National Institute Of Materials Physics - Romania

Herein we show that the Ti3SiC2 MAX phase can be used as a support for deposition of different amounts of metal oxides (MOx, M = Cu or V) (5, 10 and 20 wt%) for the direct oxidation of methane to formaldehyde using molecular oxygen, at relatively low temperatures and atmospheric pressure. The oxides were deposited using a hydrothermal method at 180 degrees C without affecting the bulk MAX phase structure. However, during the hydrothermal treatment (HT) a thin oxide layer - found to play an important role in the reaction's selectivity- was evidenced by X-ray photoelectron spectroscopy. We thus conclude that the MOx species are responsible for the CH4 activation, while the Ti3SiC2 surface is responsible for the high selectivity to formaldehyde indicating that, Ti3SiC2 has great potential for designing innovative catalysts for direct oxidation of methane using molecular oxygen and at atmospheric pressure.

Capitalizing on invasive plant species and stopping their aggressive spread might be achieved by using them as a renewable source of useful products such as cellulose. The study aimed to develop new cellulose-based food packaging materials with antioxidant and antimicrobial activity. The cellulose was extracted from the invasive plant species Robinia pseudoacacia pods, crosslinked with citric acid, used as reinforcement for polyvinyl alcohol (PVA) and functionalized with ferulic acid (FA). The obtained materials were characterized by XRD, ATR-FTIR, contact angle and SEM. The materials exhibited low solubility in water and the swelling degree was proportional to the FA content. The FA release from the matrix was assessed by HPLC and the antioxidant profile by CUPRAC, FRAP, and TEAC methods. The obtained materials inhibited the growth of bacteria, yeasts and molds, being especially active on Gram-positive bacteria and yeasts. Overall, the most promising formulation for further developing new packaging materials for products with water activity less than 0.95 was the one with the highest FA content.

Potassium ions are important for developing electrode materials because they have similar properties to lithium and sodium ions. Mixed chromium phosphates (KMIICr(PO4)2) II Cr (PO 4 ) 2 ) with substituted M II sites using divalent elements (M = Ni, Co, Cu) were synthesized using a solid-state reaction method. The samples were analyzed using various techniques such as powder X-ray diffraction, Fourier transform infrared, Raman, and electron paramagnetic resonance spectroscopy. The proposed phosphates had a monoclinic phase structure with a P21/n 1 /n space group, and they contained large tunnels occupied by K+ + cations. The dielectric properties showed that the Ni-based phosphates had slower dielectric relaxation, while the Co and Cu-based phosphates had quicker polarization and depolarization processes. Additionally, the resistance of the grains decreased from Ni to Co to Cu-based phosphates, indicating easier charge movement in each material, consistent with the increase in conductive losses and a.c. conductivity when changing the M II ions.

Kynurenic acid (KA) is an active metabolite of tryptophan with notable biological effects, such as antioxidant, neuroprotective, and anti-inflammatory properties. It often undergoes changes of the concentration in biological fluids in chronic diseases. Thus, detecting KA is of great importance for diagnosing inflammatory and neurodegenerative conditions, monitoring disease progression, and assessing responses to pharmacological treatment. This study aimed to design a tailored, flexible platform for sensitive and direct electrochemical detection of KA in biological fluids. Carbon-based electrodes were custom-printed in the lab using specialized inks and flexible substrates. The working electrodes were further functionalized with graphene oxide and subsequently electrochemically reduced to increase the sensitivity toward the analyte. An optimized differential pulse voltammetry protocol was developed for KA detection. The elaborated platform was firstly characterized and then evaluated regarding the analytical performances. It showed a good limit of detection (3 nM and demonstrated the capability to detect KA across a broad concentration range (0.01-500 mu M). Finally, the elaborated flexible platform, was succesfully applied for KA determination in serum and saliva samples, in comparison with an optimized HPLC-UV method. The developed platform is the first example of in-lab printed flexible platform reported in literature so far for KA detection. It is also the first study reported in the literature of detection of KA in raw saliva collected from 10 subjects. The sensitivity towards the target analyte, coupled with the adaptability and portability, showcases the potential of this platform for thus illustrating great potential for further development of wearable sensors and biomedical applications.

This work investigates the influence of composition on the thermal properties of the high entropy alloy family Cu5Cr35Fe35V20-X-5 (at. %), where X = Ti, Ta, W or Mo in the framework of acting as a thermal barrier between the W-based plasma-facing elements and the CuCrZr or Cu-based heat sink components of the fusion reactor. The alloys were produced by arc melting and their microstructure and mechanical properties were previously characterized by XRD, SEM, and Vickers hardness measurements. Thermal properties have been measured on as-cast at thermally treated alloys using the laser flash method in the temperature range 25 degrees C to 600 degrees C to determine the thermal diffusivity, alpha, thermal conductivity, lambda, and specific heat, C-p. Dilatometry experiments were also carried out to obtain the linear thermal expansion coefficient, CTE, as a function of temperature. For all materials, the thermal conductivity increases with temperature from 15 W/mK at RT to 28 W/mK at 600 degrees C and does not significantly depend on the thermal treatment for the Mo-HEA and W-HEA, but increases after aging for the Ta-HEA and Ti-HEA. These values are lower than those of W (similar to 122 W/mK at 600 degrees C) and much lower than for CuCrZr-IG (similar to 354 W/mK at 400 degrees C). The thermal expansion coefficients of these HEAs, similar to 10 x 10(-6) degrees C-1 at RT and similar to 2 x 10(-6) degrees C-1 at 650 degrees C are between those of CuCrZr and the W for the entire operative temperature range. These results indicate that the Cu5Cr35Fe35V20-X-5 (X = Ti, Ta, W, Mo) HEAs have a promising combination of the thermophysical properties, lambda, C-p and CTE, to act as thermal barrier in plasma-facing components that require the union of W- and Cu-based materials.

The increasing demand for greener technologies in environmental remediation makes carbon materials from biomass and its derivatives some of the most attractive resources for a sustainable future. However, integrating these materials with stable free radicals remains challenging. This study presents a straightforward one-pot hydrothermal route using raw honey as the carbon source and 4-amino 2,2,6,6-tetramethylpiperidine-1-oxyl (4-amino-TEMPO) as the free radical. The addition of TEMPO derivative initiates Maillard reactions between its amino group and the carbonyl groups of the carbohydrates in honey, resulting in the formation of a functionalized hydrochar with a spherical morphology (similar to 8 mu m). The presence of free radicals within the carbonaceous matrix was confirmed by electron spin resonance spectroscopy, supported by infrared spectroscopy, elemental analysis, thermal analysis, scanning electron microscopy, and X-ray photoelectron spectroscopy. The free radical content was estimated at 0.4 mmol center dot g(-1). The material effectively removed methylene blue, fluorescein, and doxorubicin from water in the presence of green oxidants like hydrogen peroxide and sodium hypochlorite. After 24 h, removal efficiencies reached 92% for doxorubicin, 73% for methylene blue, and 23% for fluorescein. Moreover, the hydrochar demonstrated good regeneration capability, maintaining its dye removal efficiency over several cycles.

In the current study, a porous composite material, hydroxyapatite/chitosan/microcrystalline-cellulose (CaHAp-CS-MCC), was successfully prepared and used for the adsorption of Eriochrome Black T (EBT) from water. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), differential thermal analysis (DTA), thermogravimetric analysis (TGA), specific surface area (SSA), and atomic force microscope (AFM) were used to evaluate the physicochemical properties of the prepared adsorbents. CaHAp-CS-MCC exhibited a decrease in crystallinity and reduction in crystallite size. CaHAp-CS-MCC surface exhibited cracks and pores. AFM displayed changes in surface micro-texture of CaHAp, formation of new surface structures, and variations in particle size and distribution. Upon grafting CaHAp with CS and MCC, its specific surface area decreased from 139.224 to 11.775 m2/g. BET suggested that filling CaHAp pores by CS and MCC contributed to the reduction in surface area. The pore volume values decreased from 2.56 x 10-1 (CaHAp) to 3.91 x 10-2 cm3/g (CaHAp-CS-MCC). Adsorption equilibrium was reached at about 40 min. The adsorption capacities values of CaHAp-CS-MCC and CaHAp were equal to 248 mg/g and 92 mg/g, respectively. The pseudo-second order and the Langmuir equations fitted well the adsorption phenomenon. The calculated thermodynamic parameters showed an exothermic and non-spontaneous system.

Carbon dioxide (CO2) is reversibly adsorbed and desorbed from ferroelectric (001) oriented, BaO-terminated barium titanate, as revealed in real time by high resolution and ultrafast photoelectron spectroscopy and certified by low energy electron diffraction. Desorption proceeds when the substrate is heated above its Curie temperature. The amount of CO2 adsorbed is derived to be between one molecule for a surface BaO unit cell (adsorption below room temperature) and one molecule for two unit cells (adsorption above room temperature). The molecule is bound with its carbon to surface oxygen, forming a CO3 structure. The BaTiO3(001) surface is unaffected by repeated cycles of adsorption-desorption. The relatively high amount of CO2 adsorbed and the stability of the substrate after repeated adsorption and desorption processes promotes barium titanate as a promising candidate for decarbonization technologies.

In this study, the Cu2Zn1-xCoxSnS4 (CZn1-xCoxTS) films with partial cation substitution of cobalt are synthetized by sol gel spin coating, followed by sulfurization treatment. The incorporation of cobalt cation in the CZTS crystalline lattice as well as the phase transition from kesterite to stannite were confirmed by the X-ray diffraction (XRD) and Raman spectroscopy data. The XRD pattern shows peak-shifting toward higher 2 theta by increasing the Co concentration, indicating a decrease in lattice parameters. The red shift of Raman peaks by increasing x from 0 to 0.6, confirms the phase transition. The CZn1-xCoxTS morphology was observed by scanning electron microscopy, showing large grain size as x increases and a good distribution of elements for all films. Xray photoelectron spectroscopy was employed to study the valence of cations/anions and to probe the chemical bonds. The optical band gap showed a parabolic behavior versus the molar ratio Co/(Co + Zn), this deviation from Vegard's law being induced by the difference in electronegativity between cobalt and zinc. The pure CZTS has a band gap of 1.47 eV, while for CZn0.6Co0.4TS the gap is 1.17 eV, which indicates that the incorporation of cobalt cation produces a red-shift of the band to band transition energy.

Interest in self-cleaning coatings is rising due to their potential to enhance comfort and quality of life in polluted urban environments, driving the search for materials with optimal physical properties. Convergent with this goal, this study investigates the wetting properties and photo-catalytic efficiency of reticulated TiO2 layers. It shows that these properties are significantly influenced by the topographical characteristics of the TiO2 surface, which can be precisely controlled through variations in pulverization pressure and low-temperature post-annealing treatments. Post-deposition annealing of the TiO2 layers achieves 100 % self-cleaning efficiency for both thick and thin films, with optical transmission ranging from approximately 60 %-80 % in the visible spectrum. Additionally, the TiO2 layers exhibited promising capabilities for eliminating pathogenic microorganisms and disinfecting surfaces. The underlying causal factors of these remarkable and technologically promising surface features are explored and discussed.