Work Function Describes the Electrocatalytic Activity of Graphite for Vanadium Oxidation

In many applications such as vanadium flow batteries, graphite acts as an electrocatalyst and its surface structure therefore determines the efficiency of energy conversion. Due to the heterogeneity of the material, activity descriptors cannot always be evaluated with certainty because the introduction of defects is accompanied by a change in surface chemistry. Moreover, surface defects occur in multiple dimensions, and their occurrence and influence on catalysis must be separated. In this work, we have studied the surface of graphite felt electrodes by different methods in terms of morphology and chemistry to understand the electrocatalytic activity. We then defined the interaction between the surface and the electronic structure with particular emphasis on the work function and valence band. Using model catalysts with different architectures, we established correlations between the electrocatalytic activity and the size of the conjugation and the orientation of the edges. Finally, it was possible to link the level of the work function to the electrocatalytic activity

Are Functional Groups Beneficial or Harmful on the Electrochemical Performance of Activated Carbon Electrodes?

It is a common opinion that activated carbon (AC) should be functional groups-free when employed as capacitor-type material in organic electrolytes. This work analyzes in detail the relationship between the electrochemical performance of modified activated carbon electrodes and the introduced functional groups in two organic electrolytes containing lithium salts:1M LiPF6 in EC-DMC (the commercial LP30) and 1M LiTFSI in EC-DMC. The surface functional groups (especially C=O or O–C=O) can induce higher capacitance to AC (more than 50% increase compared to commercial unmodified AC), whereas the rate capability dramatically decreases. The appropriate amount of functional groups is helpful to expand the electrochemical stability window in LP30 (2.8–2.9 V), that is responsible for the high energy and power density. Moreover, the proper functional groups inhibit the potential shift of the AC electrode. However, a large number of functionalities can result in a high amount of irreversible redox products remaining in the pores of AC, which leads to a faster capacitance fade respect to materials with less functional groups

Cucurbit[n]uril-Immobilized Sensor Arrays for Indicator-Displacement Assays of Small Bioactive Metabolites

The patterned immobilization of chemosensors into nano/microarrays has often boosted utilization in diagnostics and environmental sensing applications. While this is a standard approach for biosensors, e.g., with antibodies, other proteins, and DNA, arraying is not yet adopted widely for supramolecular chemosensors which are still predominantly used in solution systems. Here we introduce the patterned immobilization of cucurbit[n]urils (CBn) into multiplexed microarrays and elucidate their prospects for the advancement of surface-bound indicator-displacement assays to detect small molecule analytes. The microarrays were generated by microchannel cantilever spotting of functionalized CBn and subsequent self-assembly of the corresponding indicator dyes from solution. Enhanced sensitivity of surface-bound microarrays was established in demonstrations with small bioactive metabolites (spermine, amantadine, and cadaverine) compared to bulk assays. Furthermore, the integration of the CBn/indicator microarrays into microfluidic channels provides an efficient route for real-time monitoring of the sensing process, allows easier handling, and reduces need for analyte volume. The concept was further extended to differential sensing of analytes on diplex or multiplex CBn/indicator microarrays, opening up a route for multicomponent sensing of small molecule analytes in complex liquids

Coating versus Doping: Understanding the Enhanced Performance of High‐Voltage Batteries by the Coating of Spinel LiNi0.5_{0.5}Mn1.5_{1.5}O4_4 with Li0.35_{0.35}La0.55_{0.55}TiO3_3

Li$_{0.35}$La$_{0.55}$TiO$_3$ (LLTO) coated spinel LiNi$_{0.5}$Mn$_{1.5}$O$_4$ (LNMO) as cathode material is fabricated by a new method using hydrogen-peroxide as activating agent. The structure of the obtained active materials is investigated using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS), and the electrochemical properties of the prepared cathodes are probed by the charge–discharge studies. The morphology of the coating material on the surface and the degree of coverage of the coated particles is investigated by the SEM, which shows a fully dense and homogeneous coating (thickness ≈ 7 nm, determined by TEM) on the surface of active material. XRD studies of the coated active materials treated at different temperatures (between 300 °C and 1000 °C) reveal expansion or contraction of the unit cell in dependence of the coating concentration and degree of Ti diffusion. It is concluded, that for the LNMO particles calcined at low temperatures, the LLTO coating layer is still intact and protects the active material from the interaction with the electrolyte. However, for the coated particles treated at high temperatures, Ti ions migrate into the structure of LNMO during the modification process between 500 °C and 800 °C, resulting in “naked” and unprotected particles

Surface Functionalization and Patterning by Multifunctional Resorcinarenes

Plant phenolic compounds and catecholamines have been widely used to obtain substrate-independent precursor nanocoatings and adhesives. Nevertheless, there are downsides in using such phenolic compounds for surface modification such as formation of nonuniform coatings, need for multistep modification, and restricted possibilities for postfunctionalization. In this study, inspired by a strong binding ability of natural polyphenols found in plants, we used three different macrocyclic polyphenols, known as resorcin[4]­arenes, to modify the surface of different substrates by simple dip-coating into the dilute solution of these compounds. Eight hydroxyl groups on the large rim of these resorcin[4]­arenes provide multiple anchoring points to the surface, whereas the lower rim decorated with different appending groups introduces the desired chemical and physical functionalities to the substrate’s surface. Deposition of a uniform and transparent resorcinarene layer on the surface was confirmed by several surface characterization techniques. Incubation of the modified substrates in different environments indicated that the stability of the resorcinarene layer was dependent on the type of substrate and the pH value. The most stable resorcinarene layer was formed on amine-functionalized substrates. The surface was modified with alkenyl functional groups in one step using a resorcinarene compound possessing four alkenyl appending groups on its small rim. Thiol–ene photoclick chemistry was used to site-selectively postfunctionalize the surface with hydrophilic and hydrophobic micropatterns, which was confirmed by X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry. Thus, we demonstrate that resorcin[4]­arenes extend the scope of applications of plant polyphenol and mussel-inspired precursors to tailor-made multifunctional nanocoatings, suitable for a variety of potential applications in biotechnology, biology, and material science

Reactive block copolymers for patterned surface immobilization with sub-30 nm spacing

Phase-segregating block copolymers are powerful platforms for nanofabrication, particularly when employed as lithographic mask precursors. Surface-reactive polymeric films with distinct sub-30 nm domains are also proposed as covalent docking platforms for scalable, high-resolution molecular patterned immobilization. Here, the well-known self-assembling polystyrene-block-polyisoprene system is the starting point to produce a small library of derivatives with distinct reactive pendant groups (halide, azide, pentafluorophenylalkyl) by nitroxide-mediated radical polymerization. We find that controlling film thickness is crucial to obtain a perpendicular lamellar morphology and that the presence of the functional groups has a limited impact on self-assembly, yet may influence characteristic domain dimensions. Differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS), and atomic force microscopy (AFM) are utilized in concert to assess the phase behavior of the polymers and the surface features of the nanostructures. As a proof-of-concept for the surface reactivity, click chemistry-driven immobilization of a model water-soluble polymer is evidenced by X-ray photoelectron spectroscopy (XPS) and preservation of the underlying morphology is investigated by AFM

NIR-Emitting Gold Nanoclusters-Modified Gelatin Nanoparticles as a Bioimaging Agent in Tissue

Gold nanocluster (AuNC) synthesis using a well-distinguished polymer for nanoparticle-mediated drug delivery paves the way for developing efficient theranostics based on pharmaceutically accepted materials. Gelatin-stabilized AuNCs are synthesized and modified by glutathione for tuning the emission spectra. Addition of silver ions enhances the fluorescence, reaching also high quantum yield (26.7%). A simplified model can be proposed describing the nanoclusters' properties-structure relationship based on X-ray photoelectron spectroscopy data and synthesis sequence. Furthermore, these modifications improve fluorescence stability toward pH changes and enzymatic degradation, offering different AuNCs for various applications. The impact of nanocluster formation on gelatin structure integrity is investigated by Fourier transform infrared spectrometry and matrix-assisted laser desorption/ionization time of flight mass spectroscopy, being important to further formulate gelatin nanoparticles (GNPs). The 218 nm-sized NPs show no cytotoxicity up to 600 µg mL-1 and are imaged in skin, as a challenging autofluorescent tissue, by confocal microscopy, when transcutaneously delivered using dissolving microneedles. Linear unmixing allows simultaneous imaging of AuNCs-GNPs and skin with accurate signal separation. This underlines the great potential for bioimaging of this system to better understand nanomaterials' behavior in tissue. Additionally, it is drug delivery system also potentially serving as a theranostic system

Regeneration of β-Cyclodextrin Based Membrane by Photodynamic Disulfide Exchange — Steroid Hormone Removal from Water

The occurrence of steroid hormones in water and their serious impact on human and ecosystem demand high performance materials for efficient removal of such micropollutants. Here, an affinity membrane is developed for hormone removal with regenerable binding sites. By using photodynamic disulfides as a linker, UV induced detachment of β‐CD ligands from the membrane surface is demonstrated. The macroporous base membrane is first fabricated via a polymerization induced phase separation method using 2‐hydroxyethyl methacrylate (HEMA) and ethylene dimethylacrylate (EDMA) monomers. Then the affinity membranes are prepared by immobilizing β‐CD ligands to the poly(HEMA‐co‐EDMA) base membrane through the 2‐carboxyethyl disulfide linker. The β‐CD functionalized affinity membrane shows a 30% increase of E2 hormone uptake compared with the base membrane, attributed to the formation of CD‐hormone host–guest inclusion complexes. The photodynamic disulfide linkers enable UV‐induced detachment of blocked β‐CD ligands from and reattachment of fresh β‐CD ligands to the membrane surface after each adsorption cycle, thus conferring the affinity membrane with excellent regenerative properties. It is anticipated that the use of dynamic covalent bonds for binding ligands will be of interest for developing smart affinity membranes with regenerable and readjustable surface properties