Utilizing Carbonaceous Materials Derived from [BMIM][TCM] Ionic Liquid Precursor: Dual Role as Catalysts for Oxygen Reduction Reaction and Adsorbents for Aromatics and CO2.

This work presents the synthesis of N-doped nanoporous carbon materials using the Ionic Liquid (IL) 1-butyl-3-methylimidazolium tricyanomethanide [BMIM][TCM] as a fluidic carbon precursor, employing two carbonization pathways: templated precursor and pyrolysis/activation. Operando monitoring of mass loss during pyrolytic and activation treatments provides insights into chemical processes, including IL decomposition, polycondensation reactions and pore formation. Comparatively low mass reduction rates were observed at all stages. Heat treatments indicated stable pore size and increasing volume/surface area over time. The resulting N-doped carbon structures were evaluated as electrocatalysts for the oxygen reduction reaction (ORR) and adsorbents for gases and organic vapors. Materials from the templated precursor pathway exhibited high electrocatalytic performance in ORR, analyzed using Rotating Ring-Disk electrode (RRDE). Enhanced adsorption of m-xylene was attributed to wide micropores, while satisfactory CO2 adsorption efficiency was linked to specific morphological features and a relatively high content of N-sites within the C-networks. This research contributes valuable insights into the synthesis and applications of N-doped nanoporous carbon materials, highlighting their potential in electrocatalysis and adsorption processes.

Adsorption of Hydrogen Sulfide on Activated Carbon Materials Derived from the Solid Fibrous Digestate.

The goal of this work is to develop a sustainable value chain of carbonaceous adsorbents that can be produced from the solid fibrous digestate (SFD) of biogas plants and further applied in integrated desulfurization-upgrading (CO2/CH4 separation) processes of biogas to yield high-purity biomethane. For this purpose, physical and chemical activation of the SFD-derived BC was optimized to afford micro-mesoporous activated carbons (ACs) of high BET surface area (590-2300 m2g-1) and enhanced pore volume (0.57-1.0 cm3g-1). Gas breakthrough experiments from fixed bed columns of the obtained ACs, using real biogas mixture as feedstock, unveiled that the physical and chemical activation led to different types of ACs, which were sufficient for biogas upgrade and biogas desulfurization, respectively. Performing breakthrough experiments at three temperatures close to ambient, it was possible to define the optimum conditions for enhanced H2S/CO2 separation. It was also concluded that the H2S adsorption capacity was significantly affected by the restriction to gas diffusion. Hence, the best performance was obtained at 50 °C, and the maximum observed in the H2S adsorption capacity vs. the temperature was attributed to the counterbalance between adsorption and diffusion processes.

An Integrated Characterization Strategy on Board for Recycling of poly(vinyl butyral) (PVB) from Laminated Glass Wastes.

Polyvinyl butyral (PVB) is widely used as an interlayer material in laminated glass applications, mainly in the automotive industry, but also for construction and photovoltaic applications. Post-consumed laminated glass is a waste that is mainly landfilled; nevertheless, it can be revalorized upon efficient separation and removal of adhered glass. PVB interlayers in laminated glass are always plasticized with a significant fraction in the 20-40% w/w range of plasticizer, and they are protected from the environment by two sheets of glass. In this work, the aim is to develop a thorough characterization strategy for PVB films. Neat reference PVB grades intended for interlayer use are compared with properly processed (delaminated) post-consumed PVB grades from the automotive and construction sectors. Methods are developed to open opportunities for recycling and reuse of the latter. The plasticizer content and chemical nature are determined by applying well-known analytical techniques, namely, FT-IR, TGA, NMR. The issue of potential aging during the life cycle of the original laminated material is also addressed through NMR. Based on the findings, a sensor capable of directly sorting PVB post-consumer materials will be developed and calibrated at a later stage.

Synthesis of Polyamide-Based Microcapsules via Interfacial Polymerization: Effect of Key Process Parameters.

Polyamide microcapsules have gathered significant research interest during the past years due to their good barrier properties; however, the potential of their application is limited due to the fragility of the polymeric membrane. Fully aliphatic polyamide microcapsules (PA MCs) were herein prepared from ethylene diamine and sebacoyl chloride via interfacial polymerization, and the effect of key encapsulation parameters, i.e., monomers ratio, core solvent, stirring rate and time during the polymerization step, were examined concerning attainable process yield and microcapsule properties (shell molecular weight and thermal properties, MC size and morphology). The process yield was found to be mainly influenced by the nature of the organic solvent, which was correlated to the diffusion potential of the diamine from the aqueous phase to the organic core through the polyamide membrane. Thus, spherical microcapsules with a size between 14 and 90 µm and a yield of 33% were prepared by using toluene as core solvent. Milder stirring during the polymerization step led to an improved microcapsule morphology; yet, the substantial improvement of mechanical properties remains a challenge.

Kynos Through Time: Decorated Pottery Sherds from Eleven Strata of a Homeric Greek Site.

Excavations at the Kynos settlement, a Homeric site and the home of an early school of key Greek pictorial pottery painting, revealed extensive remains of several chronological horizons which continuously span the period from Middle Helladic (∼2100 BC) to Byzantine times (330 AD onwards), along with thousands of decorated sherds. The scope of the present study is the exploration of the technological traits of this pottery, which would contribute substantially to the archaeological understanding of the site. Samples from a sizeable assembly of decorated sherds were studied by means of analytical techniques, i.e., scanning electron microscopy-energy dispersive X-ray (SEM-EDX) analyzer, micro X-ray fluorescence (µXRF), and portable X-ray fluorescence (pXRF). Results indicate that the dark decorations have been achieved by versions of the iron reduction (IRe) technique using mostly materials identical to those of the red decorations, while for the white decorations contrast-enhancing Ca-Mg-enriched clays were used. All coexisting red and dark hues reflect similar compositions while the color difference is due to the thicker application of the darker decorations, which are thus not affected by the last oxidative firing stage of the IRe technique. X-ray fluorescence analysis focusing on several clay-origin markers shows that only a minority of samples is of non-local character and continuity in Kynos pottery tradition, at least as far as raw materials is suggested. Some of the local body-clays exhibit a puzzling enhanced level of Ni, Cu, and Zn at a nearly fixed ratio. Finally, we find that XRF may provide valuable nondestructive analysis in the case of fine pottery decorative layers of cultural significance.

Solution growth of spherulitic rod and platelet calcium phosphate assemblies through polymer-assisted mesoscopic transformations.

Solution growth of apatite its precursors in the presence of urea commercial gelatin is found to lead, under appropriate conditions, to a rich spectrum of morphologies, among them high aspect ratio needles in uniform sturdy spherulitic assemblies resulting from a herein documented morphological 'Chrysalis Transformation'; the latter transformation involves the growth of parallel arrays of high aspect ratio needles within micron-scale tablets the formation of a radial needle arrangement upon disruption of tablet wrapping. A different level of gelatin leads to the formation of sturdy platelet-based spherulites through another morphological transformation. We also probe the role of four simple synthetic water-soluble polymers; we find that three of them (poly(vinyl alcohol), polyvinylpyrrolidone and polyacrylamide)) also affect substantially the assembly habits of apatite; the effect is similar to that of gelatin but the attained control is less perfect/complete. The case of poly(vinyl alcohol) provides, through variation of the degree of hydrolysis, insights as regards the chain architecture features that might favor morphological transformations. Morphological transformations of particle assemblies documented herein constitute novel ways of generating dense quasi-isotropic reinforcements with high aspect ratio ceramic particles; it becomes possible to tailor calcium phosphate phases at the structural level of crystal assembly.

Simple solution routes for targeted carbonate phases and intricate carbonate and silicate morphologies.

This work deals with the preparation of ceramic phases similar to those encountered in natural biocomposites through relatively fast and low-cost aqueous routes and various simple reactants and additives such as urea, commercial gelatin and hexamethyldiamine. In addition to the crystallographic (or amorphous) character of targeted phases (calcite, vaterite, aragonite, silica and silicates) particle morphology is also of interest and among others, we have obtained fractions of particles in the form of nanofibrilar calcite networks, calcium silicate doughnuts and Gordian knots, and diatom-like perforated silica cylinders.

Grafting of imidazolium based ionic liquid on the pore surface of nanoporous materials--study of physicochemical and thermodynamic properties.

Supported ionic liquid phase (SILP) systems were prepared by immobilizing a methylimidazolium cation based ionic liquid onto the pore surface of two types of support, MCM-41 and Vycor. The "grafting to" method was applied, involving (3-chloropropyl)-trialkoxysilane anchoring on the supports' silanol groups, followed by treatment with 1-methylimidazole and ion exchange with PF(6)(-). Optimum surface pretreatment procedures and reaction conditions for enhanced ionic liquid (IL) loading were properly defined and applied for all modifications. A study on the effect of different pore sizes on the physical state of the grafted 1-(silylpropyl)-3-methylimidazolium-hexafluorophosphate ([spmim][PF(6)(-)]) was also conducted. The [spmim][PF(6)(-)] crystallinity under extreme confinement in the pores was investigated by modulated differential scanning calorimetry (DSC) and X-ray diffraction (XRD) and was further related to the capacity of the developed SILP to preferentially adsorb CO(2) over CO. For this purpose, CO(2) and CO absorption measurements of the bulk ionic liquid [bmim][PF(6)(-)] and the synthesized alkoxysilyl-IL were initially performed at several temperatures. The results showed an enhancement of the bulk IL performance to preferentially adsorb CO(2) at 273 K. The DSC analysis of the SILPs revealed transition of the melting point of the grafted alkoxysilyl-IL to higher temperatures when the support pore size was below 4 nm. The 2.3 nm MCM-41 SILP system exhibited infinite CO(2)/CO separation capacity at temperatures below and above the melting point of the bulk IL phase, adsorbing in parallel significant amounts of CO(2) in a reversible manner. These properties make the developed material an excellent candidate for CO(2)/CO separation with pressure swing adsorption (PSA) techniques.