超轻纳米纤维气凝胶的制备及其应用

超轻纳米纤维气凝胶是一种以一维纳米纤维为基本构筑单元的新型气凝胶材料,相比于传统气凝胶,其不仅具有更高的孔隙率和更低的密度,还拥有更优异的机械性能和理化性质,因此该材料的先进制备技术和在新兴领域的创新性应用是近年来超轻气凝胶领域的研究热点。本文结合国内外研究现状,按照材料体系分类系统综述了超轻纤维气凝胶的制备方法、结构特点以及在隔热、吸附、电化学、传感和生物医学等领域的重要应用,提出了现阶段该材料面临的一些挑战,并展望了其在未来的发展方向。     

三维(3D)石墨烯及其复合材料的应用

三维（3D）石墨烯通常是指具有3D结构的二维（2D）石墨烯组装体,是近年来石墨烯化学领域的新型功能性材料。将2D石墨烯片整合成具有3D结构的组装体可以有效调控石墨烯的电学、光学、机械、化学和催化特性,因此3D石墨烯材料不仅具有石墨烯固有的理化性质,其三维多孔的微/纳米结构还使其兼具比表面积大、机械强度高、电子传导能力优越及传质快速等优良特性。这些独特的性质使3D石墨烯及其复合材料在材料科学领域备受关注。研究发现,3D石墨烯及其复合材料应用于纳米电子学、能量储存和转换、化学和生物传感等研究领域均表现出优越的性能。本文结合当前研究热点,综述了3D石墨烯及其复合材料在催化、储氢/气体吸附、传感器、环境修复、超级电容器等领域中的应用进展,并简要评述目前3D石墨烯材料应用中所面临的挑战及发展前景。     

静电纺丝纳米纤维基超级电容器电极材料的研究进展

静电纺丝纳米纤维具有比表面积大、孔隙率高及密度低等优势,是电化学储能材料的理想候选者之一.本文综述了近年来静电纺丝碳纳米纤维、金属氧化物/硫化物/氮化物、导电聚合物及其复合材料在超级电容器领域的研究及应用进展,探讨了材料组成、结构与电化学电容性能之间的关系,并对静电纺丝纳米纤维基电极材料的发展前景进行了展望.这将为新型高性能超级电容器电极材料的结构设计与可控制备提供新思路.     

一维铁磁金属纳米材料的制备、结构调控及其磁性能

一维铁磁金属纳米材料不但具有普通纳米粒子的各种特殊效应,而且具有独特的形状各向异性和磁各向异性,是构筑新型电磁功能材料的重要组元,在高密度磁记录、敏感元器件、电磁波吸收、催化剂、医学和生物功能材料等领域具有重要的应用。本文以一维铁磁金属纳米材料的制备技术为评述线索,重点论述了一维铁磁金属纳米材料的形貌参数（包括直径、长度、长径比）,晶面取向等微观结构的调控方法以及结构对磁性能的影响规律,指出发展新型的一维铁磁纳米材料的结构控制方法,研究一维材料的定向排布及组装技术,并从更深层次揭示一维结构与性能的关系以及开发一维铁磁纳米材料在各领域的实际应用是未来研究的主要发展方向。     

芴类化合物的研究新进展

芴及其衍生物是一类重要的具有刚性平面联苯结构的化合物,分子内含有较大的共轭体系,这种特殊的刚性稠环结构使芴类化合物表现出许多独特的光电性能及生物活性,在光电材料、医药等多领域具有潜在的广泛应用.更为重要的是芴类化合物易于进行结构修饰,在芴环上可方便地引入各种功能基,芴类衍生物的合成及其开拓芴类化合物潜在的新用途,成为近些年来十分活跃的研究领域,且发展迅速.结合自己的工作,参考国内外文献,全面综述了芴类化合物在有机电致发光材料、双光子吸收材料、光致变色材料、太阳能电池材料和生物医药等领域的研究与开发新进展,并对其发展趋势作了展望.     

X射线吸收精细结构技术在高分子及相关材料中的应用

高分子材料由于其优异的物理和化学性能应用范围非常广泛,而同步辐射光源的发展大大提高了X射线吸收精细结构(XAFS)技术的使用.本文介绍了XAFS包括扩展X射线吸收精细结构(EXAFS)和X射线吸收近边结构(XANES)的实验原理和实验手段,综述了同行利用XAFS技术在常见高分子、有机金属高分子、钯掺杂高分子、离聚物及碳基材料等高分子领域的结构研究进展,展示了XAFS技术在高分子及其相关材料领域的重要作用和分析方法,体现了XAFS技术的优势和特点,并对XAFS技术在高分子及相关材料方面的应用进行了展望.随着同步辐射技术的发展和提高,XAFS技术在高分子领域的应用将会进一步拓展和提升.     

纳米金属-有机框架材料的制备及应用

金属-有机框架材料(MOFs)自发现以来备受关注,其独特的高孔隙率结构特性、孔径可调以及可官能化等特点,在许多领域都有潜在的应用,如储气、分离、催化和热能转化等。纳米金属-有机框架材料(NMOFs)因具有纳米尺寸,既拥有传统块状MOFs的性质,也具备特殊的物理/化学特性,表现出更为优异的性能。本文介绍了MOFs的发展,及几种经典的MOFs结构及其应用;重点论述了近年来一些重要的纳米MOFs的制备方法和应用,并对纳米MOFs在新型材料领域中的应用及其发展方向进行了展望。     

碳材料修饰铋系光催化剂及其应用

可见光半导体光催化剂具有高效利用太阳能从而解决能源及环境问题的优势,引起光催化及其他领域人们的关注.铋系光催化剂多属于窄带隙半导体材料,能够吸收太阳光谱中的大量可见光.此外,铋系光催化剂独特的层状晶体结构及较深的价带位置决定了其具有较高的催化活性,成为近年来半导体光催化领域研究的热点.碳基质材料由于具有比表面积大、热和化学稳定性高以及导电能力强等物理化学性质而被人们广泛研究.将碳材料与铋系半导体进行复合,两者之间的协同效应能够增强对反应物的吸附量,拓宽对太阳光的吸收范围,加速电子/空穴对的分离,从而提高催化活性.此外,碳材料修饰的铋光催化剂更易被分离及回收利用,可有效降低应用成本,具有潜在的应用前景.本文对近年来利用碳基质材料修饰铋系光催化剂的类型、制备方法、结构与性能、作用机理及其应用研究进行了综述,提出了目前利用碳材料修饰铋系光催化剂在材料设计、机理研究及应用等方面存在的主要问题,并对其未来发展方向进行了展望.     

CuMn2O4@GA复合材料的合成与CO转化

催化氧化法在CO消除领域广泛应用,合成了单分散多孔微球催化剂CuMn₂O₄及其石墨烯气凝胶(GA)超轻复合材料CuMn₂O₄@GA。通过扫描电子显微镜(SEM)、X射线衍射(XRD)等方法表征了材料结构。结果表明,水热法是理想的石墨烯复合材料合成方法。CuMn₂O₄@GA材料结构强度良好、质地均一,催化剂颗粒在气凝胶结构中充分分散。催化性能测试表明,CuMn₂O₄形貌与CO在其表面的吸附和催化转化行为密切相关。得益于复合材料的低密度网络结构,在60000 mL/(g(cat)·h)的高通量进气和128℃下实现了CO的完全转化。进气湿度对复合材料CO催化活性无明显影响,多次重复活化和使用测试表明复合材料具有良好的结构保持性和优良的应用经济性。     

自组装多级结构在锂离子电池中的应用

锂离子电池作为比能量最高的二次电池,在可持续能源领域扮演越来越重要的角色。为寻求下一代更高性能的锂离子电池,人们在探索许多高比容量电极材料。然而,这些材料通常具有锂化前后体积变化大、电极阻抗大等缺点,需要制备成纳米结构才能够获得较好的电化学储锂性能。而纳米结构具有比表面积高、振实密度低等缺点,导致电池的首次库仑效率低、循环寿命短和比能量低。将纳米材料组装成多级结构能够有效地降低整体的比表面积、从而限制固体界面膜形成对锂的消耗量,提高首次库仑效率;与纳米颗粒的无序堆积相比,多级结构材料往往具有较高的堆积密度和接触面积,进而提高电池的能量密度。本文主要介绍锂离子电池中多级结构的制备及其在锂离子电池中的应用：制备方面主要介绍了溶剂热法、乳液法、喷雾干燥法和模板法,以及相关参数对最终多级结构的影响;在应用方面,主要针对不同多级结构材料以提高锂离子电池性能为主线进行综述。     

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.