High-Entropy La(FeCuMnMgTi)O3 Nanoparticles as Heterogeneous Catalyst for CO2 Electroreduction Reaction.

In this work, La(FeCuMnMgTi)O3 HEO nanoparticles with a perovskite-type structure are synthesized and used in the electrocatalytic CO2 reduction reaction (CO2RR). The catalyst demonstrates high performance as an electrocatalyst for the CO2RR, with a Faradaic efficiency (FE) of 92.5% at a current density of 21.9 mA cm-2 under -0.75 V vs a saturated calomel electrode (SCE). Particularly, an FE above 54% is obtained for methyl isopropyl ketone (C5H10O, MIPK) at a partial current density of 16 mA cm-2, overcoming all previous works. Besides, the as-prepared HEO catalyst displays robust stability in the CO2RR. The excellent catalytic performance of La(FeCuMnMgTi)O3 is ascribed to the synergistic effect between the electronic effects associated with five cations occupying the high-entropy sublattice sites and the oxygen vacancies within the perovskite structure of the HEO. Finally, DFT calculations indicate that Cu plays a vital role in the catalytic activity of the La(FeCuMnMgTi)O3 HEO nanoparticles toward C2+ products.

Chondroitin sulfate and glucosamine combination in patients with knee and hip osteoarthritis: A long-term observational study in Russia.

BACKGROUND: Oral treatment of glucosamine (GA) combined with chondroitin sulfate (CS) was reportedly effective for pain relief and function improvement in osteoarthritis patients with moderate to severe knee pain in clinical trials. While the effectiveness of GA and CS on both clinical and radiological findings has been demonstrated, only a few high-quality trials exist. Therefore, controversy regarding their effectiveness in real-world clinical practice remains. AIM: To investigate the impact of GA + CS on clinical outcomes of patients with knee and hip osteoarthritis in routine clinical practice. METHODS: A multicenter prospective observational cohort study included 1102 patients of both genders with knee or hip osteoarthritis (Kellgren & Lawrence grades I-III) in 51 clinical centers in the Russian Federation from November 20, 2017, to March 20, 2020, who had started to receive oral capsules of glucosamine hydrochloride 500 mg and CS 400 mg according to the approved patient information leaflet starting from 3 capsules daily for 3 wk, followed by a reduced dosage of 2 capsules daily before study inclusion (minimal recommended treatment duration is 3-6 mo). Changes in subscale scores [Pain, Symptoms, Function, and Quality of Life (QOL)] of the Knee Injury and Osteoarthritis Outcome Score (KOOS)/Hip Disability and Osteoarthritis Outcome Score (HOOS) questionnaires during the observational period (up to 54-64 wk with a total of 4 visits). Patients' treatment satisfaction, data on the combined oral use of glucosamine hydrochloride and CS, concomitant use of non-steroidal anti-inflammatory drugs (NSAIDs), and adverse events (AEs) were also evaluated. RESULTS: A total of 1102 patients with knee and hip osteoarthritis were included in the study. The mean patient age was 60.4 years, most patients were women (87.8%), and their average body mass index was 29.49 kg/m2. All subscale scores (Pain, Symptoms, Function, and QOL) of the KOOS and HOOS demonstrated clinically and statistically significant improvements. In patients with knee osteoarthritis, the mean score increases from baseline to the end of Week 64 were 22.87, 20.78, 16.60, and 24.87 on Pain, Symptoms, Physical Function (KOOS-PS), and QOL subscales (P < 0.001 for all), respectively. In patients with hip osteoarthritis, the mean score increases were 22.81, 19.93, 18.77, and 22.71 on Pain, Symptoms, Physical Function (HOOS-PS), and QOL subscales (P < 0.001 for all), respectively. The number of patients using any NSAIDs decreased from 43.1% to 13.5% (P < 0.001) at the end of the observation period. Treatment-related AEs occurred in 2.8% of the patients and mainly included gastrointestinal disorders [25 AEs in 24 (2.2%) patients]. Most patients (78.1%) were satisfied with the treatment. CONCLUSION: Long-term oral GA + CS was associated with decreased pain, reduced concomitant NSAID therapy, improved joint function and QOL in patients with knee and hip osteoarthritis in routine clinical practice.

A Feasibility Study of High-Entropy Alloy Coating Deposition by Detonation Spraying Combined with Laser Melting.

In this work, a new two-stage approach to the deposition of high-entropy alloy coatings is proposed. At the first stage, a composite precursor coating is formed by detonation spraying of the metal powder mixtures. At the second stage, the precursor coating is re-melted by a laser, and the formation of multi-component solid solution phases can be expected upon solidification. The feasibility of the proposed approach was validated using three different mixtures of Fe, Ni, Cu, Co and Al powders. It was shown that detonation spraying allows forming composite coatings with a uniform distribution of the lamellae of different metals. The results of the structural analysis of the laser-treated coatings suggest that complete alloying occurred in the melt and face-centered cubic solid solutions formed in the coatings upon cooling.

Creation and Magnetic Study of Ferrites with Magnetoplumbite Structure Multisubstituted by Al3+, Cr3+, Ga3+, and In3+ Cations.

Multisubstituted barium ferrites with a magnetoplumbite structure were obtained by the method of solid-phase reactions with ferritization and pre-firing. Three-charged, mainly diamagnetic cations Al3+, Cr3+, Ga3+, and In3+ were chosen as substituents for the Fe3+ iron cations, the proportion of which in solid solutions did not exceed 50%. The values of the configurational mixing entropy were calculated for all the compositions. A slight deviation of the chemical composition of the obtained solid solutions from the nominal value was established by the energy-dispersive X-ray spectroscopy method. The phase purity and values of the unit cell parameters were refined from X-ray scattering data using full-profile analysis in the Rietveld method. A non-monotonic behavior of the unit cell parameters as a function of the B-sub-lattice average ionic radius of the magnetoplumbite structure was found. A minimum unit cell volume of ~667.15 Å3 was found for the composition BaFe6.11Al1.56Cr2.17Ga2.16O19 with a B-sub-lattice average ionic radius of ~7.449 Å. The average crystallite size varied within 5.5-6.5 µm. The temperature and field dependencies of the magnetization have been measured. The values of the saturation magnetization, residual magnetization, hysteresis loop squareness, and coercivity at 50 K and 300 K were extracted from the experimental data. Using the Law of Approach to Saturation, the magnetic crystallographic anisotropy coefficient and anisotropy field were calculated. Multisubstitution leads to a significant decrease in such magnetic parameters as the magnetic ordering temperature and spontaneous magnetization at both temperatures. The maximum magnetic ordering temperature of ~297.7 K was found for the composition BaFe5.84Ga6.19O19 with a B-sub-lattice average ionic radius of ~7.586 Å in a field of 500 Oe. A maximum saturation magnetization of ~24.7 emu/g was found for the composition BaFe5.84Ga6.19O19 with a B-sub-lattice average ionic radius of ~7.586 Å at 50 K. A maximum hysteresis loop squareness of ~0.72 was found for the composition BaFe6.11Al1.56Cr2.17Ga2.16O19 with an average ionic radius of ~7.449 Å at 50 K. A maximum magnetic crystallographic anisotropy coefficient of ~2.09 × 105 Erg/g was found for the composition BaFe6.19Al1.25Cr1.57Ga1.74In1.26O19 with a B-sub-lattice average ionic radius of ~7.706 Å at 50 K. The frustrated magnetic state including the nano-sized clusters with an average diameter in the range of 50-200 nm was established from the results of measuring the ZFC and FC temperature magnetizations. The interpretation of the obtained experimental data is carried out taking into account the increased stability of high-entropy phases and regular changes in the intensity of the Fe3+(Al3+, Cr3+, Ga3+, In3+)-O2--Fe3+(Al3+, Cr3+, Ga3+, In3+) indirect superexchange interactions as a result of magnetic dilution of the iron sub-lattice in the magnetoplumbite structure.

A-Site Cation Size Effect on Structure and Magnetic Properties of Sm(Eu,Gd)Cr0.2Mn0.2Fe0.2Co0.2Ni0.2O3 High-Entropy Solid Solutions.

Three high-entropy Sm(Eu,Gd)Cr0.2Mn0.2Fe0.2Co0.2Ni0.2O3 perovskite solid solutions were synthesized using the usual ceramic technology. The XRD investigation at room temperature established a single-phase perovskite product. The Rietveld refinement with the FullProf computer program in the frame of the orthorhombic Pnma (No 62) space group was realized. Along with a decrease in the V unit cell volume from ~224.33 Å3 for the Sm-based sample down to ~221.52 Å3 for the Gd-based sample, an opposite tendency was observed for the unit cell parameters as the ordinal number of the rare-earth cation increased. The average grain size was in the range of 5-8 µm. Field magnetization was measured up to 30 kOe at 50 K and 300 K. The law of approach to saturation was used to determine the Ms spontaneous magnetization that nonlinearly increased from ~1.89 emu/g (Sm) up to ~17.49 emu/g (Gd) and from ~0.59 emu/g (Sm) up to ~3.16 emu/g (Gd) at 50 K and 300 K, respectively. The Mr residual magnetization and Hc coercive force were also determined, while the SQR loop squareness, k magnetic crystallographic anisotropy coefficient, and Ha anisotropy field were calculated. Temperature magnetization was measured in a field of 30 kOe. ZFC and FC magnetization curves were fixed in a field of 100 Oe. It was discovered that the Tmo magnetic ordering temperature downward-curve decreased from ~137.98 K (Sm) down to ~133.99 K (Gd). The spin glass state with ferromagnetic nanoinclusions for all the samples was observed. The average and Dmax maximum diameter of ferromagnetic nanoinclusions were calculated and they were in the range of 40-50 nm and 160-180 nm, respectively. The mechanism of magnetic state formation is discussed in terms of the effects of the A-site cation size and B-site poly-substitution on the indirect superexchange interactions.

High Entropy Oxide Phases with Perovskite Structure.

The possibility of the formation of high entropy single-phase perovskites using solid-state sintering was investigated. The BaO-SrO-CaO-MgO-PbO-TiO2, BaO-SrO-CaO-MgO-PbO-Fe2O3 and Na2O-K2O-CaO-La2O3-Ce2O3-TiO2 oxide systems were investigated. The optimal synthesis temperature is found between 1150 and 1400 °C, at which the microcrystalline single phase with perovskite structure was produced. The morphology, chemical composition, crystal parameters and dielectric properties were studied and compared with that of pure BaTiO3. According to the EDX data, the single-phase product has a formula of Na0.30K0.07Ca0.24La0.18Ce0.21TiO3 and a cubic structure.

Extremely Polysubstituted Magnetic Material Based on Magnetoplumbite with a Hexagonal Structure: Synthesis, Structure, Properties, Prospects.

Crystalline high-entropy single-phase products with a magnetoplumbite structure with grains in the µm range were obtained using solid-state sintering. The synthesis temperature was up to 1400 °C. The morphology, chemical composition, crystal structure, magnetic, and electrodynamic properties were studied and compared with pure barium hexaferrite BaFe12O19 matrix. The polysubstituted high-entropy single-phase product contains five doping elements at a high concentration level. According to the EDX data, the new compound has a formula of Ba(Fe6Ga1.25In1.17Ti1.21Cr1.22Co1.15)O19. The calculated cell parameter values were a = 5.9253(5) Å, c = 23.5257(22) Å, and V = 715.32(9) ų. The increase in the unit cell for the substituted sample was expected due to the different ionic radius of Ti/In/Ga/Cr/Co compared with Fe3+. The electrodynamic measurements were performed. The dielectric and magnetic permeabilities were stable in the frequency range from 2 to 12 GHz. In this frequency range, the dielectric and magnetic losses were -0.2/0.2. Due to these electrodynamic parameters, this material can be used in the design of microwave strip devices.

Magnetic and Structural Properties of Barium Hexaferrite BaFe12O19 from Various Growth Techniques.

Barium hexaferrite powder samples with grains in the µm-range were obtained from solid-state sintering, and crystals with sizes up to 5 mm grown from PbO, Na2CO3, and BaB2O4 fluxes, respectively. Carbonate and borate fluxes provide the largest and structurally best crystals at significantly lower growth temperatures of 1533 K compared to flux-free synthesis (1623 K). The maximum synthesis temperature can be further reduced by the application of PbO-containing fluxes (down to 1223 K upon use of 80 at % PbO), however, Pb-substituted crystals Ba1-xPbxFe12O19 with Pb contents in the range of 0.23(2) ≤ x ≤ 0.80(2) form, depending on growth temperature and flux PbO content. The degree of Pb-substitution has only a minor influence on unit cell and magnetic parameters, although the values for Curie temperature, saturation magnetization, as well as the coercivity of these samples are significantly reduced in comparison with those from samples obtained from the other fluxes. Due to the lowest level of impurities, the samples from carbonate flux show superior quality compared to materials obtained using other methods.