白钨矿型钨酸盐和钼酸盐纳米晶/微晶制备研究进展

综述近年来自钨矿型钨酸盐和钼酸盐纳米晶/微晶制备技术领域的研究进展,重点介绍熔盐法、有机配合物前驱法、模板法、微乳液法、水热法、溶剂热法和微乳液.溶剂热法的原理和技术特点,比较各种方法的异同点,并提出白钨矿型钨酸盐和钼酸盐纳米晶/微晶制备技术的发展趋势.     

离子交换法制备LiFePO4的研究

磷酸亚铁锂(LiFePO_4)材料具有原料丰富、成本低、比容量相对较高、对环境友好、无毒无害、热稳定性好等突出的优点,是一种颇具潜力的下一代锂离子电池正极替代材料,尤其适合作为电动车用高功率电池正极材料,日益成为各国科研工作者和企业的研发热点,在我国众多企业的LiFePO_4项目已经启动。目前磷酸亚铁锂材料的制备方法主要有固相法、液相法、微波法和固腋相法。不同     

锂离子电池正极材料LiFePO_4的微波合成及结构表征

以乙酸锂、草酸亚铁、磷酸二氢铵为原料,利用微波法制备出锂离子正极材料磷酸亚铁锂,同时在不同的时间下研究其对反应物合成的影响.用X射线衍射技术、扫描电子显微镜等对产品的晶体结构进行表征,结果表明:微波合成法具有反应时间短、能耗小、合成效率高等优点,其合成的磷酸亚铁锂的晶体结晶度较好、粒度分布较均匀、晶粒比较完整;同时也证实了微波合成是一种比较好的合成方法.     

锂离子电池正极材料LiFePO4的微波合成及结构表征

以乙酸锂、草酸亚铁、磷酸二氢铵为原料,利用微波法制备出锂离子正极材料磷酸亚铁锂,同时在不同的时间下研究其对反应物合成的影响.用X射线衍射技术、扫描电子显微镜等对产品的晶体结构进行表征,结果表明：微波合成法具有反应时间短、能耗小、合成效率高等优点,其合成的磷酸亚铁锂的晶体结晶度较好、粒度分布较均匀、晶粒比较完整;同时也证实了微波合成是一种比较好的合成方法.     

离子交换法制备LiFePO4的研究

磷酸亚铁锂（LiFePO4）材料具有原料丰富、成本低、比容量相对较高、对环境友好、无毒无害、热稳定性好等突出的优点，是一种颇具潜力的下一代锂离子电池正极替代材料，尤其适合作为电动车用高功率电池正极材料，日益成为各国科研工作者和企业的研发热点，在我国众多企业的LiFePO4项目已经启动。目前磷酸亚铁锂材料的制备方法主要有固相法、液相法、微波法和固／液相法。不同前驱体种类和制备方法对材料的纯度、结晶状况影响很大，最终体现在电化学性能方面各异。     

YBO3:Eu荧光粉的水热法制备及形貌控制

用水热法在低于300℃成功地制备出具有不同形貌的YBO3:Eu3+荧光粉,其反应温度比固相反应了约800℃.研究了初始原料、pH值、反应温度、反应溶剂和催化剂等条件对目的产物形貌及粒度的,得到了具有Vaterite结构、粒度分布均匀的球形荧光粉的最佳合成工艺.在254nm激发下,水热法的球形Y0.95Eu0.05BO3荧光粉最强发射峰位于598nm处,属于Eu3+的5D0→7F1的跃迁,是固相反应所品的1.5倍.这些结果表明,在PDP和荧光灯等显示和照明用荧光粉的制备中水热法具有潜在的应用.     

光还原Pt掺杂三维有序大孔ZrO2复合材料的光降解与光解水制氢

同体催化剂的微观结构及表面形貌等对其催化性能有显著影响,因此催化剂的制备已经成为催化领域的研究焦点.在诸多催化剂制备方法中,溶剂热法以其操作简单、反应速度快、条件温和、结晶度高及粒度可控性好等独特的优势脱颖而出.我们以乙二醇和离子液体为典型溶剂阐述了溶剂热法的特点及工艺过程中的主要影响冈素,综述了近年来溶剂热法在金属氧化物、分子筛以及贵金属等催化剂制备中的运用,对溶剂热法制备催化剂进行了展望.     

不同制备方法对Pd/Y-ZrO_2消除HC催化性能的影响

采用水热法、共沉淀法和柠檬酸溶胶-凝胶法合成Y-ZrO_2载体并负载贵金属Pd,研究了制备方法对Pd/Y-ZrO_2催化氧化CH_4及C_3H_8性能的影响。实验结果表明水热法制备的Y-ZrO_2载Pd催化剂具有较高的催化活性及最低的起燃温度。通过BET,XRD,TEM等分析可知,水热法制备的Y-ZrO_2热稳定性最好,有利于t相ZrO_2的稳定及体相PdO的还原。催化剂中t相ZrO_2所占的比率及Pd粒子的尺寸影响催化剂对HC的催化活性。     

纳米二氧化钛的制备及其光催化性能

分别采用水热法和溶胶-凝胶法制备了TiO2纳米粉体;利用X射线衍射仪和扫描电镜分析了两种方法制备的TiO2粉体的形貌和晶体结构,并测定了纳米TiO2粉体对罗丹明B的光催化降解活性.结果表明:采用水热法制备的TiO2纳米粉体含有锐钛矿相和金红石相,粒径较小,大约为50nm,而且分散均匀,光催化性能良好;采用溶胶-凝胶法制备的TiO2粉体经过550℃煅烧后仍然为锐钛矿相,而且粒径较大,大约为80nm.     

不同合成方法对LiFePO4/C正极材料性能的影响

以磷酸亚铁为原料,分别采用磷酸亚铁与磷酸锂的直接合成法(直接法)和磷酸亚铁与原位合成磷酸锂的合成法(磷酸锂原位合成法)合成了橄榄石型LiFePO4/C复合正极材料.用X射线衍射(XRD)、扫描电镜(SEM)、以及充放电测试等方法对材料进行了结构表征和电化学性能测试.实验结果表明两种不同方法得到的样品具有橄榄石晶体结构....     

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%.     

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.     

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.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Copper catalyzed/mediated synthetic methodology for ebselen and related isoselenazolones

Scope of the copper catalyzed/mediated selenium-nitrogen coupling reaction has been studied for the synthesis of isoselenazolones. It is noticed that the 2-chloro, 2-bromo-, and 2-iodo-aryl amides substrates can be exploited in the selenium-nitrogen coupling reaction by employing 25-100 mol % of CuI/1,10-phenanthroline (L) and potassium carbonate as a base in DMF. Furthermore, electron rich 2-chloro-arylamides also underwent selenium-nitrogen coupling reaction to give biologically important selenium-nitrogen heterocycles. Also, copper-catalyzed selenium-nitrogen coupling reaction has been meticulously applied for the synthesis of diaryl diselenides having methoxy, amine, and amide functionality from respective aryl iodides in the presence of stoichiometric amount of succinimide as an external Se-N coupling partner.