掺杂纳米晶铁酸盐表面电子重组能与光伏特性的关系

通过表面光伏（SPV）和电场诱导表面光伏(EFISPV)技术，以光量子激发空间电荷区内电荷的转移跃迁作为电子探针，测定纳米晶铁酸镧样品中掺杂锶前后表面光电阈值的变化.结果发现，在相同的敏感气体环境下，与纳米晶铁酸镧样品相比，掺杂的纳米晶铁酸锶镧的光电阈值显著降低，表现出更加明显的表面效应.提出利用掺杂前后样品阈值能量的改变，定量计算掺杂样品表面电子重组能的方法.分析并讨论产生上述表面电子重组能的主要原因.     

尺寸可控氢氧化镧纳米棒的水热合成及表征

以硝酸镧为镧源、三乙胺为碱源和络合剂,通过简便的水热法成功合成了大量均一的氢氧化镧纳米棒。详细研究了三乙胺的用量、表面活性剂、反应温度和时间对产物形貌及尺寸的影响。基于实验结果,提出了氢氧化镧纳米棒的形成机理。同时制备了稀土掺杂的氢氧化镧纳米棒。利用X射线衍射（XRD）、透射电子显微镜（TEM）、选区电子衍射（SAED）和高分辨透射电子显微镜（HRTEM）对所得产物的物相、结构和形貌进行了表征分析。     

La0．5Nao．5TiO3纳米晶的制备及光致发光研究

以硬脂酸、硝酸镧、氢氧化钠和钛酸四丁酯为原料制备了La0．5Nao．5TiO3纳米晶，粒度最小可达14nm，烧成温度为500℃，低于传统固相反应的合成温度。光致发光研究表明：用392nm光作激发光，在室温下观察到了一个强的蓝光发射带，并且它的强度和半宽度随粒度发生明显变化。     

空气—乙炔焰中高氯酸镧对锶的增感效应及其分析应用

本文试验了稀土元素对空气－乙炔火焰原子吸收测定锶的影响，并且选择镧作了重点研究，发现不同镧盐对测定锶的影响各不相同，当存在每ｍＬ１５００μｇ镧（高氯酸盐）时，硝酸浓度在比较宽的范围内不影响锶的测定，本文建立建立了Ｓｒ－Ｌａ（ＣｌＯ４）３－ＨＮＯ３体系中测量锶的新方法，该方法用于人工混合稀土样品中Ｓｒ的测定，获得满意的结果。     

溶剂热法制备银纳米晶

以聚乙烯吡咯烷酮(PVP)作为表面活性剂,利用乙二醇溶剂热法成功制备了银纳米颗粒;利用场发射扫描电子显微镜(FE-SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)分析了样品的形貌和晶体结构,并考察了溶剂组成等因素对银纳米颗粒形貌的影响.研究结果表明所得银纳米晶粒径均一,直径约为90nm;增大PVP的加入量会降低产物的粒径,溶剂中水的引入会影响银纳米晶的形貌.     

La_(0.5)Na_(0.5)TiO_3纳米晶的制备及光致发光研究

以硬脂酸、硝酸镧、氢氧化钠和钛酸四丁酯为原料制备了La0 .5Na0 .5TiO3 纳米晶 ,粒度最小可达 1 4nm ,烧成温度为 50 0℃ ,低于传统固相反应的合成温度。光致发光研究表明 :用 392nm光作激发光 ,在室温下观察到了一个强的蓝光发射带 ,并且它的强度和半宽度随粒度发生明显变化。     

不同粒径八面体纳米CeO_2的制备及其影响因素的探究

由于纳米CeO_2粒径和形貌的不同,导致其性质和应用的不同。本文以硝酸铈和磷酸钠为原料,采用水热法研究了不同粒径八面体纳米CeO_2的制备,考察了水热温度、磷酸钠的加入量、分散剂的种类和焙烧温度等因素对其粒径的影响规律,利用XRD和SEM对纳米颗粒的粒径和形貌进行表征分析。研究结果表明,通过控制反应条件,采用水热法可制备出平均粒径范围为35.2-67.3 nm的八面体纳米CeO_2,且分散度好,结晶性高。     

纳米块体金属钆和镝的磁性相变分析

对纳米晶钆(Gd)和镝(Dy)块体材料的磁性进行了研究.与多晶比较,通常纳米晶的磁化强度减小,居里温度TC降低,但平均粒径为10 nm的纳米晶Dy的居里温度TC反而升高到100 K,平均粒径为10 nm的纳米晶Gd中还存在明显的反铁磁相.通过RKKY交换作用的计算知道,晶面晶界处原子的交换积分会发生正负号的变化,能量最低的稳定状态对应三种有序相:铁磁相、反铁磁相和扇相,晶粒中在一定条件下出现三相共存.对于平均粒径为10 nm的纳米晶,晶面晶界处原子所占比例很大,三相叠加的结果,对于Gd,即是在相变点附近出现磁化强度尖峰;对于Dy,则是磁化强度随温度升高下降缓慢,表现为居里温度TC比多晶升高.     

La（Oxin）3·3H2O纳米晶的一步固相化学合成及表征

在近室温条件和超声波作用下,通过固相化学反应一步合成了La（Oxin）3·3H2O（8-羟基喹啉镧）纳米晶。用X射线衍射及电子衍射法分析了固相产物的物相,用透射电子显微镜观测粒子的大小、形貌、粒径及粒径分布。结果表明,产物为颗粒大小均匀、平均粒径约为40nm的纳米晶,产率为95．9％。改变反应物、反应物配比、掺人惰性物质、加入微量溶剂或表面活性剂、研磨不同时间等固相反应条件对合成纳米晶的晶粒形貌、粒度和粒径分布有一定影响。合成的纳米晶材料具有操作方便、合成工艺简单、产率高、选择性好、粒径均匀、且粒度可控、污染少,同时又可以避免或减少液相中易出现的硬团聚现象等突出优点。     

La3+,Ce4+对制备堇青石材料晶相转变及烧结性能的影响

以菱镁矿风化石、工业氧化铝和二氧化硅微粉为原料,加入不同含量氧化镧、氧化铈添加剂,通过固相反应合成制备堇青石材料。用XRD法和SEM法表征试样中的晶相组成和显微结构,用X’Pert Plus软件计算主晶相的晶格常数、晶胞体积和试样的相对结晶度,用半定量法计算试样中各晶相含量,用Scherrer公式计算主晶相的粒径大小。研究分析了La3+,Ce4+对制备堇青石材料晶相组成、主晶相粒径大小、晶胞常数、试样相对结晶度、显微结构及烧结性能的影响。结果表明:氧化镧比氧化铈具有更好的助堇青石烧结性,加入氧化镧的堇青石试样具有更好的致密性;随着氧化镧、氧化铈加入量的增加,堇青石晶胞常数和晶胞体积呈现先增大后减小趋势;Ce4+更高的电场强度促进了堇青石材料更容易发生晶相转变形成莫来石。     

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.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

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.     

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.