Project description:The synthesis of ester compounds is one of the most important chemical processes. In this work, Zn-Mg-Al mixed oxides with different Zn2+/Mg2+ molar ratios were prepared via co-precipitation method and supported gold nanoclusters to study the direct oxidative esterification of aldehyde and alcohol in the presence of molecular oxygen. Various characterization techniques such as N2-physical adsorption, X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and CO2 temperature programmed desorption (TPD) were utilized to analyze the structural and electronic properties. Based on the results, the presence of small amounts of Zn2+ ions (~5 wt.%) provoked a remarkable modification of the binary Mg-Al system, which enhanced the interaction between gold with the support and reduced the particle size of gold. For oxidative esterification reaction, the Au25/Zn0.05MgAl-400 catalyst showed the best performance, with the highest turnover frequency (TOF) of 1933 h-1. The active center was believed to be located at the interface between metallic gold with the support, where basic sites contribute a lot to transformation of the substrate.
Project description:Mixed oxides of aluminum and magnesium derived from hydrotalcites were prepared by means of a sol-gel method mediated by an emulsified sol as pore template. The emulsion consisted of ethanol as the continuous phase and n-dodecane droplets as the dispersed phase, which was stabilized by the presence of the surfactant Pluronic P123. The use of such an emulsion was essential for obtaining materials with a porous structure that were assessed by mercury intrusion porosimetry and nitrogen physisorption. Additional characterization by NH3 and CO2 temperature programmed desorption confirmed that despite the enhancement of their textural properties, the number of acid and base sites was reduced in comparison to a reference and conventionally prepared Al-Mg mixed oxide, as a consequence of the depletion of surface hydroxyls during condensation of the precursors around the nonpolar droplets of the emulsion. Catalytic conversion of 2-propanol under conditions of controlled mass and heat diffusion on the texturally improved Al-Mg mixed oxides evidenced the preparation of a more effective catalyst than the poorly porous reference.
Project description:Metal oxides (MOs) having Mg and Al with Mg/Al ratios of 1, 2, 3, and 4 were synthesized via calcination of the layered double hydroxides (LDH). The X-ray diffraction analysis revealed that all the MO consisted of periclase (MgO) crystallite with comparable crystallinity regardless of the metal ratio. According to the 27Al magic-angle spinning nuclear magnetic resonance, the phase transformation from LDH to MO upon calcination facilitated the evolution of the Al3+ ions with unsaturated coordination at the surface of MO. The specific surface area values of MOs were not significantly different from each other, ranging between 100 and 200 m2/g, suggesting that the metal ratio did not strongly influence the porous structure of MO. The temperature-dependent desorption of ammonia demonstrated that the Lewis acidity of the Al-rich MOs was the largest with an Mg/Al ratio of 1, attributed to the efficient exposure of the surface-active site Al3+-O2- pairs. The acidity of heterogenous Al-rich MOs significantly increased with the exposed tetrahedral Al site on the surface and dramatically diminished when the molar ratio (Mg/Al) was over two.
Project description:Aimed at the green synthesis of supported noble metal nanoparticles without any additional reducing agents or stabilizers at room temperature, a new strategy in which monodispersed Pd nanoparticles were successfully immobilized on Mg-Al mixed metal oxides derived from layered double hydroxides was developed, and the reduction mechanism was also proposed. It allowed the in situ immobilization of monodispersed Pd nanoparticles with a face-centered cubic structure, using only alcohols with α-hydrogen atom as the solvent and reducing agent. Control over the mean particle size and content of Pd nanoparticles was realized by adjusting the temperature, initial concentration, and type of alcohol. With the content of Pd varied from 6.4 to 42.3 mg/g, the mean particle size of Pd increased from 1.1 to 4.9 nm. The as-prepared catalyst showed high catalytic activity for oxidation of benzyl alcohol: when the Pd content was 6.4 mg/g, conversion of 60.3% and selectivity of 99.2% were obtained with a turnover frequency of 4807 h-1. Similarly, on the basis of the high stand electrode potentials, immobilized Ag (5.6 nm) and Au (4.7 nm) nanoparticles were also prepared through this methodology. Moreover, the choice of supports was extended to other powder supports that would react with the byproduced acid. Overall, this facile method opens up new opportunities for controllable synthesis of supported nanoparticle catalysts in a green way.
Project description:Cocoa and coffee are two of the world's most important crops. Therefore, their by-products are generated in large quantities. This work proposes a simple method for the valorization of these residues by obtaining phenolic compounds and melanoidins by solid-liquid extraction using different hydroalcoholic solutions as extracting solvents (0, 25, 50, 75, 100% ethanol). Extracts of both by-products presented the highest antioxidant capacity and total phenolic and melanoidin content when using 50-75% ethanol in the solvent. Among all the extracts, those obtained from spent coffee grounds at 75% ethanol showed the highest concentrations of total phenolic compounds (13.5 ± 1.3 mmol gallic acid equivalents/g dry matter) and melanoidins (244.4 ± 20.1 mg/g dry matter). Moreover, the sun protection factor values of the coffee extracts obtained with 50 and 75% of ethanol as extraction solvent (7.8 ± 0.9 and 8.5 ± 0.7, respectively) showed their potential for use in the cosmetic sector. The most important phenolic compounds identified in the coffee by-products extracts were phenolic acids, and most of them were found in higher concentration in extracts obtained with lower percentages of ethanol (0-25%). Protocatechuic acid was the most abundant phenolic in cocoa extracts, with concentrations ranging from 18.49 ± 2.29 to 235.35 ± 5.55 µg/g dry matter, followed by 4-hydroxybenzoic acid, (-)-epicatechin and (+)-catechin. Esculetin was found in both coffee and cocoa extracts, which had not been reported to date in these residues. In summary, the use of 75% ethanol as an extraction solvent seems a good strategy to obtain extracts rich in phenolic compounds from food by-products rich in melanoidins, such as coffee and cocoa by-products. The high antioxidant potential of these extracts makes them of great interest for the cosmetic and nutraceutical industries.
Project description:In this work, we focus on Mg-Fe-O and Mg-Ni-O with Mg-rich compositions as positive-electrode materials for magnesium rechargeable batteries, and prepare them by a thermal decomposition of precipitates obtained by a solution method. It is indicated from X-ray diffraction patterns that the Mg-Fe-O and Mg-Ni-O samples have the spinel and rocksalt structures, respectively. X-ray absorption near edge structures indicate that Fe and Ni are trivalent and divalent, respectively, in the Mg-rich oxides. From charge/discharge cycle test, it is demonstrated that the Mg-Fe-O shows higher discharge capacity than the other and then has good cycle performance while keeping a discharge capacity over 100 mA h g-1. To gain deeper understanding on a relationship between the electrode properties and the crystal structure of the Mg-Fe-O, the crystal structure is investigated by a Rietveld refinement using a synchrotron X-ray diffraction profile and an analysis on total correlation functions. It is indicated from these studies that a vacant octahedral site in the spinel structure is partially occupied by the excess Mg in the synthesized sample. This structural feature might result in a stable charge/discharge cycle performance of the Mg-rich Mg-Fe-O.
Project description:Single-phase magnesium-aluminium layered double hydroxide (LDH) intercalated with dihydrogen phosphate was successfully produced by hydration of nanopowder of the respective mixed metal oxide (MMO) obtained using sol-gel based method followed by a two-step anion exchange hydroxide-to-chloride and chloride-to-phosphate. The MMO with the metal cation ratio of Mg/Al = 2:1 was prepared using the aqueous sol-gel method. Processes of the parent Mg2Al-OH LDH formation and the successive anion-exchanges, ОН- → Cl- and Cl- → H2PO4-, were considerably accelerated via the application of high-power (1.5 kW) ultrasound. The crystalline phases formed at all stages of the Mg2Al-H2PO4 LDH production were characterized using X-ray diffraction, scanning electron microscopy, scanning transmission electron microscopy, inductive coupled plasma optical emission spectroscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis. Based on the data of chemical analysis and the XRD data, the type of the intercalated phosphate anion was determined and the arrangement of this anion in the interlayer was modelled.
Project description:This paper is focused on the heterogeneously catalyzed transesterification (in a batch reactor) of vegetable oil, including the determination of leached metals. The oil was obtained from the short-season crop Camelina sativa. The reaction was catalyzed by mixed oxides, which were synthesized from Mg/Al hydrotalcites with built-in different types of divalent cations such as Mn, Ca, Co, Ni, and Fe. The various physicochemical properties like the structure by X-ray diffraction, acidity, basicity, and textural properties were measured and the effect of the added cation type on catalyst properties and activity was compared. A noticeable relationship between the cation type and catalytic activity in the transesterification reaction was observed. The highest ester content of 96.6 wt % after 7 h of transesterification was observed for catalysts with nickel and iron. The statistical analysis of results showed that the catalyst activity was mainly influenced by middle-temperature basic sites. The novelty lies in transesterification over five different heterogeneous catalysts-mixed oxides with added divalent metals at the same reaction conditions of C. sativa oil.
Project description:Engineering magnetic nanoparticles with tunable structural properties and magnetism is critical to develop desirable magnetic particle imaging (MPI) tracers for biomedical applications. Here we present a new superparamagnetic metal oxide nanoparticle with a controllable chemical composition and magnetism for imaging tumor xenografts in living mice. Superparamagnetic Zn/Fe mixed metal oxide (ZnFe-MMO) nanoparticles are fabricated via a facile one-pot co-precipitation method in water followed by thermal decomposition with tunable Zn/Fe ratios and at various calcination temperatures. This work, for the first time, presented LDH-derived metal oxides for an MPI application. The metal composition is tunable to present an optimized MPI performance. The analytical results demonstrate that ZnFe-MMO nanoparticles at the designed molar ratio of Zn/Fe = 2:1 after 650 °C calcination demonstrate a higher saturation magnetization (MS) value and optimal MPI signal than the samples presented with other conditions. The excellent biocompatibility of ZnFe-MMO is demonstrated in both breast cancer cells and fibroblast cell cultures. In vivo imaging of 4T1 tumor xenografts in mice using ZnFe-MMO as a tracer showed that the mean signal intensity is 1.27-fold higher than the commercial tracer VivoTrax at 72 h post-injection, indicating ZnFe-MMO's promise for prolonged MPI imaging applications.
Project description:Herein, we demonstrate the bottom-up synthesis of 2D cyano-bridged Cu-Ni coordination polymer (CP) nanoflakes through a controlled crystallization process and their conversion to Cu-Ni mixed oxides via a thermal treatment in air. The chelating effect of citrate anions effectively prevents the rapid coordination reaction between Cu2+ and K₂[Ni(CN)₄], resulting in the deceleration of the crystallization process of CPs. Specifically, with addition of trisodium citrate dehydrate, the number of nuclei formed at the early stage of the reaction is decreased. Less nuclei undergo a crystal growth by interacting with [Ni(CN)₄]2-, leading to the formation of larger Cu-Ni CP nanoflakes. Following heat treatment in air, the -CN- groups present within the CP nanoflakes are removed and nanoporous Cu-Ni mixed oxide nanoflakes are generated. When tested as an electrode material for supercapacitors using a three-electrode system, the optimum Cu-Ni mixed oxide sample shows a maximum specific capacitance of 158 F g-1 at a current density of 1 A g-1. It is expected that the proposed method will be useful for the preparation of other types of 2D and 3D CPs as precursors for the creation of various nanoporous metal oxides.