National Institute Of Materials Physics - Romania

Personal and industrial use of internal combustion engines (ICEs) is projected to continue until 2050 and beyond. Yet demands to reduce global dependence on petrochemicals and fossil fuel-derived lubricants are increasing and environmentally necessary. New strategies for maintaining and enhancing ICE performance by reducing friction, wear, fuel consumption, and exhaust emissions will reduce the depletion of mineral and fossil fuel reserves and environmental pollution. This paper reports the tribological enhancement of nano-bio lubricants formulated using 2D nanocomposites of Al2O3/graphene as novel additives in coconut oil, whose performance as a lubricant compares favorably with the mineral-based engine oil 15W40. Structural, compositional, and morphological characterization of the Al2O3/graphene nanocomposite revealed an ultra-fine particle size (< 10 nm) with spherical/laminar morphology and a rich sp2 domain, exhibiting a consistent colloidal stability when formulated as nanofluid. Through the use of various characterization techniques, including friction and wear analysis we gained valuable insight into the tribological mechanism. Our optimization of this 2D tribological system using coconut oil formulation resulted significant reductions in the coefficient of friction (28 %), specific fuel con-sumption (8 %), and exhaust pollutant emissions (CO, SO2, and NOx). This work demonstrates the benefits of using nano-bio lubricant formulated using coconut oil and 2D-based hybrids as base stock and additives, delivering solutions to global challenges such as improving fuel consumption while reducing environmental pollution; solutions that can be transferred to other areas where lubricants are a necessity.

Zeolite Y samples with microporous and hierarchical structures containing Ti-Ni and Ti-Co oxides were obtained as active photocatalysts. Different Ti amounts (5, 10% TiO2) were supported, followed by the loading of Ni or Co oxides (5%). X-ray diffraction evidenced the presence of TiO2 as an anatase. N-2 adsorption-desorption results showed type IV isotherms for hierarchical zeolite Y samples, and a combination of type IV and I isotherms for zeolite Y samples. UV-Vis diffuse reflectance spectra showed a shift in the absorption band to visible with increasing Ti loading and especially after Co and Ni addition. A significant effect of the support was evidenced for Ti and its interaction with Co/Ni species. The zeolite Y support stabilized Ti in the 4+ oxidation state while hierarchical zeolite Y support favored the formation of Ti3+ species, Ni-0 and Ni2+ and the oxidation of Co to 3+ oxidation state. Photocatalytic activity, under UV and visible light irradiation, was evaluated by the degradation of amoxicillin, used as a model test. The photocatalytic mechanism was investigated using ethanol, p-benzoquinone and KI as & BULL;OH and & BULL;O-2(-) radicals and hole (h(+)) scavengers. The best results were obtained for the immobilized Ni-Ti species on the hierarchical zeolite Y support.

Nanostructured oxides (SiO2, TiO2) were synthesized using the sol-gel method and mod-ified with noble metal nanoparticles (Pt, Au) and ruthenium dye to enhance light harvesting and promote the photogeneration of reactive oxygen species, namely singlet oxygen (O-1(2)) and hydroxyl radical (center dot OH). The resulting nanostructures were embedded in a transparent polyvinyl alcohol (PVA) hydrogel. Morphological and structural characterization of the bare and modified oxides was performed using scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), UV-Vis spectroscopy, and X-ray photoelectron spectroscopy (XPS). Additionally, electrokinetic potential measurements were conducted. Crystallinity data and elemental analysis of the investigated systems were obtained through X-ray diffraction and X-ray fluorescence analyses, while the chemical state of the elements was determined using XPS. The engineered ma-terials, both as simple powders and embedded in the hydrogel, were evaluated for their ability to generate reactive oxygen species (ROS) under visible and simulated solar light irradiation to establish a correlation with their antibacterial activity against Staphylococcus aureus. The generation of singlet oxygen (O-1(2)) by the samples under visible light exposure can be of significant importance for their potential use in biomedical applications.

Nanostructured surfaces based on silver nanoparticles decorated ZnO-CuO core-shell nanowire arrays, which can assure protection against various environmental factors such as water and bacteria were developed by combining dry preparation techniques namely thermal oxidation in air, radio frequency (RF) magnetron sputtering and thermal vacuum evaporation. Thus, high-aspect-ratio ZnO nanowire arrays were grown directly on zinc foils by thermal oxidation in air. Further ZnO nanowires were coated with a CuO layer by RF magnetron sputtering, the obtained ZnO-CuO core-shell nanowires being decorated with Ag nanoparticles by thermal vacuum evaporation. The prepared samples were comprehensively assessed from morphological, compositional, structural, optical, surface chemistry, wetting and antibacterial activity point of view. The wettability studies show that native Zn foil and ZnO nanowire arrays grown on it are featured by a high water droplet adhesion while ZnO-CuO core-shell nanowire arrays (before and after decoration with Ag nanoparticles) reveal a low water droplet adhesion. The antibacterial tests carried on Escherichia coli (a Gram-negative bacterium) and Staphylococcus aureus (a Gram-positive bacterium) emphasize that the nanostructured surfaces based on nanowire arrays present excellent antibacterial activity against both type of bacteria. This study proves that functional surfaces obtained by relatively simple and highly reproducible preparation techniques that can be easily scaled to large area are very attractive in the field of water repellent coatings with enhanced antibacterial function.

We reported on the sequential development of a high-operative photocatalyst with penta-component inorganic bulk heterojunction for improved charge trapping characteristics at particle-particle interfaces for enhanced solar light-driven photocatalytic degradation of active tetracycline antibiotic. Structural, morphological, optical, and electronic properties of the synthesized samples were investigated using a series of complementary char-acterization techniques, such as XRD, FE-SEM, HR-TEM, XPS, as well as hard and soft XAS in both total electron yield (TEY) and fluorescence yield (TFY). For the case of the carbon composite material, SrTiO3@NiFe2O4@-Fe0@Ni0@CNTs, a reduced crystallinity when compared to the starting support material was noticed, although this translated into a significant improvement of the morphology and the photocatalytic performance. The SrTiO3@NiFe2O4@Fe0@Ni0@CNTs fibrous photocatalyst can efficiently achieve a high-to-total degradation of tetracycline antibiotic under visible light irradiation in less than two hours, following a non-linear PFO kinetic model with an apparent reaction rate of about 0.0606 min-1 and an 98% photodegradation activity. The XPS and XAS analysis demonstrated unequivocally the appearance of nanoscale zero-valent iron (Fe0) and zero-valent nickel (Ni0) on the photocatalyst surface, which facilitates the separation of photogenerated e+ and h+ pairs, and the appearance of more active sites.

The aim of this work is to highlight the influence of blends based on TiO2 nanoparticles and reduced graphene oxide (RGO) on the photodegradation of acetaminophen (AC). To this end, the catalysts of TiO2/RGO blends with RGO sheet concentrations equal 5, 10, and 20 wt. % were prepared by the solid-state interaction of the two constituents. The preferential adsorption of TiO2 particles onto the RGO sheets' surfaces via the water molecules on the TiO2 particle surface was demonstrated by FTIR spectroscopy. This adsorption process induced an increase in the disordered state of the RGO sheets in the presence of the TiO2 particles, as highlighted by Raman scattering and scanning electron microscopy (SEM). The novelty of this work lies in the demonstration that TiO2/RGO mixtures, obtained by the solid-phase interaction of the two constituents, allow an acetaminophen removal of up to 95.18% after 100 min of UV irradiation. This TiO2/RGO catalyst induced a higher photodegradation efficiency of AC than TiO2 due to the presence of RGO sheets, which acted as a capture agent for the photogenerated electrons of TiO2, hindering the electron-hole recombination. The reaction kinetics of AC aqueous solutions containing TiO2/RGO blends followed a complex first-order kinetic model. Another novelty of this work is the demonstration of the ability of PVC membranes modified with Au nanoparticles to act both as filters for the removal of TiO2/RGO blends after AC photodegradation and as potential SERS supports, which illustrate the vibrational properties of the reused catalyst. The reuse of the TiO2/RGO blends after the first cycle of AC photodegradation indicated their suitable stability during the five cycles of pharmaceutical compound photodegradation.

The aim of this work is to highlight the influence of blends based on TiO2 nanoparticles and reduced graphene oxide (RGO) on the photodegradation of acetaminophen (AC). To this end, the catalysts of TiO2/RGO blends with RGO sheet concentrations equal 5, 10, and 20 wt. % were prepared by the solid-state interaction of the two constituents. The preferential adsorption of TiO2 particles onto the RGO sheets' surfaces via the water molecules on the TiO2 particle surface was demonstrated by FTIR spectroscopy. This adsorption process induced an increase in the disordered state of the RGO sheets in the presence of the TiO2 particles, as highlighted by Raman scattering and scanning electron microscopy (SEM). The novelty of this work lies in the demonstration that TiO2/RGO mixtures, obtained by the solid-phase interaction of the two constituents, allow an acetaminophen removal of up to 95.18% after 100 min of UV irradiation. This TiO2/RGO catalyst induced a higher photodegradation efficiency of AC than TiO2 due to the presence of RGO sheets, which acted as a capture agent for the photogenerated electrons of TiO2, hindering the electron-hole recombination. The reaction kinetics of AC aqueous solutions containing TiO2/RGO blends followed a complex first-order kinetic model. Another novelty of this work is the demonstration of the ability of PVC membranes modified with Au nanoparticles to act both as filters for the removal of TiO2/RGO blends after AC photodegradation and as potential SERS supports, which illustrate the vibrational properties of the reused catalyst. The reuse of the TiO2/RGO blends after the first cycle of AC photodegradation indicated their suitable stability during the five cycles of pharmaceutical compound photodegradation.

The phosphate KCoCr-(PO4)(2) and iron-substitutedvariants KCoCr1-x Fe x (PO4)(2) (x =0.25, 0.5, and 0.75) were synthesized by a solid-state reaction route,while a high substitution level of Fe was achieved. Their structureswere refined using powder X-ray diffraction and indexed in a monoclinicsystem with a P2(1)/n spacegroup. A 3D framework with six-sided tunnels parallel to the [101]direction was formed in which the K atoms are located. Mo''ssbauerspectroscopy confirms the exclusive presence of octahedral paramagneticFe(3+) ions, with isomer shifts increasing slightly with x substitution. Electron paramagnetic resonance spectroscopyconfirmed the presence of paramagnetic Cr3+ ions. The activationenergy, determined by dielectric measurements, shows that the iron-containingsamples present higher ionic activity. Relative to the electrochemicalactivity of K, these materials could be good candidates for positiveand/or negative electrode materials for energy storage applications. The synthesized phosphate KCoCr-(PO4)(2) and Fe-substituted variants KCoCr1-x Fe x (PO4)(2) (x = 0.25, 0.5, and 0.75) present a 3D frameworkwith six-sided tunnels in which the K atoms are located. The activationenergy, determined by dielectric measurements, shows that the iron-containingsamples present improved ionic activity, making these materials goodcandidates for positive and/or negative electrode materials for energystorage applications.