高能振动球磨法制备纳米钙钛矿粉体La_(0.8)Ca_(0.2)MnO_3

利用高能振动球磨法,以氧化镧、氧化钙和二氧化锰为原料,制备出纳米氧化物粉体La0.8Ca0.2MnO3。采用XRD分析了球磨过程中粉体的晶化过程;以TEM观察了制备出的粉体的颗粒尺寸和分散状况。结果表明,采用高能振动球磨法20 h就能制备出颗粒尺寸在50~100 nm,属正交晶系的纳米钙钛矿粉体La0.8Ca0.2MnO3;在该反应体系的球磨过程中,产物晶粒经历了先长大后细化的过程。将球磨法制备出的粉体压成电极,进行放电分析。结果表明采用该方法制备出的纳米La0.8Ca0.2MnO3粉体具有很好的电催化活性。     

NdFeB材料微波吸收特性的研究

采用高能球磨和晶化热处理方法制备钕铁硼吸波粉体,研究制备工艺对钕铁硼粉体吸波性能的影响。结果发现:高能球磨和适当晶化热处理可改善NdFeB粉体的组织结构、复介电常数和复磁导率;NdFeB粉体的反射率最小值为-15.5 dB,高能球磨48 h后粉体的反射率最小值降到-23 dB,高能球磨粉体经600℃晶化热处理后反射率最小值为-19 dB;高能球磨和晶化热处理可降低NdFeB粉体的吸收峰频率;高能球磨会使NdFeB粉体的吸波带宽变窄,经600℃晶化热处理后吸波带宽变宽,并且随着晶化热处理的温度升高,吸波带宽变得更宽。     

在纳米晶Co—Mo／Ni复合电极上的析氢反应

采用复合电镀的方法将不同球磨时间制备的高催化活性的纳米晶Ｃｏ－Ｍｏ合金粉直接镀在电极表面，用稳态极化曲线及交流阻抗技术测试了这些电极析氢的电化学活性，并用Ｘ射线衍射，透射电镜及Ｘ射线光电子能谱，扫描电镜监测了Ｃｏ－Ｍｏ合金粉的物相结构，晶粒尺寸和复合镀的成份，形貌，实验结果表明，Ｃｏ－Ｍｏ纳米晶合金粉有较高的析氢催化活性，球磨使钴钼粉合金化成为纳米晶，一方面增加了复合镀层的真实表面积，另一方面由于     

高压变质二氧化硅矿物的合成及表征

根据高能机械球磨与地球板块碰撞之间具有的碰撞局域性和剪切应力相似的特点, 采用高能机械球磨和静高温高压技术, 以α-石英与石墨混合粉末为原料, 提出了人工合成地表柯石英的一种新方法. 利用高能机械球磨制备了α-石英和石墨纳米非晶混合粉末, 其高温高压合成柯石英的最低条件是970 K和3.7 GPa. 合成的柯石英有10个Raman峰, 分别位于120, 152, 179, 206, 270, 329, 357, 428, 467和521 cm-1, 是目前最全的柯石英Raman谱.     

Y2O3:Eu纳米晶的硝基取代苯甲酸配合物固相热解制备和性能

以苯甲酸、邻硝基苯甲酸、间硝基苯甲酸、对硝基苯甲酸、3，5－二硝基苯甲酸等为配体制备了Y^3 、Eu^3 二元配合物，配合物中Y^3 与Eu^3 的摩尔比为9：1，利用这些配合物的爆炸式热分解特性通过固相热解反应制备了一系列Y2O3：Eu纳米晶。透射电镜观察，可以看出所得纳米晶呈球形，粒度介于40－60nm，X射线衍射分析表明实验所得纳米晶属立方晶系，粒径与电镜观察所得结果基本一致；Eu^3 的引入并不影响Y2O3的晶相组成；配体类型对纳米晶的结构没有显著影响，不过相对于硝基取代苯甲酸配合物，苯甲酸配合物热解所得Y2O3：Eu纳米晶团聚严重；退火温度显著影响纳米晶粒度，退火温度高，纳米晶粒度大，反之亦然。荧光光谱测定表明所有Y2O3：Eu纳米晶具有相似的发光行为，其中以苯甲酸配合物分解所得Y2O3：Eu纳米晶发光性能最为优越。     

球磨形成的Ni-Mo纳米晶复合镀层上的析氢反应

采用复合电镀的方法将不同球磨时间制备的高催化活性的纳米晶，Ｎｉ－Ｍｏ合金粉直接镀于电极表面，并用稳态极化曲线及交流阻抗技术测试了这些电极析氢的电化学活性，同时用Ｘ射线衍射，透射电镜及扫描电镜监测了Ｎｉ－Ｍｏ合金粉的物相结构，晶粒尺寸及复合电极表面的形貌，并初步探讨了这些复合电极的析氢机理，实验结果表明，球磨不仅可使镍钼粉合金化成为纳米晶，同时随着球磨时间的增加，纳米晶晶粒继续细化，电极的析氢催化活     

纳米Eu_(0.12)Y_(1.88-x)La_xO_(3-δ)的光致发光性能及晶粒生长动力学

以超声波作用下的均匀沉淀法制备了Eu0.12Y1.88-xLaxO3-δ纳米晶荧光粉,用X射线粉末衍射(XRD)、透射电镜(TEM)、荧光光谱对其进行表征,考察了不同La3+掺杂含量下Eu0.12Y1.88-xLaxO3-δ(x=0～0.30)的晶格常数及晶粒尺寸的变化,研究了掺杂含量对样品激发光谱及发射光谱的影响.结果表明,Eu0.12Y1.88-xLaxO3-δ的晶格常数在1.060～1.068nm之间,晶粒尺寸在6.8～26.1nm之间,当x=0.10时,Eu0.12Y1.78La0.10O3-δ的平均粒径为35nm,发光性能优于未掺杂的Y2O3∶Eu3+荧光材料.根据晶粒生长动力学理论计算Eu0.12Y1.78La0.10O3-δ晶粒长大的活化能为9.24kJ·mol-1,表明热处理过程中纳米晶粒的长大为扩散生长机制.     

溶胶-凝胶法制备α-Fe_2O_3纳米晶

研究了在硝酸铁 -乙二醇甲醚体系中用溶胶 -凝胶法制备氧化铁纳米晶 .利用 TEM、XRD和 TG- DTA手段对产物进行了表征。结果表明 ,体系中加入十二烷基磺酸钠有助于纯相α- Fe2 O3纳米晶的生成 ,而加入钛酸四丁酯则显著缩短凝胶时间 ,所得粉体的原始晶粒尺寸为 30 nm左右 .若加入硅酸乙酯替代钛酸四丁酯 ,则最终产物为 γ氧化铁和 α氧化铁的混晶相 ( γ- Fe2 O3为主晶相 ) ,晶粒尺寸约 10 nm .     

铁酸锌纳米晶的机械化学合成

以αFe₂O₃和ZnO粉体为原料,在高能球磨的作用下,室温(约25℃)合成了铁酸锌(ZnFe₂O₄)纳米晶.用XRD、TEM、M?sbauer谱及IR光谱等方法对纳米晶进行了表征.结果表明:所得纳米晶具有非正型分布的尖晶石结构,为超顺磁性;纳米晶内存在着较多的缺陷.     

低温合成纳米α-Si3N4材料及结构表征

本文报道在机械驱动下力，通过机械合金化途径使氮或氨直接在室温下的逐步细化的，新鲜的，高反应活性的硅界面上充分扩散，形成亚稳态系统，在８００℃真空炉处理后得到纳米α－Ｓｉ３Ｎ４粉末。发现气氛对合成Ｓｉ３Ｎ４纳米粉末有很大影响。在氮气中，高能球磨前硅粉表面形成的氧化膜在高能球磨过程中与氮反应生成Ｓｉ２Ｎ２Ｏ保护层，阻止氮的进一步扩散，使反应产物含有大量未反应的游离硅。在氨气中可以避免生成了Ｓｉ２Ｎ２ｏ     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.