ZnFe2O4 nanoparticles: A green and recyclable magnetic catalyst for fast and regioselective conversion of epoxides to vicinal hydroxythiocyanates using NH4SCN under solvent-free conditions

ZnFe₂O₄ nanoparticles were synthesized and used as recyclable magnetic catalyst in the solvent-free conversion of different epoxides to vicinal hydroxythiocyanates with NH₄SCN at room temperature. The reactions were carried out by grinding in a mortar with perfect regioselectivity within short times (2-25 min) and with high to excellent yields (75–95%). The nanocatalyst was separated easily using an external magnet and reused for four consecutive cycles without any noticeable loss of efficiency or magnetic property.     

InCl3 catalyzed carbene insertion into O-H bonds: efficient synthesis of ethers

An efficient InCl₃ mediated insertion of the carbene fragment (:CHCO₂Et), generated in situ from ethyl diazoacetate into O-H bond of a series of saturated and unsaturated alcohols under mild conditions has been developed to afford the corresponding ethers as exclusive products in good to high yields (70-95%) and in shorter reaction times. In the case of unsaturated alcohols, the reaction proceeded with unprecedented selectivity resulting in ethers as the only products and in high yields.     

γ-Fe_2O_3:A magnetic separable catalyst for synthesis of 5-substituted 1H-tetrazoles from nitriles and sodium azide

<正>An efficient route for the synthesis of 5-substituted 1H-tetrazole via[2+3]cycloaddition of nitriles and sodium azide is reported usingγ-Fe_2O_3 nanoparticles as a magnetic separable catalyst.Under optimized conditions,the moderate to good yields(71-95%) can be obtained.The catalyst can be easily separated by a magnet and reused for several circles.     

Diastereoselective Mukaiyama aldol reaction of (N-alkyl) isatins with 2-(trimethylsilyloxy)furan by using lanthanum triflate

An efficient vinylogous Mukaiyama aldol reaction (VMAR) of 2-(trimethylsilyloxy)furan with various (N-alkyl)isatins is described in the presence of lanthanum(III) triflates (5 mol %). The reaction proceeds rapidly and affords the corresponding 3-hydroxy-(5-oxo-2,5-dihydrofuran-2-yl)indolin-2-one in high yields with good diastereoselectivities (threo:erythro ratio up to ≤95:5).     

低浓度甲烷甲醇深度氧化Ag/La0.6Sr0.4MnO3催化剂

Ag-modified La0.6Sr0.4MnO3 catalysts were prepared and their catalytic performance for deep oxidation of CH4 and CH3OH at low concentrations were investigated. The results showed that the La0.6Sr0.4MnO3 host catalyst with the perovskite-type nano-crystallite structure displayed considerably high catalytic activity for deep oxidation of CH4 and CH3OH at low concentrations. Ag modification to the La0.6Sr0.4MnO3 host catalyst resulted in significant enhancement of the catalyst activity, making the T95 (the reaction temperature needed for conversion of 95%of CH4 or CH3OH) lowered down to 735K (for CH4) and 421K (for CH3OH) from 813 and 465 K over the Ag-free system under the reaction conditions:0.1MPa,CH4/O2/N2=2/12/86(molar ratio),GHSV=45000 h-1 and CH3OH/O2/N2= 0.2/1.0/98.8 (molar ratio),GHSV=58000 h-1,respectively.The carbon containing product was almost CO2 and the contents of HCHO and CO in the reaction exit gas were both under GC detectable limit in both cases.
The results of spectroscopic characterization indicated that modification by proper amount of Ag-dopant did not change the perovskite structure of the La0.6Sr0.4MnO3 host catalyst as a whole. Interaction of Ag-dopant with the surface of the host catalyst,La0.6Sr0.4MnO3,was in favor of high dispersion of the Ag component at the catalyst surface and led to the oxidation of part of the Mn3+species to Mn4+,resulting in an increase of amounts of the reducible Mnn+ species and a decrease of their reduction temperature. On the other hand, this interaction led also to enhancement of adsorption ability of the catalyst toward O2 at relatively low temperature. High activity of the Ag modified La0.6Sr0.4MnO3 catalyst for CH4 and CH3OH complete oxidation was closely related to high redox-activity of the catalyst and its prominent adsorption-activation ability to O2 at relatively low temperatures.     

Performance of H2/O2 fuel cell using membrane electrolyte of phosphotungstic acid-modified 3-glycidoxypropyl-trimethoxysilanes

Proton-conducting membranes based on phosphotungstic acid (PWA) and 3-glycidoxypropyl-trimethoxysilane (GPTMS) was investigated as the electrolyte for low temperature H₂/O₂ fuel cell. Parameters determining the conductivity and elastic modulus of the membranes were characterized by thermogravimetry/differential thermal analysis and infrared spectroscopic measurements. The composite containing 5% of PWA exhibited an elastic modulus below 100 MPa at room temperature and a high proton conductivity of 1.0 × 10⁻² S/cm at 80 °C and 100% RH. Low elastic modulus of the membrane was found to be useful for both the reduction of the membrane thickness and the better contact with the electrodes. The performance of the membrane electrode assemblies (MEA) was systematically studied as an effect of preparation conditions. A maximum power density of 45 mW/cm² and the current density of 175 mA/cm² at 0.2 V were achieved at 90 °C and 100% RH for the membrane of 5PWA·95GPTMS composition and 0.2 mm thickness.     

非晶态铁基固体碱催化剂的酯交换性能

通过化学还原法和共沉淀法分别制备了非晶态和晶态的FeCeOx/SiO2固体碱催化剂。与晶态的FeCeOx/SiO2相比,非晶态的FeCeOx/SiO2催化剂对梨醇酯与甲醇的酯交换活性显著提高。通过电感耦合等离子体质谱(ICP-MS)、N2吸附-脱附、透射电子显微镜(TEM)结合选区电子衍射(SAED)、X射线衍射(XRD)、X射线光电子能谱(XPS)、CO2-TPD和NH3-TPD等对催化剂进行表征。结果表明催化剂的活性与其碱性密切相关,非晶态FeCeOx/SiO2显示出相对于晶态FeCeOx/SiO2更强的碱性。使用非晶态FeCeOx/SiO2催化剂进行梨醇酯酯交换反应,在130℃下反应10 h,梨醇酯的转化率达到95%,异戊烯醇的选择性达到96%。在重复使用10次后,催化剂活性基本不变。对新鲜的和套用10次后的FeCeOx/SiO2催化剂进行X射线衍射分析,表明该催化剂在套用10次后仍未晶化,证实其具有良好的稳定性,说明该催化剂在非均相催化酯交换反应中具有应用价值。     

Sol-Gel Synthesis of Metal Nanoclusters-Silica Composite Films

In a program on the development of metal nanoclusters in sol-gel derived thin films, attempts were made to synthesize pure and mixed metal clusters, control the cluster size and increase the volume fract f the clusters. Thus, Ag, Cu and Ag-Cu nanoclusters were prepared in silica films using dip- and spin-coating techniques. The annealing of Ag/SiO₂ films in different atmospheres (air, argon and 5% H₂-95% N₂ gas) caused modifications of Ag nanoclusters resulting in changes in their surface plasmon resonance (SPR) peak positions. The Cu and Ag-Cu codoped films were annealed in reducing atmosphere (5% H₂-95% N₂ gas). In order to prepare Cu nanoclusters of different sizes, the concentrations of Cu in Cu/SiO₂ composite films were varied from 8 to 30 mol% and annealed at 800°C for different times for growth. The size of the Cu nanoclusters was measured from the half band width of Cu SPR peak (appearing within 570–557 nm range) and X-ray diffraction. In this way Cu-nanoclusters of size ranges from about 3.5 to 10 nm (average diameters) were prepared . The Ag-Cu nanocluster-containing silica films show the existence of both Ag and Cu SPR peaks with some blue shifting in comparison with to their pure analogues depending on the Ag:Cu ratio.     

SiO2/TiO2-xCx/C的制备、表征及其吸附和可见光催化性能

以SiO2为成核中心,钛酸四丁酯为钛源,分别以多羟基化合物乙二醇、丙三醇、葡萄糖和聚乙烯醇为联接剂,采用水解沉淀法制备了碳掺杂和包覆的多孔SiO2/TiO2-xCx/C可见光响应型光催化剂。采用X-射线衍射(XRD)、透射电子显微镜(TEM)、X-射线光电子能谱(XPS)、傅里叶变换-红外光谱(FTIR)、比表面积(BET)和紫外-可见(UV-Vis)漫反射光谱对样品进行表征。对不同结构样品的形成机理进行了分析。以次甲基蓝(MB)溶液为模拟废水,对样品的吸附性能和可见光催化性能进行了评价。结果表明,多羟基化合物对材料的结构和性能有重要影响。碳的掺杂和包覆使材料的吸收光谱包含了整个可见光区,而多孔结构使材料的吸附性能得到提高。以聚乙烯醇为原料所得样品吸附性能最好,30 min内吸附率达到70%;而以丙三醇为原料所得样品具有最好的可见光催化性能,40 min内次甲基蓝的降解率达到95%。     

Physico-chemical properties of ambiently dried sodium silicate based aerogels catalyzed with various acids

Experimental results on the physico-chemical properties of ambiently dried sodium silicate based aerogels catalyzed with various acids are reported. The aerogels were prepared by hydrolysis and polycondensation of sodium silicate followed by subsequent washings, surface chemical modification and ambient pressure drying using 10 various acid catalysts consisting of strong and weak acids. The strength and concentration of acids have the major effect on the gelation of sol and hence the physico-chemical properties of the silica aerogels. Strong acids such as HCl, HNO₃ and H₂SO₄ resulted in shrunk (70–95%) aerogels whereas weak acids such as citric and tartaric acids resulted in less shrunk (34–50%) aerogels. The physical properties of silica aerogels were studied by measuring bulk density, volume shrinkage (%), porosity (%), pore volume, thermal conductivity, contact angle with water, Transmission Electron Microscopy (TEM), Atomic Absorption Spectroscopy (AAS), Fourier Transform Infrared Spectroscopy (FTIR), Thermo Gravimetric-Differential Thermal (TG-DT) analyses and N₂ adsorption–desorption BET surface analyzer. The best quality silica aerogels in terms of low density (0.086 g/cm³), low volume shrinkage (34%), high porosity (95%), low thermal conductivity (0.09 W/m K) and hydrophobic (148°) were obtained for molar ratio of Na₂SiO₃:H₂O:citric acid:TMCS at 1:146.67:0.72:9.46 with 20 min gelation time. The resulting aerogels exhibited the thermal stability up to around 420 °C.     

The Importance of Precursors and Modification Groups of Aerogels in CO2 Capture

The rapid growth of CO₂ emissions in the atmosphere has attracted great attention due to the influence of the greenhouse effect. Aerogels’ application for capturing CO₂ is quite promising owing to their numerous advantages, such as high porosity (~95%); these are predominantly mesoporous (20–50 nm) materials with very high surface area (>800 m²∙g⁻¹). To increase the CO₂ level of aerogels’ uptake capacity and selectivity, active materials have been investigated, such as potassium carbonate, K₂CO₃, amines, and ionic-liquid amino-acid moieties loaded onto the surface of aerogels. The flexibility of the composition and surface chemistry of aerogels can be modified intentionally—indeed, manipulated—for CO₂ capture. Up to now, most research has focused mainly on the synthesis of amine-modified silica aerogels and the evaluation of their CO₂-sorption properties. However, there is no comprehensive study focusing on the effect of different types of aerogels and modification groups on the adsorption of CO₂. In this review, we present, in broad terms, the use of different precursors, as well as modification of synthesis parameters. The present review aims to consider which kind of precursors and modification groups can serve as potentially attractive molecular-design characteristics in promising materials for capturing CO₂.     

Mg-Zn-Al三金属类水滑石的合成及其复合氧化物的催化性能

水滑石（[Mg_６Al_２（OH）_(１６)[CO_３·４H_２O）是一种类似于水镁石结构的层状阴离子黏土，其骨架为阳离子，层间为阴离子。如改变骨架中的金属阳离子或在层间引入不同的阴离子，就可形成各种新组成的类水滑石。水滑石对有机分子反应具有较高的催化活性和选择性，且可以作为复合氧化物催化剂的前体，应用广泛。它作为碱催化剂，可用于醇醛缩合；作为氧化还原催化剂，用于水煤气转化、NO的还原、甲烷氧化反应等犤１，２犦。作为一种具有特殊结构的化合物，各种双金属组分的水滑石或类水滑石的合成、性质与应用已受到广泛的重视犤３…     

An efficient approach for the synthesis of novel methyl sulfones in acetic acid medium and evaluation of antimicrobial activity

A series of nine methyl sulphones ( 3a –3 i ) starting from the aldehydes ( 1a–1i ) were synthesized in two consecutive steps. In the first step, preparation of allyl alcohols ( 2a–2i ) from their corresponding aldehydes by the reaction of sodium borohydride in methanol at room temperature is reported. Finally, methyl sulphones are synthesized by condensing sodium methyl sulfinates with allyl alcohols in the presence of BF ₃ .Et ₂ O in acetic acid medium at room temperature for about 2–3 h. The reaction conditions are simple, yields are high (85%–95%), and the products were obtained with good purity. All the synthesized compounds were characterized by their ¹ H, ¹³ C NMR, and mass spectral analysis. All the title compounds were screened for antimicrobial activity. Among the compounds tested, the compound 3f has inhibited both Gram positive and Gram negative bacteria effectively and compound 3i has shown potent antifungal activity. These promising components may help to develop more potent drugs in the near future for the treatment of bacterial and fungal infections.     

溶剂热法合成Fe-CeO2与N-Fe-CeO2纳米粉体及其光催化性能

采用溶剂热法合成了不同Fe掺杂含量的Fe-CeO₂纳米粉体及不同氮源掺杂的N-10% Fe-CeO₂（n_Fe/（n_Fe+n_Ce）=10%）纳米粉体。利用TEM、XRD、XPS、Raman和UV-Vis等技术对其微观结构与形貌进行了表征,并通过降解亚甲基蓝溶液对其光催化性能进行了研究。结果表明,Fe掺杂可以提高CeO₂的光催化性能,以10% Fe-CeO₂催化效率最高,对亚甲基蓝的降解率从纯CeO₂的67%提高到95%。而N的掺杂可调节10% Fe-CeO₂催化性能。以浓氨水为氮源的N-10% Fe-CeO₂（NH₃·H₂O-N-10% Fe-CeO₂）的降解率可进一步提高到97%,并且具有较好的稳定性,经5次循环使用,对亚甲基蓝的光催化降解率仍高达89%。CeO₂催化活性的提高主要由于掺杂Fe和N改变了CeO₂的晶体结构与能带结构,促进了光生电子与空穴的产生与催化反应。     

溶剂热法合成Fe-CeO2与N-Fe-CeO2纳米粉体及其光催化性能

采用溶剂热法合成了不同Fe掺杂含量的Fe-CeO_2纳米粉体及不同氮源掺杂的N-10%Fe-CeO_2(n_(Fe)/(n_(Fe)+n_(Ce))=10%)纳米粉体。利用TEM、XRD、XPS、Raman和UV-Vis等技术对其微观结构与形貌进行了表征,并通过降解亚甲基蓝溶液对其光催化性能进行了研究。结果表明,Fe掺杂可以提高CeO_2的光催化性能,以10%Fe-CeO_2催化效率最高,对亚甲基蓝的降解率从纯CeO_2的67%提高到95%。而N的掺杂可调节10%Fe-CeO_2催化性能。以浓氨水为氮源的N-10%Fe-CeO_2(NH_3·H_2O-N-10%Fe-CeO_2)的降解率可进一步提高到97%,并且具有较好的稳定性,经5次循环使用,对亚甲基蓝的光催化降解率仍高达89%。CeO_2催化活性的提高主要由于掺杂Fe和N改变了CeO_2的晶体结构与能带结构,促进了光生电子与空穴的产生与催化反应。     

Reaction of NO at low temperature by ACF loading urea and rare-earth element oxides (La2O3, CeO2)

Loaded catalysts of 10–50% (w/w) urea loaded on activated carbon fibers (ACF), referred to as urea/ACF, and 10%urea–5–15% (w/w) La₂O₃/ACF and CeO₂/ACF were prepared by an impregnation method and used for removal of NO at low temperature (30–120°C). The experimental results showed that the catalytic activity of urea/ACF could be greatly improved by loaded rare-earth element oxides. Furthermore, 10%urea–5%La₂O₃/ACF and 10%urea–10%CeO₂/ACF could maintain high and stable catalytic activity at 100°C.     

High Temperature Electrophoresis for Monitoring the Thermal Behavior of Cytochrome b5

Abstract

Electrophoresis at high temperature was applied for studying the thermal behaviour of the membrane bound protein cytochrome b₅. Approximately 95% cytochrome b₅ remains in the associated state after thermal transition. Thus, the transition obtained by physical methods is not due to a dissociation of the octameric cytochrome b₅ but to changes in chape. The described method of high temperature electrophoresis seems to be an important tool for distinguishing between dissociation and unfolding processes.     

Pd-Cu/γ-Al2O3催化苯乙炔选择性加氢反应

为了提高苯乙炔加氢反应中的苯乙烯选择性, 本文采用“胶体-等体积浸渍”两步法制备了Pd-Cu/γ-Al₂O₃双金属催化剂. 利用高分辨率透射电镜(HRTEM)、X射线光电子能谱(XPS)、CO脉冲化学吸附、N2物理吸附、电感耦合等离子体原子发射光谱(ICP-AES)等技术表征了Pd-Cu/γ-Al₂O₃的结构性质, 考察了Cu/Pd 摩尔比、Pd负载量以及金属引入顺序对Pd-Cu/γ-Al₂O₃催化苯乙炔选择性加氢性能的影响. 结果表明, 与Pd/γ-Al₂O₃单金属催化剂相比, Pd-Cu/γ-Al₂O₃的苯乙烯选择性大幅度提高, 尤其是当Pd负载量为0.3%(w), 且Cu/Pd摩尔比为0.6时, Pd-Cu/γ-Al₂O₃表现出优异的加氢选择性; 在0.1 MPa和40 ℃下, 当苯乙炔转化率为90%时, 双金属催化剂的苯乙烯选择性可达95%; 当转化率达到99%以上时, 苯乙烯选择性仍保持在82%左右. 分析表明, Pd-Cu/γ-Al₂O₃中形成了Pd-Cu合金, 但是两种金属间不存在电子转移, Cu对Pd的几何效应才是导致Pd-Cu/γ-Al₂O₃苯乙烯选择性增加的主要原因.     

Facile Access to Mono-Cinchona Alkaloid-Derived Ligands

Two facile accesses to mono-cinchona alkaloid-derived ligands, by conventional heating conditions and solvent-free microwave irradiation, are described. 1,4-Dichlorophthalazine (PHAL) or 3,6-dichloropyridazine (PYDZ) reacted with quinine (QN), cinchonine (CN), or cinchonidine (CND) by using CaH₂ as acid-bonding reagent in DMF at 90–100°C to provide mono-cinchona alkaloid-derived ligands 2a–f (87–95%) in 1.5 h. However, the coupling reactions were performed under solvent-free microwave conditions to yield 2a–f (64–89%) within 15 min.     

不同焙烧温度对Cu/γ-Al2O3催化剂铜物种结构的影响

用XRD和EXAFS研究了焙烧温度(35─1000 ℃)和负载量(质量分数为5－15％Cu)对于Cu/γ-Al_2O_3催化剂铜物种的影响。低于700 ℃焙烧时,铜以高分散状态存在。根据Cu~(2+)同时占据八面体(Oh)和四面体(Td)两种位置,对第一壳层的Cu-O配位峰进行了拟合。结果显示,随着焙烧温度增加,铜氧配位距离逐渐增加,Cu~(2+)(Oh)/Cu~(2+)(Td)的比例降低,并且Cu~(2+)(Oh)与氧的平均配位数从5.1变成6.0．这表明Cu~(2+)离子由Oh位向Td位迁移,同时向内层扩散使表面配位不饱和的氧缺顶畸变八面体部分变为配位饱和的对称八面体。900 ℃和更高温度的焙烧,使铜离子扩散进载体相形成CuAl_2O_4。