Preparation of New Functionality Materials by Means of Soft Chemistry

软化学制备新型功能材料

• 批准号: 01470070
• 负责人: KINOMUTA Nobukazu
• 金额: $ 4.67万
• 依托单位: Faculty of Engineering, Yamanashi University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1989
• 资助国家: 日本
• 起止时间: 1989 至 1990
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-01470070/
• 关键词: Layered compounds; Solid Acids; Intercalation; Organic bases; Alkylamines; Alkyldiamines; Conformation; リシエ-ション; トポタクティック反応; イオン交換; ペロブスカイト型構造; コロンバイト型構造; ソフト化学; 水和リン酸ニオブ; LiNbO_3型構造

New compounds were prepared by various soft chemical methods such as ion exchange, intercalation, deintercalation and lithiation.(1) Preparation of LiNbO_3-type compounds from CuMb_2O_6 (M=Nb, Ta).Chemical insertion of lithium into CuNb_2O_6 and CuTa_2O_6 which have a distorted perovskite-type and the columbite-type structure, repectively, was carried out in the hexane solution of n-butyllithium at room temperature and 50^ﾟC, yielding new compounds, Li_<1-x>Cu_xMO_3, where part of Cu ion was extracted. When M=Ta, the product was found to have the LiNbO_3-type structure as a result of topotactic structural change on lithiation. On the other hand the framework of CuNb_2O_6 was intact on lithiation, but by heating at elevated temperatures in Ar atmosphere, the compounds transformed to the LiNbO_3 type structure. Although the transformation accompanies rearrangement of cations, it was considered to be a topochemical change, because the hexagonal close packed oxygen array was preserved in b … More oth structural types. The crystal structure of Li<@21-x<@>D2Cu<@D2x@>D2MO<@D23@>D2 was refined by the X-ray powder Rietveld method, revealing the arrangement of cation is very similar to that of ferroelectric LiMO<@D23@>D2.(2) Intercalation of organic bases into layered compounds with controlled charge densities of the layer.(H, Na)_xMo_2O_4・nH_2O and HTaWO_6・nH_2O were reacted with n-alkylamines, n-alkyldiamines and various organic bases having lower pKa than them at room temperature and 90^ﾟC for 3 days to 2 weeks in a sealed glass tube. In spite of difference in the charge density, the basal spacings of intercalation compounds from (H, Na) _x Mo_2O_4・nH_2O and H_xWOP_2O_7・nH_2O were similar for the same number of carbon atoms in the alkyl chains. The odd-even alternative change of the basal spacings was observed for n-alkyldiamine derivatives, indicating regular paraffin type structure in the interlayer spaces. The basal spacings of diamine deivatives indicated the gauche form of alkylchain for intercalation compounds of HTaWO_6・nH_2O and very declined arrangement of alkylchains to the layer for (H, Na) _xMo_4・nH_2O and H_xWOP_2O_7・nH_2O with low charge densities. The trans-cis transition of alkyl chain which is reported for some n-alkylamine derivatives of layered compounds was observed for the diamine derivatives of (H, Na)_xMo_2O_4・nH_2O.The intercalation of quinoxaline with pKa of 0.56 indicates that HTaWO_6・nH _2O is stronger acid than layered titanates, niobates and molybdates. The characteristic feature of this compound is its capability of intercalation of rigid molecules such as p-aminoazobenzene which have been thought difficult to be intercalated. As indicated by the fact that isoquinoline derivative shows photochromisim on radiation of X-ray, HTaWO_6・nH_2O is a potential material for new functional material based on the interaction between molecules in the interlayer spaces or guest molecule and host as well as for catalyst. Less

通过离子交换、嵌入、脱嵌、锂化等多种软化学方法制备了新化合物。(1)以CuMb_2O_6(M=Nb,Ta)为原料制备LiNbO_3型化合物。在具有畸变钙钛矿型和铌铁矿型的CuNb_2O_6和CuTa_2O_6中化学嵌入锂。 在室温和50℃下，分别在正丁基锂的己烷溶液中进行结构分析，得到新化合物Li_<1-x>Cu_xMO_3，其中部分Cu离子被萃取。当M=Ta时，由于锂化时拓扑结构的变化，产物具有LiNbO_3型结构。另一方面，CuNb_2O_6 的骨架在锂化时保持完整，但通过在 Ar 气氛中高温加热，化合物转变为 LiNbO_3 型结构。尽管这种转变伴随着阳离子的重排，但它被认为是一种拓扑化学变化，因为六方密排氧阵列在其他结构类型中都得到了保留。采用X射线粉末Rietveld法精修了Li<@21-x<@>D2Cu<@D2x@>D2MO<@D23@>D2的晶体结构，揭示了阳离子的排列与铁电LiMO<@D23@>D2的排列非常相似。(2)有机碱嵌入层状化合物中，层状化合物的电荷密度受控。(H, 将Na)_xMo_2O_4·nH_2O和HTaWO_6·nH_2O与n-烷基胺、n-烷基二胺和pKa低于它们的各种有机碱在室温和90℃下在密封玻璃管中反应3天至2周。尽管电荷密度存在差异，但对于相同烷基链碳原子数，(H, Na) _x Mo_2O_4·nH_2O 和 H_xWOP_2O_7·nH_2O 插层化合物的底间距相似。对于正烷基二胺衍生物，观察到基础间距的奇偶交替变化，表明层间空间具有规则的石蜡型结构。二胺衍生物的基础间距表明，HTaWO_6·nH_2O 插层化合物的烷基链呈稀疏形式，而电荷密度较低的 (H, Na) _xMo_4·nH_2O 和 H_xWOP_2O_7·nH_2O 的烷基链向层的排列非常下降。 (H,Na)_xMo_2O_4·nH_2O 的二胺衍生物观察到了一些层状化合物的正烷基胺衍生物中烷基链的反顺式转变。pKa 为 0.56 的喹喔啉的插入表明 HTaWO_6·nH _2O 的酸性比层状钛酸盐、铌酸盐和 钼酸盐。该化合物的特征是能够嵌入刚性分子，例如对氨基偶氮苯，而此前人们认为这些分子很难嵌入。异喹啉衍生物在X射线辐射下表现出光致变色的事实表明，HTaWO_6·nH_2O是一种潜在的基于层间分子或客体分子与主体相互作用的新型功能材料以及催化剂材料。较少的

项目成果

N. Kinomura et. al.: "Synthesis of Inorganic Compounds by Means of Soft Chemical Methods" Nyu Seramikkusu. 3. 29-36 (1990)

N.Kinomura 等。

木野村 暢一: "ソフト化学的手法による無機化合物の合成" ニユ-セラミックス. 3. 29-36 (1990)

Nobuichi Kinomura：“软化学方法合成无机化合物”《新陶瓷》3. 29-36 (1990)。

N.Kinomura: "Intercalation of nーAlkylamines and nーAlkyldiamines into HTAWO_6・nH_2O" Solid State Ionics. 37. 317-321 (1990)

N.Kinomura：“将 n-烷基胺和 n-烷基二胺插入 HTAWO_6·nH_2O”固态离子学 37. 317-321 (1990)。

N.Kumada: "A New Lithium Insertion Compound,(Li,Cu)TaO_3,with the LiNbO_3 Type Structure" Inorganic Chemistry. 28. 3592-3595 (1989)

N.Kumada：“一种新型锂插入化合物，(Li,Cu)TaO_3，具有LiNbO_3型结构”无机化学。

N. Kinomura et. al.: "Intercalation Compounds of n-Alkyldiamines and Pyridine from H _xWOP_2O_7・nH_2O"

N. Kinomura 等人：“H _xWOP_2O_7·nH_2O 中的正烷基二胺和吡啶的插层化合物”