Fundamental Study on Development of Anion Adsorbent of Anti-Hofmeister Type

抗霍夫迈斯特型阴离子吸附剂研制的基础研究

基本信息

批准号：
03650607
负责人：
JYO Akinori
金额：
$ 1.15万
依托单位：
KUMAMOTO 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：
1991
资助国家：
日本
起止时间：
1991 至 1992
项目状态：
已结题

项目摘要

Adsorbents for anions with anti-Hofmeister anion-selectivity sequences were developed based on cobalt(III) complex of the dioxocyclam (1,4,8,11-tetraazacyclotetradecane-5,7-dione) moiety. Significant results of this work can be summarized as follows:(1) The cobalt(III) complex of dioxocyclam moiety selectively recognizes nitrite or thiocyanate in the presence of excess nitrate or perchlorate in weakly acidic aqueous solutions.(2) The cobalt(III) complex of alkylated dioxocyclam (6-octadecyl-1,4,8,11-tetraazacyclotetradecane-5,7-dione) in chloroform extracts thiocyanate in preference to perchlorate from weakly acidic solutions, indicating an anti-Hofmeister anion selectivity.(3) The hydrophobic cobalt(III) complex adsorbed on Amberlite XAD-7 also shows the anti-Hofmeister anion selectivity; the Amberlite XAD-7 modified with the complex mentioned above (2) takes up nitrite in the presence of nitrate in large excess. However, this approach is not promising, since the loading of the complex larger than ca. 0.3 mmol/g is difficult to achieve.(4) The chelating resin (RGD), which was obtained by the reaction of dioxocyclam with macroreticular glycidyl methacrylate-divinylbenzene copolymer beads, adsorbs cobalt(III) up to 0.6 - 0.7 mmol/g. The cobalt(III) loaded RGD acts as an anion-exchanger with the anti-Hofmeister anion selectivity. For example, this newly developed anion-adsorbent takes up thiocyanate under conditions that molar ratio of thiocyanate to perchlorate is 1:10, while a conventional anion exchange resin adsorbs little thiocyanate under the same conditions. The adsorbed anions were easily and rapidly eluted with aqueous alkaline solutions, and columnar approach has clarified that repeated use of the adsorbent is also possible.

基于二氧环酰胺（1,4,8,11-四氮杂环十四烷-5,7-二酮）部分的钴（III）络合物，开发了具有抗霍夫迈斯特阴离子选择性序列的阴离子吸附剂。这项工作的重要成果可概括如下：（1）二氧环酰胺部分的钴（III）配合物在弱酸性水溶液中存在过量硝酸盐或高氯酸盐的情况下选择性识别亚硝酸盐或硫氰酸盐。（2）钴（III）配合物烷基化二氧环酰胺（6-十八烷基-1,4,8,11-四氮杂环十四烷-5,7-二酮）复合物氯仿从弱酸性溶液中优先萃取硫氰酸根，而不是高氯酸根，表现出抗霍夫迈斯特阴离子选择性。(3)吸附在Amberlite XAD-7上的疏水性钴(III)配合物也表现出抗霍夫迈斯特阴离子选择性；用上述络合物(2)改性的Amberlite XAD-7在大量过量的硝酸盐存在下吸收亚硝酸盐。然而，这种方法前景并不乐观，因为复合物的负载量大于约。 0.3 mmol/g很难达到。(4)双氧环胺与大网络甲基丙烯酸缩水甘油酯-二乙烯基苯共聚物珠反应得到的螯合树脂(RGD)对钴(III)的吸附量高达0.6～0.7 mmol/g。负载钴 (III) 的 RGD 充当具有抗霍夫迈斯特阴离子选择性的阴离子交换剂。例如，这种新开发的阴离子吸附剂在硫氰酸盐与高氯酸盐摩尔比为1:10的条件下吸附硫氰酸盐，而传统阴离子交换树脂在相同条件下吸附很少的硫氰酸盐。吸附的阴离子可以用碱性水溶液轻松快速地洗脱，并且柱状方法表明吸附剂的重复使用也是可能的。