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Study on Synthesis and Structural Chemistry of Tungstate Family Using Host-Guest Reactions

主客体反应钨酸盐族的合成及结构化学研究

基本信息

批准号：
01550592
负责人：
MIYAKE Michihiro
金额：
$ 1.34万
依托单位：
Yamanashi University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
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

项目摘要

The host-guest reaction can create metastable isomorphic or polymorphic forms which cannot be prepared by the ordinary synthetic methods, i. e., fusion, solid-state reaction, hydrothermal techniques and so on. Thus, the unique functions are expected to be manifested in the new compounds. In this study, the host-guest reactions on tungstate family have been investigated.1. Interlayer Na^+ions in Na_2W_4O_<13> with layer structure were found to be topotactically exchanged for univalent cations in molten nitrate salts. Consequently, new Li_2W_4O_<13>, K_2W_4O_<13> and Rb_2W_4O_<13>, which are isostructural with Na_2W_4O_<13>, were successfully synthesized. The Li_2W_4O_<13> showed much lower ionic conductivity than the original Na_2W_4O_<13>.2. K^+ions in K_2W_4O_<13> with its tunnel framework structure were found to be topotactically exchanged for univalent cations in molten nitrate salts. Consequently, new LiKW_4O_<13>, Na_<1.4>K_<0.6>W_4O_<13>, Rb_<0.8>K_<1.2>W_4O_<13>, and Ag_<1.5>K_<0.5>W_4O_<13>, which are isostructural with K_2W_4O_<13>, were successfully synthesized. Proton-exchanged potassium tungstates (H_<0.25>K_<1.75>W_4O_<13>), which is isostructural with K_2W_40_<13>, were also found to have the feasibility of the potassium memorized exchangers.3. The cation-exchanges of K_2Mn_4O_8 in aqueous solutions and molten salts revealed to be able to produce new hydrous R_2Mn_4O_8・nH_2O (R=Li, Na, Ag, and NH_4 ; n=1-2) and anhydrous R_2Mn_4O_8 (R=Li, Na, and NH_4) with layer structures.

主客体反应可以产生亚稳态的同晶型或多晶型形式，这些形式不能通过普通的合成方法制备，即。例如，聚变、固相反应、水热技术等，这些独特的功能有望在新化合物中得到体现。本论文主要研究了钨酸盐类化合物的主-客体反应.在<13>熔融硝酸盐中，层状结构的Na_2W_4O_3中的层间Na^+离子与一价阳离子发生拓扑交换。在此基础上，成功地合成了与Na_2W_4O_3同构的新的<13>Li_2W_4O_3、K_2W_4O_3<13>和<13>Rb_2W_4O_3<13>。Li_2W_4O_2<13>的离子电导率比Na_2W_4O_2低得多<13>。在<13>熔融硝酸盐中，隧道结构的K_2W_4O_3中的K^+离子与一价阳离子发生拓扑交换。在此基础上，成功地合成了与K_2W_4O_具有同构结构的LiKW_4O_<13>，<1.4>Na_K_W_4O<0.6>_<13>，<0.8>Rb_K_W_4O<1.2>_<13>，<1.5>Ag_K_W_4O_4<0.5><13><13>。与K_2W_40_结构相同的质子交换钨酸钾（H_<0.25>K_<1.75>W_4O_<13>）<13>也具有作为钾记忆交换剂的可行性. K_2Mn_4O_8在水溶液和熔盐中的阳离子交换实验表明，可以生成新的层状结构的水合R_2Mn_4O_8·nH_2O（R=Li，Na，Ag，NH_4 ; n=1-2）和无水R_2Mn_4O_8（R=Li，Na，NH_4）。