Publications

This work examines the effect of incorporating a third cation M (M = Mg, Al, Mn, or Fe) into Nb-promoted NiO catalysts (Ni0.85Nb0.15O) on their physicochemical properties and catalytic performance in the oxidative dehydrogenation (ODH) of ethane into ethylene. Therefore, a series of mixed oxides with the composition Ni0.765Nb0.135M0.1O was synthesized, characterized, and analyzed for catalytic behavior. The addition of the third cation markedly modified the redox and semiconductive properties of the catalysts, thus affecting their ODH performance. The selectivity toward ethylene was strongly dependent on the cation modifier, as it modulated the density of nonselective sites on the catalyst surface. In the low-temperature region, Mn-NiNbO demonstrated the highest conversion rates but with the lowest ethylene selectivity, whereas Fe-NiNbO, despite being less active than the undoped NiNbO, exhibited the highest ethylene selectivity. Overall, undoped NiNbO emerged as the best catalyst in terms of both activity and selectivity at isoconversion. All catalysts underwent partial reduction under reaction conditions, with the degree of reduction inversely correlated with the specific reaction rates. Although none of the catalysts remained stable at 400 degrees C, Al-NiNbO showed the least deactivation over time. The deactivation was linked to a reduction in p-type conductivity and a loss of redox functionality during operation.

Rare-earth doped GdF3 nanocrystals embedded in silica glassy matrix have been prepared by controlled crystallization of the xerogel; the influence of rare-earth ion (Pr, Sm, Eu, Tb, Dy, Er, Yb) and additional Li-codopant on structural and optical properties was discussed. The precipitation of RE-doped GdF3 nanocrystalline phase is the result of Gd-trifluoracetate thermolysis revealed as a strong exothermic peak at around 300 degrees C. Structural analysis of RE-doped SiO2-GdF3 glass-ceramic sample calcined at 525 degrees C showed the occurrence of GdF3 nanocrystals of about 25 nm size, showing hexagonal or orthorombic structure depending on the RE-ion. Under UV-light excitation at 273 nm of Gd3+ ions (S-8(7/2) -> I-6(13/2,15/2) transition), photoluminescence spectra showed characteristic RE3+ luminescence due to the non-radiative energy transfer between the excited Gd3+ and acceptor RE ions; the highest energy transfer (congruent to 80 %) was observed for Tb3+ and lowest (congruent to 21 %) for Sm3+.

There has been increased interest in the synthesis of benfotiamine during the past few years, most likely as a direct consequence of growing market demand. It has much higher bioavailability than thiamine (vitamin B1) and therefore is more suitable for therapeutic purposes, especially in oral form. We report herein our research in an academic-private R&D project in which we investigate all aspects of the process on small and large scales. The procedure involves two labor-intensive steps, starting from thiami3ne chloride hydrochloride with the key intermediate thiamine monophosphate phosphate (TMP-the phosphate ester of thiamine monophosphate). We obtained the crystalline form of benfotiamine directly from the synthesis in the crystalline form required on the market, as proven by XRD powder spectroscopy, IR, and RAMAN.

Atomically clean SrTiO3(001) is characterized by low energy electron diffraction, core level and valence band photoelectron spectroscopy, the latter also with spin resolution. Samples prepared by a sputtering-annealing procedure exhibited in-gap states in the valence band spectra, Ti3+ components in Ti 2p core level spectra and a noticeable spin asymmetry in the 3-9 eV binding energy range, which corresponds to valence states of mainly O 2p character. Upon annealing in oxygen, the spin asymmetry vanishes, accompanied by the intensity decrease of the contribution of titanium low ionization states and of in-gap states, indicating that these three phenomena are mutually connected. The observed spin asymmetry may be generated by indirect exchange mediated by the in-gap states between O 2p orbitals, or by the partial Ti 3d character of these states, which acquire non-zero spin in case of incomplete oxygen coordination.

We study the dependence of photo-spectral intensity on tri- and multilayers of SiO2/[SiGe [ dSiGe]/SiO2]N with repetitions N = 1 to 10 and thicknesses dSiGe=5-100 nm. Photocurrent analysis reveals a bimodal spectral feature. A comparison of the photocurrent analysis between tri- and multilayers shows that in the multilayer structures, the photo-spectral intensity increases with increasing repetition N. The change in intensity could then be further tuned by changing the thickness of the SiGe layers dSiGe. We attribute the change in intensity to an increase in tensile strain, along with increased Ge atomic concentration and reduced SiGe-nano cluster size.

15 at.% Yb3+:YAG/YAG transparent composite ceramics with a coaxial geometry were synthesized by a ceramic forming method combined with the reactive sintering at 1800 degrees C. Densification peculiarities, microstructure, optical properties, and laser characteristics of composite ceramic samples were studied. Powder mixtures of Yb3+:YAG and YAG stoichiometric compositions demonstrate almost the same densification enabling uniform shrinkage of composite without differential sintering. It was shown that in-line optical transmittance of 15 at.% Yb3+:YAG/YAG composite ceramics reaches 80 % at 1030 nm wavelength. The effective diffusion coefficient of Yb3+ ions in garnet structure has been determined. Efficient laser emission was generated from Yb3+:YAG/YAG composite ceramics with a slope efficiency of eta(sa) = 0.30.

Fabrication aspects of PdO thin films and coatings are reviewed here. The work provides and organizes the up-to-date information on the methods to obtain the films. In recent years, the interest in Pd oxide for different applications has increased. Since Pd can be converted into PdO, it is instructive to pay attention to the preparation of the pure and the alloyed Pd films, heterostructures, and nanoparticles synthesized on different substrates. The development of PdO films is presented from the early reports on coatings' formation by oxidation of Pd foils and wires to present technologies. Modern synthesis/growth routes are gathered into chemical and physical categories. Chemical methods include hydrothermal, electrochemical, electroless deposition, and coating methods, such as impregnation, precipitation, screen printing, ink jet printing, spin or dip coating, chemical vapor deposition (CVD), and atomic layer deposition (ALD), while the physical ones include sputtering and cathodic arc deposition, laser ablation, ion or electron beam-induced deposition, evaporation, and supersonic cluster beam deposition. Analysis of publications indicates that many as-deposited Pd or Pd-oxide films are granular, with a high variety of morphologies and properties targeting very different applications, and they are grown on different substrates. We note that a comparative assessment of the challenges and quality among different films for a specific application is generally missing and, in some cases, it is difficult to make a distinction between a film and a randomly oriented, powder-like (granular), thin compact material. Textured or epitaxial films of Pd or PdO are rare and, if orientation is observed, in most cases, it is obtained accidentally. Some practical details and challenges of Pd oxidation toward PdO and some specific issues concerning application of films are also presented.

Over the past two decades, the CICECO-hub scientists have devoted substantial efforts to advancing bioactive inorganic materials based on calcium phosphates and alkali-free bioactive glasses. A key focus has been the deliberate incorporation of therapeutic ions like Mg, Sr, Zn, Mn, or Ga to enhance osteointegration and vascularization, confer antioxidant properties, and impart antimicrobial effects, marking significant contributions to the field of biomaterials and bone tissue engineering. Such an approach is expected to circumvent the uncertainties posed by methods relying on growth factors, such as bone morphogenetic proteins, parathyroid hormone, and platelet-rich plasma, along with their associated high costs and potential adverse side effects. This comprehensive overview of CICECO-hub ' s significant contributions to the forefront inorganic biomaterials across all research aspects and dimensionalities (powders, granules, thin films, bulk materials, and porous structures), follows a unified approach rooted in a cohesive conceptual framework, including synthesis, characterization, and testing protocols. Tangible outcomes [injectable cements, durable implant coatings, and bone graft substitutes (scaffolds) featuring customized porous architectures for implant fixation, osteointegration, accelerated bone regeneration in critical-sized bone defects] were achieved. The manuscript showcases specific biofunctional examples of successful biomedical applications and effective translations to the market of bone grafts for advanced therapies.

In this study, six different donor-pi-acceptor1-pi-donor-acceptor2 type random co-polymers containing benzodithiophene as a donor, benzooxadiazole (BO), and thieno[3,4-c]pyrrole-4,6-dione (TPD) as acceptor, have been synthesized and characterized. In addition to the acceptor core ratio at different values, the effect of aromatic bridge structures on the optical, electronic, and photovoltaic properties of six different random co-polymers is investigated by using thiophene and selenophene structures as aromatic bridge units. To investigate how the acceptor unit ratio and replacement of aromatic bridge units impact the structural, electronic, and optical properties of the polymers, density functional theory (DFT) calculations are carried out for the tetramer models. The open-circuit voltage (VOC), which is strongly correlated with the HOMO levels of the donor material, is enhanced with the increasing ratio of the TPD moiety. On the other hand, the short-circuit current (JSC), which is associated with the absorption ability of the donor material, is improved by the increasing ratio of BO moiety with the pi-bridges. BO moiety dominant selenophene pi-bridged co-polymer (P4) showed the best performance with a power conversion efficiency (PCE) of 6.26%, a JSC of 11.44 mA cm2, a VOC of 0.80 V, and a fill factor (FF) of 68.81%. Synthesis and design of six new D - pi - A1 - pi - D - A2 type copolymers performed. Density functional theory (DFT) calculations are carried out. All polymers showed good solubility in common organic solvents. The effect of the acceptor core ratio and aromatic bridging units on polymers is revealed. OSCs containing P4 donor polymer achieved a maximum PCE of 6.26%. image

Background/Objectives: A biocomposite based on magnesium-doped hydroxyapatite and enriched with amoxicillin (MgHApOx) was synthesized using the coprecipitation method and is presented here for the first time. Methods: The stability of MgHAp and MgHApOx suspensions was evaluated by ultrasound measurements. The structure of the synthesized MgHAp and MgHApOx was examined with X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS). The crystalline structure was determined by X-ray diffraction. The FTIR data were collected in the range of 4000-400 cm-1. The morphology of the nanoparticles was evaluated by scanning electron microscopy (SEM). Furthermore, the biocompatible properties of MgHAp, MgHApOx and amoxicillin (Ox) suspensions were assessed using human fetal osteoblastic cells (hFOB 1.19 cell line). The antimicrobial properties of the MgHAp, MgHApOx and Ox suspension nanoparticles were assessed using the standard reference microbial strains Staphylococcus aureus ATCC 25923, Escherichia coli ATCC 25922 and Candida albicans ATCC 10231. Results: X-ray studies have shown that the biocomposite retains the characteristics of HAp and amoxicillin. The SEM assessment exhibited that the apatite contains particles at nanometric scale with acicular flakes morphology. The XRD and SEM results exhibited crystalline nanoparticles. The average crystallite size calculated from XRD analysis increased from 15.31 nm for MgHAp to 17.79 nm in the case of the MgHApOx sample. The energy-dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) analysis highlighted the presence of the constituent elements of MgHAp and amoxicillin. Moreover, XPS confirmed the substitution of Ca2+ ions with Mg2+ and the presence of amoxicillin constituents in the MgHAp lattice. The results of the in vitro antimicrobial assay demonstrated that MgHAp, MgHApOx and Ox suspensions exhibited good antimicrobial activity against the tested microbial strains. The results showed that the antimicrobial activity of the samples was influenced by the presence of the antibiotic and also by the incubation time. Conclusions: The findings from the biological assays indicate that MgHAp and MgHApOx are promising candidates for the development of new biocompatible and antimicrobial agents for biomedical applications.