SrCeFeNiO6催化剂的制备及其催化甲烷燃烧性能研究

采用共沉淀法、溶胶凝胶法和水热法制备了双钙钛矿型催化剂SrCeFeNiO₆,其结构和性能经X-射线衍射(XRD)、扫描电镜(SEM)、程序升温还原(H₂-TPR)、比表面积测定(BET)、热重分析(TG-DSC)和甲烷燃烧活性测试表征。结果表明：3种方法制备的催化剂经800 ℃焙烧4 h后均可形成完整的双钙钛矿晶型,催化性能和高温稳定性较好。其中,采用共沉淀法制备的SrCeFeNiO₆催化剂催化甲烷燃烧活性最好,起燃温度T_10℃为432 ℃,完全转换温度T_90℃为582 ℃,比表面积为15.4 m²·g^-1,活化能为43.4 kJ·mol^-1。     

碳微球模板制备LaMnO3及其电化学性能研究

以葡萄糖为碳源采用水热法制备出碳微球,再将其作为模板剂,柠檬酸作为络合剂,去离子水和乙醇作为溶剂,经混合搅拌、沉淀和去除模板剂等步骤,由La(NO₃)₃·6H₂O和Mn(NO₃)₂制备LaMnO₃。采用粉末X射线衍射、场发射扫描电镜、N₂吸附-脱附等对LaMnO₃进行表征分析,并对其电化学性能进行了测试。结果表明,碳微球模板可制备出层状多孔结构的LaMnO₃,其具有良好的氧还原反应(ORR)和析氧反应(OER)催化活性,比表面积为26m²/g,将其制备成铝-空气电池空气电极催化剂,在电流密度20mA·cm^-2时放电电压可达1.476V,高于共沉淀法制备的LaMnO₃的放电电压。     

高倍率性能锂离子电池Li[Ni1/3Co1/3Mn1/3]O2正极材料的制备及其电化学性能

采用改进的碳酸盐共沉淀与高温固相法相结合的方法制备出了高倍率性能的锂离子电池正极材料Li[Ni_1/3Co_1/3Mn_1/3]O₂, 通过X射线衍射(XRD)、扫描电镜(SEM)、循环伏安扫描(CV)、电化学阻抗谱(EIS)和电化学性能测试等手段对材料进行表征. 结果表明, 该方法制备的材料具有良好的α-NaFeO₂型层状结构(R3m(166)), 一次粒径平均大小为157 nm, 二次颗粒成球形. 同传统碳酸盐制备得到的材料相比, 该材料具备良好的倍率性能和循环性能, 在2.7-4.3 V 电压范围内, 0.1C (1.0C=180 mA·g^-1)倍率下, 首次放电比容量为156.4mAh·g^-1, 库仑效率为81.9%. 在较高倍率下, 即0.5C、5.0C和20C时, 其放电比容量分别为136.9、111.3、81.3mAh·g^-1. 在1C倍率下100次循环容量保持率为92.9%, 高于传统共沉淀法得到的材料(87.0%).     

高性能LiFePO4/碳纳米笼锂离子电池正极材料

以具有高比表面积、分级孔结构和优良导电性的碳纳米笼（CNCs）为载体,制得了粒子尺寸为10～25 nm且高度分散的LiFePO₄/CNCs复合物.以LiFePO₄/CNCs复合物作为锂离子电池的正极材料,在0.1 C倍率下首次放电比容量达到163 mAh·g^-1,15 C和30 C倍率下的放电比容量可达96和75 mAh·g^-1;在15 C倍率下循环200圈后,其放电比容量仍保持在92 mAh·g^-1,显著优于LiFePO₄/CNTs复合物.这些结果表明,LiFePO₄/CNCs复合物具有优异的倍率性能和循环稳定性,是一种性能优良的锂离子电池正极材料,其性能源自CNCs载体的高比表面积、分级孔结构和优异导电性以及LiFePO₄颗粒的纳米化和高结晶度.     

壳聚糖基多孔碳材料的制备及其超级电容性能

以胶态SiO₂纳米粒子为模板,壳聚糖为碳源,ZnCl₂为活化剂,制备了具有不同比表面积和孔体积的氮掺杂介孔碳。采用多种表征手段对碳材料的微观形貌、比表面积和孔道结构进行了表征,探究了壳聚糖与SiO₂纳米粒子的比例以及ZnCl₂活化剂对碳材料孔体积和比表面积的影响。结果表明,在未使用活化剂时碳材料(CSi-1.75)的孔体积高达4.53 cm³·g^-1,但其比表面积最小(729 m²·g^-1);使用ZnCl₂作为活化剂制备的碳材料(CSi-1.75-Zn)比表面积为1 032 m²·g^-1,但其孔体积下降到1.99 cm³·g^-1,且具有最多的吡啶氮和吡咯氮。在以6.0 mol·L^-1KOH为电解液的三电极体系中,当电流密度为0.5 A·g^-1时,CSi-1.75...     

喷雾干燥-高温烧结的NaMnPO4制备及其电化学性能

采用喷雾干燥制备前驱体,经高温烧结制得有电化学活性的钠离子电池NaMnPO₄正极材料. X射线衍射分析（XRD）证明,合成的NaMnPO₄材料系正交晶系、Pmnb空间群的磷钠锰矿（Natrophilite）型材料. 扫描电镜（SEM）及透射电镜（TEM）结果显示,喷雾干燥得到的前驱体为空心球粒子,经高温烧结后,该材料由粒径几十纳米的NaMnPO₄纳米晶一次颗粒及无定形碳网络结构相互连接组成的微米级二次颗粒构成. 电化学测试表明,NaMnPO₄/C复合结构显著改善了材料的离子电导与电子电导,首次报道电流密度为7.75 mA·g^-1、电压范围为1.0 ~ 4.5 V (vs. Na⁺/Na)时,钠离子电池NaMnPO₄正极材料的可逆放电比容量达90 mAh·g^-1.     

铝掺杂及钨酸锂表面包覆双效提升富锂锰基正极材料的循环稳定性

采用溶胶-凝胶法合成Al掺杂富锂锰基Li_1.2Mn_0.54-xAl_xNi_0.13Co_0.13O₂（x=0、0.03）锂离子电池正极材料,之后采用一步液相法制备Li₂WO₄包覆层,系统地研究了Al掺杂和Li₂WO₄包覆双效改性对富锂锰基正极材料电化学性能的影响.结果表明,Al掺杂后明显提升富锂锰基正极材料的循环稳定性,包覆层Li₂WO₄明显改善其倍率性能和放电平台电压衰减问题.Li₂WO₄包覆量为5% Li_1.2Mn_0.51Al_0.03Ni_0.13Co_0.13O₂正极材料在2.0~4.8 V充放电电压区间及1000 mA·g^-1电流密度下比容量仍高达110 mAh·g^-1左右,同时在100 mA·g^-1的电流密度下循环300次容量保持率为78%,而且循环过程中放电平台电压衰减也明显减缓.该工作为解决锂离子电池富锂锰基正极材料循环稳定性和平台电压衰减提供了新的思路.     

三维网状结构Ru/石墨烯/碳纳米管复合材料作为锂氧电池正极催化剂的性能

利用物理浸渍和冷冻干燥等方法制备了具有三维网状结构的Ru/石墨烯/碳纳米管复合材料, 对该材料的结构、 形貌及电化学性能进行了表征和研究. 结果表明, 当Ru含量为30%, 热处理温度为500 ℃时, 材料的催化性能最优. 将其用作锂氧电池的正极催化剂, 以50 mA/g电流密度进行首次充放电时, 放电比容量约为5800 mA·h/g, 且在放电比容量为4000 mA·h/g以内时, 其极化电压仅为0.9 V; 当以50 mA/g电流密度进行恒容(500 mA·h/g)充放电循环时, 在极化电压低于1.1 V时, 仍能稳定循环12周. 复合材料电催化机理的研究结果表明, 三维网状结构不仅提供了O₂和Li⁺的传输通道, 更增加了放电产物Li₂O₂的储存场所. 金属钌纳米粒子的负载既增加了复合材料的反应活性位点, 又促进了放电产物Li₂O₂的分解.     

Sol-gel法制备La1-xSrxMnO3巨磁电阻薄膜材料

利用sol-gel法在单晶硅Si(100)衬底上,制备了钙钛矿La_1-xSr_xMnO₃(LSMO)低织构纳米晶薄膜.考察了制备条件对LSMO成相、晶粒的粒度和表面形貌的影响,研究了其磁特性和磁电阻性能.结果表明,La_0.7Sr_0.3MnO₃薄膜磁电阻效应在相当宽的温度范围内不随温度改变,在6T磁场中室温下磁电阻比MR值可达-30%.     

放电态Li-AgVO3一次电池作为可充Li-O2电池再利用研究

废弃电池中活性材料再利用是目前处理废弃的一次电池既节约又节能的方法.基于此,本工作详细地研究了废弃的Li-AgVO₃一次电池作为可充Li-O₂电池的再利用.结果显示放电后的Li-AgVO₃电池可以作为Li-O₂电池被再次激活.在Li-AgVO₃电池放电过程中,原位生长在钒氧化物电极上的银纳米颗粒可以进一步有效地催化Li-O₂电池中氧还原和氧析出反应（ORR/OER）.通过控制Li-AgVO₃一次电池的放电深度,可以得到具有不同尺寸和分布状态的Ag纳米颗粒的银/钒氧化物复合电极.将这些不同放电状态的复合电极作为Li-O₂电池的空气正极并测试了它们的电化学性能.电化学测试结果表明,放电到2.3 V的复合电极电化学性能最优,比容量高达9000 mAh·g_carbon^-1,充放电过电位最低,可稳定循环95周.其优异电化学性能归因于银纳米颗粒合适的尺寸和均匀的分布,明显提高了电极导电能力并为ORR/OER电催化反应提供了丰富的活性位点.     

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.     

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.     

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.     

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.