负热膨胀材料研究进展

本文介绍了负热膨胀材料的制备技术、结构、性能、应用及热缩机理研究的主要进展。分析了负热膨胀材料合成及其应用中存在的主要问题,讨论了刚性单元模模型及其局限性,给出了热缩机理理论和实验特别是第一性原理声子谱计算和拉曼光谱研究的最新进展、存在问题及发展趋势。指出了负热膨胀材料研究中应重点解决的一些重要问题。     

普鲁士蓝类化合物负热膨胀及机理

负热膨胀化合物可调控材料的热膨胀系数, 在复合材料、 精密仪器等方面具有重要的应用前景, 成为近年来化学、 物理和材料工程领域的研究热点之一. 因其晶体结构主要由—M—CN—M—含有双原子氰根(CN)链组成, 许多普鲁士蓝类化合物呈现反常的热膨胀性质. 本文综述了普鲁士蓝类负热膨胀化合物结构、 热膨胀机制与系数调控等方面的研究进展. 以氰根配体数量为分类主线, 将具有反常热膨胀性的氰根配体化合物分为氰化物、 六氰基和八氰基普鲁士蓝类化合物等进行介绍, 从局域结构和平均结构角度分析了N和C原子的横向振动对负热膨胀贡献的角度解释了机理, 从客体离子或分子嵌入的方法分析了热膨胀调控原理, 并对新型普鲁士蓝类负热膨胀化合物的设计及应用进行了展望.     

不同形貌聚吡咯对SnO_2负极电化学性能的改善

在预先原位合成的聚吡咯溶液中通过简单沉淀得到SnO2/聚吡咯负极材料,对材料的结构、形貌进行了表征并对材料的电化学性能进行了研究.发现不同形貌的聚吡咯对负极材料的电化学性能存在一定影响:SnO2负极材料在球状聚吡咯体系中比在管状聚吡咯体系中的电化学性能优越,首次库仑效率提高至77.6%,60次循环后仍剩余600 mA·h/g的可逆比容量.     

顶杆法热膨胀仪在材料研究中的应用

利用顶杆法膨胀仪,探讨了材料结构、密度与热膨胀的关系,用其它实验方法交叉结合对材料的相变进行了研究,并通过热膨胀曲线确定某些材料的特定工艺参数,实验证实了热膨胀在材料热学性能研究领域中是一种非常简捷、可靠、实用的工具之一     

两种金属-有机钙钛矿材料的负热膨胀性质

通过变温单晶X射线衍射和透射电镜实验对2种金属-有机钙钛矿材料[C(NH2)3][Mn(HCOO)3](1)和[(CH2)3NH2][Mn(HCOO)3](2)进行表征,分析了其晶体结构和晶格常数随温度变化的关系,发现2种材料沿c轴方向都表现出负的热膨胀行为,其效应分别为:αc1=-1.2(1)×10~(-5)K~(-1),αc2=-6.1(11)×10~(-5)K~(-1)。采用一种"铰链"结构模型对这2种框架材料的负热膨胀机理进行了详细解释:温度升高会诱导框架中主体和客体铵基之间的氢键长度及键角发生改变,引起钙钛矿框架结构发生变形,进而导致其沿框架对角线方向(c轴方向)的负热膨胀行为。     

顶杆法热膨胀仪在材料研究中的应用

利用顶杆法膨胀仪,探讨了材料结构,密度与热膨胀的关系,用其它实验方法交叉结合对材料的相变进行了研究,并通过热膨胀曲线确定某些材料的特定工艺参数,实验证实了热膨胀在材料热学性能研究领域中是一种非常简捷,可靠,实用的工具之一。     

Y_(2-x)Ho_x(WO_4)_3的制备及其热膨胀性能研究

采用固相化学反应法制取Y2-xHox(WO4)3(x=0.0~0.8,1.5~2.0)系列固溶体,利用高、低温X射线衍射方法研究Y2-xHox(WO4)3系列固溶体的热膨胀性能,并用热重法分析Y2-xHox(WO4)3所带的结晶水分子数目。由TOPAS软件计算出的晶胞参数随温度的变化可以看出,Y2-xHox(WO4)3{x=0.2,1.8}的化合物沿着3个晶向都是呈负热膨胀变化的,表明Y2-xHox(WO4)3这一系列固溶体均有负热膨胀性。     

第一性原理计算钛酸铅A位掺杂对其负热膨胀性的影响

近年来,实验发现钛酸铅基材料具有负热膨胀性,且其热膨胀程度会受到掺杂元素的影响.目前所研究的A位掺杂体系中,仅Cd原子掺杂能使钛酸铅负热膨胀性增强.所以研究A位掺杂钛酸铅,比较Cd原子与其他原子在掺杂钛酸铅时化学键的异同,有助于深刻理解钛酸铅负热膨胀的本质.本文利用第一性原理,分别优化了Sr、Ba、Cd掺杂钛酸铅的晶格常数,计算了它们的态密度和电荷密度.结果表明Cd―O键的共价性强于Pb―O键,而Ba―O键和Sr―O键几乎呈离子性,Ba/Sr对Pb的替代削弱了化合物的共价性,降低了自发极化强度.与实验测量的热膨胀系数对比可以发现,A位原子与氧原子之间的共价性增强,化合物负热膨胀程度升高;若A位原子与氧原子之间的共价性削弱,负热膨胀程度降低.可见A位原子与氧原子之间的共价性影响了钛酸铅基化合物负热膨胀性.     

第一性原理计算钛酸铅A位掺杂对其负热膨胀性的影响

近年来,实验发现钛酸铅基材料具有负热膨胀性,且其热膨胀程度会受到掺杂元素的影响. 目前所研究的A位掺杂体系中,仅Cd原子掺杂能使钛酸铅负热膨胀性增强. 所以研究A位掺杂钛酸铅,比较Cd原子与其他原子在掺杂钛酸铅时化学键的异同,有助于深刻理解钛酸铅负热膨胀的本质. 本文利用第一性原理,分别优化了Sr、Ba、Cd掺杂钛酸铅的晶格常数,计算了它们的态密度和电荷密度. 结果表明Cd―O键的共价性强于Pb―O键,而Ba―O键和Sr―O键几乎呈离子性,Ba/Sr对Pb的替代削弱了化合物的共价性,降低了自发极化强度. 与实验测量的热膨胀系数对比可以发现,A位原子与氧原子之间的共价性增强,化合物负热膨胀程度升高;若A位原子与氧原子之间的共价性削弱,负热膨胀程度降低. 可见A位原子与氧原子之间的共价性影响了钛酸铅基化合物负热膨胀性.     

新型固体电解质La2Mo2O9的制备及其性能

用固相法制备了新型固体电解质La2Mo2O9, 用热膨胀仪、 X射线衍射仪和Raman光谱分析了La2Mo2O9相的形成过程. 用交流阻抗谱和热膨胀仪对合成样品的电学和热学性能进行了研究, 分析了热处理温度对La2Mo2O9相的形成过程和电学性能的影响, 确定了样品获得高电学性能的最佳条件. 研究结果表明: 600 ℃时样品中开始形成La2Mo2O9相, 700 ℃以上烧结的样品可获得具有完整氧空位的La2Mo2O9相. 900 ℃烧结10 h可获得具有高密度和高电导率的La2Mo2O9氧离子导体. 样品的电学性能随烧结温度的升高而增大, 900 ℃时烧结的样品在800 ℃时的电导率为0.067 S·cm-1, 远高于同温度下YSZ的电导率, 与晶粒电阻相比, 晶界电阻非常小. 用热膨胀仪测得La2Mo2O9在555 ℃时有一个一级相变, 对应α-La2Mo2O9到β-La2Mo2O9的相变.     

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.     

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.     

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.     

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.     

Microwave-assisted copper-catalyzed stereoselective ring expansion of three-membered heterocycles with α-diazo-β-dicarbonyl compounds

Microwave-assisted copper-catalyzed ring expansions of three-membered heterocycles with α-diazo-β-dicarbonyl compounds were investigated. Thiiranes generated 3-acyl-5,6-dihydro-1,4-oxathiines in the presence of copper sulfate and trans-3-acyl-5,6-dihydro-1,4-oxathiines as stereospecific products for 1,2-disubstituted cis-thiiranes through an intramolecular S_N2 process. Oxiranes gave rise to 2-acyl-5,6-dihydro-1,4-dioxines under the catalysis of copper hexafluoroacetylacetonate and cis-3-acyl-5,6-dihydro-1,4-dioxines as stereospecific products for 1,2-disubstituted cis-oxiranes via an intimate ion-pair mechanism. The current method provides a direct and simple strategy in efficient preparation of 3-acyl-5,6-dihydro-1,4-oxathiines and 2-acyl-5,6-dihydro-1,4-dioxines, important agents in medicinal and agricultural chemistry, from readily available thiiranes and oxiranes, respectively.     

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.