采用新颖喷墨打印技术制备的薄膜LiCoO2电极及其电化学性能

采用喷墨打印技术制备了LiCoO2薄膜电极. 用X射线衍射、扫描电镜(SEM)、循环伏安和恒电流充放电试验对薄膜电极进行结构表征和电化学性能测试. SEM结果表明, 所制备的薄膜电极表面粒子分布均匀, 厚度约为1.27 μm. 经过轻微热处理(450 ℃, 30 min)的薄膜LiCoO2电极呈现出稳定的充放电循环性能. 当以20 μA/cm2进行充放电时, 第50次循环容量保持率约为首次放电容量(81 mA·h/g)的87%, 10次循环后的充放电过程的充放电效率均接近100％.     

0/1/2维混合纳米形貌V2 O5的制备与储锂性能

以P123为结构导向剂,采用溶胶-凝胶法结合冷冻干燥技术制备了0/1/2维混合纳米形貌的正交相V₂O₅电极活性材料.利用XRD和SEM表征了样品的结构和形貌,通过循环伏安法、恒流充放电和交流阻抗谱测试研究了样品的储锂性能.结果显示,这种0/1/2维混合纳米形貌V₂O₅具有较高的储锂容量、优异的电化学循环稳定性和出色的大倍率充放电性能,在1 A/g电流密度下循环500次后放电比容量稳定在117.5 mA·h/g,容量保持率为94.4%,在5 A/g大电流密度下,其放电比容量仍保持在88.2 mA·h/g,性能明显优于未添加P123制备的2D片状V₂O₅材料.     

纳米ZnO改性锌电极的性能

纳米ZnO改性锌电极的性能;纳米ZnO;锌电极;循环可逆性;放电容量     

纳米锡锌复合氧化物贮锂材料的合成和性质

用液相沉淀-热解法合成了一系列结构和组成不同的锂离子电池纳米锡锌复合氧化物贮锂材料, 通过XRD、TEM和电化学测试对材料进行了表征. 测试结果表明, 非晶态ZnSnO3负极材料的初始可逆贮锂容量为844 mA·h/g, ZnO·SnO2负极材料的初始可逆贮锂容量为845 mA·h/g, SnO2·Zn2SnO4复合物负极材料初始可逆贮锂容量为758 mA·h/g, 循环10周后, 三者的充电容量分别为695, 508和455 mA·h/g, 表明非晶态结构的锡锌复合氧化物具有较好的电化学性质, 随着样品中晶体的形成, 该类型负极材料的贮锂性能下降.     

含稀土钇电极材料的声化学制备及电化学性能

通过超声浸渍法以不同浓度的Y(NO3)3溶液成功地制得几种声化学改性锌粉, 以期改善碱性电池锌电极的电化学性能. 利用扫描电镜(SEM)、X射线衍射(XRD)及电化学测试等方法考察了改性锌粉上Y(OH)3/Y2O3的形成及相应锌电极的耐腐蚀和循环性能. 结果表明, Y(NO3)3浓度为0.036 mol·L-1时, 声化学改性锌粉表面均匀分布着颗粒状的Y(OH)3/Y2O3, 且这些钇化合物优先生长在锌粉表面的缺陷位置, 阻挡了电化学过程中锌酸根离子向碱性电解液中的溶解与扩散, 使得相应锌电极的缓蚀效率达79.6%, 且20次循环伏安曲线的阴、阳极峰电位差比空白样减小了285 mV. 将这种改性锌粉和空白锌粉组装成模拟锌银电池, 在250 mA·cm-2的高放电电流密度下测试发现, 声化学改性锌粉的锌电极从1次到30次循环的放电容量损失仅为62.7 mAh·g-1; 且放电容量在50周期时达到322.6 mAh·g-1, 说明声化学改性锌粉可明显提高电极的放电容量和循环寿命.     

微波-固相复合加热技术合成LiNi0.5Co0.5O2及其性能研究

用高分子分散及微波-固相复合加热技术合成了层状锂离子电池正极材料LiNi0.5Co0.5O2. 采用循环伏安、充放电循环、扫描电子显微镜(SEM)以及X射线粉末衍射(XRD)等测试技术, 研究了煅烧条件对材料微观形貌、相结构以及电化学性能的影响规律. 研究结果表明: 在750 ℃煅烧4 h即可得到形状为类球形的纯相层状LiNi0.5Co0.5O2正极材料, 该材料的最大放电容量达到154 mA·h/g, 循环10周后放电容量仍保持在148 mA·h/g以上.     

复合掺杂改性的尖晶石LiMn1.98Cr0.02O4-yCly的研究

采用改进的高温固相法合成了阴阳离子复合掺杂改性的锂离子电池尖晶石结构正极材料LiMn1.98Cr0.02O4-yCly(y=0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.10). 采用X射线衍射手段对材料的晶体结构进行了表征. 从材料的晶体结构、充放电容量、循环性能和倍率放电特性等方面分析了复合掺杂在稳定晶体结构和改善材料电化学性能方面的作用. 实验结果表明, 由于复合掺杂的综合作用, 改性后的材料既保持了高的初始容量, 又具有优良的循环性能, 倍率放电性能也得到了有效的改善. 其中LiMn1.98Cr0.02O3.96Cl0.04的综合性能最优, 初始放电比容量达到127 mA·h/g以上, 循环50次后仍有110 mA·h/g的放电比容量.     

以Fe2O3为原料制备LiFePO4/C复合材料及其性能研究

以Fe2O3为铁源原料, 利用热还原法成功地制备了LiFePO4/C复合材料. 用XRD以及SEM对材料的晶体结构以及表面形貌进行了表征. 通过循环伏安和充放电测试研究了材料的电化学性能. 研究结果表明， 于700 ℃下制备的LiFePO4/C复合材料在0.1C的倍率下可以得到放电容量144.8 mA·h/g, 在循环160次后, 容量仍保持在141.4 mA·h/g. 这种以廉价的Fe2O3代替目前常用的二价铁盐原料方法, 具有减少LiFePO4合成成本的优点.     

锌的添加方式对氢氧化镍结构和性能的影响

研究了以共沉淀、包覆、机械混合等不同方式添加或不添加锌对微乳液法合成的氢氧化镍结构和性质的影响。XRD、循环伏安和恒电流充放电测试结果表明：微乳液法的合成物仍是具有六方晶体结构的B-Ni(0H)2,但其晶粒度很小,且化学计量比不等于1／2,所以材料的活性和放电比容量下降;锌的添加增加了Ni(OH)2的晶体缺陷,改善了Ni(OH)2的结构,增加了电极中电子和质子的传递能力,从而提高了氢氧化镍电极的可逆性,强化了电极的析氧极化,其充电效率和放电比容量也随之提高;其中,以共沉淀方式添加锌,氢氧化镍电极的性能最好。     

新型超大容量电容器电极材料—纳米水合MnO_2的研究

本文用KMnO4氧化MnSO4制得纳米水合MnO2粉末。以该粉末作为活性物质制成电极分别在物质的量浓度为0.1mol·L-1的Na2SO4、0.5mol·L-1的Na2SO4、2.0mol·L-1的NH42SO4水溶液中在0.0～0.85VSCE电位范围内用循环伏安考察电极的电容性能循环伏安结果表明该材料在0.5mol·L-1Na2SO4水溶液中表现出良好的电容性能用恒流充放电测得其比容量可达177.5F·g-1。经5000次循环电极容量保持90%以上。     

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.     

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.     

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.     

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.     

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.