Spray-Flame Synthesis of LaFexCo1-xO3 (x = 0.2, 0.3) Perovskite Nanoparticles for Oxygen Evolution Reaction in Water Splitting: Effect of Precursor Chemistry (Acetates and Nitrates).

The product properties of mixed oxide nanoparticles generated via spray-flame synthesis depend on an intricate interplay of solvent and precursor chemistries in the processed solution. The effect of two different sets of metal precursors, acetates and nitrates, dissolved in a mixture of ethanol (35 Vol.%) and 2-ethylhexanoic acid (2-EHA, 65 Vol.%) was investigated for the synthesis of LaFexCo1-xO3 (x = 0.2, 0.3) perovskites. Regardless of the set of precursors, similar particle-size distributions (dp = 8-11 nm) were obtained and a few particles with sizes above 20 nm were identified with transmission electron microscopy (TEM) measurements. Using acetates as precursors, inhomogeneous La, Fe, and Co elemental distributions were obtained for all particle sizes according to energy dispersive X-ray (EDX) mappings, connected to the formation of multiple secondary phases such as oxygen-deficient La3(FexCo1-x)3O8 brownmillerite or La4(FexCo1-x)3O10 Ruddlesden-Popper (RP) structures besides the main trigonal perovskite phase. For samples synthesized from nitrates, inhomogeneous elemental distributions were observed for large particles only where La and Fe enrichment occurred in combination with the formation of a secondary La2(FexCo1-x)O4 RP phase. Such variations can be attributed to reactions in the solution prior to injection in the flame as well as precursor-dependent variations in in-flame reactions. Therefore, the precursor solutions were analyzed by temperature-dependent attenuated total reflection Fourier-transform infrared (ATR-FTIR) measurements. The acetate-based precursor solutions indicated the partial conversion of, mainly La and Fe, acetates to metal 2-ethylhexanoates. In the nitrate-based solutions, esterification of ethanol and 2-EHA played the most important role. The synthesized nanoparticle samples were characterized by BET (Brunauer, Emmett, Teller), FTIR, Mössbauer, and X-ray photoelectron spectroscopy (XPS). All samples were tested as oxygen evolution reaction (OER) catalysts, and similar electrocatalytic activities were recorded when evaluating the potential required to reach 10 mA/cm2 current density (∼1.61 V vs reversible hydrogen electrode (RHE)).

Liquid-Phase Cyclohexene Oxidation with O2 over Spray-Flame-Synthesized La1-x Srx CoO3 Perovskite Nanoparticles.

La1-x Srx CoO3 (x=0, 0.1, 0.2, 0.3, 0.4) nanoparticles were prepared by spray-flame synthesis and applied in the liquid-phase oxidation of cyclohexene with molecular O2 as oxidant under mild conditions. The catalysts were systematically characterized by state-of-the-art techniques. With increasing Sr content, the concentration of surface oxygen vacancy defects increases, which is beneficial for cyclohexene oxidation, but the surface concentration of less active Co2+ was also increased. However, Co2+ cations have a superior activity towards peroxide decomposition, which also plays an important role in cyclohexene oxidation. A Sr doping of 20 at. % was found to be the optimum in terms of activity and product selectivity. The catalyst also showed excellent reusability over three catalytic runs; this can be attributed to its highly stable particle size and morphology. Kinetic investigations revealed first-order reaction kinetics for temperatures between 60 and 100 °C and an apparent activation energy of 68 kJ mol-1 for cyclohexene oxidation. Moreover, the reaction was not affected by the applied O2 pressure in the range from 10 to 20 bar. In situ attenuated total reflection infrared spectroscopy was used to monitor the conversion of cyclohexene and the formation of reaction products including the key intermediate cyclohex-2-ene-1-hydroperoxide; spin trap electron paramagnetic resonance spectroscopy provided strong evidence for a radical reaction pathway by identifying the cyclohexenyl alkoxyl radical.

Complete chemical and structural characterization of selenium-incorporated hydroxyapatite.

Hydroxyapatite (HAp) has long been used as synthetic bone tissue replacement material. Recent advances in this area have led to development of dual-functional bioceramics exhibiting high biocompability/osteoconductivity together with the therapeutic effect. Selenium, in that respect, is an effective therapeutic agent with promising antioxidant activity and anticancer effects. In this study, selenium-incorporated hydroxyapatite (HAp:Se) particles have been synthesized by modified aqueous precipitation method using calcium (Ca(NO3)2·4H2O) and phosphate ((NH4)2HPO4) salts and sodium selenite (Na2SeO3). The effects of selenium incorporation and post-synthesis calcination treatment (900-1100 °C) on physical, chemical properties and crystal structure of resultant HAp powders have been investigated. Complete chemical identification was performed with spectroscopical analyses including Fourier transform infrared and x-ray photoelectron spectroscopy to elucidate the mechanism and chemical nature of selenium incorporation in HAp. Meanwhile, detailed x-ray diffraction studies by Rietveld refinement have conducted to explain changes in the HAp crystal structure upon selenium incorporation.

Use of canonical variate analysis biplot in examination of choline content data of some foods.

Adequate intake (AI) of choline as part of the daily diet can help prevent major diseases. Low choline intake is a major risk factor for liver and several neurological disorders. Extreme choline consumption may cause diseases such as hypotension, sweating, diarrhea, and fishy body odor. The AI of choline is 425 mg/day for adult women; higher for pregnant and lactating women. The AI for adult men is 550 mg/day. The total choline content of foods is calculated as the sum of free choline, glycerophosphocholine, phosphocholine, phosphatidylcholine and sphingomyelin. These are called the choline variables. Observed values of choline variables may be different in amounts of nutrients. So different food groups in terms of choline variables are useful to compare. The present paper shows the advantages of using canonical variate analysis biplot to optimally separate groups and explore the differentiality of choline variables amounts in foods.

Assessment of quadriceps angle in children aged between 2 and 8 years.

AIM: The quadriceps angle is the angle between the line drawn from the spina iliaca anterior superior to the midpoint of the patella, and the line drawn from the midpoint of the patella to the tuberositas tibiae. It is important for lower extremity posture. The aim of this study was to determine the normative quadriceps angle value by measurement, and to assess the probable effect of factors such as measurement position, age, sex, and presence of pes planus on these values. MATERIAL AND METHODS: A total of 599 children consisting of 296 (49.4%) girls and 303 (50.6%) boys aged between 2 and 8 years, were included in the study. The children were divided into three groups by age as 2-4 years, 4-6 years, and 6-8-years. After the children's demographic data were collected, the quadriceps angle was measured using an electronic goniometer. Pes planus was assessed by drawing the Feiss line. RESULTS: In bilateral measurement, it was found that the quadriceps angle decreased with age both in the supine and standing positions (p<0.05). It was observed that sex and presence of pes planus had no effect on the quadriceps angle independent from measurement positions (p>0.05). A low negative correlation was found between body mass index and the quadriceps angle in both measurement positions (p<0.05). CONCLUSION: It was found that positional changes and weight bearing on limbs did not cause any change in knee position in healthy children. We consider that the decrease in quadriceps angle in this age group is due to growth rate asymmetry between the femur shaft and pelvic diameter.

Examination of relation between nutrient components and fruits: biplot approach.

Adequate intake of fruits and vegetables as part of the daily diet may help prevent major diseases. Low fruit intake is a major risk factor for cancer, coronary heart disease and stroke. The World Health Organization recommends eating at least five portions of a variety of fruit, which is nearly 400 g/day. Essential nutrients, water, carbohydrates, oils and vitamins are needed in appropriate quantities in order to have a well-functioning body. In this study we try to carry out a food composition study to identify and determine the chemical nature of the organic and inorganic macro-nutrient and micro-nutrient properties of the main fruit types that affect human nature, by a biplot graphical approach. The biplot can be considered as multivariate equivalents of scatter plots that have been used for graphically analyzing bivariate data. Biplot approaches show a simultaneous display of fruits and nutrient components in low dimensions. In the present study, the theory of biplot and different types of biplot will be given and than an application of the biplot approach will be applied to the real data.

Towards Mechanistic Understanding of Liquid-Phase Cinnamyl Alcohol Oxidation with tert-Butyl Hydroperoxide over Noble-Metal-Free LaCo1-x Fex O3 Perovskites.

Noble-metal-free perovskite oxides are promising and well-known catalysts for high-temperature gas-phase oxidation reactions, but their application in selective oxidation reactions in the liquid phase has rarely been studied. We report the liquid-phase oxidation of cinnamyl alcohol over spray-flame synthesized LaCo1-x Fex O3 perovskite nanoparticles with tert-butyl hydroperoxide (TBHP) as the oxidizing agent under mild reaction conditions. The catalysts were characterized by XRD, BET, EDS and elemental analysis. LaCo0.8 Fe0.2 O3 showed the best catalytic properties indicating a synergistic effect between cobalt and iron. The catalysts were found to be stable against metal leaching as proven by hot filtration, and the observed slight deactivation is presumably due to segregation as determined by EDS. Kinetic studies revealed an apparent activation energy of 63.6 kJ mol-1 . Combining kinetic findings with TBHP decomposition as well as control experiments revealed a complex reaction network.