Understanding Electrodeposition of Chitosan-Hydroxyapatite Structures for Regeneration of Tubular-Shaped Tissues and Organs.

Tubular-shaped hydrogel structures were obtained in the process of cathodic electrodeposition from a chitosan-hydroxyapatite solution carried out in a cylindrical geometry. The impact of the initial concentration of solution components (i.e., chitosan, hydroxyapatite, and lactic acid) and process parameters (i.e., time and voltage) on the mass and structural properties of deposit was examined. Commercially available chitosan differs in average molecular weight and deacetylation degree; therefore, these parameters were also studied. The application of Fourier-transform infrared spectroscopy, scanning electron microscopy, and time-of-flight secondary ion mass spectrometry allowed obtaining fundamental information about the type of bonds and interactions created in electrodeposited structures. Biocompatible tubular implants are highly desired in the field of regeneration or replacement of tubular-shaped tissues and organs; therefore, the possibility of obtaining deposits with the desired structural properties is highly anticipated.

The Influence of Carbon Nature on the Catalytic Performance of Ru/C in Levulinic Acid Hydrogenation with Internal Hydrogen Source.

The influence of the nature of carbon materials used as a support for Ru/C catalysts on levulinic acid hydrogenation with formic acid as a hydrogen source toward gamma-valerolactone was investigated. It has been shown that the physicochemical properties of carbon strongly affect the catalytic activity of Ru catalysts. The relationship between the hydrogen mobility, strength of hydrogen adsorption, and catalytic performance was established. The catalyst possessing the highest number of defects, stimulating metal support interaction, exhibited the highest activity. The effect of the catalyst grain size was also studied. It was shown that the decrease in the grain size resulted in the formation of smaller Ru crystallites on the catalyst surface, which facilitates the activity.

Impact of Support (MCF, ZrO2, ZSM-5) on the Efficiency of Ni Catalyst in High-Temperature Conversion of Lignocellulosic Biomass to Hydrogen-Rich Gas.

The main objective of this work was to evaluate an impact of a support on the efficiency of nickel catalysts in the high-temperature conversion of lignocellulosic biomass to hydrogen-rich gas. The most important parameters influencing catalytic performance of the catalysts were identified. The properties of three materials (ZSM-5, ZrO2, and MCF (mesostructured cellular foam)) used as a support differing in surface acidity, surface area, pore structure, ability to interact with an active phase, and resistance to coking, have been studied. The results revealed that Ni/MCF, characterized by large pore size and pore volume, low acidity, small NiO crystallites size, and moderate interaction with the active phase, is the most efficient among studied catalysts, while an application of Ni on ZSM-5 support with high-acidity was not beneficial. The results suggest that structure of the support, in particular larger pore size and a better contact between an active phase and reaction intermediates, play an important role in the formation of gaseous products during thermal decomposition of lignocellulosic feedstock. On the other hand, high acidity of the support did not increase the formation of large amounts of hydrogen-rich gaseous products.

Enhanced Production of γ-Valerolactone with an Internal Source of Hydrogen on Ca-Modified TiO2 Supported Ru Catalysts.

Calcium-modified titania supported Ru catalysts were synthesized and evaluated for the hydrogenation of levulinic acid with formic acid as an internal hydrogen source and water as a green solvent. A new elegant photoassisted method was developed for the synthesis of uniform-size and evenly distributed Ru particles on the titania surface. Compared with the counterpart catalysts prepared by classical wet impregnation, enhanced levulinic acid conversion and γ-valerolactone yield were obtained and further improved through modification of the support by introduction of calcium into the titania support. This synthesis approach resulted in a change of the surface and bulk properties of the support, namely a decrease in the anatase crystallite size and the formation of a new calcium titanate phase. As a consequence, the properties of the catalysts were modified, and smaller ruthenium particles that had stronger interactions with the support were obtained. This affected the strength of the CO adsorption on the catalyst surface and facilitated the reaction performance. The optimum size of Ru particles that allowed for most efficient levulinic acid conversion was established.

Solar Light Induced Photon-Assisted Synthesis of TiO2 Supported Highly Dispersed Ru Nanoparticle Catalysts.

Ru/TiO2 are promising heterogeneous catalysts in different key-reactions taking place in the catalytic conversion of biomass towards fuel additives, biofuels, or biochemicals. TiO2 supported highly dispersed nanometric-size metallic Ru catalysts were prepared at room temperature via a solar light induced photon-assisted one-step synthesis in liquid phase, far smaller Ru nanoparticles with sharper size distribution being synthesized when compared to the catalysts that were prepared by impregnation with thermal reduction in hydrogen. The underlying strategy is based on the redox photoactivity of the TiO2 semi-conductor support under solar light for allowing the reduction of metal ions pre-adsorbed at the host surface by photogenerated electrons from the conduction band of the semi-conductor in order to get a fine control in terms of size distribution and dispersion, with no need of chemical reductant, final thermal treatment, or external hydrogen. Whether acetylacetonate or chloride was used as precursor, 0.6 nm sub-nanometric metallic Ru particles were synthesized on TiO2 with a sharp size distribution at a low loading of 0.5 wt.%. Using the chloride precursor was necessary for preparing Ru/TiO2 catalysts with a 0.8 nm sub-nanometric mean particle size at 5 wt.% loading, achieved in basic conditions for benefitting from the enhanced adsorption between the positively-charged chloro-complexes and the negatively-charged TiO2 surface. Remarkably, within the 0.5⁻5 wt.% range, the Ru content had only a slight influence on the sub-nanometric particle size distribution, thanks to the implementation of suitable photo-assisted synthesis conditions. We demonstrated further that a fine control of the metal Ru nanoparticle size on the TiO2 support was possible via a controlled nanocluster growth under irradiation, while the nanoparticles revealed a good resistance to thermal sintering.

Wide band gap Ga2O3 as efficient UV-C photocatalyst for gas-phase degradation applications.

α, ß, γ, and δ polymorphs of 4.6-4.8 eV wide band gap Ga2O3 photocatalysts were prepared via a soft chemistry route. Their photocatalytic activity under 254 nm UV-C light in the degradation of gaseous toluene was strongly depending on the polymorph phase. α- and ß-Ga2O3 photocatalysts enabled achieving high and stable conversions of toluene with selectivities to CO2 within the 50-90% range, by contrast to conventional TiO2 photocatalysts that fully deactivate very rapidly on stream in similar operating conditions with rather no CO2 production, no matter whether UV-A or UV-C light was used. The highest performances were achieved on the high specific surface area ß-Ga2O3 photocatalyst synthesized by adding polyethylene glycol (PEG) as porogen before precipitation, with stable toluene conversion and mineralization rate into CO2 strongly overcoming those obtained on commercial ß-Ga2O3. They were attributed to favorable physicochemical properties in terms of high specific surface area, small mean crystallite size, good crystallinity, high pore volume with large size mesopore distribution and appropriate surface acidity, and to the possible existence of a double local internal field within Ga3+ units. In the degradation of hydrogen sulfide, PEG-derived ß-Ga2O3 takes advantage from its high specific surface area for storing sulfate, and thus for increasing its resistance to deactivation and the duration at total sulfur removal when compared to other ß-Ga2O3 photocatalysts. So, we illustrated the interest of using high surface area ß-Ga2O3 in environmental photocatalysis for gas-phase depollution applications.

The Studies of Archaeological Pottery with the Use of Selected Analytical Techniques.

Modern analytical methods play an important role in archaeological objects, including ceramics. This review focuses on the use of analytical methods such as: gas chromatography coupled mass spectrometry, Fourier transform infrared spectroscopy, time-of-flight secondary ion mass spectrometry (ToF-SIMS), powder X-ray diffraction with thermal analysis to study the chemical and mineralogical composition of archaeological samples and organic residues preserved inside. In this paper, special attention was paid to the ToF-SIMS method, which allows the determination of characteristic ions on the surface of ceramic samples.

Role of water in metal catalyst performance for ketone hydrogenation: a joint experimental and theoretical study on levulinic acid conversion into gamma-valerolactone.

While Ru is a poor hydrogenation catalyst compared to Pt or Pd in the gas phase, it is efficient under aqueous phase conditions in the hydrogenation of ketones such as the conversion of levulinic acid into gamma-valerolactone. Combining DFT calculations and experiments, we demonstrate that water is responsible for the enhanced reactivity of Ru under those conditions.

Surface studies of heterogeneous catalysts by time-of-flight secondary ion mass spectrometry.

The aim of this paper was to present potentialities of time-of-flight secondary ion mass spectrometry (ToF- SIMS) in the studies of heterogeneous catalysts. The results of ToF-SIMS investigations of Co/Al2O3, Mo/Al2O3, Co-Mo/Al2O3, Au/Al2O3, Pt/TiO2 and Pd/TiO2 systems were described. It was demonstrated that, in this case, an application of ToF-SIMS makes possible the determination of surface composition of investigated catalysts (including an identification of surface contaminants), characterization of interactions between an active phase and support, estimation of active phase dispersion on the analyzed surface, comparison of the degree of metal oxidation after treatment of the catalyst in different conditions, investigation of catalyst deactivation processes (formation of new chemical compounds, adsorption of various impurities and poisons on the catalyst surface) and determination of organic precursors of catalysts.