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.

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.