Synthesis of manganese titanate and its precursors from xerogel

An overview of research on the synthesis of manganese titanates is presented. The xerogel of Mn–Ti–O–C–H composition was synthesized from manganese acetate and titanium tetrabutylate via liquid-phase method using organic solvents. The calcination of xerogel in air at 450 °C and 700 °C yielded manganese titanate precursors in the form of a nanostructured mixture of Mn₂O₃ and TiO₂. Annealing at 1000 °C, manganese metatitanate MnTiO₃ was obtained. Reference experiments with initial reagents included, separately, thermal decomposition of Mn(CH₃COO)₂×4H₂O and the product of Ti(OC₄H₉)₄ hydrolysis. The composition, structure, and properties of the products were studied using X-ray diffraction, scanning electron microscopy, elemental analysis, diffuse reflectance IR Fourier spectroscopy, thermogravimetry, and by measuring specific surface area. The data presented by these different techniques are basically consistent with each other (with an increase in the annealing temperature, an increase in globule size and decrease in specific surface area are observed; structuring occurs within the long- and short-range order; the size of the crystallites does not exceed that of the globules; elemental composition correlates with phase composition; the endothermic character of the reaction of MnTiO₃ formation at 900 °C is confirmed by a thermodynamic calculation). Nevertheless, some unexpected effects were revealed (based on the FTIR diffuse reflection spectra, mixed oxide Mn–Ti–O is formed in the surface layer of particles already at 450 °C and 700 °C; etc.). Application of the proposed technique for modifying Al₂O₃ powders, with the aim of implementing low-temperature sintering of corundum ceramics, is discussed.     

Dye removal by polymer derived ceramic nanobeads

Emulsion processed polymer derived ceramic (PDC) nanobeads are used for Methylene Blue dye removal from aqueous solutions. The PDC nanobeads, produced at 600 °C and 1200 °C pyrolysis, are subsequently coated with titania (anatase). Titania-coated nanobeads show less than 35%, i.e., limited dye adsorption capability in dark. Instead, enhanced total removal efficiency (∼97%) is obtained when the initial adsorption is succeeded by photodegradation under UV. Direct reusability tests show that even after the third cycle, very high regeneration efficiencies being above 92% are observed for titania-coated nanobeads.     

Fully renewable limonene‐derived polycarbonate as a high‐performance alkyd resin

Limonene‐derived polycarbonate‐based alkyd resins (ARs) have been prepared by copolymerization of limonene dioxide with CO₂, catalysed by a β‐diiminate zinc–bis(trimethylsilyl)amido complex, and subsequent chemical modification with soybean oil fatty acids using triphenylethylphosphonium bromide as the catalyst. This quantitative partial modification was realized via epoxy–carboxylic acid chemistry, affording ARs with higher oil lengths, lower polydispersities and higher glass transition temperatures (T_g) in comparison to a conventional polyester AR based on phthalic acid, multifunctional polyol pentaerythritol and soybean fatty acid. The novel limonene polycarbonate AR and the conventional polyester AR were evaluated as coatings and both the physical drying (without the presence of the oxidative drying accelerator Borchi® Oxy Coat) and chemical curing (with Borchi® Oxy Coat) processes of these coatings were monitored by measuring the König hardness and complex modulus development with time. A better performance was obtained for the alkyd paint containing polycarbonates modified with fatty acids (FA‐PCs), which showed a faster chemical drying, a higher König hardness and a higher T_g in coating evaluation, demonstrating that the fully renewable FA‐PCs are promising resins for alkyd paint applications. © 2019 Society of Chemical Industry     

Preparation of highly crystalline titanium-based ceramic microfibers from polymer precursor blend by needle-less electrospinning

The aim of the present contribution is to study the influence of the post-spinning heat - treatment of single TiO₂/PVP precursor fibers on the properties and morphology of the final titanium-based microfibers. The post-spinning treatment conditions were: calcination in air at 450–600?°C and pyrolysis in argon at 1000–1700?°C. Calcination resulted in a production of anatase-rich and pure rutile fibers. The use of an alternative sintering method, the low-temperature plasma treatment, led to the crystallization of the composite Magnéli phases/polymer fibers. As a result of the same one precursor, pyrolysis at 1000?°C, the Carbon/TiO₂ composite fibers were obtained. Rising the treatment temperature in inert atmosphere led to the formation of the titanium carbide fibers. The formation process and all the obtained products were characterized by differential scanning calorimetry accompanied with thermogravimetric analysis (DSC/TGA), scanning and transmission electron microscopy (SEM, TEM), X-ray diffraction (XRD), and image analysis techniques.     

Mixed-Metal MOF-74 Templated Catalysts for Efficient Carbon Dioxide Capture and Methanation

The vast chemical and structural tunability of metal–organic frameworks (MOFs) are beginning to be harnessed as functional supports for catalytic nanoparticles spanning a range of applications. However, a lack of straightforward methods for producing nanoparticle-encapsulated MOFs as efficient heterogeneous catalysts limits their usage. Herein, a mixed-metal MOF, NiMg-MOF-74, is utilized as a template to disperse small Ni nanoclusters throughout the parent MOF. By exploiting the difference in Ni O and Mg O coordination bond strength, Ni²⁺ is selectively reduced to form highly dispersed Ni nanoclusters constrained by the parent MOF pore diameter, while Mg²⁺ remains coordinated in the framework. By varying the ratio of Ni to Mg in the parent MOF, accessible surface area and crystallinity can be tuned upon thermal treatment, influencing CO₂ adsorption capacity and hydrogenation selectivity. The resulting Ni nanoclusters prove to be an active catalyst for CO₂ methanation and are examined using extended X-ray absorption fine structure and X-ray photoelectron spectroscopy. By preserving a segment of the Mg²⁺-containing MOF framework, the composite system retains a portion of its CO₂ adsorption capacity while continuing to deliver catalytic activity. The approach is thus critical for designing materials that can bridge the gap between carbon capture and CO₂ utilization.     

Enhancement of thermal,mechanical, ignition and damping response of magnesium using nano-ceria particles

Magnesium (Mg)-based nanocomposites owing to their low density and biocompatibility are being targeted for transportation and biomedical sectors. In order to support a sustainable environment, the prime aim of this study was to develop non-toxic magnesium-based nanocomposites for a wide spectrum of applications. To support this objective, cerium oxide nanoparticles (0.5?vol%, 1?vol%, and 1.5?vol%) reinforced Mg composites are developed in this study using blend-press-sinter powder metallurgy technique. The microstructural studies exhibited limited amounts of porosity in Mg and Mg-CeO₂ samples (< 1%). Increasing presence of CeO₂ nanoparticles (up to 1.5?vol%) led to a progressive increase in microhardness, dimensional stability, damping capacity and ignition resistance of magnesium. The compressive strengths increased with the increasing addition of the nanoparticles with a significant enhancement in the fracture strain (up to ~48%). Superior energy absorption was observed for all the composite samples prior to compressive fracture. Further, enhancement in thermal, mechanical and damping characteristics of pure Mg is correlated with microstructural changes due to the presence of the CeO₂ nanoparticles.     

负载型复合载体及其镍基催化剂的性能

采用溶胶-凝胶法制备了负载型ZrO_2/Al_2O_3和ZrO_2/Al_2O_3-SiO_2复合载体,研究了不同复合载体对Ni基催化剂CO_2重整甲烷反应和性能的影响,并用XRD、IR、TPR、TPD和BET等方法对复合载体及催化剂进行了表征。结果表明,ZrO_2负载在基载体后比表面积、碱性、活性组分Ni的分散度和Ni与ZrO_2的相互作用增大。NiO在复合载体表面的分散容量与ZrO_2的负载量有关,ZrO_2的负载量为37．5%时NiO的分散容量达最高值(24．0%)。与Ni/ZrO_2相比,Ni/ZrO_2/Al_2O_3-SiO_2和Ni/ZrO_2/Al_2O_3催化剂对CO_2的吸附能力增大,CO_2吸附量增加,酸强度降低,CO_2重整CH_4反应活性提高,其中以Ni/ZrO_2/Al_2O_3催化剂的活性最好。