electrostatic interactions. Inspired by such transit mechanisms of ion channels, we propose an interesting strategy to facilitate the rapid desolvation of electrode surface ions with low-energy transport.
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