Up-scaling a Sol-Gel Process for the Production of a Multi-Component Xerogel Powder.

A sol-gel process for the synthesis of a multi-component oxide material from the system SiO2-ZrO2-Al2O3underwent optimization and up-scaling. Initially, on a laboratory scale, components including precursors, catalysts, and additives were methodically evaluated to ensure a safe and efficient transition to larger volumes. Subsequently, the equipment for the whole setup of the sol-gel process was strategically selected. Leveraging insights from these optimizations, the process was successfully scaled-up to pilot-scale operation, conducting hydrolysis, condensation reactions, gelation, aging, and drying within a single, integrated conical dryer system for an 80 L batch. A visual test and FTIR spectroscopy were applied for process control and monitoring.

Characteristics and properties of nano-LiCoO2 synthesized by pre-organized single source precursors: Li-ion diffusivity, electrochemistry and biological assessment.

BACKGROUND: LiCoO2 is one of the most used cathode materials in Li-ion batteries. Its conventional synthesis requires high temperature (>800 °C) and long heating time (>24 h) to obtain the micronscale rhombohedral layered high-temperature phase of LiCoO2 (HT-LCO). Nanoscale HT-LCO is of interest to improve the battery performance as the lithium (Li+) ion pathway is expected to be shorter in nanoparticles as compared to micron sized ones. Since batteries typically get recycled, the exposure to nanoparticles during this process needs to be evaluated. RESULTS: Several new single source precursors containing lithium (Li+) and cobalt (Co2+) ions, based on alkoxides and aryloxides have been structurally characterized and were thermally transformed into nanoscale HT-LCO at 450 °C within few hours. The size of the nanoparticles depends on the precursor, determining the electrochemical performance. The Li-ion diffusion coefficients of our LiCoO2 nanoparticles improved at least by a factor of 10 compared to commercial one, while showing good reversibility upon charging and discharging. The hazard of occupational exposure to nanoparticles during battery recycling was investigated with an in vitro multicellular lung model. CONCLUSIONS: Our heterobimetallic single source precursors allow to dramatically reduce the production temperature and time for HT-LCO. The obtained nanoparticles of LiCoO2 have faster kinetics for Li+ insertion/extraction compared to microparticles. Overall, nano-sized LiCoO2 particles indicate a lower cytotoxic and (pro-)inflammogenic potential in vitro compared to their micron-sized counterparts. However, nanoparticles aggregate in air and behave partially like microparticles.

Surface chemistry at Swiss Universities of Applied Sciences.

In the Swiss Universities of Applied Sciences, a number of research groups are involved in surface science, with different methodological approaches and a broad range of sophisticated characterization techniques. A snapshot of the current research going on in different groups from the University of Applied Sciences and Arts Western Switzerland (HES-SO), the Zurich University of Applied Sciences (ZHAW) and the University of Applied Sciences and Arts Northwestern Switzerland (FHNW) is given.

Non-destructive localization and identification of active pharmaceutical compounds by Raman chemical imaging.

Raman spectroscopy is a powerful and non-destructive technique for chemical and structural identification. Based on inelastic scattering of laser light by molecular vibrations, the analysis can be localized on a microscopic area when combined with a microscope. Thus, by moving the sample under the microscope objective and recording a Raman spectrum at each point, a map of the intensity of specific Raman bands can be generated, effectively creating a chemical image of the sample at the microscale. Here, we present an application of this technique for identifying and localizing active pharmaceutical ingredients in a polymer matrix.

Electrodeposition of gold thin films with controlled morphologies and their applications in electrocatalysis and SERS.

Here, an easy and effective electrochemical route towards the synthesis of gold thin films with well-controlled roughness, morphology and crystallographic orientation is reported. To control these different factors, the applied potential during deposition played a major role. A tentative nucleation and growth mechanism is demonstrated by means of electrochemical characterizations and a formation mechanism is proposed. Interestingly, the differences in geometry and orientation of the different gold deposits have shown a clear correlation with the electrocatalytical activity in the case of oxygen sensing. In addition, not only the electrocatalytical activity but also the surface-enhanced Raman scattering of the gold deposits have been found to depend both on the roughness and on the size of the surface nanostructures, allowing a fine tuning by controlling these two parameters during deposition.

Simple synthetic route for SERS-active gold nanoparticles substrate with controlled shape and organization.

We report a simple synthetic route based on electroless deposition (galvanic displacement) and natural lithography to simultaneously control the shape and organization of Au nanoparticles (NPs). We show for the first time the formation of organized extended domains of Au nanoflowers and nanocrowns with single crystalline tips. The dimension and morphology of the desired nanostructures (NSs) can be tuned easily by controlling the deposition conditions at room temperature using saccharin as an organic additive. The exact role of saccharin on the crystal growth process of Au NPs is also discussed. A systematic surface enhancement Raman spectroscopy (SERS) study of large, ordered areas of organized gold nanoflowers using p-mercaptoaniline (pMA) as the probe molecule shows massive and reproducible enhancements of the Raman signal. By comparing the relative enhancement of the different vibrational modes as a function of the morphology, the specific charge-transfer (chemical effect) SERS mechanism can be distinguished from the general electromagnetic field enhancement (physical effect). A wide range of applications can be envisaged for these SERS substrates.

A Nano-Rattle SnO2@carbon Composite Anode Material for High-Energy Li-ion Batteries by Melt Diffusion Impregnation.

The huge volume expansion in Sn-based alloy anode materials (up to 360%) leads to a dramatic mechanical stress and breaking of particles, resulting in the loss of conductivity and thereby capacity fading. To overcome this issue, SnO2@C nano-rattle composites based on <10 nm SnO2 nanoparticles in and on porous amorphous carbon spheres were synthesized using a silica template and tin melting diffusion method. Such SnO2@C nano-rattle composite electrodes provided two electrochemical processes: a partially reversible process of the SnO2 reduction to metallic Sn at 0.8 V vs. Li+/Li and a reversible process of alloying/dealloying of LixSny at 0.5 V vs. Li+/Li. Good performance could be achieved by controlling the particle sizes of SnO2 and carbon, the pore size of carbon, and the distribution of SnO2 nanoparticles on the carbon shells. Finally, the areal capacity of SnO2@C prepared by the melt diffusion process was increased due to the higher loading of SnO2 nanoparticles into the hollow carbon spheres, as compared with Sn impregnation by a reducing agent.

Melt-Spun Nanocomposite Fibers Reinforced with Aligned Tunicate Nanocrystals.

The fabrication of nanocomposite films and fibers based on cellulose nanocrystals (P-tCNCs) and a thermoplastic polyurethane (PU) elastomer is reported. High-aspect-ratio P-tCNCs were isolated from tunicates using phosphoric acid hydrolysis, which is a process that affords nanocrystals displaying high thermal stability. Nanocomposites were produced by solvent casting (films) or melt-mixing in a twin-screw extruder and subsequent melt-spinning (fibers). The processing protocols were found to affect the orientation of both PU hard segments and the P-tCNCs within the PU matrix and therefore the mechanical properties. While the films were isotropic, both the polymer matrix and the P-tCNCs proved to be aligned along the fiber direction in the fibers, as shown using SAXS/WAXS, angle-dependent Raman spectroscopy, and birefringence analysis. Tensile tests reveal that fibers and films, at similar P-tCNC contents, display Young's moduli and strain-at-break that are within the same order of magnitude, but the stress-at-break was found to be ten-times higher for fibers, conferring them a superior toughness over films.

Application of transient evanescent grating techniques to the study of liquid/liquid interfaces.

Transient grating experiments performed with evanescent fields resulting from total internal reflection at an interface between a polar absorbing solution and an apolar transparent solvent are described. The time evolution of the diffracted intensity was monitored from picosecond to millisecond time scales. The diffracted signal originates essentially from two density phase gratings: one in the absorbing phase induced by thermal expansion and one in the transparent solvent due to electrostriction. A few nanoseconds after excitation, the latter grating is replaced by a thermal grating due to thermal diffusion from the absorbing phase. The speed of sound and the acoustic attenuation measured near the interface are found to be essentially the same as in the bulk solutions. However, after addition of a surfactant in the polar phase, the speed of sound near the interface differs substantially from that in the bulk with the same surfactant concentration. This effect is interpreted in terms of adsorption at the liquid/liquid interface. Other phenomena, which are not observed in bulk experiments, such as acoustic echoes and a fast oscillation of the signal intensity, are also described.

Helicates of chiragen-type ligands and their aptitude for chiral self-recognition.

Two (-)-5,6-pinene-bipyridine moieties connected by a para-xylylene bridge (so-called chiragen-type ligands), (-)-L1, undergo self-assembly upon reaction with equimolar amounts of CuI to form enantiopure circular hexanuclear P-helicates. If both enantiomers of L1 are used, mixtures of P and M hexanuclear helicates are exclusively obtained through a complete chiral recognition; that is, no mixing of the (+) and (-) ligands, respectively, occurs upon complexation. This was proven by a) NMR spectroscopy where identical spectra to those for complexes with the enantiomerically pure ligands were obtained and b) circular dichroism (CD) spectroscopy. The reaction is completely changed by the use of the corresponding meso-L1. Instead of well-defined species, oligomeric mixtures are observed, a result demonstrating the crucial role played by ligand chirality in self-assembly processes. Structural variations on the chiral ligand L1, such as a meta-xylylene bridge instead of a para-xylylene one (in L4) or four pinene groups instead of two (in L5 and L6), favor nondiscrete coordination assembly.