National Institute Of Materials Physics - Romania

Plastics are indispensable materials for packaging and many products from our daily life, and their recycling is essential to ensure a circular economy. In this study, -SO3H-modified, Ti3C2-MXene was used as a recoverable solid acid catalyst for upcycling of polyethylene terephthalate (PET) to terephthalic acid (TPA) and ethylene glycol by hydrolysis. For the grafting of -SO3H groups to the Ti3C2Tx surface (where T-x represents the surface moieties, such as -OH or -O), sulfonation with an aryl diazonium salt obtained from sulfanilic acid was employed. X-ray photoelectron and Fourier transform infrared spectroscopy analyses provided a direct indication that sulfonation of the Ti3C2Tx was successfully performed, while X-ray diffraction and transmission electron microscopy analyses evidence the presence of -SO3H groups between the Ti3C2Tx layers due to the increases of the interlayer spacing through the intercalation of functional groups. The higher the concentration of acid groups, the higher the interlayer spacing. The depolymerization of PET in water occurred with a very good isolated yield in TPA (99%) for the MXene with the highest amount of sulfonic acid groups. We conclude that the acidity is mandatory to perform the hydrolysis reaction, in agreement with the acidity measurements, which show that the MXenes modified with the highest amount of derived sulfonic acids are the most active. Nevertheless, the accessibility to the acidic sites is a key factor that promotes the 2D acid-modified MXene materials as important catalysts for PET upcycling to TPA.

TiO2-based mixed oxide-carbon composite support for Pt electrocatalysts provides higher stability and CO tolerance under the working conditions of polymer electrolyte membrane fuel cells compared to traditional carbon supports. Non-traditional carbon materials like graphene nanoplatelets and graphite oxide used as the carbonaceous component of the composite can contribute to its affordability and/or functionality. Ti(1-x)MoxO2-C composites involving these carbon materials were prepared through a sol-gel route; the effect of the extension of the procedure through a solvothermal treatment step was assessed. Both supports and supported Pt catalysts were characterized by physicochemical methods. Electrochemical behavior of the catalysts in terms of stability, activity, and CO tolerance was studied. Solvothermal treatment decreased the fracture of graphite oxide plates and enhanced the formation of a reduced graphene oxide-like structure, resulting in an electrically more conductive and more stable catalyst. In parallel, solvothermal treatment enhanced the growth of mixed oxide crystallites, decreasing the chance of formation of Pt-oxide-carbon triple junctions, resulting in somewhat less CO tolerance. The electrocatalyst containing graphene nanoplatelets, along with good stability, has the highest activity in oxygen reduction reaction compared to the other composite-supported catalysts.

Curcumin, an important bioactive compound and natural photosensitizer, which exhibits various biological properties, was loaded into inorganic carriers MgAl/ZnAl layered double hydroxides (LDH). The supporting matrices were obtained by co-precipitation, and a surfactant was used for including the organic drug. The structural, morphological, and spectral properties of the obtained composites were followed by X-ray diffraction, FTIR, SEM, UV-Vis, and fluorescence spectroscopy in solid state and in different solvents. The prepared formulations, the curcumin-loaded carriers, were introduced in alcohol-aqueous mixtures and the effect of solvent on the spectral properties of the formulations was investigated. Interactions between the keto-enol group of the pigment and the metals in LDHs laminates as well as inter-molecular bonds between alcohols and curcumin were evidenced. As a consequence, it was concluded that the composition of the carrier as well as the nature of the solvent determine the structural changes of the formulations. MgAl-LDH in powder has better spectral characteristics in the low-energy range (UV-Vis and fluorescence) than ZnAl-LDH. Their spectra are altered when methanol and water are present in the solvent mixture. The released curcumin concentration is in the range for photosensitization applications. The results have potential utilizations in many fields such as food, pharmaceutical, and biology.

We report on the Matrix Assisted Pulsed Laser Evaporation, laser technology for depositing biocompatible, antimicrobial, hydrophilic, and biodegradable complex hybrid polymeric system loaded with essential cypress-oil and magnetite nanoparticles as resorbable implants, capable of targeting possible hyperthermia applications, an anticancer moderate field heating therapy. Magnetite nanoparticles based on iron oxide (Fe3O4) coated with Cypress essential oil (denoted: Fe3O4- Cypress) and embedded in PLGA (poly(lactic-co-glycolic acid) (denoted: PLGA-Fe3O4- Cypress-) and PLGA - poly(3,4ethylene dioxythiophene) doped with poly(styrene sulfonate) anions) (PEDOT: PSS) mixture (denoted: PLGA-Fe3O4- Cypress- PEDOT: PSS) were used as MAPLE targets. The controlled drug delivery of the active Cypress oil, an antimicrobial therapeutic agent from Fe3O4- Cypress nanoparticles could be possible by applying an external radio frequency (RF) magnetic field. The Fe3O4-Cypress-based powders as well as the final hybrid coatings have been characterized in terms of stoichiometry, morphology, magnetic, antimicrobial properties, biocompatibility, and response to external physical stimuli. FTIR analyses confirmed the quasi-stoichiometric laser transfer of organic compounds while the XRD evidenced the semicrystalline structure of deposited thin films. SEM and AFM images evidence that conductive polymer addition led to the films' relief flattening and a decrease in the coatings' thickness and roughness by changing the polymeric packaging. The samples containing conductive polymer exhibited 3 times higher current and corrosion rate values. All coatings are hydrophilic and revealed enhanced cellular viability when cultured with osteoblast-like MG-63 cells. The composite structures exhibited significant antimicrobial activity against Gram-positive (Staphylococcus aureus), and Gram -negative (Escherichia coli ) bacteria, as well as to the opportunistic yeast Candida albicans.

Magneto-optical measurements enable the identification of Fe2+ and Fe3+ in the R and S blocks of BaFe12O19 Mhexaferrite powder obtained by sol -gel processing, followed by thermal annealing at 900 C for 3 hours. The ferromagnetic phase is evidenced by the spin-majority configuration (Fe3+) due to their unpaired electrons between d -d orbitals, while the Fe2+ in the low spin possesses diamagnetic behavior strongly dependent on the surrounded crystal field. Additionally, the irradiation with gamma rays changes the ratio between Fe2+/Fe3+, mainly on the surface of BaFe12O19 nanocrystals. These changes were confirmed by X-ray Photoelectron Spectroscopy measurements, in which the concentration of Fe2+ increased from 69% to 82%, while the one of Fe3+ decreased from 31% to 18%. he thermoluminescent measurements reveal the same changes of Fe3+ in Fe2+ by electron capturing during irradiation, which is released as a red emission after recombination processes. The changes are explained by the increasing of some Fe-O bonds along the c-axis, mainly due to breaking a part of these bonds. The X-ray analysis confirms the changing of the parameters for the BaFe12O19 hexagonal structure.

To advance gas sensor technologies, it is essential to identify materials that exhibit both high selectivity and sensitivity. Here, we unravel the gas-sensing capabilities of indium sulfide (InS) nanosheets, particularly in relation to nitrogen dioxide (NO2) detection. Utilizing a synergistic approach that combines in situ and operando experimental methodologies with density functional theory calculations, we demonstrate that these nanosheets offer outstanding sensitivity toward NO2, characterized by a remarkably low detection threshold of 180 ppb at an operational temperature of 350 degrees C. This remarkable sensitivity is ascribed to the electronic charge redistribution around the Fermi level, facilitated by an oxygen-deficient In2O3-x surface layer that forms naturally when the InS surface is exposed to ambient conditions. A pivotal aspect of our investigation was the exploration of the influence of sulfur abstraction on these surface modifications. We demonstrate that sulfur abstraction plays a critical role in the formation and operational efficacy of the In2O3-x layer, thereby acting as a key element in the sensor mechanism. This unique surface chemistry not only amplifies the sensitivity to NO2 but also confers unparalleled selectivity over other gases and volatile organic compounds. Notably, this level of performance exceeds that of other 2D semiconductors and metal oxides, thus establishing InS nanosheets as an ideal platform for high-performance gas sensors suitable for demanding environments. Moreover, unlike many state-of-the-art sensor materials, InS-based sensors can withstand a wider variety of environmental conditions due to their superior water adsorption resistance.

This work presents the ability of WO3-based sensors to detect low traces of acetone, specifically within the range of 0.25-5 ppm, specific to the in -field atmosphere. The WO3 powder was synthesised through the hydrothermal method. Morpho-structural investigations showed a monoclinic structure and a good crystallization of the WO3 powder, containing well -grown and faceted grains along low -index crystallographic planes. The paste obtained by mixing the powder with propanediol was screen -printed as a thick layer onto commercial alumina substrates, obtaining the chemical sensors. A dynamic computer -controlled Gas Mixing System was utilized to ensure controlled airflow with variable relative humidity and acetone concentrations. The sensor response was explained based on physico-chemical equations, taking into consideration pre -adsorbed species of oxygen and water, both of which are relevant constituents of atmospheric conditions. The results highlight the applicative potential of WO3, having a good signal-to-noise ratio in relative humidity conditions up to 90% and a pronounced sensitive selectivity to acetone.

The outstanding properties exhibited by the p-type NiO nanostructures can be greatly affected by morpho-structural and defect characteristics with constructive or competing effects. We have conducted an in-depth study on NiO nanoparticles obtained by hydrothermal synthesis and submitted to various thermal treatments, to monitor the evolution of their structural properties and the effect of the thermal history on their CO sensing. Correlated electron paramagnetic resonance and analytical transmission electron microscopy investigations evidenced an amount of up to 1 % metallic nickel clusters close to surface in the NiO nanoparticles calcined at 400 degrees C and 500 degrees C for 8 h. Subsequent annealing in vacuum and in air of the sample calcined at 400 degrees C resulted in different size distributions and morphology of the NiO nanoparticles and an increase/decrease of the nickel phase, respectively. Comparative CO sensing tests on the two pristine samples and on the sample calcined at 400 degrees C and further annealed in air at 500 degrees C for 2 h showed an increase in the baseline resistance of the later due to the decrease of free charge carriers induced by the dissolution of the nickel clusters. The overall CO sensing results show a strong dependence on the samples thermal history.

In this work, the formation of the orthorhombic phase of ZrO2 together with the minor monoclinic phase were elucidated by X-ray diffraction and transmission electron microscopy. Moreover, oxidized W can be responsible for the formation of oxygen vacancies in the ZrO2 through oxygen scavenging. The ferroelectric properties of the W/ZrO2/W film capacitors were investigated through piezoresponse force microscopy (PFM) and polarizationvoltage measurements. A second-order phase transition from the polar orthorhombic phase to the non-polar tetragonal phase was observed. Density functional theory calculations confirm our experimental results and propose that oxygen vacancies are responsible for the Curie-Weiss temperature of 130 degrees C, significantly lower than the theoretical value for the bulk.