National Institute Of Materials Physics - Romania

We investigate the second-order Floquet topological (SOFT) phase transitions, from the perspective of spatial symmetries. In this respect, we consider a generic honeycomb lattice Floquet topological insulator (FTI), realized by circularly polarized light irradiation, in the presence of spin-orbit coupling (Kane-Mele model). We find that our studied FTI presents chiral symmetry on a preferential direction in Fourier space, the same property that protects the topological phases in the Su-Schrieffer-Heeger (SSH) model. Thus we were allowed to characterize the SOFT phases in terms of mirror-graded winding numbers (Zak phase). Moreover, our model exhibits C2 and C3 symmetry in Fourier space, a property which lead us to investigate two finite structures having the aforementioned symmetries, namely, rhombic and triangular shapes. Indeed, we find that both of them undergo SOFT phase transitions, characterized by the appearance of 0D corner states symmetrically localized over the whole sheet. Finally, we investigate the C2 and C3 symmetry breaking. Interestingly, we reveal that the corner states are not destroyed, but localize at preferential corners instead, giving rise to a corner polarization.

The catalytic hydrodeoxygenation (HDO) of lignocellulose-derived pyrolysis oil is a critical process for producing high-quality biofuels. This study investigates the effect of the Mg/Al molar ratio on the catalytic performance of CuMg(Al)O mixed oxide catalysts in the HDO reaction of benzyl alcohol as a model oxygenated compound. They were synthesized by coprecipitation with a fixed Cu content of 15 at. %, with respect to cations, and different Mg/Al molar ratios (0/1, 1/1, 3/1, 5/1, and 1/0). The catalysts were characterized using X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), UV-vis spectroscopy, nitrogen adsorption-desorption isotherms, temperature-programmed reduction with hydrogen (H2-TPR), and temperature-programmed desorption (TPD) of CO2 and NH3. It has been shown that the Mg/Al molar ratio strongly influences the physicochemical characteristics of the CuMg(Al)O mixed oxides and, hence, their catalytic performance. Catalytic tests were conducted in a stainless-steel autoclave reactor and the obtained results indicated that the systems with Mg/Al molar ratios of 3/1 and 5/1, issued from layered double hydroxide precursors, exhibited the highest activity, with yields to toluene higher than 85%. This superior performance is attributed to the well-dispersed copper species on the catalyst surface combined with appropriate acid-base properties. As the CuMg(Al)O system with Mg/Al molar ratio of 5/1 was the best in terms of benzyl alcohol conversion, i.e., ca. 98% at 230 degrees C, under 5 atm of H2, for 3 h of reaction time, with high selectivity to toluene of ca. 87%, the influence of the reaction time, temperature and reusability over multiple reaction cycles on its performance were investigated.

Photoanodes based Ce-doped ZnO nanorods arrays were prepared by hydrothermal method in order to improve photoelectrochemical efficiency of ZnO photoanodes in water splitting process. Scanning electron microscopy investigation showed ZnO based nanorods with length of around 500 nm and different thicknesses and growth directions. Some morphological changes were noted following the thermal treatment. Energy-dispersive X-ray analysis and X-ray photoelectron spectroscopy measurements proved the presence of cerium species both in bulk and on the surface of ZnO nanorods. A current density of 2.44 mA/cm(2) at 1.23 V against the reversible hydrogen electrode (0.265 V vs. Ag/AgCl) was obtained for Ce-doped ZnO sample, which is >162% increase over that of ZnO sample. The increased photocurrent value obtained for this sample was correlated with the passivation of surface defects evidenced by photoluminescence study and the increased concentration of Ce3+ on the surface. Also, the electrochemical impedance spectroscopy measurements suggested that Ce doping improves the charge transfer in bulk.

Herein, alpha-MoO3 micro- and nanoparticles were synthesized by a modified Pechini method, and the impact of the crystal structure and crystal growth orientation on the formation of ionic defects and, consequently, on the catalytic performance of the materials in the ethylic transesterification reaction for biodiesel production was investigated. Structural refinements from X-ray diffraction data and Raman spectra revealed the formation of alpha-MoO3 in a Pbnm orthorhombic phase, with nanoplate-like morphology at 500 degrees C (thickness between 100 and 260 nm) or ribbon-like morphology at 700 degrees C (thickness between 400 and 900 nm). An anisotropic crystal orientation along the [010] direction was observed with an increase of the calcination temperature. We emphasize the dependence of the orientation change with the elimination of ionic-type defects (oxygen vacancies and reduced Mo5+ centers) by the temperature using complementary techniques such as X-ray photoelectron and electron paramagnetic resonance spectroscopies. The catalytic activity of the samples depends on the orientation process and the presence of defects that act as acid-active sites on the catalyst surface and therefore play an important role in biodiesel production. This effect was confirmed by surface stability and reactivity simulated by density functional theory calculations, suggesting that the Mo and O surface terminals greatly impacted the interface catalytic reaction. The highest catalytic performance toward the biodiesel conversion (89% of conversion at 150 degrees C for 2 h) was achieved for the polycrystalline catalyst calcined at 500 degrees C, which was correlated with random crystal orientation and the presence of reduced Mo5+ and oxygen vacancy centers on the different facets exposed on the surface. The biodiesel production was confirmed by H-1 and C-13 NMR spectroscopy and gas chromatography analysis.

In photocatalysis, a common challenge is the rapid recombination of photogenerated electrons and holes, coupled with low surface reaction efficiency in aqueous environments. This study addresses these issues by improving the photocatalytic performance of Al3+-doped SrTiO3 perovskite through the strategic loading of CoOOH onto its surface. We successfully demonstrated that the combined approach of Al3+ doping and CoOOH co-catalyst functionalization significantly enhances the photocatalytic performance of SrTiO3. The Al3%:SrTiO3 was functionalized with CoOOH using a two-step process. This process involved the oxidation of Co2+ ions to Co3+ ions, followed by the precipitation of cobalt oxyhydroxide (CoOOH) onto the surface of Al3%:SrTiO3, resulting in the formation of an Al3%:SrTiO3@CoOOH composite heterostructure. The UV-Vis data shows an enhanced light absorption capabilities into the visible spectrum with a direct band gap of 1.73 eV in contrast to 3.24 eV for the pristine perovskite. XPS analysis confirms the surface functionalization with CoOOH co-catalyst and the determined 1:1 Sr:Ti stoichiometry, the reduced state of Al, and the absence of oxygen vacancies were identified as beneficial properties for photocatalytic applications, as shown in DFT calculations. The oxacillin photodegradation was tested at three different concentrations of Al3%:SrTiO3@CoOOH photocatalyst (0.25 g/L; 0.5 g/L and 1 g/L) and we observed that the removal efficiency significantly varies from 99 % for 1 g/L Al3%: SrTiO3@CoOOH to 78 % and 44 % for 0.5 g/L and, respectively 0.25 g/L. Additionally, under visible light irradiation, the Al3%:SrTiO3@CoOOH composite achieved an exceptional degradation rate of the (3-lactam antibiotic oxacillin of up to 99 %, with holes identified as key players in the photocatalytic process. This study highlights that effective surface modification using a well-chosen co-catalyst can substantially boost the photocatalytic efficiency of semiconductor-based materials, offering a promising strategy for developing advanced photocatalysts for environmental remediation applications.

Recently, spin asymmetry in O 2p related deep valence states was evidenced in SrTiO3(001) [Popescu et al., Phys. Scr. 99(10), 105925 (2024)]. In this work, we report the detection of a much higher (about four times) spin asymmetry in SrTiO3(011) by spin resolved photoelectron spectroscopy, with samples characterized also by core level x-ray photoelectron spectroscopy and low energy electron diffraction. The explanation of a so important spin asymmetry is related to the partial neutralization of O-2(4-) or SrTiO(4+) end layers. Missing electrons from O 2p states in the case of O-2 terminations enable robust atomic spins, according to Hund's rule. The parallel analysis of core level shifts for surface atoms and the amplitude of spin asymmetry suggests that 50% of the oxygens from the surface SrO layer of SrTiO3(001) have a 2p(5) configuration with an unpaired electron (the rest are in a 2p(6) configuration), while in the case of O-2 terminated SrTiO3(011), about 50% of surface oxygens have a 2p(5) configuration and 50% of surface oxygens are neutral (2p(4)), yielding a net charge per O-2 surface unit cell of (-1) instead of (-4). The magnetization is oriented along the rows formed by the (4 x 1) reconstruction in the 011 in-plane direction. (c) 2025 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license(https://creativecommons.org/licenses/by/4.0/).

We theoretically study the 2D Su-Schrieffer-Heeger model in the context of Floquet topological insulators (FTIs). FTIs are systems which undergo topological phase transitions, governed by Chern numbers, as a result of time reversal symmetry (TRS) breaking by a time periodic process. In our proposed model, the condition of TRS breaking is achieved by circularly polarized light irradiation. We analytically show that TRS breaking is forbidden in the absence of second order neighbors hopping. In the absence of light irradiation, we identify a symmetry-protected degeneracy and prove the appearance of a flat band along a specific direction in the momentum space. Furthermore, we employ a novel method to show that the four unit cell atoms, in the absence of irradiation, can be interpreted as conserved spin states. With the breaking of TRS via light irradiation, these spin states are no longer conserved, leading to the emergence of chiral edge states. We also show how the interplay between the TRS breaking and dimerization leads to some complex topological phase transitions. The validity of our findings is substantiated through Chern numbers, spectral properties, localization of chiral edge states and simulations of quantum Hall transport. Our model is suitable not only for condensed matter (materials), but also for cold gases trapped in optical lattices or topolectrical circuits.

In the last decade, it has been observed that the field of biomaterials has gained the attention of the researchers. This study presents the physicochemical and biological properties of coatings based on chromium-doped hydroxyapatite (CrHAp) and chromium-doped hydroxyapatite enriched with amoxicillin (CrHApAx). The coatings were obtained for the first time using the dip coating technique, beginning from dense suspensions of CrHAp and CrHApAx. The obtained layers were then analyzed by various methods in order to have a comprehensive overview of their physicochemical properties. Stability studies performed using ultrasound measurements showed that the CrHAp suspension has very good stability (S = 6.8610-6 s-1) compared to double-distilled water. The CrHApAx suspension (S = 0.00025 s-1) shows good but weaker stability compared to that of the CrHAp suspension. Following XRD studies, a single hydroxyapatite-specific phase was observed in the CrHAp sample, while in the case of the CrHApAx sample, an amoxicillin-specific peak was also observed. The AFM results showed that the CrHAp coatings had a surface topography of a homogenous and uniform layer, with no significant cracks and fissures, while the CrHApAx coatings exhibited a surface morphology of homogenous layers formed of particles conglomerates. The biocompatibility of CrHAp and CrHApAx coatings was assessed using the MG63 cell line. The cytotoxicity of the coatings was evaluated by measuring cell viability with the aid of an MTT assay after 24, 48, and 72 h of incubation with the CrHAp and CrHApAx coatings. The results demonstrated that both CrHAp and CrHApAx coatings exhibited good biocompatibility for all the tested time intervals. The in vitro antibacterial activity of the coatings was also assessed against Pseudomonas aeruginosa 27853 ATCC (P. aeruginosa) bacterial cells. The potential of P. aeruginosa bacterial cells to adhere and develop on the surfaces of CrHAp and CrHApAx coatings was also investigated using AFM analysis. The findings of the biological assays suggest that CrHAp and CrHApAx coatings could be considered as promising candidates for biomedical applications, including the development of novel antimicrobial materials.

In this work, we report for the first time the development and complex characterization of new bioceramics based on hydroxyapatite (HAp, Ca10(PO4)6(OH)2). On the other hand, the lyophilization process was used for the first time in this research. The samples were obtained by a modified coprecipitation method and were dried by lyophilization (lyophilized hydroxyapatite (HApLF) and lyophilized zinc-doped hydroxyapatite (5ZnHApLF)). Valuable information about the HApLF and 5ZnHApLF stability was obtained through nondestructive ultrasound measurements. The X-ray diffraction (XRD) studies revealed the phase and the effects of the incorporation of Zn ions into the HAp structure. The chemical composition of the samples was evaluated by energy dispersive X-ray analysis (EDS) and X-ray photoelectron spectroscopy (XPS). Information about the functional groups present in the HApLF and 5ZnHApLF was obtained using Fourier Transform Infrared Spectroscopy (FTIR) studies. The morphology of HApLF and 5ZnHApLF pellets was observed by scanning electron microscopy (SEM). The surface topography of HApLF and 5ZnHApLF pellets was studied with the aid of atomic force microscopy (AFM). Details regarding the roughness of the samples were also obtained using AFM topographies and SEM images. A complementary study was also carried out on a larger analysis surface using a Scanning Acoustic Microscope (SAM). The SAM was used for the first time to analyze the surface of HAp and 5ZnHAp pellets. The biological properties of the HApLF and 5ZnHApLF pellets was investigated with the aid of MG63 and human gingival fibroblasts (HGF-1) cell lines. The results of the cell viability assay highlighted that both the HApLF and 5ZnHApLF pellets exhibited good biological activity. Moreover, SEM and AFM studies were conducted in order to emphasize the development of MG63 and HGF-1 cells on the pellet's surface. Both SEM and AFM images depicted that the pellets' surface favored the cell attachment and development of MG63 and HGF-1 cells. Furthermore, the antimicrobial properties of the HApLF and 5ZnHApLF were evaluated against Escherichia coli ATCC 25922, Staphylococcus aureus ATCC 25923, and Candida albicans ATCC 10231. The results of the antimicrobial assays highlighted that the 5ZnHApLF exhibited a strong antimicrobial activity against the tested microbial strains. The results of the biological assays suggested that the samples show great potential for being used in the development of novel materials for biomedical applications.

Due to their conductive properties and optoelectronic tunability, MXenes have revolutionized the area of electrocatalysis and active materials in supercapacitors. In comparison, there are only a few reports on MXenes as thermal catalysts for general organic reactions. Herein, the unprecedented catalytic activity of Ti3C2 MXene for the hydroamination of alkynes is reported, overcoming the limitations of poor activity, lack of selectivity, and stability, which are generally encountered in the solid catalysts known so far. In the case of Ti3C2, hydroamination exhibits almost complete selectivity for the anti-Markovnikov regioisomer, for both aliphatic amines and less-reactive aromatic amines. Ti3C2 also efficiently catalyzes intramolecular hydroamination, leading to the formation of indol heterocycles. The catalytic hydroamination of C-C multiple bonds is a reaction with complete atom efficiency that may form C-N bonds from convenient reagents. The maximum number of hydroamination sites on the Ti3C2 nanosheets is quantified by thermoprogrammed NH3 desorption. The measured TOF values are on the order of 102 h-1, with the highest TOF value being 350 h-1 for 1-hexyne hydroamination by n -butylamine. Therefore, Ti3C2 is among the few heterogeneous hydroamination catalysts studied, with its activity per site being comparable to the best hydroamination catalysts reported so far. Density functional theory calculations on the models indicate the cooperation of neighboring Ti atoms in the mechanism. Considering the compositional and structural versatility of MXenes, the present findings open the door for further application of MXenes in other general organic reactions.