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Selective transport of solutes across a membrane is critical for many biological, water treatment and energy conversion and storage systems. When a charged membrane is equilibrated with an electrolyte, an unequal distribution of ions arises between phases, generating the so-called Donnan electrical potential at the solution/membrane interface. The Donnan potential results in the partial exclusion of co-ion, providing the basis of permselectivity. Although there are well-established ways to indirectly estimate the Donnan potential, it has been widely reported that it cannot be measured directly. Here we report the first direct measurement of the Donnan potential of an ion exchange membrane equilibrated with salt solutions. Our results highlight the dependence of the Donnan potential on external salt concentration and counter-ion valence, and show a reasonable agreement with current theoretical models of IEMs, which incorporate ion activity coefficients. By directly measuring the Donnan potential, we eliminate ambiguities that arise from limitations inherent in current models.

Room temperature ionic liquids continue to be at the forefront of chemistry, covering a broad spectrum of research areas from electrochemistry and energy to catalysis and green chemistry. Therefore, it is of great value to fully understand the chemical and electrochemical reactivity and stability of ionic liquids utilized in these applications. In this context, we have investigated the electrochemical generation of an N-heterocyclic carbene and its CS2 adduct from the ionic liquid [bmim][PF6], and X-ray photoelectron spectroscopy (XPS) proved to be a highly effective spectroscopic tool to study such systems. Initially, the dithiocarboxylate adduct was chemically synthesized as a reference compound starting from both [bmim][PF6] and [bmim][OAc], and characterized by HRMS, and 1H- and 13C-NMR, FTIR, visible and X-ray photoelectron spectroscopy. While a simple mixture of [bmim][PF6] and CS2 revealed no evidence of adduct formation, the application of an electrochemical stimulus led to the formation of the dithiocarboxylate adduct as evidenced optically and through the newly formed S2p peak in the XP spectrum. Further evidence for the electrochemical reduction of [bmim][PF6] to the corresponding N-heterocyclic carbene came from the XPS analysis via the appearance of a new N1s peak in the XP spectrum. [ABSTRACT FROM AUTHOR]

Room temperature ionic liquids continue to be at the forefront of chemistry, covering a broad spectrum of research areas from electrochemistry and energy to catalysis and green chemistry. Therefore, it is of great value to fully understand the chemical and electrochemical reactivity and stability of ionic liquids utilized in these applications. In this context, we have investigated the electrochemical generation of an N-heterocyclic carbene and its CS2 adduct from the ionic liquid [bmim][PF6], and X-ray photoelectron spectroscopy (XPS) proved to be a highly effective spectroscopic tool to study such systems. Initially, the dithiocarboxylate adduct was chemically synthesized as a reference compound starting from both [bmim][PF6] and [bmim][OAc], and characterized by HRMS, and 1H- and 13C-NMR, FTIR, visible and X-ray photoelectron spectroscopy. While a simple mixture of [bmim][PF6] and CS2 revealed no evidence of adduct formation, the application of an electrochemical stimulus led to the formation of the dithiocarboxylate adduct as evidenced optically and through the newly formed S2p peak in the XP spectrum. Further evidence for the electrochemical reduction of [bmim][PF6] to the corresponding N-heterocyclic carbene came from the XPS analysis via the appearance of a new N1s peak in the XP spectrum. [ABSTRACT FROM AUTHOR]

The properties of water on both molecular and macroscopic surfaces critically influence a wide range of physical behaviors, with applications spanning from membrane science to catalysis to protein engineering. Yet, our current understanding of water interfacing molecular and material surfaces is incomplete, in part because measurement of water structure and molecular-scale properties challenges even the most advanced experimental characterization techniques and computational approaches. This review highlights progress in the ongoing development of tools working to answer fundamental questions on the principles that govern the interactions between water and surfaces. One outstanding and critical question is what universal molecular signatures capture the hydrophobicity of different surfaces in an operationally meaningful way, since traditional macroscopic hydrophobicity measures like contact angles fail to capture even basic properties of molecular or extended surfaces with any heterogeneity at the nanometer length scale. Resolving this grand challenge will require close interactions between state-of-the-art experiments, simulations, and theory, spanning research groups and using agreed-upon model systems, to synthesize an integrated knowledge of solvation water structure, dynamics, and thermodynamics.

Liquid poly(ethylene glycol) (molecular weight, ∼600 Da) with a low vapor pressure is used as droplets in an ultrahigh-vacuum X-ray photoelectron spectrometer (XPS) chamber with traditional electrowetting on dielectric (EWOD) device geometry. We demonstrate that, using XPS data, independent of the sign of the applied voltage, the droplet expands on the substrate with the application of a nonzero voltage and contracts back when the voltage is brought back to zero. However, the main focus of the present investigation is about tracing the electrical potential developments on and around the droplet, using the shifts in the binding energy positions of the core levels representative of the liquid and/or the substrate in an noninvasive and chemically specific fashion, under imposed electrical fields, with an aim of shedding light on numerous models employed for simulating EWOD phenomenon, as well as on certain properties of liquid/solid interfaces. While the lateral resolution of XPS does not permit to interrogate the interface directly, we explicitly show that critical information can be extracted by probing both sides of the interface simultaneously under external bias in the form of potential steps or direct current. We find that, even though no potential drop is observed at the metal-wire electrode/liquid interface, the entire potential drop develops across the liquid/solid-substrate interface, which is faster than our probe time window (∼100 ms) and is promptly complying with the applied bias until breakdown. No indication of band bending nor additional broadening can be observed in the C 1s peak of the liquid, even under electrical field strengths exceeding 10 7 V/m. Moreover and surprisingly, the liquid recovers within seconds after each catastrophic breakdown. All of these findings are new and expected to contribute significantly to a better understanding of certain physicochemical properties of liquid/solid interfaces.