Physical properties of microwave and solid state synthesized La0.7Na0.3MnO3

We report the structural, magnetic, electrical and broadband microwave absorption in La_0.7Na_0.3MnO₃ sample synthesized by microwave (MW) irradiation (Na_0.3LMO_MW) and compare them to the sample synthesized by solid-state (SS) reaction method (Na_0.3LMO_SS). Single phase Na_0.3LMO_MW was synthesized at 800 °C in 30 min, whereas, Na_0.3LMO_SS sample was obtained by sintering at 1200 °C for 48 h. Although both these samples show ferromagnetic transition at T_C ～324.8 K, the MW-synthesized sample shows distinct physical properties: broad ferromagnetic transition, smaller saturation magnetization, a large difference between the magnetic ordering and metal-insulator transition temperatures, a large high-field magnetoresistance, a table top-like magnetocaloric effect, and a large low-field microwave absorption compared to the solid state synthesized sample. These differences are suggested to arise from magnetic heterogeneity induced by smaller grain size and surface spin disorder in the MW synthesized La_0.7Na_0.3MnO₃.     

Self-optimized and renewable Ni–Co alloy@Co–Co2C catalyst for higher alcohols synthesis from syngas

Higher alcohols synthesis (HAS) from syngas (CO/H₂) has attracted widespread attention, while the low selectivity and poor stability of the catalysts mainly stumbled its industrial application. In the work, Ni–Co alloy nanoparticles (NPs) derived from Co_1-xNi_xAl₂O₄ loaded on the SiO₂ with large specific surface area were prepared; and during reaction, the highly dispersed Ni–Co alloys were self-optimized to Ni–Co alloy@Co–Co₂C. Importantly, Ni–Co alloy@Co–Co₂C can be regenerated through oxidation - reduction - self-optimization process. Characteristic results indicated that the structural liberalization during the reaction process inhibited the loss of Ni, regulated and balanced the dual active sites of the catalyst and the Ni–Co alloys were regenerated after the re-oxidation and re-reduction process. The optimized catalyst exhibited excellent catalytic performance, including a high total selectivity to alcohols of 39.3% and an excellent catalytic stability at 250 °C, 3.5 MPa (H₂/CO = 2) and a space velocity of 6000 mL (g_cat h)^?1. In addition, the Ni–Co alloy@Co–Co₂C catalyst after stability test could recover its original catalytic performance after re-oxidation and re-reduction. The renewable characteristics and superior catalytic performance of Ni–Co alloy@Co–Co₂C made the catalyst to be one of the potential industrial catalysts for HAS.     

Crystallization behavior and density functional theory study of solution combustion synthesized silicon doped calcium phosphates

The influence of heat-treatment temperatures (700 °C, 900°C, 1200 °C) on the phase, physical properties, crystallization rate, and in vitro properties of the solution combustion synthesized silicon-doped calcium phosphates (CaPs) were investigated. The thermodynamic aspects (enthalpy, entropy, and free energy) of the synthesis process and the crystallographic properties of the final samples were first predicted and then confirmed using density functional theory (DFT). Results demonstrated that the crystallization rate was controlled by the fuel(s) type (glycine, citric acid, and urea) and the amounts of Si⁴⁺ ions (0, 0.1, 0.4 mol). The highest calculated crystallization rate values of the un-doped, 0.1, and 0.4 mol Si-doped samples were 64%, 22%, 38%, respectively. The obtained results from the DFT simulation revealed that crystal growth in the direction of c-axis of hydroxyapatite (HAp) structure could change the stability of (001) surface of (HAp). Also, the computational data confirmed the adsorption of Si–OH groups on the (001) surface of HAp during the SCS process with an adsorption energy of 1.53 eV. AFM results in line with DFT simulation showed that the observed change in the surface roughness of Si-doped CaPs from 2 to 8 nm could be related to the doping of Si⁴⁺ ions onto the surface of CaPs. Besides, the theoretical and experimental investigation showed that crystal growth and doping of Si⁴⁺ ions could decrease the activation energy of oxygen reduction reaction (ORR). Furthermore, the results showed that the crystallized HAp structure could have great potential to efficiently reduce oxidative stress in human body.     

Techno-economic-environmental evaluation of a combined tri and dry reforming of methane for methanol synthesis with a high efficiency CO2 utilization

Production of methanol, as a green energy, from syngas is coming into focus. However, natural gas based methanol plants, which are used steam reforming of methane for syngas production, have a high CO₂ emission resulting in the global warming. In this study, a novel process for methanol synthesis is proposed to reduce CO₂ emission. In this regard, natural gas and flue gas are fed to a parallel-series system with tri and dry reforming of methane for syngas production with the optimized stoichiometric number. Then, the produced syngas is converted to methanol in a reactor. Finally, the produced methanol is purified by two distillation towers. The proposed method is compared to a referenced method in the view of technological, economic and environmental metrics. The techno-economic-environmental analysis of the processes reveals that not only the proposed method, as compared to the referenced one, increases CO₂ conversion from 20.93% to 99.22%, but also it is more economical and environmentally friendly. In addition, the global warming potential of the proposed method is almost 60% lower than that for the referenced method due to the lower CO₂ emission. Therefore, the proposed method can save above MUS$ 8 a year by CO₂ capture.     

Formation of single-crystalline BaTiO3 nanorods from glycolate by tuning the supersaturation conditions

We have studied peculiarities in the formation of single-crystalline barium titanate (BaTiO₃) nanorods from a glycolate-mediated complex via a single-step hydrothermal process under different supersaturation (S_R) conditions. X-ray diffraction (XRD) showed the formation of pure BaTiO₃ with an S_R of above 19. The tetragonality for the BaTiO₃ (c/a) reached 1.013 at S_R = 19–29 and dropped to 1.010 for S_R = 39. According to the transmission electron microscopy (TEM) and XRD analyses, the rod-shaped particles exhibited single crystallinity and crystal growth along the [001] plane. With scanning electron microscopy (SEM), the morphological evolution from a plate-shaped intermediate precursor (S_R = 6–9) to a rod-shaped product with an aspect ratio of 6–9 (S_R = 19–29), and to non-polar material with an irregular structure (S_R = 39), was observed. The negative slope, linear dependence of the particles’ width and length on the supersaturation level in the range S_R = 19–39 was established for the first time. The replacement of the prevailing crystallization mechanism from in-situ topotactic transformation into dissolution-precipitation above S_R = 19 was observed. It was shown that with a simple regulation of the S_R, the structural and morphological characteristics of the obtained BaTiO₃ nanoparticle can be effectively tuned.     

Photoluminescence and hydrogen evolution properties of ZnS:Eu quantum dots

In the era of Photonics, design and development of novel rare earth ion-doped quantum dots (QDs) for optoelectronic applications has gained significant interest owing to their outstanding characteristics. Simultaneously, the creation of a new class of photocatalytic materials on the nanoscale is also imperative for environmental purification. Thus, we report on wet chemical synthesis, the structural, morphological, and optical characteristics, fluorescence, and hydrogen evolution of ZnS:Eu (0, 2, 4, and 6 at%) QDs for optoelectronic and photocatalytic applications. Comprehensive structural studies depicted that Eu³⁺ ions were efficiently substituted into the host matrix and altered the original structure of the ZnS compound. The emission spectra of the ZnS:Eu QDs exhibited distinctive red fluorescence owing to the transition of dopant ions in ⁵D₀ - ⁷F₁, ⁵D₀ - ⁷F₂, ⁵D₀ - ⁷F₃, and ⁵D₀ - ⁷F₄ energy levels of the 4f orbital of the Eu³⁺ ions. Moreover, the photocatalytic properties of ZnS:Eu (6 at%) QDs possess better catalytic efficiency toward hydrogen evolution through a water splitting mechanism under simulated sunlight irradiation. The observed photocatalytic phenomenon in the synthesized samples agreed well with the luminescence properties exhibited by the QDs.     

Synthesis of thermoresponsive copolymer/silica-coated magnetite nanoparticle composite and its application for heavy metal ion recovery

To enhance chemical stability and suppress of aggregation of magnetite nanoparticles (MNPs), which are used as a support for thermoresponsive copolymer immobilization, silica coating of the MNPs is applied via the electrooxidation method. Although the resulting silica coated-MNPs also formed aggregates, the size distribution of the aggregate shifted to smaller size range. Because of that, the surface area available for copolymer immobilization increased approximately 6.7 times at maximum as compared with that of the uncoated MNPs. It contributed to the increase of the amount of the immobilized copolymer on the silica-coated MNPs, which is approximately four times larger than that on the uncoated MNPs. Fe₃O₄ dissolution test confirmed enhancement of chemical stability of MNPs. The thermoresponsive copolymer immobilized on the silica-coated MNPs shows the ability to recycle Cu(II) ion from Cu(II) containing solution by changing temperature with significantly shorter time than those in other thermoresponsive adsorbents in gel form.     

Solution-Synthesized Multifunctional Janus Nanotree Microswimmer

Synthetic active matters are perfect model systems for non-equilibrium thermodynamics and of great potential for novel biomedical and environmental applications. However, most applications are limited by the complicated and low-yield preparation, while a scalable synthesis for highly functional microswimmers is highly desired. In this paper, an all-solution synthesis method is developed where the gold-loaded titania-silica nanotree can be produced as a multi-functional self-propulsion microswimmer. By applying light, heat, and electric field, the Janus nanotree demonstrated multi-mode self-propulsion, including photochemical self-electrophoresis by UV and visible light radiation, thermophoresis by near-infrared light radiation, and induced-charge electrophoresis under AC electric field. Due to the scalable synthesis, the Janus nanotree is further demonstrated as a high-efficiency, low-cost, active adsorbent for water decontamination, where the toxic mercury ions can be reclaimed with enhanced efficiency.     

Effect of crystal structures on nucleation mechanism in hydrothermal synthesis of MZrO3 (M=Ba,Sr, Ca)

Hydrothermal method is widely used in the synthesis of perovskite-type oxides, whereas few studies are reported for the nucleation mechanism, so that the relationship between the crystal structures and reactive activities of reactants and products is still unknown. Herein, the reaction processes are analyzed on the basis of XRD, SEM and Raman characterizations, and the nucleation mechanism is investigated for the hydrothermal synthesis of MZrO₃ (M = Ba, Sr, Ca). We propose that the negative charged cyclic tetramer complexes [Zr₄(OH)₈(OH)₁₆]^8- form in the hydrothermal reaction, which play major roles in the nucleation process. The tetramer complexes continually dehydrate and condensate to form substructural units composed of alkali-earth ions and 6-fold Zr tetramers; substructural units further dehydrate and distort to form perovskite structures. The reactive activation energy increases with the decreasing of M²⁺ (M = Ba, Sr, Ca) ionic radius because the incorporation of smaller A site ions in the perovskite structure is accompanied by greater rotation and distortion of the ZrO₆ octahedra, leading to the decrease of reactive activity accordingly. In a word, the proposed nucleation mechanism in this paper is of great significance for the study of perovskite.     

Investigation of structural,optical, magnetic,and dielectric properties of calcium hexaferrite synthesized in presence of Azadirachta indica and Murraya koenigii leaves extract

M-type calcium hexaferrite- CaFe₁₂O₁₉ (CaM) has been prepared in presence of Azadirachta indica, and Murraya koenigii leaves extracts, followed by calcination at 650 °C for 3h. It was observed that the presence of phytochemicals in both leaves extract plays a vital role in deciding the structural, optical, microstructural, magnetic, and dielectric properties of prepared CaM hexaferrites. Prepared samples were characterized using FT-IR, XRD, UV–Vis, SEM, VSM, and dielectric measurements. FTIR, UV– Vis, and antioxidant assay confirmed the presence of phenolic content and antioxidant property of plant extract. This further resulted in the formation of a pure hexagonal phase as revealed by the XRD analysis. The surface morphology of prepared ferrites modified through this greener route was illustrated by the spongy appearance of ferrites in SEM micrographs.The saturation magnetization for the CaM powder prepared using Murraya koenigii leaves extract is 11.78 Am²/kg, while that prepared from Azadirachta indica leaves extract is 3.56 Am²/kg. Both samples show a magnetically soft nature, with a multidomain structure. The energy bandgap was also observed to be 2.01 eV. Moreover, the calcium ferrite synthesized by Murraya koenigii leaves had ε’_max ～ 25 and that synthesized in presence of Azadirachta indica leaves had ε’_max ～ 200 at ～20 Hz.