Green synthesis of the 1-substituted 1H-1, 2, 3, 4-tetrazoles over bifunctional catalyst based on copper intercalated into Mg/Al hydrotalcite modified magnetite nanoparticles

An effective one-pot, convenient process for the synthesis of 1- substituted 1H-tetrazoles from triethyl orthoformate, amines, and sodium azide is described using copper (II) doped and immobilized on functionalized magnetic hydrotalcite (Fe₃O₄/HT-NH₂ Cu^II) as a novel recyclable catalyst. The application of this catalyst allows the synthesis of a variety of tetrazoles in good to excellent yields in water. The new catalyst was characterized using Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), thermogravimetric analysis (TGA), vibration sample magnetometry (VSM) and inductively coupled plasma analysis (ICP-OES). This new procedure offers several advantages such as short operational simplicity, practicability, and applicability to various substrates and the absence of any tedious workup or purification. The loading amount of Cu^II (doped and immobilized) on functionalized magnetic hydrotalcite was indicated to be 4.66 mmol g⁻¹, obtained from the ICP-OES analysis. Also, the excellent catalytic performance, thermal stability, and separation of the catalyst make it an excellent heterogeneous system and a useful alternative to other heterogeneous catalysts. Also, the catalyst could be magnetically separated and reused six times without significant loss of catalytic activity.     

Electrospun poly(lactic acid) nanofibers loaded with silver sulfadiazine/[Mg–Al]‐layered double hydroxide as an antimicrobial wound dressing

Poly(lactic acid) (PLA) is a versatile, bioabsorbable, and biodegradable polymer with excellent biocompatibility and ability to incorporate a great variety of active agents. Silver sulfadiazine (SDZ) is an antibiotic used to control bacterial infection in external wounds. Aiming to combine the properties of PLA and SDZ, hydrotalcite ([Mg–Al]‐LDH) was used as a host matrix to obtain an antimicrobial system efficient in delivering SDZ from electrospun PLA scaffolds intended for wound skin healing. The structural reconstruction method was successfully applied to intercalate silver sulfadiazine in the [Mg–Al]‐LDH, as evidenced by X‐ray diffraction and thermogravimetric analyses. Observations by scanning electron microscopy revealed a good distribution of SDZ‐[Mg–Al]‐LDH within the PLA scaffold. Kinetics studies revealed a slow release of SDZ from the PLA scaffold due to the intercalation in the [Mg–Al]‐LDH. In vitro antimicrobial tests indicated a significant inhibitory effect of SDZ‐[Mg–Al]‐LDH against Escherichia coli and Staphylococcus aureus. This antibacterial activity was sustained in the 2.5‐wt% SDZ‐[Mg–Al]‐LDH–loaded PLA nanofibers, which also displayed excellent biocompatibility towards human cells. The multifunctionality of the PLA/SDZ‐[Mg–Al]‐LDH scaffold reported here is of great significance for various transdermal applications.     

A FT-IR and V-UV Spectroscopic Study of Nickel-Containing Hydrotalcite-Like Compounds, [Ni1−xAlx(OH)2](CO3)x/2.nH2O

Hydrotalcite-like compounds containing Ni(II) and Al(III) cations and with different Ni/Al ratios in the brucite layers have been prepared and studied using FT-IR and V-UV/DR spectroscopies. It has been found that the local environment of the Ni(II) cations is the same in all cases, occupying octahedral holes, but the orientation of the interlayer carbonate anions changes with the Ni/Al ratio.     

Aqueous-phase catalytic hydrogenation of furfural to cyclopentanol over Cu-Mg-Al hydrotalcites derived catalysts: Model reaction for upgrading of bio-oil

A series of Cu-Mg-Al hydrotalcites derived oxides with a (Cu+Mg)/Al mole ratio of 3 and varied Cu/Mg mole ratio (from 0.07 to 0.30) were prepared by co-precipitation and calcination methods, then they were introduced to the hydrogenation of furfural in aqueous-phase. Effects of Cu/Mg mole ratio, reaction temperature, initial hydrogen pressure, reaction time and catalyst amount on the conversion rate of furfural as well as the selectivity toward desired product cyclopentanol were systematically investigated. The conversion of furfural over calcined hydrotalcite catalyst with a Cu/Mg mole ratio of 0.2 was up to 98.5% when the reaction was carried out under 140 °C and the initial hydrogen pressure of 4 MPa for 10 h, while the selectivity toward cyclopentanol was up to 94.8%. The catalysts were characterized by XRD and SEM. XRD diffraction of all the samples showed characteristic pattern of hydrotalcite with varied peak intensity as a result of different Cu content. The catalytic activity was improved gradually with the increase of Cu component in the hydrotalcite.     

Partial oxidation of simulated hot coke oven gas to syngas over Ru-Ni/Mg（Al）O catalyst in a ceramic membrane reactor

Hydrogen amplification from simulated hot coke oven gas (HCOG) was investigated in a BaCo0.7Fe0.2Nb0.1O3−δ (BCFNO) membrane reactor combined with a Ru-Ni/Mg(Al)O catalyst by the partial oxidation of hydrocarbon compounds under atmospheric pressure. Under optimized reaction conditions, the dense oxygen permeable membrane had an oxygen permeation flux around 13.3 ml/(cm2·min). By reforming of the toluene and methane, the amount of H2 in the reaction effluent gas was about 2 times more than that of original H2 in simulated HCOG. The Ru-Ni/Mg(Al)O catalyst used in the membrane reactor possessed good catalytic activity and resistance to coking. After the activity test, a small amount of whisker carbon was observed on the used catalyst, and most of them could be removed in the hydrogen-rich atmosphere, implying that the carbon deposition formed on the catalyst might be a reversible process.     

阴-非离子表面活性剂复合改性水滑石的表面性质研究

采用十二烷基苯磺酸钠（SDBS）、吐温-80（Tween-80）及两种表面活性剂复合改性镁铝水滑石,得到SDBS-LDHs,Tween-LDHs及SDBS/Tween-LDHs₃种改性水滑石。利用反相气相色谱法（IGC）对样品进行表面性质的研究,定量计算了表面吸附自由能（ΔG₀）和表面能色散组分（γ_s^d）。结果表明,改性材料的ΔG₀与γ_s^d值均比未处理的镁铝水滑石小,其中阴-非离子表面活性剂复合改性后的水滑石的ΔG₀与γ_s^d值最小,说明阴-非离子表面活性剂复合改性水滑石较单一改性水滑石更有利于提高材料的稳定性。此外,各类水滑石的γ_s^d值均随着温度的升高而减小,因此,在制备聚合物/水滑石类材料时,可以利用提高温度来改善其与聚合物的相容性。     

Preparation of Mg–Al hydrotalcite from the effluent of Friedel–Crafts reaction and its application as a catalyst in Knoevenagel reaction

Abstract

Hydrotalcite containing magnesium and aluminium (Mg–Al HT) with a molar ratio of Mg(II)/Al(III) = 2.5 has been prepared by a co-precipitation method using the effluent of a Friedel–Crafts acylation reaction. The HT was calcined at 500°C and reconstructed with deionized water. The synthesized HT was characterized by XRD and FT-IR spectroscopy and was successfully used as a catalyst in the Knoevenagel reaction of aldehydes and active methylene compounds. The catalyst was found to be reusable.     

Suzuki cross‐coupling reaction of aryl and heterocyclic bromides and aromatic polybromides on a Pd(II)‐hydrotalcite catalyst

The Suzuki cross‐coupling reaction of various bromine‐containing substrates and phenylboronic acid in toluene at 90 °C on a Pd(AcO)₂Py₂ catalyst supported on an Mg? Al hydrotalcite, using K₂CO₃ as the base, was studied. The conversion and selectivity results obtained for many of the substrates were excellent and similar to those provided by more active or even homogeneous catalysts. The reactions of aryl polybromides and phenylboronic acid gave the corresponding polyaromatic compounds in variable yields depending on the particular substrate. Arylation occurred in a consecutive manner by substitution of the different Br atoms. ICP‐MS measurements of the palladium content of the catalyst performed prior to and after the reaction revealed that part of the metal is incorporated into the bulk solution; therefore, the catalytic process is not purely heterogeneous. Copyright © 2008 John Wiley & Sons, Ltd.     

Catalyst design of hydrotalcite compounds for efficient oxidations

Various Mg-Al type hydrotalcites were examined as catalysts for the epoxidation of olefins and N-oxidation of pyridines using hydrogen peroxide. The catalytic activity of hydrotalcites increased with increasing the basicity of their surface. Adding cationic surfactants, e.g., n-dodecyltrimethylammonium bromide, to the above system remarkably accelerated the reaction rate. The hydrotalcites, into which were introduced both Ru and Co cations in the Brucite layers, were found to be good catalysts for the oxidation of various alcohols in the presence of molecular oxygen. Moreover, these hydrotalcites could smoothly catalyze also the oxygenation of diphenylmethane, fluorene, and xanthene at benzylic position with excellent yields. The hydrotalcite catalysts could be easily separated from the reaction mixture and reused with retention of their high catalytic performance for the above oxidations.